Corrosion Testing

7.
CORROSION TESTING
7.1. INTRODUCTION
Corrosion can lead to failures in plant infrastructure and machines that can be costly to repair, costly in terms of lost or
contaminated product, in terms of environmental damage, and ultimately costly in terms of human safety. Decisions regarding
the future integrity of a structure or its components depend entirely upon an accurate assessment of the conditions affecting
its corrosion and rate of deterioration.
Corrosion tests are probably the simplest means to avoid using materials under unsuitable conditions or using a more
expensive material than is required. Corrosion tests also help in the development of new materials that perform more
inexpensively, efficiently, longer, or more safely than materials presently in service. Quality control corrosion tests are
additionally a means of ensuring that the materials will perform as expected.
Corrosion testing programs may be relatively simple and be completed in a few minutes or hours, or they may be complex and
require the combined work of a number of investigators over a period of weeks, months, or even years. Corrosion tests are
divided into two broad categories: (1) tests made in the laboratory under controlled conditions, and (2) tests made in the field
under natural or service conditions.1
7.2. LABORATORY-CONTROLLED TESTS

Tests in the laboratory are made with pure chemicals under closely controlled conditions. Each test should be somewhat
reproducible in repeat runs of fixed duration. If reproducible conditions can be achieved, it may be assumed that differences in
the test results truly reflect a difference in the resistance to corrosion of the materials being tested.
Laboratory tests provide an early indication of what can happen in actual practice. However, the time required for an "indication"
depends on the purpose and nature of the tests. Laboratory corrosion tests generally are conducted over a period of time
ranging from a few minutes to as long as a year or even longer.
7.2.1. Tests of the Metal

Laboratory tests are usually conducted with small metal specimens of specified shapes and sizes. Some typical test
specimens are shown in Fig. 7.1. Such specimens have the advantages of being relatively inexpensive, small, and reproducible.
They are intended to evaluate the corrosion response characteristics of a given metal. For example, they should show how
"Steel A" responds differently from "Steel B," or how some other metal would perform under these same test conditions.
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Figure 7.1 Various corrosion coupon shapes and forms for laboratory and field testing. (Courtesy of
Metal Samples.)
Even for the relatively simple types shown (disc, panels, and tensile specimens), a variety of sizes and shapes are employed.
Certain specimens contain the full thickness of the product, such as flat tensile specimens and cast and sheet panels. Others,
such as the round tensile specimens and the stepped panels, are machined from a particular region of thicker products.
For testing of protective coating, panels generally have well-rounded edges to facilitate uniform coating formation. Sometimes
coated or clad specimens are intentionally damaged, one form of coating damage being various scribe marks through the
protective film (Fig. 7.2a and b). Other forms of damage might be impact blows to cause crazing, or countersunk holes.
Figure 7.2 (a) Test coupons with protective coatings scribed for accelerated testing, and (b) test
rack to expose specimens to an outdoor environment.
Many other types of specimens are used to evaluate the effect of applied stress on corrosion.2 Such specimens are typically
designed to optimize the evaluation of the stress corrosion resistance of the alloy. Certain types, such as the two tensile bars
and the sheet tensile specimen, are exposed unstressed as well as stressed. Such procedure allows the determination of the
effect of stress on reduction of strength by corrosion.
7.2.2. Tests of Fabricated Items

7.2.2. Tests of Fabricated Items
Fabricated items are also evaluated in laboratory corrosion tests. Usually, this is done on a limited scale in order to establish
correlations between the corrosion performance of machined specimens and fabricated items to verify that results obtained
with small test specimens much cheaper to prepare are providing valid results. This may be necessary when the final product is
so complex that test data obtained for each component may not provide a true evaluation of the behavior of the final assembly.
7.3. FIELD TESTS

Field tests, which are typically much closer to the end user applications than laboratory tests, normally range in duration from
several months to many years. Some tests have been conducted for more than half a century at well-established outdoor
facilities. Field tests, for example, may consist of exposure to natural environments such as illustrated in Figs. 7.3 and 7.4 or
they may attempt to accelerate the corrosive conditions of particular service conditions (Fig. 7.5).
Figure 7.3 Seawater erosion-corrosion test rig. (Courtesy of Corrpro Companies.)
Figure 7.4 Tidal wave test rack. (Courtesy of Corrpro Companies.)
Figure 7.5 Salt corrosion/temperature/humidity chamber is designed to provide accelerated
corrosion life testing of body, frame, and undercarriage components of passenger cars and trucks
(a) as well as full vehicles (b). (Courtesy of Despatch Industries.)
Most field tests use small cut or machined specimens, but assemblies and complete systems are sometimes tested as
illustrated in Fig. 7.5. Field tests are often conducted for many of the same reasons that laboratory tests are. New and
promising materials must be evaluated, changes in the environment and the effect on materials of construction must be
monitored, and a constant appraisal of the corrosion occurring in many environments is necessary. Such testing is obviously of
great value when preparing maintenance programs, for example, and can improve the economics and safety of a system.
7.4. TEST OBJECTIVES

7.4. TEST OBJECTIVES
Corrosion tests can also be classified as a function of their basic objectives, which in turn may depend on the types of
environment and test durations an investigator is interested in. During fundamental corrosion research, an investigator seeks to
determine how or why a particular form of corrosion occurs. The aims of the investigation are not necessarily tied to any
particular product or use, and seldom is there a set time for completion of the testing objectives. Tests in this area are almost
exclusively conducted in a laboratory setting using small specimens and highly specialized techniques such as those described
in the later sections of this chapter.
In the search for new and maybe more performing alloys to make better for tomorrow the materials and products of today,
investigators may want the bridge, automobile, or home of tomorrow to be more resistant to deterioration by corrosion than
those presently in service. The aims of such efforts are tied directly to related applications with the intent of achieving
improvements in the near future. Such investigation will typically start with small specimens and laboratory tests and, as the
material shows promise, will proceed through all phases of testing.
An engineer working on a new design or designing equipment for a new process must decide which of many available materials
should be used. Often, data developed by suppliers must be relied upon to provide this information. If this is insufficient,
comparative corrosion tests must be conducted among candidate materials for the specific application. One area that must be
considered is the compatibility of different alloys with contacting metallic or nonmetallic materials. Actual parts testing may be
involved, but test durations usually are short term and are geared toward answering questions about a particular application or
environment. As such, the tests conducted must be directly correlated with the end use of the material.
After a choice has been made of the material for an application, the fabricator and purchaser then need to know if the quality of
incoming material is as specified. Quality control corrosion tests, such as the Huey test (5 to 48 hours in boiling 65% nitric acid)
and Strauss test (72 hours in boiling 3% cupric sulfate, 10% sulfuric acid) for stainless steels, or the intergranular corrosion test
(6 hours in 1% hydrogen peroxide, 5% sodium chloride at 30°C for heat-treatable aluminum alloys)3 ensure that the material
meets specifications. Such tests must be sufficiently rapid to avoid undue delay of metal shipments. Corrosion tests of this
type do not require any particular correlation to end use. These tests are used to ensure that the metal shipped has the same
corrosion resistance as the metal previously tested.
As indicated previously, corrosion tests are important in maintaining the reliability of facilities and equipment already in service.
Periodic tests are great tools to evaluate whether a given material still fulfills its initial design requirements. Such tests may
involve cut specimens, coated and uncoated, exposed under operating conditions. They might also involve the evaluation of
parts removed from the actual facility. Tests of this type may also yield some valuable information for the selection of
materials for future projects.
7.5. PROCUREMENT OF TEST MATERIALS

The first step of any corrosion testing program is to acquire some of the material to be tested. In some cases, such as quality
control tests or failure analyses, the type and lot of material to be tested are predetermined. In most other cases, there is
considerable freedom of choice.
7.5.1. Commercial Alloys
If commercial alloys are to be tested, the best procedure is to obtain mill-fabricated material, representative of current
production. If possible, a fabrication history should be obtained listing the major fabricating steps, together with a precise
analysis of the metal composition. Table 7.1 shows an example of one method used to report the fabrication history. A
standard form is prepared and the pertinent data is then merely filled in. While the data required may vary with the type of metal
and product being made, the more important data, such as ingot size, composition, times, and temperatures of heat treatments,
and tensile properties, are required for all metal systems and products.
Table 7.1 Fabrication History for Standard Evaluations of Aluminum Alloy Extrusions
At the very least, the material should be certified as being within the composition limits specified for the alloy and meeting the
strength or hardness specifications. Microscopic examination may also be necessary to ensure that the material is in proper
metallurgical condition. Such basic information may prevent misleading conclusions as a result of off-composition or improper
fabrication.
7.5.2. Nonstandard Alloys

When nonstandard alloys or tempers are to be evaluated, it may be economically impractical to fabricate them using large
production equipment. In such cases, small laboratory casts or heats should be made. While this is a valid procedure for initial
tests before starting a full production, for example, it should be evaluated several times using specimens from quantities of
material large enough to be representative of production variations. Evaluation of several production lots may be necessary
because all, too often, promising results from a single lot of material are not reproduced on subsequent fabrication runs.
7.5.3. Metal Form

Another preliminary decision is the form of the metal to be tested. Metals are available in two basic forms: cast and wrought.
These two forms usually cannot be interchanged in testing. The various methods of casting (such as die, permanent mold, sand
mold, and so forth) and of hot-working (such as drawing, extruding, forging, rolling, and so forth) will affect grain structure and
homogeneity that, in turn, affect the corrosion resistance. The metal procured should be as nearly as possible of the type that
will be used in the final product.
If it is anticipated that the final use of a metal will be in a cast form, cast specimens should be evaluated. The same applies for
wrought metal specimens. Data obtained from cast and wrought metal forms cannot be interchanged reliably.
7.6. SPECIMEN PREPARATION

7.6.1. Size and Shape
Having selected and procured the test material, the next step is to prepare test specimens. The size and shape of the specimen
should be limited by the material being tested and the test environment. The type of specimen used must permit ready
evaluation. If several characteristics are to be evaluated, more than one type of specimen may be required. In addition, the
following considerations can be important.
7.6.1.1. Visual Examination.

Visual examinations of the specimens should be made in all corrosion tests. When the appearance of the end product is
important, such as for decorative trim or architectural applications, a fairly large surface area should be used, typically 0.25 m2
or larger, to permit a reliable appraisal if corrosion is not uniform. Specimens of only a few square centimeters can give
misleading results.
7.6.1.2. Depth of Attack.

7.6.1.2. Depth of Attack.
Specimens used to evaluate corrosion by measurement of the depth of penetration should be thick enough so that they are not
perforated by the corrosion attack. Other than this thickness consideration, no particular size or shape is required, but the size
or area of the specimen will determine the amount of corrosive agent needed. Also, the specimen should be large enough, or a
sufficient number of small specimens should be exposed, to include all important metallurgical or manufacturing variables.
Specimens for this purpose usually are kept as small as possible for convenience, and, because there are no strict
requirements, data often can be obtained from specimens designed for some other test.
7.6.1.3. Weight Loss or Gain.

Weight change measurement also does not require any definite size or shape, but a large area-to-volume ratio is used for better
sensitivity. Usually, a flat square or rectangle is used to simplify measurement of surface area. Specimens should be kept
relatively small to permit simple and accurate weight measurements. It is accepted practice to use a standardized size and
shape for all specimens in a given test series so that the same surface area is exposed with the same degree of accuracy in
measurement and calculations.
7.6.1.4. Loss in Tensile Properties.

If loss in tensile properties is to be evaluated, the best procedure is to use one of the standard ASTM tensile specimens, such as
those shown in Fig. 7.1. Round tensile specimens are machined prior to exposure. When sheet or thin plate, for example up to
1.3 cm in thickness, is to be tested, a full-thickness, flat tensile specimens of the type shown in Fig. 7.1 can be used. In this
case, tensile specimens can either be fully machined before exposure or they can be machined from a corroded panel after
completion of the corrosion test.
Full-thickness specimens machined before exposure will give an earlier indication of the effect of corrosion, but the indicated
degree of loss in tensile properties, particularly elongation, usually is unrealistically high because of notch effects produced by
corrosion of the edges of the specimen. When edge corrosion is not critical in actual applications, for example roofing sheet, a
more realistic appraisal of the loss in strength and elongation can be obtained by machining full-thickness specimens from a
corroded test panel, and in this way avoid edge corrosion effects in the appraisal.
7.6.1.5. Stress Corrosion Cracking Tests.

The selection of a specimen for stress corrosion cracking (SCC) tests is complex but is primarily dependent upon the ability to
apply stress uniformly in a specific metallurgical direction. (A more detailed discussion of these factors is provided in Chap. 5.)
7.6.1.6. Corrosivity of the Test Environment.

Another important factor to be considered in conducting a corrosion test is the corrosivity of the test environment. Shorter
exposure times and thicker specimens are required when the test conditions are highly corrosive. If too small a specimen is
used and it is completely dissolved, perforated, or if some of its fragments are lost, only limited information can be obtained.
Conversely, it is also a mistake to use a specimen that is so thick that the overall effect of corrosion is too slight to be
accurately determined.
7.6.1.7. Suitability to Other Test Purposes.

7.6.1.7. Suitability to Other Test Purposes.
Finally, if factors other than the metal and the corrosive environment are to be evaluated, the investigator must be sure that the
specimen is suited to the particular test purpose. For example, if protective paints or metallic coatings are to be evaluated, the
corners of the specimen should be well rounded before coating. Films are always thin or otherwise disturbed at sharp corners,
and this presents unrealistically weak points for corrosion to begin. If galvanic corrosion is to be evaluated, the cathode/anode
size ratios and geometry must be known and controlled.
7.6.2. Specimen Identification

An investigator never relies on memory to ensure identification. This is especially important when many specimens are tested,
when tests are conducted over several months, or when several persons process the same specimens.
A suitable identification, usually a specimen number, should be given to each specimen. The first part of the number should be
the identification given to the particular lot of metal from which the specimen was obtained. The second part of the number,
sometimes called a dash number, is the identification of the particular specimen. When several specimens are taken from the
same lot of metal, the various dash numbers may be assigned in numerical order. Frequently, a code letter is used to indicate a
particular type of specimen or environment. In such a case, the various specimens of the same type or for the same purpose are
then numbered consecutively. The important feature is that the investigator must be sure that each specimen can be fully
identified.
Whenever possible, the identification number should be marked on the specimen. The mark on the specimen should be such
that it can withstand the entire corrosion test. The most common and best method is an impression stencil, except for cases
where it is known that the performance of the specimen would be affected by the stresses or surface damage introduced. SCC
has often been detected around these numbers.
When only minor corrosion is expected, scribing with an engraving tool, indelible ink, or paint markers may be adequate. If
extensive corrosion is expected, the specimen number should be protected with a suitable inert masking material such as wax,
tape, or paint. Another method is to attach a nonmetallic marker that is not affected by the corrosive medium. Strips of plastic
sheet, scribed with an engraving tool and fastened with plastic cord are excellent for this purpose.
If test conditions are such that paint or other "foreign" substances might affect the results, they should not be used. In such
cases, specimen identity is retained by marking the rack or container and recording the location of the specimen. The common
"lead" pencil should never be used for marking specimens, as the clay-graphite mixture is electrochemically reactive and can
initiate sites of galvanic corrosion on most metals.
7.6.3. Replicate Specimens

A certain amount of data scatter is inevitable in any testing procedure. The amount of unavoidable scatter depends upon
1. The uniformity of the material tested
2. The accuracy in preparing the test specimens
3. The stability of test conditions
All these factors add up to degrade the accuracy of corrosion testing. Therefore, good testing procedure will provide some
method of cross-comparison or double-checking to eliminate the possibility of an incorrect conclusion based on a single
nontypical result.
The use of a single specimen may be a valid procedure, provided more than one measurement can be made on the specimen.
For example, loss in strength can be determined at several places in a single, corroded, 10- × 23-cm panel. Using a single
specimen may be a poor procedure, however, if it provides only one value, such as loss in strength on a pre-machined tensile
specimen, or failure of a single SCC specimen. This becomes especially important if it is known that the test procedure can
vary. In such tests, a cross-check is provided by the use of multiple specimens.
Generally, three or more specimens are used to establish a trend (Figs. 7.6 and 7.7). Duplicate specimens are not suitable
because they may result in two widely different values and create some confusion as to which result is really representative of
the material being tested. The number of specimens used in a test must be a compromise among
Figure 7.6 Bank of 50 NACE TM0177 method "A" constant strain test facility with uniaxially loaded
tensile specimens. (Courtesy of Bodycote Materials Testing.)
Figure 7.7 Parallel inhibitor testing in the presence of hydrogen sulfide with polarization
measurements made on many similar systems at the same time. (Courtesy of CAPCIS Ltd.)
1. The accuracy needed (statistical evaluation)
2. The cost of a test
3. The known reproducibility of the test
4. The number of variables investigated
7.6.4. Machining of Specimens

Many products, such as sheet, certain structural shapes, tube, and pipe are used in service just as they are received from the
supplier. Consequently, if their surface condition is fairly consistent, it may be possible to test the corrosion resistance of these
products after simple degreasing. When the surface is inconsistent because of dirt, scale, or oxide, steps must be taken to
reach a more uniform metal surface. Generally, an acid pickle or a caustic etch is used, depending on the metal.
Other products such as plate, rod, bar, or forgings are generally machined into the final configuration before they are used. Such
products are best tested with a machined surface, employing good shop procedure to minimize roughness variations.
Close dimensional tolerances are required for specimens used in tests to evaluate characteristics such as loss in strength or
resistance to SCC. Accordingly, such specimens should be made by experienced machinists. A few of the more important
considerations during machining are
1. Properly sharpened tools and appropriate feed rates to avoid heating or mechanically damaging the specimen.
2. Noncorrosive cutting lubricants (especially important if water-soluble oils are used in certain cases, dry machining may be
necessary).
3. Dissimilar metals such as steel, brass, and aluminum should be finished on separate pieces of equipment to prevent
contamination of one metal with particles or chips of another metal. This is especially important when using grinding
equipment.
A sawed edge may be used if the specimen is evaluated merely for depth attack on the surface. Edges should be filed,
machined, or ground smooth if edge attack is to be determined or if weight loss will be used in the final determination. Sheared
or blanked edges must be machined, ground, or filed to remove the layer of severely cold-worked metal resulting from this
operation. The amount of metal removed should be at least equal to the thickness of the piece. Drilled or reamed holes can be
left as is, but punched holes should be treated as sheared edges, unless the purpose of the investigation is to evaluate the
effect of cold work.
The usual procedure in preparing specimens is to keep the area of cut edges small in comparison to the surface area because
this is generally the case in actual parts. In any case, the edge-to-surface area ratio should be known and kept uniform from test
to test.
7.6.5. Simulated Machining of Specimens

If machine shop facilities are not available, only the simpler type specimens such as coupons or panels can be prepared. These
can be evaluated by depth of attack or weight loss. The usual method of simulating a machined surface is to polish the metal
on a suitable abrasive cloth or paper, or to scrub it with a fine abrasive such as wet pumice. Such specimens are most often cut
from sheet or thin plate.
Other methods of producing specimens of very hard metals are electrical discharge (EDM) or electrochemical machining (ECM)
techniques. In these somewhat complicated methods, special precautions are required.
7.6.6. Degreasing and Final Measurements

7.6.6. Degreasing and Final Measurements
After machining, if weight loss or loss in strength after corrosion is to be determined, the specimens should be degreased just
prior to initial measurements of weight and dimensions. The easiest method of removing oils and greases (except silicone oils)
is to use a solvent vapor degreaser. If such equipment is not available, the specimens should be wiped with a fast-drying, low-
residue solvent such as alcohol, acetone, or methyl ethyl ketone (MEK). Solvents that are highly flammable (gasoline), toxic
(carbon tetrachloride), or that leave a film residue (kerosene) should not be used.
The specimens should be weighed and measured as carefully as possible because subsequent data can be no more accurate
than the original data. When the accuracy needed is dependent upon the expected weight loss, measurements should be carried
to enough significant figures to keep the possible error in calculations less than 1%. In some cases, particularly for large or
heavy specimens, measurement to the first decimal place is sufficient. However, measurements generally are made to as many
decimal places as is practicable, for example to the nearest 0.01 mm and 0.0001 g for small specimens measured with a
micrometer and a microbalance, respectively.
To remove contamination caused by handling, the specimen should be degreased again just prior to exposure to the corrosive
medium. After this final degreasing, specimens should be given a "white glove" treatment and handled only at edges in order to
prevent fingerprinting or other contamination that can cause accelerated corrosion. If, for some reason, the specimens cannot
be exposed in a reasonably short time, they should either be stored in a desiccator or coated with a protective oil and stored in
a dry, dust-free place. If the latter method is used, the specimen will, of course, have to be degreased again just prior to
exposure.
7.7. CONTROLS
An important consideration in the corrosion testing of metals is the use of suitable controls, both for the metal and for the test
environment. This aspect of corrosion testing is perhaps the greatest single source for error, even by experienced investigators.
7.7.1. Control of the Metal

7.7.1. Control of the Metal
Control data for the uncorroded metal consists of measurement of those properties that can be affected by corrosion so that
they may be used to assess the effects of corrosion. Typical metal properties used as controls are strength, electrical
conductivity or resistance, and reflectivity. Specimens used to obtain control data should be from the same vicinity in the metal
stock and of the same type as those used for corrosion tests. Also, the same method of measurement and degree of accuracy
should be used for both sets of specimens. This ensures that any differences in data before and after exposure represent only
the effects of corrosion.
When corrosion tests are of a short duration or when the metal is such that the characteristic being evaluated is not changed
during long-term storage, the original control data may be obtained just once prior to any corrosion tests and used for reference
when needed. Sometimes, certain characteristics will change in time, even in the absence of corrosion. In such cases, a set of
control specimens must be provided for each period of corrosion testing. This set is then tested at the same time as the
corroded specimens. Some metals, for example, gradually change in strength over long periods of time at room temperature,
and the strength of most metals is affected by time at elevated temperatures.
Specimens to be used for periodic controls should also be protected from corrosion and stored at the same temperature at
which the corrosion tests are conducted. In long-term field tests, for which temperature obviously cannot be controlled (such as
tests in natural atmospheres), it may be desirable to store the controls on-site in dry, air-tight containers. This ensures that both
the corrosion and control specimens are exposed to the same time-temperature conditions.
In tests at elevated temperatures, special precautions may be necessary to ensure that the control specimens themselves do
not undergo high-temperature corrosion.
7.7.2. Control of the Test Environment

7.7.2. Control of the Test Environment
The other required control is a method of determining whether the corrosive medium maintains the intended degree of
corrosivity. When an alloy is repeatedly tested by the same method, as in quality control tests, the investigator may be
sufficiently experienced to know whether the visual appearance and resultant data are of the order expected. Often this is not
so, especially with new alloys or products, when corrosion performance is unpredictable.
The usual procedure is to expose a well-established, previously tested alloy as a control to determine whether the results on it
are consistent with past experience. If they are, the new alloy is considered to have received a valid exposure. However, if the
effects of corrosion on the well-known alloy are not typical, the investigator is alerted to the possibility of an error in the test
environment and the need for a rerun.
Another control method is to expose specimens for several periods of increasing duration. At least three periods of exposure
usually are used (Fig. 7.8). Changes in the corrosion rates of metals can be caused either by a change in the condition of the
metal itself or by a change in the corrosive environment. A properly designed corrosion test should enable the investigator to
determine which of these two factors was operative, or whether both had an effect. Comparison of the data on the different
groups of specimens then permits evaluation of whether the corrosion rate of the metal was constant (linear rate) or varied with
time (either an accelerating or a self-limiting rate).
Figure 7.8 This f. shows why data from several exposure periods are essential. Better resistance of
alloy A was not evident until fourth year of testing. Extrapolation rates based on 1-year data are in
error for both alloys.
7.8. SPECIMEN ARRANGEMENT FOR CORROSION TESTS

7.8. SPECIMEN ARRANGEMENT FOR CORROSION TESTS
Another point to consider, before selecting the corrosion tests themselves, is the manner in which specimens should be
arranged or framed for exposure. In laboratory beaker tests, usually one specimen per container is desirable. If more than one
specimen of the same lot of metal is used, multiple specimens may be run in the same container, provided the volume of
corrosive medium is sufficient to maintain its original properties throughout the exposure.
For plant and field tests, some sort of framing sequence is needed, depending upon the type of specimen and test method. An
example of specimens racked for exposure is given in Fig. 7.9.1 The important considerations are as follows.
Figure 7.9 Typical specimen exposure rack. Note specimens are electrically separated from each
other and from rack. Specimens with bolted-on straps may register galvanic, edge, or crevice
effects and the influence of materials such as gaskets. Sequence of specimens should be carefully
recorded. (From Ref. 1, by permission)
1. All the specimens must be electrically isolated from one another and from direct contact with the racks. Inert,
nonabsorptive racks or spacers of polymeric material or porcelain are usually used for this purpose.
2. The specimens should be arranged so that corrosion products from one specimen will not contaminate other specimens.
3. The corrosive environment should be equally accessible to all specimens.
4. In liquid immersion tests, specimens of different metals should not be exposed in the same container because one metal
can affect the corrosion of another, even though they are not in contact. In fact, even in the same metal system, it may be
desirable to separate one alloy type from another. For example, aluminum alloys containing copper are often separated
from copper-free aluminum alloys.
In cases where metal containers are used to hold the test media, special precautions are required to prevent metal-to-metal
contact between the container and the specimens.
7.9. EFFECTS OF VARIABLES
The results of a corrosion test on metals can be affected significantly by variations in environmental factors. The single or
combined effects of these factors are not always known, but it is essential that the corrosion investigator appreciates their
complex interactions.
7.9.1. Temperature
The temperature of the test solution should be controlled to within ±1.0°C in any laboratory corrosion test. If the temperature of
the solution differs from that of the metal, it is important to know the actual metal temperature. This can be measured by use of
a control specimen equipped with a peened-in thermocouple. In such a case, the thermocouple contact point and leads should
be masked by a sleeve or suitable coating. The difference between ambient and metal temperatures becomes especially
important in a vapor or humidity test.
Vapors condense on surfaces that are colder than the environment. Consequently, near 100% humidity at 38°C, condensation
may have little or no effect on metals warmer than 38°C. In the case of aluminum alloys, condensation produces water
staining, a surface discoloration. If the aluminum alloy is above the humidity test temperature, condensation and possibly
staining do not occur.
When appraising the effect of heat transfer through a metal, the simple exposure of a specimen in the appropriate solution at a
given temperature may not provide the desired information. The metal surface should be heated on one side and cooled on the
other to obtain proper results. This is particularly true when determining the corrosion or pitting rate of a metal surface to be
used to boil a liquid.
Higher temperatures, above 100°C, generally produce a more aggressive corrosion attack. While the condensation in these
cases is not a problem, the actual temperature can determine the thickness of the corrosion product oxide layer and extent of
attack.
7.9.2. Solution Concentration

The effect of solution concentration may be an even more important variable than small variations in temperature. Often,
metals are corroded by dilute solutions and not corroded by more concentrated ones. Solutions react with metals in a variety of
ways, including the following:
1. Some plate out metallic components (cations) on cathodic areas and concentrate anionic (negatively charges ions)
components at anodic (corroding) areas.
2. Some solutions corrode metals vigorously for a time and then cease action abruptly.
3. Some organic solutions do not react for a time (induction time) and then react vigorously with the metal.
Hydrogen ions (H+) and hydroxyl ions (OH−), which reflect the acidity or alkalinity of a solution expressed as its pH, are also
produced or consumed by the corrosion reactions. These values can be quite variable on local areas of the metal surface and in
the solution, depending upon initial solution concentration, agitation, and corrosion activity. The important considerations are
1. The bulk solution concentrations must be known and controlled before, during, and after the test.
2. The volume of the solution should be sufficient to avoid expending it before the test is completed.
3. The bulk solution concentration can be quite different from the solution concentrations on the metal surface.
Parts per million of contaminants in a solution may be responsible for essentially all of the corrosion occurring, and their effect
must be recognized.
7.9.3. Agitation
7.9.3. Agitation
In order to assess the comparative corrosion effects on metals of quiescent and moving solutions, they are mildly stirred or
otherwise circulated by pumps or jets. Agitation changes the concentrations of the solution on the local anodes and cathodes
and provides a more homogeneous test environment.
Simple stirring of a solution is not adequate to determine the actual effect of velocity where liquid flow rate across the
specimen face must be under control. An appropriate standard test should be used when evaluating the effect of agitation. A
recent publication by NACE International provides a good introduction to this subject.4
In gaseous test environments, it is usually necessary to provide some agitation to be certain that vapor concentrations are
uniform in the test chamber. In humidity tests, where vapor pressures can vary markedly in a quiet test chamber, air flow
ensures equilibrium.
7.9.4. Aeration
Aeration, or oxygenation, has a marked effect on the corrosion of metals. Consequently, oxygen is often added by bubbling it
through the test solution. Fine gas bubbles are better than large ones because there is more opportunity for the gas to dissolve
in the solution during the time it rises to the solution surface.
The counterpart of aeration is deaeration, which can be controlled in a number of ways. Oxygen can be discouraged from
entering the test solution by use of a closed system equipped with a trap. Another method is to deaerate by introducing an
excess of an inert gas, such as nitrogen, into and above the test solution. Oxygen scavengers, such as hydrazine, are also
available for use in minimizing the free oxygen content of solutions.
Under special test conditions, other gases such as carbon monoxide, carbon dioxide, hydrogen sulfide, ozone, nitrous oxide, and
sulfur dioxide are metered into liquid or gaseous test chambers to produce special effects on metal corrosion reactions.
7.9.5. Ultraviolet Light

Some chemical reactions are altered photochemically; that is, light of certain wavelengths can alter the chemistry of solutions,
gases, or corrosion reactions. Of special interest is the photochemical oxidation of nitrous oxide to peroxyacetal nitrate in the
atmosphere, which contributes to air pollution and produces smog. In this case, the sunlight acts on the combined nitrous oxide
and hydrocarbons from automobile exhausts.
7.9.6. Microbial Effects

In any one set of environmental conditions, several species of fungi or bacteria often may grow and reproduce in solutions,
nonmetallics, and on metal surfaces. Their metabolic (life cycle) process can produce concentrations of organic or inorganic
acids. General examples are corrosion by sulfate-reducing bacteria under anaerobic (oxygen-free) conditions, crude oil tank
bottoms, and aircraft jet fuel tank corrosion.
Other organisms produce slime films that can screen oxygen or concentrate metal ions. Each of the innumerable species has
its peculiar requirement for food, oxygen, and temperature. Variations in corrosion test results are caused by changing growth
rates and balance of bacterial species.
Although detailed testing for biological corrosion is beyond the scope of this chapter, it is important to recognize that corrosion
tests, particularly long-term ones where organic nutrients are present, may be affected by biochemical influences in moist air or
aqueous environments.
7.10. CONDUCTING THE TEST
7.10.1. Records
It is essential that a detailed record be kept for each specimen to help in the eventual analysis of the test. The laboratory
notebook and/or other permanent record forms are used for this purpose. When possible, these records should be in a
tabulated form that permits easy insertion of test results as they are obtained. Meaningful data should be reduced to the
minimum and recorded promptly to avoid accumulation of unnecessary or confusing paperwork.
7.10.2. Interim Inspections

Usually, an exposure time is used which experience has shown will yield meaningful results. Because each test probes the
unknown, the experimenter must be alert for unexpected trends. During the test, frequent examinations should be made and
observations recorded for any unusual effects on the specimens or in the test environment. In the case of laboratory tests,
interim inspections will often allow to correct problems with the specimens or environment.
A regular schedule of examinations usually is established at the beginning of the test, with more frequent inspections in the
beginning. Appropriate records of specimen condition and environment stability are often necessary to explain unexpected
results. Personal judgment must be used to decide whether the original plans for interim inspections were correct. Often,
progress reports are advisable to summarize segments of the work separately.
7.10.3. The Unexpected

When a test contains appropriate comparison specimens, it is unlikely that small environmental variations will be cause for
alarm. Sometimes, when tests "accidents" occur, the shrewd investigator can turn the mishap into a "lucky" accident. Many
valuable inventions have been the result of such accidents that were observed, evaluated, and reproduced by intelligent
investigators who did not hastily discard unexpected results. After all, if the answers are already known, why conduct the test?
7.10.4. Concluding the Test

7.10.4. Concluding the Test
Obviously, a decision to terminate an investigation is easiest when there is a fail, no-fail criterion. If an earlier investigator has
established the proper test durations, the work can be greatly simplified. Innovative tests, on the other hand, rarely signal that
the program is completed. The investigator must make such a judgment after weighing results and interpreting trends.
The danger of ending a test too soon is obvious when one realizes how many corrosion processes progress through nonlinear
trends. The use of duplicate or multiple specimens helps to predict the long-range results by giving periodic indications of
progress. When the graph of results is anything but a straight line with respect to time, periodic reviews are necessary to
develop an understanding of what is happening. When satisfied that there is little to gain by continuation of the test, the
investigator terminates it. Often, the decision is hastened because of
1. Shortage of test space
2. Backlog of other programs
3. Requests by those who need information
4. Curiosity
The investigator must weigh these pressures and arrive at a decision. Once it has been decided to end the test, posttest
appraisals of the specimen will often prevent its reexposure. A new test would then be required if the data obtained were
insufficient.
7.11. POSTTEST APPRAISALS

7.11.1. Before Cleaning
When laboratory tests are concluded, it is advisable to perform certain tasks rather quickly in order to avoid changes in
specimen appearance or additional corrosion. Depending upon the goals, initial steps may include
1. Visual examination before cleaning
2. Photographs before cleaning
3. Careful collection of corrosion products for chemical or other analyses
4. Saving test solutions for chemical study
Visual examination before cleaning should include the apparent distribution of corrosion products (the relative severity and
extent of corrosion will be recorded after cleaning). Also, it should be noted whether the identification number of each specimen
has survived the exposure. If not, one should be able to determine the number from the location of the specimen in the frame or
other cross-check methods included in the test procedure for such a contingency.
Before discarding any test solutions, the investigator must decide on the possible need for a chemical analysis to evaluate how
the solutions may have changed during the test.
7.11.2. Analyses of Products and Solutions

7.11.2. Analyses of Products and Solutions
Selection of techniques for analysis of corrosion products and solutions is a rather complex procedure requiring background
experience. Some typical methods include the following:
1. Analyses for pH and certain ion concentrations using a technique such as ion chromatography for anions, e.g., sulfates and
nitrates, and atomic absorption spectroscopy for cations, e.g., potassium, sodium, and most other ions of metals.
2. X-ray powder diffraction analysis of dry corrosion products. This technique is unique because it can reveal the
crystallographic nature of minerals and some corrosion products.
3. Measurement of conductivity is a simple method to monitor changes in the ionic makeup of a test solution.
7.11.3. Cleaning the Specimens

Before the extent of corrosion on metal specimens can be completely evaluated, it is usually necessary to clean them according
to approved methods.5 It is essential that special care be exercised in this procedure in order that the cleaning will
1. Not remove any metal
2. Remove all adherent corrosion products
3. Facilitate the program of evaluation that will follow
In some instances, it may be desirable to weigh the specimen before removing the corrosion product to obtain a measure of the
weight gained during the test. This is done when the entire corrosion product is intact, as it is often the case in high-
temperature corrosion experiments on some metals.
7.11.4. Weighing
After rinsing and thoroughly drying the specimens, they should be weighed carefully, using the same equipment and care as
used before the corrosion test.
A laboratory notebook should be used to tabulate final weights, as well as any changes in weight produced by the test. Usually,
the level of significant numbers has been predetermined. For example, if a 30-g sample of metal is tested, the weights may be
recorded to the sixth significant number. That is, the record may show
Weight in grams
Original weight: 30.0186
Final weight: 27.3243
Weight loss 2.6943
In the case of a 500-g sample, it may be decided that accuracy to 0.1 g is sufficient. Hence
Weight in grams
Original weight: 531.6
Final weight: 486.2
Weight loss 45.4
After the weight change data have been obtained, it is necessary to convert the raw information into suitable units. Obviously,
some units may vary between countries or for special criteria. Where possible, however, unique methods of reporting should be
avoided. Unusual data forms distract the reader and thereby diminish the effectiveness of communication.
Corrosion data are either reported as relative percent changes in the measured property of a corroded specimen after cleaning,
for example loss in weight, strength, elongation, and conductivity, or as corrosion rates. There are basically two types of
corrosion rate expressions.
Engineering expressions: microns per year (μm/y) or milli-inches (mils) per year (mpy)
Laboratory expressions: milligrams/square decimeter/day (mdd) or mm per year (mm/y)
7.11.4.1. Sample Calculation.

If a specimen having a surface area of 6.4516 dm2 lost 7.3216 g (7321.6 mg) in 50 days,
a. The corrosion rate in mdd would be
b. For steel (density 7.87 g/cm3 ) the corrosion rate may also be expressed in mpy (mils per year) as
The conversion scheme provided in Table 7.2 for all metals or Table 7.3 adapted to iron or steel provides a simple way to make
the conversion between the most common corrosion rate units, including the corrosion current measurements associated with
most electrochemical techniques.
Table 7.2 Conversion between Current, Mass Loss, and Penetration Rates for all Metals*
mA · cm−2 mm · y−1 mpy g · m −2 · day−1
mA · cm −2 1 3.28 M/nd 129 M/nd 8.95 M/n
mm · y−1 0.306 nd/M 1 39.4 2.74 d
mpy 0.00777 nd/M 0.0254 1 0.0694 d
g · m −2 · day −1 0.112 n/M 0.365/d 14.4/d 1
Table 7.3 Conversion between Current, Mass Loss, and Penetration Rates for Steel*
mA · cm−2 mm · y−1 mpy g · m −2 · day−1
* This table should be read from left to right, i.e., 1 mA · cm −2 = 11.6 mm · y −1 = 456 mpy = 249 g · m −2 · day−1.
mA · cm −2 1 11.6 456 249
mm · y−1 0.0863 1 39.4 21.6
mpy 0.00219 0.0254 1 0.547
g · m −2 · day −1 0.00401 0.0463 1.83 1
7.11.5. Visual Examination

7.11.5. Visual Examination
Visual examination of cleaned specimens is not made until weighing has been completed. This avoids unnecessary handling
that could affect weight. Generally, the appearance of the test specimens should be recorded in the laboratory notebook in a
form that will facilitate a stepwise appraisal of each specimen. Here are some typical examples of frequent observations on
cleaned specimens:
1. An SCC specimen represents a fail, no-fail investigation, ordinarily requiring only a record of the time to failure. However, any
unusual failures, such as failure outside of the most highly stressed region, should be noted. A general examination may be
desirable on specimens that complete a predetermined exposure period without failing.
2. A panel, bar, or coupon specimen should be examined with some of the following questions in mind:
a. Was corrosion uniform, or was it located at pits, edges, identification marks, or mounting areas?
b. Is there any pattern to the corrosion? Does it follow work lines, edges, and so forth?
c. What is the shape and texture of the corrosion sites (blisters, exfoliation, minute pits, broad smooth pits, and
brightness)?
When the sites of attack are numerous, the tedious job of counting can be eliminated by using rating charts such as shown
in the section Pitting Corrosion of Chap. 5. A weighting factor, to account for the form of the corrosion, might also be used.
Caution should be exercised in conversion to numerical values, so as not to imply greater accuracy than warranted.
3. An assembly of components should be examined in a few additional ways.
a. What is the galvanic effect between parts (accelerated or decelerated corrosion)?
b. How far does the effect extend?
c. Are crevices (faying surfaces) attacked?
7.11.6. Photographs
Photographs, micrographs, and x-ray radiographs are great to supplement the visual examination report. Entire specimen
groups, representative ones, or even a magnified view of a typical area of one panel can be quite valuable in reducing the extent
to which the visual examination must be recorded. Radiographs, particularly useful for flat sheet specimens, help to show
severity (depth) of the corrosion sites, as well as their locations. All photographs should be accompanied by descriptive
identifications of the specimen(s) and magnifications used.
7.11.7. Mechanical and Physical Tests

7.11.7. Mechanical and Physical Tests
The next step in the appraisal may be to obtain data required to establish effects of the test on mechanical properties. Usually,
ultimate strength (tensile strength) and elongation (stretching caused by tensile testing) tests are compared on specimens that
have and have not been corrosion-tested. The differences are attributed to corrosion. Generally, the final data are recorded as
percent losses. An example is given in Table 7.4.
Table 7.4 Mechanical Test Data for Corrosion Test Panels Exposed 12 weeks to 3.5% Sea Salt by Alternative Immersion
Steel Tensile strength (MPa) Yield strength (MPa) Elongation (%)
The exposed specimens are those that were corrosion-tested. They were cut from the same material for which the "unexposed" data
are cited. The calculations therefore represent the losses as a percentage of original values.
Before
Mild 283 128 34
A 530 347 22.5
B 545 344 19.3
After
Mild 211 91 23
A 356 242 11.3
B 405 262 11.8
Difference (%)
Mild 25.3 28.4 32.4
A 32.8 30.2 49.8
B 25.7 23.9 38.9
Special note is taken of any unusual failure observed during testing (failure outside gauge length, at a scratch, etc.) in order to
decide whether these data should be ignored in the final appraisal.
7.11.8. Microscopic Studies

One of the best corrosion test evaluation tools is the metallurgical microscope. A careful selection must be made of metal
areas to be studied. Special samples may be corroded specifically for this purpose, or remnants of test specimens, previously
evaluated by other methods, may be used. A skilled metallographer then sections through the corrosion sites, polishes the cut
surfaces, and examines them for
1. Type of corrosion (relationship of corrosion with metallurgical structure)
2. Corrosion depth
3. Path of corrosion
4. Other changes caused by corrosion
Metallographers use a variety of procedures, including cutting, polishing, chemical or electrochemical etching, and illumination
techniques to permit high-magnification views of the corrosion damage. Generally, the metallographer works closely with the
investigator to prepare appropriate photomicrographs for use in the investigator's report.
Experience is necessary to select and interpret micrographs. From proper high-magnification photographs of surfaces and
cross sections, the trained investigator is often able to identify factors relating to the mechanism of corrosion, as well as the
type, depth, and metallurgical condition of the metal, and the presence of any unusual conditions. The composite series of
micrographs in Fig. 7.10 shows a few of the types of corrosion that may be encountered.1
Figure 7.10 Examples of several types of corrosive attack on aluminum alloys. Pitting corrosion: (a)
surface pitting; (b) edge pitting; (c) undermining pitting of surface; (d) "cubic" pitting attack.
Intercrystalline corrosion: (e) interdendritic attack in cast structure; (f) interfragmentary attack in
wrought, nonrecrystallized structure; (g) intergranular attack in wrought, recrystallized structure;
and (h) exfoliation attack. (a), (b), and (h), X100; others X500. (From Ref. 1, by permission)
7.11.9. The Notebook

7.11.9. The Notebook
All entries and calculations should be shown carefully in a permanent notebook. Although each company has its own
requirements, everyone agrees that a notebook is a very important document and often serves to establish initial records for
patent protection. Most patent attorneys will advise an investigator to write clearly, make a carbon copy of each entry, and have
each page of the notebook witnessed and dated by someone who understands the entry. The carbon copy pages are usually
stored at another location in order to minimize the possibility of loss of records.
7.12. ELECTROCHEMICAL TEST METHODS

Given the fundamental electrochemical nature of corrosion processes, it is not surprising to see that electrochemical
measurements are so extensively used across the whole spectrum of corrosion science and engineering, from fundamental
studies to monitoring and control in service.
7.12.1. DC Polarization Test Methods

DC polarization methods involve changing the potential of the working electrode and monitoring the current that is produced as
a function of time or potential. For anodic polarization, the potential is changed in the anodic (or more positive direction)
causing the working electrode to become the anode and forcing electrons to be withdrawn from the metal being tested. For
cathodic polarization, the working electrode becomes more negative and electrons are added to the metal, sometime causing
electrodeposition. For cyclic polarization, both anodic and cathodic polarizations are performed in a cyclic manner.6 The
instrumentation for carrying polarization testing as illustrated in. Fig. 7.11 consists of
Figure 7.11 Electrochemical instrumentation to carry out potentiodynamic measurements in which

a potentiostat/galvanostat power controller is used to pass current through the sample, or working
electrode (W), and an auxiliary electrode (AUX) while monitoring the potential of the working
electrode with a reference electrode.
A potentiostat is needed that will maintain the potential of the working electrode close to a preset value.
A current-measuring device for monitoring the current produced by the applied potential. The ability of the current-
measuring device to autorange or to change the scale automatically is also important.
The ability of the data to be stored directly in a computer, or plotted out directly is also important.
Polarization cells: Several test cells are available commercially for making polarization measurements. Polarization cells
can have various configurations specific to the testing requirements from testing small coupons, to sheet materials, to
testing inside autoclaves. In a plant environment the electrodes may be inserted directly into a process stream. Some of the
features of a cell include6
a. The working electrode, i.e., the test sample, which may be accompanied by one or more auxiliary or counter electrodes.
b. The reference electrode that is often separated from the solution by a solution bridge or a capillary Luggin probe F
( ig.
7.12). This combination eliminates solution interchange with the reference electrode but allows it to be moved very
close to the surface of the working electrode to minimize the effect of the solution resistance.
Figure 7.12 Experimental setup to measure the corrosion potential of a specimen.
c. A temperature-monitoring device.
d. An inlet and outlet for gas to allow deaeration, aeration, or the introduction of specific gases into the solution.
e. An electrical connection can be made directly with the working electrode, which will not be affected by the solution.
f. The working electrode must be introduced into the solution completely to eliminate any crevice at the solution interface,
unless this is a desired effect.
g. The test cell itself must be composed of a material that will not corrode or deteriorate during the test and will not
contaminate the test solution. The volume of the cell must be large enough to allow removal of the corroding ions from
the surface of the working electrode without affecting the solution potential.
h. It may be necessary to include a mechanism for stirring the solution such as a stirring bar, or bubbling gas to ensure
uniformity of the solution chemistry.
There are several accepted methods to carry out DC polarization of specimens for corrosion testing.
7.12.1.1. Potentiodynamic Polarization.

Potentiodynamic polarization refers to a polarization technique in which the potential of the electrode is varied over a relatively
large-voltage domain at a selected rate by the application of a current through the electrolyte. Figure 7.13 is an example of a
polarization plot obtained with a S43000 steel specimen in a 0.05-M H2 SO 4 solution.
Figure 7.13 Typical anodic polarization plot for S43000 steel in a 0.05-M H2SO4 solution.
A potentiodynamic polarization variant is cyclic voltammetry that involves sweeping the potential in a positive direction until a
predetermined value of current or potential is reached; then the scan is reversed toward more negative values until the original
value of potential is reached. In some cases, this scan is done repeatedly to determine changes in the current-potential curve
produced with scanning.
Another variation of potentiodynamic polarization is the potentiostaircase method. This refers to a technique for polarizing an
electrode in a series of potential steps where the time spent at each potential is constant, while the current is often allowed to
stabilize prior to changing the potential to the next step. The step increase may be small, in which case the technique resembles
a potentiodynamic curve.6
Electrochemical potentiodynamic reactivation (EPR) is another polarization method that evaluates the degree of sensitization
of stainless steels such as S30400 and S30403 steels. This method uses a potentiodynamic sweep over a range of potentials
from passive to active (called reactivation).
However, probably the most popular variant is the cyclic polarization test. This test is often used to evaluate the pitting
susceptibility of a material. The potential is swept in a single cycle or slightly less than one cycle usually starting the scan at the
corrosion potential. The voltage is first increased in the anodic or noble direction (forward scan). The voltage scan direction is
reversed at some chosen current or voltage toward the cathodic or active direction (backward or reverse scan) and terminated
at another chosen voltage. The presence of the hysteresis between the currents measured in the forward and backward scans
is believed to indicate pitting, while the size of the hysteresis loop itself is often related to the amount of pitting.
This technique has been especially useful to assess localized corrosion for passivating alloys such as S31600 stainless steel,
nickel-based alloys containing chromium, and other alloys such as titanium and zirconium. Though the generation of the
polarization scan is simple, its interpretation can be difficult.7
In the following example, the polarization scans were generated after 1 and 4 days of exposure to a chemical product
maintained at 49°C. The goal of these tests was to examine if S31600 steel could be used for short-term storage of a 50%
commercial organic acid solution (aminotrimethylene phosphonic acid) in water. A small amount of chloride ion (1%) was also
potentially present in this acidic chemical.
In this example, the potential scan rate was 0.5 mV/s1 and the scan direction was reversed at 0.1 mA/cm2 . Coupon immersion
tests were run in the same environment for 840 hours. The S31600 steel specimens were exposed to the liquid, at the
vapor/liquid interface, and in the vapor. The reason for the three exposures was that in most storage situations, the
containment vessel would be exposed to a vapor/liquid interface and a vapor phase at least part of the time. Corrosion in these
regions can be very different from liquid exposures. The specimens were also fitted with artificial crevice formers.
Figure 7.14 shows the polarization scan generated after 1 day, and Fig. 7.15 shows the polarization scan generated after 4 days
of exposure. The important parameters considered were the position of the "anodic-to-cathodic" transition relative to the
corrosion potential, the existence of the repassivation potential and its value relative to the corrosion potential, the existence of
the pitting potential and its value relative to the corrosion potential, and the hysteresis (positive or negative). The interpretation
of the results is summarized in Table 7.5.
Figure 7.14 Polarization scan for S31600 steel in 50% aminotrimethylene phosphonic acid after 1
day of exposure (the arrow indicates scanning direction)
Figure 7.15 Polarization scan for S31600 steel in 50% aminotrimethylene phosphonic acid after 4
days of exposure (the arrow indicates scanning direction)
Table 7.5 Features and Values Used to Interpret Figs. 7.14 and 7.15
Feature Value in Fig. 7.14 Value in Fig. 7.15
Repassivation potential—corrosion potential 0.12 V 0.0 V
Pitting potential—corrosion potential 0.22 V 0.12 V
Potential of anodic-to-cathodic transition—corrosion potential 0.12 V 0.0 V
Hysteresis Negative Negative
Active-to-passive transition No No
The presence of the negative hysteresis would typically suggest that localized corrosion is possible depending on the value of
the corrosion potential relative to the characteristic potentials present in these polarization plots. After the first day of exposure,
pitting was not expected to be a problem because the pitting potential was far away from the corrosion potential. The currents
generated were much higher than those normally associated with S31600 steel in a passive state. These observations
suggested that there was a risk of initiation of corrosion, particularly in localized areas where the pH can decrease drastically.7
After 4 days, the risk of localized corrosion increased. At this time, the repassivation potential and the potential of the change
from anodic to cathodic current were equal to the corrosion potential. The pitting potential was only about 0.1 V more noble
than the corrosion potential and the hysteresis still negative. The risk of pitting had increased to become a concern.
Coupon immersion tests confirmed the long-term predictions. Slight attack was found under the artificial crevice formers in the
complete liquid exposure. The practical conclusion of this in-service study was that, because localized corrosion often takes
time to develop, a few days of exposure to this chemical product could be acceptable. However, it was recommended to avoid
long term exposure since both pitting and crevice corrosion would be expected for longer exposure periods.
7.12.1.2. Linear Polarization Resistance (LPR).
Another widely used polarization method is LPR. The polarization resistance of a material is defined as the slope of the
potential-current density (ΔE/Δi) curve at the free corrosion potential (Fig. 7.16), yielding the polarization resistance Rp that can
be itself related to the corrosion current (icorr) with the help of the following Stern-Geary equation.8
(7.1)
where Rp = the polarization resistance
icorr = the corrosion current
B = an empirical polarization resistance constant that can be related to the anodic (ba) and cathodic (bc) Tafel slopes with
Eq. (7.2)
Figure 7.16 Hypothetical linear polarization plot.
(7.2)
The Tafel slopes in this equation can be evaluated experimentally using real polarization plots as described inFig. 7.17 or
obtained from the literature.8 The corrosion currents can then be converted into other corrosion rate units using Faraday's law
or, more simply, by using a conversion scheme provided in Table 7.2 or 7.3. An example of the use of LPR for the determination
of the efficiency of a corrosion inhibitor system is described in Chap.10.
Figure 7.17 Plot of η against log |i| or Tafel plot showing that the exchange current density can be
obtained with the intercept.
In a plant situation, it is necessary to use a probe as one of those shown inFig. 7.18 such that it enters the vessel in the area
where the corrosion rate is desired (Fig. 7.19). An electronic power supply polarizes the specimen from the corrosion potential.
The resulting current is recorded as a measure of the corrosion rate. Several commercially available probes and analyzing
systems can be directly interfaced with remote computer data-acquisition systems. Alarms can also be used to signal plant
operators when high corrosion rates are experienced. 9,10
Figure 7.18 Commercial sensor elements to carry out linear polarization resistance (LPR)
measurements. (Courtesy of Metal Samples Company, www.metalsamples.com.)
Figure 7.19 Typical linear polarization resistance (LPR) probe (a) and probe in pipe tee (b).
LPR probes are typically a two- or three-electrode configuration with either flush or projecting electrodes. With a three-electrode
system, corrosion measurements are made on the test electrode. Because these measurements take only a few minutes, the
need for a stable reference electrode is minimized. For field monitoring, the reference electrode is typically made of stainless
steel or of the same alloy as that being monitored on the test electrode. The auxiliary electrode is also normally of the alloy
being monitored. The proximity of the reference electrode to the test electrode governs the degree to which compensation for
solution resistance is effective. With a two-electrode system, the corrosion measurement is an average of the rate for both
electrodes. Both electrodes would then be made of the alloy being monitored.11
A combination of LPR and zero-resistance ammeter[1] (ZRA) measurements has been used in a special study to evaluate the
rate of localized corrosion in a flowing environment by placing a large-area electrode in fast-flow conditions and one small
electrode in slow flow conditions in a side-stream differential flow cell schematically shown in Fig. 7.20.12,13 When the large-
area electrode and the small electrode were connected together through a ZRA, the large electrode became a cathode and the
small electrode an anode, due to differential aeration forcing the small electrode to experience preferential corrosion. As
immersion time increased, the small electrode became covered with deposits and its corrosion rate a good representation of an
underdeposit or localized corrosion situation.
Figure 7.20 Schematic of differential flow cell with a fast-flow electrode (FE), a slow-flow electrode
(SE), a reference electrode (RE), and an inert counter electrode.
There are several limitations to corrosion monitoring with LPR. The corroding environment must be an electrolyte with
reasonably low resistivity. High-resistivity electrolytes produce erroneously low corrosion rates. This need for a sufficiently
conductive medium precludes the use of this technique for many applications in oil and gas, refinery, chemical, and other low-
conductivity applications.
Another problem with the technique is that the vessel or pipe wall must be penetrated, and this involves concerns regarding
leaks, personnel safety, and other problems. The ability to use direct wiring from the probe location to a remote control room is
desirable, but the installation of these wiring systems is costly. In addition, LPR measurements do not provide information on
localized corrosion, such as pitting and SCC, and, because the corrosion-rate values obtained with LPR are at best approximate,
the method is best suited for use during periods when substantial corrosion-rate changes may occur.10,14
7.12.1.3. Complications with Polarization Methods.

The widespread use of these polarization techniques does not mean that they are without complications. Both linear
polarization and Tafel extrapolation need special precautions for their results to be valid. The main complications or obstacles
in performing polarization measurements can be summarized in the following categories:
Effect of scan rate: The rate at which the potential is scanned may have a significant effect on the amount of current
produced at all values of potential.6 The rate at which the potential is changed is an experimental parameter over which the
user has control. The goal is for the polarization scan rate to be slow enough to minimize surface capacitance charging. If
not, some of the current being generated serves to charge the surface capacitance in addition to the corrosion process with
the result that the measured current can be greater than the current actually generated by the corrosion reactions alone.
Effect of solution resistance: The distance between the Luggin probe (Fig. 7.12) and the working electrode is purposely
minimized in most measurements to limit the effect of the solution resistance. In solutions that have extremely high
resistivity, e.g., concrete, soils, and organic solutions, this can be an extremely significant effect.
Changing surface conditions: Because corrosion reactions take place at the surface of materials, when the surface is
changed, due to processing conditions, active corrosion, or any other reasons, the potential is usually also changed. This
can have a strong effect on the polarization curves.6
Determination of pitting potential: In analyzing polarization curves, the presence of a hysteresis loop between the forward
and reverse scans often indicates that localized corrosion, e.g., pitting or crevice corrosion, is in progress.
7.12.2. Electrochemical Impedance Spectroscopy

Electrochemical impedance spectroscopy (EIS) has been successfully applied to the study of corrosion systems and proven to
be a powerful and accurate method for measuring corrosion rates for a few decades. In this approach for determining the
polarization resistance of a metal, a measure of the electrochemical impedance (sometimes called AC impedance) is made at a
series of predetermined frequencies. ASTM G106 contains an appendix reviewing this technique that typically uses a small-
amplitude sinusoidal potential to probe the working electrode at a number of discrete frequencies.15
An important advantage of EIS over other electrochemical techniques is the possibility of using very-small-amplitude signals
without significantly disturbing the properties being measured. However, in order to estimate the polarization resistance (Rp),
that is proportional to the corrosion rate at the monitored interface according to Eq. (7.1), EIS results have to be interpreted
with the help of a model of the interface.
Among the numerous equivalent circuits that have been proposed to model electrochemical interfaces only a few really apply in
the context of a freely corroding system. The first circuit is the simplest equivalent circuit that can describe a metal/electrolyte
interface (Fig. 7.21). Its behavior is described by Eq. (7.3).
(7.3)
Figure 7.21 The equivalent circuit models proposed for the interpretation of EIS results measured in
corroding systems: (a) simplest representation of an electrochemical interface, (b) one relaxation
time constant with extended diffusion.
where Rs is the solution resistance, Rp′ the polarization resistance, ω the frequency, and Cdl′ the double-layer capacitance.
The term Q, in Fig. 7.21, describes the "leaky capacitor" behavior corresponding to the presence of a constant phase element
(CPE).16 Figure 7.22a illustrates the complex plane presentation of the EIS model circuit in Fig. 7.21a where Rs = 10 Ω, Rp = 100
kΩ and Q decomposes into Cdl = 40 μF, and n = 0.8, and Fig. 7.22b shows how the same data would appear in a Bode plot
format.
Figure 7.22 (a) Complex plane and (b) Bode plots of simulated data corresponding to the model
circuit (a) in F. 7.21, where Rs = 10 Ω, Rp = 100 kΩ and Q decomposes into Cdl = 40 μF, and n = 0.8.
The second circuit (Fig. 7.21b) was proposed by Hladky et al. 17 to take into account a diffusion-limited behavior corresponding
to a Warburg component that can be described by Eq. (7.4). The exponent n in Eq. (7.4) can vary between 0.5 and 0.25
depending on the smoothness of the metallic surface, that is, 0.5 for highly polished surfaces and 0.25 for porous or very rough
materials.18 R and C, in Eq. (7.4), are the resistance and capacitance associated with the distributed R-C line of infinite length,
respectively.
(7.4)
Figure 7.23a illustrates the complex plane presentation of simulated data corresponding to model circuit in Fig. 7.21b where Rs
= 10 Ω, Rp = 100 kΩ, Cdl = 40 μF, and the exponent n of the Warburg component = 0.4.Figure 7.23b shows the same data in a
Bode representation.
Figure 7.23 (a) Complex plane and (b) Bode plots of simulated data corresponding to model circuit
(b) in F. 7.21 where Rs = 10 Ω, Rp = 100 kΩ, Cdl = 40 μF, and the exponent n of the Warburg
component = 0.4.
A critical problem in EIS, as well as any other scientific measurements, is the validation of the experimental data. To address the
validation of impedance data, the use of Kramers-Kronig (KK) transforms has been proposed.19 The KK algorithm is
commercially available and is used routinely in some laboratories to assess the quality of the measured impedance data. These
integral transforms were derived assuming four basic conditions, which are discussed prior to stating the transforms
themselves.
Linearity: A system is said to be linear if the response to a sum of individual inputs is equal to the sum of the individual
responses. Practically, this implies that the impedance (or admittance) of a system should not be a function of the
magnitude of the probing signal.
Causality: The response of a system should be solely due to the input. Physically, this means that the system being tested
should not generate noise independent of the applied signal. This is an important consideration in electrochemical systems,
because charge transfer interfaces are often active and do in fact generate noise in the absence of any external stimulus.19
Stability: A system is said to be stable if it comes back to its original state after a perturbation is removed. This condition
ensures that there is no negative resistance in the system. This apparent restriction on the presence of negative resistance
has often been associated the presence of active-to-passive transitions in the system being investigated.19
Finite value: The real and imaginary components of a complex impedance must be finite over the entire frequency range
sampled.
If a system satisfies the conditions of linearity, stability, and causality, it will a priori satisfy the KK transforms, provided that the
frequency range is sufficiently broad for the integrals to be evaluated. Modern equipment often contains, in their control
software, a KK transform algorithm to simplify this otherwise complicated validation process.
However, a simple validity test is often sufficient to ascertain that the EIS measurements are indeed meaningful. For
measurements made in real time, that is, by changing the frequency for each frequency point, the validity of a forward frequency
scan can be verified by scanning in the opposite direction. Repeated measurements during two successive scans in opposite
direction should generally satisfy KK transforms.
For corrosion monitoring, the measurement cycle time with EIS is quite critical and depends on the frequency range used,
especially the low frequencies. A single frequency cycle at 1 mHz, for example, takes 15 minutes. A high- to low-frequency scan
going to such a low frequency would take more than 2 hours. In order to make routine corrosion monitoring with EIS certain
simplifications are needed to maximize the use of high-frequency data and drastically shorten the measurement time. It is also
important to simplify the data processing and analysis to make the technique user friendly for field corrosion monitoring. For
this purpose, a method was developed that consists of finding the geometric center of an arc formed by three successive data
points on a complex impedance diagram (Fig. 7.24).20,21
Figure 7.24 Schematic of the extrapolation method to obtain the polarization resistance from EIS
data.
This technique was designed as an improvement over the two point method based on the comparison of high- and low-
frequency data points for which the impedance would be proportional to the Rs at the high-frequency point and the summation
of Rs and Rp at the low-frequency point.22 In real-world situations, one difficult assumption to satisfy with the two-point method
is that data points should contain negligible imaginary components (i.e., 0 phase shift), a condition usually hard to achieve in a
meaningful manner at low measuring frequencies.
The three-point analysis technique was further developed by permuting the data points involved in the projection of centers in
order to obtain a population of projected centers. This improvement has permitted to automate the data analysis while
providing some information concerning the adherence of the results with the resistive-capacitive (RC) behavior described in Eq.
(7.3) that is assumed for the evaluation of the parameters associated with uniform corrosion.21
More recently, a full-spectrum, relatively low-cost EIS corrosion monitoring system has been developed, which is wireless, small
(5 cm diameter, 1.2 cm height), requires nominally 10-mW power during its 200-second measurement period, and has an
electronic identifier, which allows for a single data logger to monitor multiple devices in the same general vicinity (Fig. 7.25a
and 7.25b).23
Figure 7.25 (a) Test and demonstration of breadboard coating health monitor (CHM), including
wireless communication. Inset shows transceiver unit attached to laptop computer; (b) block
diagram of the electronics. (Courtesy of Guy D. Davis, DACCO SCI, Inc.)
The wireless EIS sensor determines the impedance at 15 to 20 independent frequencies, by measuring amplitude and phase at
each frequency (Fig. 7.26). It computes corrosion rate, conductivity, and coating impedance, and transmits the result wirelessly
to a data logger. The miniature and wireless features make it suitable for embedding in concrete or placing in hidden and
inaccessible locations, for example, in HVAC systems. Its minimal power-consuming aspect lends itself useful for long-term
monitoring of coating integrity. The miniature EIS system has been tested in various environments, namely concrete, water and
under coatings (Fig. 7.27a and 7.27b).
Figure 7.26 Magnitude of impedance of a coating versus frequency. Low-frequency impedance
values show good correlation with long-term exposure behavior. (Courtesy of Guy D. Davis, DACCO
SCI, Inc.)
Figure 7.27 (a) Schematic of the coating health monitor (CHM) with a tape sensing element
mounted on a coated metal and (b) actual sensor tape electrode and electronics housing mounted
on the frame of a commercial vehicle. (Courtesy of Guy D. Davis, DACCO SCI, Inc.)
7.12.3. Electrochemical Noise

7.12.3. Electrochemical Noise
Fluctuations of potential or current of a corroding metallic specimen are a well-known and easily observable phenomenon. The
evaluation of electrochemical noise (EN) as a corrosion tool has increased steadily since Iverson's paper in 1968.24 The study
of EN has been found to be uniquely appropriate for monitoring the onset of events leading to localized corrosion and
understanding the chronology of the initial events typical of this type of corrosion.
During localized corrosion EN is believed to be generated by a combination of stochastic processes, such as passivation
breakdown and repassivation events, and deterministic processes that can be caused by film formation or pit propagation
processes.
7.12.3.1. Electrode Configuration.

An appreciable level of effort has been directed toward developing electrode arrangements for monitoring localized corrosion
with EN, in particular pitting, such as the use of both very small (≤1 mm2 ) or very large (≥100 cm2 ) electrodes as well as
electrode arrays. One simple electrode configuration that enables EN measurements involves connecting a ZRA between two
nominally identical corroding electrodes immersed in the same solution. A third, nominally identical electrode can be immersed
in solution and connected to the first two using a high-impedance voltmeter. This electrode serves as a "noisy"
pseudoreference electrode. This approach is attractive in field applications due to the rugged nature of the metallic electrode
compared to laboratory electrodes. A great variety of instrumental configurations have been used to carry out EN
measurements25:
Three identical electrodes, configured as two coupled via a ZRA and one pseudo-reference, with simultaneous F
( ig. 7.28) or
sequential (Fig. 7.29) measurements of current and potential.
Figure 7.28 Simultaneous current and potential monitoring using three identical electrodes.
(Adapted from Ref. 25.)
Figure 7.29 Sequential current and potential logging of three electrodes: (a) the open-circuit
potential of WE2, and (b) switched-on mode of operation. (Adapted from Ref. 25.)
Three identical electrodes configured in potentiostatic mode (working, reference, and auxiliary) with the reference potential
set at 0 V (Fig. 7.30), with simultaneous measurement of current and potential. This particular arrangement is useful in that
the potentiostatic control may be used to perform other controlled polarization measurements such as LPR or HDA.
Figure 7.30 Three identical electrodes simultaneous current and potential measurement. (Adapted
from Ref. 25.)
Multiple electrode arrays of the test material using scanning techniques to measure current and/or potential between
individual or combinations of elements in order to identify locally anodic behavior on one or more of the electrodes (Fig.
7.31).26
Figure 7.31 Multielectrode array multiplexed current and/or potential measurement. (Adapted from
Ref. 26.)
Single electrode probe consisting of a working electrode with current (Fig. 7.32) or potential (Fig. 7.33) measured with
respect to the structure of interest. As with the three electrode arrangement, this may also be used to evaluate polarization
response.
Figure 7.32 Single-electrode measurement of current with respect to plant. (Adapted from Ref. 25.)
Figure 7.33 Single-electrode measurement of potential with respect to plant. (Adapted from Ref.
25.)
7.12.3.2. Signal Analysis.

Electrochemical noise analysis (ENA), begun a few decades ago, has only been recently introduced as a credible corrosion
monitoring technique. In this context, the pioneering work of Eden et al. has been instrumental in introducing the idea of a
corrosion cell with two working electrodes (WE), where both current and voltage fluctuations can be measured.27 The
remaining question was how to establish the data interpretation on a firm basis. Because EN measurements on a single
corroding electrode are not sufficient to evaluate corrosion rates, most applications in the field are based on the use of cells
with two identical electrodes (same material, same size, same surface preparation), connected through a ZRA so as to have
both working electrodes set at a common corrosion potential. 28
The analysis of EN results obtained between two working electrodes. (WEs) with an imposed or naturally developing
asymmetry can be carried out by considering Eq. (7.5) that indicates that the noise impedance of a cell (Z n) depends on the
impedances of the two WEs, as well as their noise levels, represented by the power density spectra (Ψi1 and Ψi2 ) obtained by
performing the analysis of noise signals with either fast Fourier transform (FFT) or with the maximum entropy method (MEM).
(7.5)
For the simplest case of two WEs with the same impedance (Z 1 = Z 2 ), the noise impedance is equal to the modulus of the
electrode impedance |Z(f)|. This result is valid independently of the origin of the noise signals (localized or uniform corrosion,
bubble evolution due to the cathodic reaction) and the shape of the impedance plot, even if the noise levels of the two
electrodes are different. In such case, noise measurements are equivalent to impedance measurements for which the external
signal perturbation has been replaced by the internal noise generated by the corrosion processes. 28
However, when the two WEs do not have the same impedance, the noise impedance analysis requires a more cautious
interpretation. Depending on the source of the current noise, the measured impedance may either be that of a quiet cathode or
that of a quiet anode while in intermediate cases the results of the measurement of Z n would show a mixed behavior and be
more difficult to interpret. For example, if hydrogen bubbles are evolving on the cathode while the anode undergoes generalized
corrosion, the noise of the cathode is orders of magnitude larger than that of the anode, so that Z n becomes equal to the
impedance modulus of the anode, |Z a|. In these conditions, while the time records appear to show only the cathodic processes,
the impedance measured is that of the anode, using the noise of the cathode as input signal.
An opposite case would be a cell where the anode is undergoing pitting, while the cathodic reaction is the reduction of dissolved
oxygen or an imposed galvanic situation. Because the anodic noise is preponderant, Eq. (7.5) shows that Z n is equal to the
impedance modulus of the cathode, |Z c|. The anodic noise is the internal signal source utilized for the measurement of the
impedance of the cathode.
There are many cases, particularly in field applications where the use of low-noise reference electrodes commonly used in
laboratories would be impractical. In these cases, one can use a third electrode made of material similar to the other two
working electrodes. Obviously, such a reference electrode would contribute to the noise of the system. It turns out, however,
that in such an arrangement the noise impedance Z n is equal to a fraction of the total noise impedance (Z), that is, √3|Z|, so that
a simple correction is sufficient to correct the problem. However, a more serious concern is that the noise signals depend on
the three electrodes having the same impedance and contributing the same noise. As every corrosion worker knows, initially
identical electrodes tend to diverge in behavior with time. Experience has shown that this is particularly troublesome in the case
of localized corrosion for which it could introduce significant errors difficult to correct.
There are basically three categories of ENA: visual examination, sequence-independent methods that treat the collection of
voltage or current values without regard to their position in the sequence of readings (moments, mean, variance, standard
deviation, skewness, and kurtosis), and those that take the sequence into account (autocorrelation, power spectra, fractal
analysis, stochastic process analysis).29
Visual examination of the time record trace can give indications as to the type of corrosion processes that are occurring. The
following example illustrates how a simple examination of EN measurements could reveal the corrosivity of various points of an
industrial gas scrubbing system where highly corrosive thin-film electrolytes may form.30 These conditions arise when gas
streams are cooled to a temperature below the dewpoint. The resulting thin electrolyte layer (moisture) is often highly
concentrated in corrosive species.
The corrosion probe used in this example is illustrated inFigs. 7.34 and 7.35. A retractable probe with flexible depth was
selected, in order to mount the sensor surface flush with the internal scrubber wall surface. The close spacing of the carbon
steel sensor elements was designed to work with a discontinuous thin surface electrolyte film. This corrosion sensor was
connected to a handheld multichannel data recorder by shielded multistrand cabling (Figure 7.36). As the ducting of the gas
scrubbing tower was heavily insulated, no special precautions were taken to cool the corrosion sensor surface.
Figure 7.34 Corrosion sensor and access fitting used for thin-film corrosion monitoring. (Courtesy
Kingston Technical Software.)
Figure 7.35 Close-up of corrosion sensing elements used for thin-film corrosion monitoring.
(Courtesy Kingston Technical Software.)
Figure 7.36 Field corrosion monitoring using electrochemical noise recorded with a handheld data
logger. (Courtesy of Kingston Technical Software.)
Potential noise and current signals recorded during the first hour of exposure at the conical base of the gas scrubbing tower are
presented in Fig. 7.37. According to the operational history of the plant, condensate had a tendency to accumulate at this
location where highly corrosive conditions had been noted. The high levels of potential noise and current noise in Fig. 7.37 are
indicative of a massive pitting attack that is consistent with the operational experience. It should be noted that the current noise
is actually off-scale for most of the monitoring period, in excess of 10 mA. The high corrosivity indicated by the electrochemical
noise data from this sensor location was confirmed by direct evidence of severe pitting attack on the sensor elements, revealed
by scanning electron microscopy (Fig. 7.38). In contrast, both current and voltage signals remained relatively constantly small
at a position higher up in the tower, where the sensor surface remained mostly dry.
Figure 7.37 Potential and current noise records at two locations in a gas scrubbing tower.
Figure 7.38 Scanning electron microscope image of a sensor element surface after exposure at the
base of the scrubbing tower clearly showing corrosion pits.
An improvement over this simple analysis is commonly practiced in industry by tracking the width of the potential and current
signals as an indication of corrosion activity in the system being monitored. Fig. 7.39 illustrates how the decrease in the current
band obtained with a monitoring system was interpreted as a reduction in general corrosion activity in a debutanizer overhead
piping where the interaction between operational changes and the corrosion mechanism were being investigated.
Figure 7.39 Electrochemical current noise (large band) and potential noise (lower signal) in a
debutanizer overhead piping obtained with the Concerto VT noise system. (Courtesy of CAPCIS
Ltd.)
Most ENA techniques have been developed to relate sometimes subtle features in the noise data records to changes in the
corrosivity of a system and particularly on how these changes affect localized corrosion. Three techniques have also been
proposed for obtaining the polarization resistance as a measure of uniform corrosion rate if the Tafel constants of the system
are known or measured.
The noise resistance (Rn), a sequence-independent method, is the ratio of the standard deviation of potential to the standard
deviation of current. The impedance resistance (Rimp), a sequence-dependent method, is the ratio of the square root of the
potential power to the square root of the current power in the low-frequency limit. The potential and current power densities are
calculated from power spectrum distribution (PSD) techniques such as FFT or MEM.31 In addition finally the EN transient
resistance (Rtran ) is the ratio of the amplitude of potential to current for single transients.32 Rtran provides the most exact
corrosion resistance value, but the data analysis is also the most complicated because the technique hinges on finding
transients amenable to a clear interpretation.
While these techniques have been extensively used in controlled laboratory experiments, the high variability of field
environments combined with the availability of well-established methods such as electric resistance (ER), LPR, or the use of
coupons have created the impression that ENA is not an appropriate option for obtaining corrosion rates when uniform
corrosion is the prevalent corrosion mechanism.
In contrast, localized corrosion processes such as pitting and SCC have characteristic transients in the time record traces that
may help to distinguish between various possible types of corrosion. The modern success of ENA is in great part based on this
unique property because more traditional online techniques are quite ineffective in this area. This success is also due to the
fact that most forms of localized corrosion are much more troublesome in the management and operation of many
engineering systems than uniform corrosion.
The effect of localized corrosion on EN signals tends to create a deviation from a normal distribution (Poisson distribution) as
may be determined from the skewness and kurtosis of the EN signals. If techniques such as LPR and harmonic distortion
analysis (HDA) are also used, then independent derivation of the general corrosion current (Icorr) is possible. The ratio of the
current noise (standard deviation of the current) to the general corrosion current may then be used as an improved indicator of
localized corrosion activity.33
31
The localization parameter is the ratio of the standard deviation of the current, σ,I to the root mean square (rms) current.31
However, the rms current is related to the mean coupling current, which over an infinite period of time with two similar
electrodes is zero. This gives the localization parameter the possibility of having the unfortunate value of infinity. The pitting
factor is a modification of the localization parameter.10 The idea is to use a measure of icorr instead of rms current. If one
assumes that Rn is representative of the polarization resistance, the pitting factor is equivalent to the ratio of the standard
deviation of potential, σ V, to the Stern-Geary constant (B).
Figures 7.40 and 7.41 illustrate how the corrosion pitting indication and associated system instability were tracked during the
debutanizer overhead piping evaluation project mentioned earlier.
Figure 7.40 Increased pitting activity at end of period from large current transients observed in a
debutanizer overhead piping obtained with the Concerto VT noise system. (Courtesy of CAPCIS
Ltd.)
Figure 7.41 Moderate pitting events on fairly regular intervals observed in a debutanizer overhead
piping with the Concerto VT noise system. (Courtesy of CAPCIS Ltd.)
7.12.4. Harmonic Distortion Analysis

7.12.4. Harmonic Distortion Analysis
With this technique, a low-frequency sinusoidal potential is applied to a three-electrode measurement system, and the resulting
current is measured. As the corrosion process is nonlinear in nature, a potential perturbation by one or more sine waves should
generate responses at more frequencies than the frequencies of the applied signal. Current responses can be measured at zero,
harmonic, and intermodulation frequencies.
Measuring the direct current (DC) at frequency "zero" is called theFaraday rectification (FR) technique. The FR technique can be
used for corrosion rate measurements if at least one of the Tafel parameters is known. The corrosion rate and both Tafel
parameters can be obtained with one measurement by analyzing the harmonic frequencies. The speed with which the Tafel
slopes can be determined (typically < 1 minute) is a particular attraction of the technique.34
With harmonic distortion analysis (HDA) a single, low-frequency, and low-distortion sinusoidal voltage is applied to the
corroding interface. As a quality check, three different frequencies are used to verify the repeatability of the technique. The
amplitude is in the range of 10 to 30 mV peak to peak. The frequency used is typically 0.1 to 10 Hz. Other frequencies can be
used depending on the corrosion process.
The theoretical analysis for the computation of Tafel slopes and corrosion current makes no assumptions about solution
resistance effects, and measurements cannot be performed unless the system is free of significant electrical noise in the
frequency range of the applied measurement potential, or one of its harmonic frequencies.11
In principle, analyzing the primary frequency and the harmonics makes it possible to extract all the information to calculate
Tafel slopes and corrosion rate. In practice, this has been used in a very limited number of applications to date. A serious
limitation of the existing nonlinear techniques is that their application has been restricted mainly to activation-controlled
corrosion processes, for example corrosion rate measurements in acid media with and without inhibitors.
Besides FR, variations of HDA developed have been called nonlinear EIS (NLEIS), harmonic analysis (HA), harmonic impedance
spectroscopy (HIS), and electrochemical frequency modulation (EFM). These techniques all analyze nonlinear response of a
corrosion system after perturbation with a mono- or biharmonic signal and, on this basis, allow extraction of the required kinetic
parameters of the corrosion process. Except for the FR method, all other HAD techniques allow the simultaneous determination
of corrosion current and both Tafel coefficients.35
7.12.5. Zero-Resistance Ammetry

7.12.5. Zero-Resistance Ammetry
With this electrochemical technique, galvanic currents between dissimilar electrode materials are measured with a zero-
resistance ammeter (ZRA). The design of dissimilarities between sensor elements may be made to target a feature of interest in
the system being monitored (e.g., different compositions, heat treatments, stress levels, or surface conditions). The technique
may also be applied to nominally identical electrodes in order to reveal changes occurring in the corrosive environment and
thus serve as an indicator of changing corrosion rates.
The main principle of the technique is that differences in the electrochemical behavior of two electrodes exposed to a process
stream give rise to differences in the redox potential at these electrodes. Once the two electrodes are externally electrically
connected, the more noble electrode becomes predominantly cathodic, while the more active electrode becomes predominantly
anodic and sacrificial. When the anodic reaction is relatively stable, the galvanic current monitors the response of the cathodic
reaction to the process stream conditions. When the cathodic reaction is stable, it monitors the response of the anodic reaction
to process fluctuations.11
This technique has been found particularly useful to study depolarization effects of the cathode of a galvanic pair of electrodes
to obtain feedback of low levels of dissolved gases, particularly oxygen, or the presence of bacteria, which depolarize the
cathode of the galvanic pair and increase the coupling current. When used for detection of low levels of oxygen, other dissolved
gases may interfere. Calibration against a dissolved oxygen meter is usually required if quantitative values are needed.
The zero-resistance ammetry (ZRA) method can provide a quantitative measure if the number of influencing factors is limited
and preferably verifiable through other means. For monitoring the effect of dissolved gases, the conversion of the signal to a
gas concentration level is not accurate. When other factors play a role as well, for example, during the formation of biofilm
compounds or in the presence of inhibitors, the method cannot really provide a quantitative indication of any kind.
Additionally, results from galvanic probes do not always reflect the actual galvanic corrosion rates, because galvanic corrosion
depends on the relative areas and specific geometries of the components, which can easily vary between a probe design and
the actual plant components being monitored. The ZRA method cannot either distinguish between activation of the anodic or
cathodic reaction. For example, an increase in the measured current can result from cathodic activation by increased dissolved
oxygen, from anodic activation by increased bacterial activity, or by a combination of these. Separate analysis is sometimes
performed if it is necessary to distinguish between these electrochemical components.
7.13. ACCELERATED TEST ENVIRONMENTS

Laboratory corrosion tests have been proven to be a reliable and simple means to generate information for the selection of
materials by exaggerating the corrosion factors of a specific corrosion attack. These tests fall into three categories: cabinet
tests, immersion tests, and high-pressure/high-temperature tests.
7.13.1. Cabinet Tests

Corrosion cabinet tests are conducted in closed cabinets in which the conditions of exposure are controlled to emulate specific
corrosion mechanisms. These tests are generally used to determine the corrosion performance of materials intended for use in
natural atmospheres. In order to correlate test results with service performance, it is necessary to establish acceleration
factors and to verify that the corrosion mechanisms are indeed following the same paths. Modern surface analysis techniques
can be quite useful to ascertain that the corrosion products have the same morphologies and crystallographic structures that
are typically found on equipment used in service. There are basically four types of cabinet tests.
7.13.1.1. Controlled-Humidity Test.
Tests of this sort are used to evaluate staining characteristics or temporary protective coatings. Commercial test equipment is
available that can be set for any combination of percent relative humidity and temperature. When only a few small specimens
are to be exposed, an inexpensive method is to store them above water in a sealed glass container (Fig. 7.42).1 The vessel is
then stored in a controlled temperature location. When lower humidity is desired, it be obtained by using a mixture of water and
sulfuric acid (Table 7.6) rather than pure water. 36 Another method is to use salt solutions that produce specific relative
humidity (Table 7.7).
Figure 7.42 Specimens exposed to high humidity in a sealed container. (From Ref. 1, by
permission)
Table 7.6 Constant Humidity with Sulfuric Acid Solution.*
Desired percent relative humidity Specific gravity of required acid-water solution mL of acid to be added †
* Listed above are concentrations of sulfuric acid-water solutions that provide different percent relative humidity at 20°C.
†To a liter of water to give a solution of the required specific gravity.
100 1.00 None
95 1.09 69
90 1.14 135
85 1.17 190
80 1.20 229
70 1.25 309
60 1.29 379
50 1.34 469
40 1.37 586
30 1.44 766
20 1.49 945
10 1.59 1422
Table 7.7 Constant Humidity with Salt Solutions*
Percent relative humidity Solid phase
* This table shows the percent humidity at 20°C within a closed space above a supersaturated aqueous solution of the given solid
phase. Solutions of these types can be used to provide a constant relative humidity in tests of the type illustrated in Fig. 7.42.
100 None
95 Na2SO3 · 7H 2O
90 ZnSO 4 · 7H 2O
86 KHSO4
80 NH 4C1
75 NaClO3
66 NaNO2
58 NaBr · 2H 2O
52 NaHSO 4 · H 2O
42 Zn(NO3)2 · 6H 2O
32 CaCl2 · 6H 2O
20 KC2H3O 2
10 H3PO 4 · ½H 2O
There are numerous ASTM standards relating different variations of creating and controlling fog and humidity in cabinets for
corrosion testing of a broad spectrum of products, from decorative electrodeposited coatings to the evaluation of the
corrosivity of solder fluxes for copper tubing systems. The basic humidity test is most commonly used to evaluate the corrosion
behavior of materials or the effects of residual contaminants. Cyclic humidity tests are conducted to simulate exposure to high
humidity and heat typical of tropical environments.
The cabinet performing such tests should be equipped with a solid-state humidity sensor reading the current humidity condition
and a feedback controller. The mechanism used to control the humidity moves chamber air via a blower motor and passes it
over a heater coil in the bottom of the chamber with an atomizer nozzle fogging into this air stream Fig. 7.43.
Figure 7.43 Controlled-humidity test chamber.
7.13.1.2. Corrosive Gas Test.

Of considerable interest in recent years is the laboratory simulation and acceleration of atmospheric pollution effects used to
evaluate degradation of materials. These tests involve injection of a variety of gases, vapors, and particulate matter into a
controlled pressure chamber with controlled condensation on metal specimens. Sometimes, ultraviolet light is used to produce
photochemical changes in the gases or vapors, such as are known to occur under present-day smog conditions.
In these tests, controlled amounts of corrosive gases are added to humidity to replicate more severe environments. The ASTM
B775 (Test Method for Porosity in Gold Coatings on Metal Substrates by Nitric Acid Vapor) and B799 (Test Method for Porosity
in Gold or Palladium Coatings by Sulfurous Acid/Sulfur-Dioxide Vapor) employ very high concentrations of corrosive gases to
amplify the presence of pores in gold or palladium coatings. The moist SO2 test (ASTM G87) is intended to produce corrosion in
a form resembling that in industrial environments. A very sophisticated variation of these tests is the flowing of mixed-gas test
(ASTM B827) that consists in introducing parts per billion levels of pollutants such as chlorine, hydrogen sulfide, and nitrogen
dioxide in a chamber at controlled temperature and humidity. This test is particularly adapted to the needs of the electronics
industry.
7.13.1.3. Salt Spray Testing.

7.13.1.3. Salt Spray Testing.
The oldest and most wildly used cabinet test is ASTM B117 [Test Method of Salt Spray (Fog) Testing], a test that introduces a
spray in a closed chamber where some specimens are exposed at specific locations and angles. The concentration of the
sodium chloride (NaCl) solution has ranged from 3.5 to 20%. There is a wide range of chamber designs and sizes, including
walk-in rooms that are capable of performing this test. Although used extensively for specification purposes, results from salt
spray testing seldom correlate with service performance.
Hot, humid air is created by bubbling compressed air through a bubble (humidifying) tower containing hot deionized water. Salt
solution is typically moved from a reservoir through a filter to the nozzle by a gravity-feed system (Fig. 7.44). When the hot,
humid air and the salt solution mix is at the nozzle, it is atomized into a corrosive fog. This creates a 100% relative humidity
condition in the exposure zone. For a low-humidity state in the exposure zone of the chamber, air is forced into the exposure
zone via a blower motor that directs air over the energized chamber heaters (Fig. 7.45).
Figure 7.44 Controlled salt fog test chamber during a humid cycle.
Figure 7.45 Controlled salt fog test chamber during a dry cycle.
7.13.2. Immersion Testing
Probably the most common corrosion test method is immersion in a liquid. Obvious differences in test procedures are the
solutions used, agitation rates, and temperature. The environmental conditions that must be simulated and the degree of
acceleration that is required often determine the choice of a laboratory test. In immersion testing, acceleration is achieved
principally by
Lengthening the exposure to the critical conditions that are suspected to cause corrosion damage. For example, if a vessel
is to be batch-processed with a chemical for 24 hours, laboratory corrosion exposure of 240 hours should be considered
By intensifying the conditions in order to increase corrosion rates, i.e., increasing solution acidity, salt concentration,
temperature or pressure, and so forth.
By provoking localized environmental changes that can result in the formation of acidic/high chloride conditions furthering
the initiation and propagation of crevice corrosion of susceptible alloys, e.g., ASTM G78 (Fig. 7.46).37
Figure 7.46 Crevice forming assembly in a beaker immersion test (a); components of the assembly
and S30400 washer coupons after 30 days in a solution containing 4% NaCl and 8% FeCl3 (b). (See
also color insert.)
Once the environmental conditions have been determined and the test designed, it should be repeated a sufficient number of
times to determine whether it meets the desired standard for reproducibility. Immersion tests can be divided into two
categories.
7.13.2.1. Simple Immersion Tests.

7.13.2.1. Simple Immersion Tests.
In these tests, small sections of the candidate material are exposed to the test medium and the loss of weight of the material is
measured for a period of time. Immersion testing is a powerful method of screening and eliminating from further consideration
those materials that should not be considered for specific applications. However, while these tests are quick and economical
means for providing a preliminary selection of best suited materials, there is no simple way to extrapolate the results obtained
from these simple tests to the prediction of system lifetime.
7.13.2.2. Alternative Immersion Tests.

Another variation of the immersion test are the cyclic tests in which a test specimen is immersed for a period of time in a test
environment, then removed and dried before being reimmersed to continue the cycle. Normally hundreds of these cycles have
to be completed during the course of a test program (Fig. 7.47).1
Figure 7.47 This large alternative immersion testing machine is timed to rotate the racks 60° every
10 minutes, thus immersing specimens for 10 minutes every hour and exposing them to air for 50
minutes. (From Ref. 1,, by permission)
7.13.2.3. Immersion Tests Under Load.

The study of environmentally assisted cracking in its most basic sense involves the consideration and evaluation of the
inherent compatibility between a material and the environment under conditions of either applied or residual stress. This is a
very broad topic encompassing many possible combinations of materials and environments. Over the past 20 years a number
of laboratory test methods to predict the behavior of steels in sour service have been developed, for example in Fig. 7.6.
One of the best ways of assessing pipeline steels is to stress a full ring specimen of the linepipe in a sour environment.38 This
can be achieved by welding end caps onto the sample and pressurizing it with a suitable gas or liquid medium (Figs. 7.48 and
7.49) or by applying external loading as illustrated in Fig. 7.50. The advantage of the full ring test is that it is not necessary to
pressurize the linepipe full ring specimen in order to achieve the required stress loading. Equivalent stresses can be produced
using mechanical means to deform the pipe by ovalisation.
Figure 7.48 Full ring test in preparation for a 45-in pipe. (Courtesy of CAPCIS Ltd.)
Figure 7.49 The 24-in-diameter full ring test as per OTI 95-635 containing 300 L of NACE TM0177-
96 solution saturated with H2S. (Courtesy of Bodycote Materials Testing.)
Figure 7.50 Super 13% Cr weldable pipe with external load in secondary containment tanks to
totally exclude oxygen ingress. (Courtesy of Bodycote Materials Testing.)
7.13.3. Flow-Induced Corrosion Testing

A laboratory apparatus for carrying out flow-induced corrosion testing must have a well-defined flow field in order to provide a
realistic comparison to field systems of interest. Surface shear stress and mass-transfer coefficient measurements have been
used to provide this required correlation between different flow conditions. Similarity of the local hydrodynamics can be
assumed if shear stresses are maintained the same between the field environment and a laboratory experiment. Laboratory
corrosion rates can then be used to establish realistic correlations with the actual operating system conditions as illustrated in
Fig. 7.51.39 The following assumptions need to be respected for the process to be valid40:
Figure 7.51 Process for relating laboratory data to real operating systems using hydrodynamic
conditions. The operating flow rate allows calculation of the wall shear stress, which is then
correlated through the wall shear stress to the measured laboratory corrosion rate.
The parameter calculation is valid.
The calculated parameters are those controlling corrosion or are directly related to them.
The scale up of these parameters to facility operations with respect to corrosion is valid.
Both the wall shear stress and mass transfer coefficient meet these basic criteria. A summary of advantages and
distinguishing features of some experimental systems is provided in Table 7.8.41
Table 7.8 A Summary of Advantages and Distinguishing Features of Some Experimental Systems
Feature Rotating disk (laminar Rotating Impinging jet (in stagnation Flow
flow) cylinder region) loop
* This feature applies only when the entrance region is large enough so that the flow over the coupon is fully developed.
† Optically based in situ surface-analysis techniques require flat, stationary coupons.
Well-characterized flow pattern Yes Yes Yes Yes*
Uniform mass transfer Yes Yes Yes No
Uniform primary-current distribution No Yes/No No No
Uniform shear distribution No Yes No Yes*
Possibility of noise at rotating contacts Yes Yes No No
Possibility of wobble-induced errors Yes Yes No No
Requires pump No No Yes Yes
Potential for leaks Low Low High High
Suitable for application of in situ surface No No Yes Yes†

analysis
Suitable for well-defined studies of mass Yes Yes Yes No

transfer
Suitable for well-defined studies of shear No Yes Yes No
Suitable for qualitative screening studies Yes Yes Yes Yes
The following example of a comparative analysis between field and laboratory test results has been carried out during an
evaluation of the best methods for screening inhibitors used in oil field operations. The study first surveyed the technical
literature and other available information from pipeline companies.42 Twelve laboratory methodologies used to assess inhibitor
performance were then critically evaluated. Field monitoring was carried out at three oil field facilities to support the laboratory
evaluation and define the conditions under which specific laboratory methodologies could be used with confidence. A
quantitative comparison of field and laboratory general corrosion rates, pitting corrosion rates, and percentage inhibition
calculated from general corrosion rates and pitting rates under these field conditions was then established and reported. The
ranking procedure was developed with the following considerations:
Field experiments were carried out for 15 days, whereas laboratory experiments were carried out in 1 day.
The steel material, gas, brine composition, and temperature used in laboratory experiments were the same as those in the
field.
For elevated pressure experiments, the total pressure and partial pressures in the laboratory were the same as in the field.
For atmospheric pressure experiments, the gas ratios (e.g., 20% H2 S, 2.5% CO2 , balance argon) were the same as in the
field.
In the field, the corrosion rates are typically higher at the bottom of a pipe than in the middle, and they are less at the top.
Data from bottom coupons was therefore used in the analysis because this would reflect the worst scenario required to
perform a system life assessment.
The ranking of the laboratory methodologies was based on the following criteria:
Comparison of the logarithm of the ratio of the laboratory general corrosion rate to the general corrosion rate of the bottom
coupon in the field where corrosion is generally more severe
Comparison of the logarithm of the ratio of the laboratory pitting corrosion rate to the pitting corrosion rate of the bottom
coupon in the field
Comparison of the percent inhibition (calculated from both corrosion rate and pitting corrosion rate) in the laboratory and in
the field
In this analysis the rotating cage method was found to provide the best estimates of field performance and was targeted for
international standardization efforts. 42
7.13.3.1. Mass-Transfer Coefficient.

Mass transfer defines the chemical and electrochemical effects of fluid flow on the transport of reactive chemical species from
the bulk solution to and from a solid surface through a transition or boundary layer. The mass-transfer coefficient defines the
movement of corrosive species to the metal surface and the movement of corrosion products away from the metal surface.
The diffusion layer, in which the mass transfer occurs, is roughly defined by the diffusion mass flux density as expressed in the
Nernst diffusion model. The mass-transfer coefficient (km ) is defined as the proportionality between the mass flux density and
the concentration gradient, expressed as Eq. (7.6)40:
(7.6)
Substituting in this equation, the definition of the flux density the mass-transfer coefficient is redefined asEq.
[ (7.7)]:
(7.7)
Mass-transfer coefficients are usually determined experimentally. A large number of techniques have been used, but the most
widely used are the dissolving wall method, the limiting current density technique (LCDT), and the analogy with heat transfer.43
7.13.3.1.1. Dissolving Wall Method.

7.13.3.1.1. Dissolving Wall Method.
In the dissolving wall method, a specimen is made of or coated with a material that is sparingly soluble in the test environment.
Typical material environmental combinations that have been used include43:
Transcinnamic acid and water
Benzoic acid in glycerin/water mixtures
Plaster of Paris in waters
With this technique the surface roughens with time rapidly making difficult to determine initial smooth values. With solid
models it is difficult to reproduce complex geometries such as tight bends in tubes where both changes in wall thickness and
shape will occur. With coated specimens it is difficult to produce uniform coating thickness, thus creating problems with the
accuracy of thickness loss measurements. Furthermore, with the dissolving wall technique it is possible to induce pure erosion
that might be synergistic with the dissolution process. It is thus essential to assess the occurrence of any erosion by using a
saturated test solution and starting with a roughened surface.
Mass-transfer coefficients can also be measured by using the dissolution of a corroding specimen. This technique has been
tested with a number of specimens having a varying mass-transfer profile.43 The method involves corroding copper
components in dilute hydrochloric acid containing ferric ions. In this system the corrosion rate is controlled by the arrival of
ferric ions at the copper surface where they are reduced to ferrous ions in Eq. (7.8), the anodic reaction being the dissolution of
copper to a monovalent state in Eq. (7.9) as a chloride complex. An important advantage of this technique is that the
developing roughness is less than that in the chemical dissolution technique.
(7.8)
(7.9)
7.13.3.1.2. Limiting Current Density Technique (LCDT).

With the LCDT, a single electrochemical reaction is driven at such a potential that its rate becomes diffusion controlled. Various
systems have been suggested, but the most frequently used in practice is an aqueous solution of the redox couple potassium
ferri/ferrocyanide [Eq. (7.10)] with the addition of a nonreacting electrolyte such as NaOH to minimize ionic migration effects
and increase the conductivity of the solution.44
(7.10)
While this reaction is to provide good reproducibility in different flow geometries, certain precautions must be taken. Three
problems can arise with the usage of the ferri/ferro cyanide redox couple 45:
Slow decomposition of the potassium ferrocyanide from exposure to daylight.
Poisoning of the working electrode and counter electrode as a result of hydrogen cyanide (HCN) formation from the
aforementioned decomposition.
The presence of dissolved oxygen in the cell can interfere with the above electrochemical reaction, particularly at low
concentrations.
The exact rate of decomposition of these cyanide complexes has not yet been quantified. However, it has been suggested that
it could be practically eliminated if the electrolyte was an alkaline solution kept in darkness. Purging with nitrogen will also
practically eliminate oxygen from the solution.
A typical experiment involves a sweep of the potential at a scan rate of 5 mV/s 0.5 V above and 1.7 V below the open-circuit
potential measured against a saturated silver/silver chloride reference electrode (0.22 V in Fig. 7.52).45 It is obvious in Fig. 7.52
that the cathodic reaction offers a broader potential "window" where the limiting current is clearly measurable with a plateau
nearly 1 V wide when compared to the anodic reaction where it is only 200 to 300 mV wide. However, a lack of reproducibility of
the cathodic current can be observed probably caused by the slow decomposition of the ferrocyanide ion in the presence of light
occurring most likely as reaction [Eq. (7.11)].
(7.11)
Figure 7.52 Test of repeatability in experiments with the ferri/ferro cyanide system and a rotating
cylinder turning at 2000 rpm. The two curves were obtained 5 days apart using the same
electrolyte: 0.1-M potassium ferri and ferro cyanide and 0.5-M KOH.
Conversely, the limiting currents associated with the anodic reaction may be much more reproducible.
7.13.3.1.3. Analogy with Heat Transfer.

Mass-transfer coefficients may also be obtained from heat-transfer data (HTD) using the analogy between heat and mass
transfer, but these measurements have similar drawbacks to their mass-transfer counterparts. Furthermore, the Prandtl number
used to characterize heat transfer is usually much lower than the Schmidt number producing up to a tenfold decrease in the
resolution of the measurements.43
7.13.3.1.4. Mass-Transfer Coefficient, Surface Geometry, and Corrosion Rates.

7.13.3.1.4. Mass-Transfer Coefficient, Surface Geometry, and Corrosion Rates.
The mass-transfer coefficient km can be calculated once the flow geometry is assumed. However, the expected simple linear
relationship between mass transfer and erosion-corrosion does not always hold for a variety of reasons that include46:
Change in controlling step: Disruption of a protective film above a certain mass-transfer threshold can lead to a sudden
increase in the erosion-corrosion of the bare substrate.
Spatial separation of anodic and cathodic areas: The localization of anodic and cathodic areas can lead to a lack of
conformity with mass-transfer expectations.
Series control: There are situations in which two processes in series control the erosion-corrosion rate, leading to a lower
dependency on mass transfer.
Coupled reactions: For coupled reactions, increasing flow can increase both mass-transfer and possibly lower the corrosion
potential that could lead to an increase in the surface film solubility.
Inappropriate mass-transfer values: Most mass-transfer data (MTD) is for smooth surfaces. As a surface is submitted to
erosion, its surface roughness can change. It has been suggested that when this occurs, the roughness factor can become
more important than the original shape in controlling the mass transfer.
Examples of some effects caused by these factors and the resulting mass-transfer erosion-corrosion behavior are shown in
Fig. 7.53.47
Figure 7.53 Possible relationships between mass transfer and corrosion rates.
7.13.3.2. Rotating Systems
7.13.3.2.1. Rotating Disc.

7.13.3.2.1. Rotating Disc.
The rotating disc is commonly employed in electrochemical research because it has a well-defined fluid-flow pattern and is
relatively easy to use. The specimen to be studied is machined into a cylinder and is typically encased in an inert material such
as epoxy or polytetrafluorethylene (PTFE) so that only the circular face of the metal is exposed to solution. A good-grade
metallographic epoxy to shroud the coupon can help prevent the formation of a crevice that is occasionally experienced.41
The velocity profile induced by the rotation has nonzero components in the axial, radial, and angular directions. If the
electrochemical reaction is limited by the rate of transport of species to or from the electrode, the current distribution on the
disc is uniform and the average current density is given by a version of the Levich equation [Eq. (7.12)].48
(7.12)
When Re is greater than 2 × 105 , the overall mass transfer rate comprises contributions from the laminar and transition regions
and above 3.5 × 105 from the turbulent region. Above approximately Re of 106 , turbulence dominates. In corrosion studies it is
rather important to know how the mass-transfer rate varies locally. At Re values up to Recrit mass transfer is uniform and is
described by the Levich equation [Eq. (7.12)]. However, because the mass-transport rate is uniform across the surface in
laminar flow, a uniform corrosion rate may occur. Consequently, laminar flow results do not reveal much information
concerning the interaction of ohmic drop, electrochemical kinetics, and mass transfer to determine overall corrosion rates and
their distribution. Above Recrit, when the flow regime changes from being laminar to being turbulent, a central laminar region is
surrounded by transition and turbulent zones where mass transfer will be increasing with increasing radial distance.49
The advantages and disadvantages of the rotating disc technique are listed inTable 7.9.41 One word of caution with this
technique is the use of a bearing-guided shaft to minimize wobble. Another problem to avoid is the creation of vortices that can
cause entrainment of air and associated impingement of entrained bubbles onto the electrode surface.
Table 7.9 Advantages and Disadvantages of the Rotating Disk Technique for Corrosion Testing
Advantages Disadvantages
• Hydrodynamic flow is well defined. Mathematical models for current • The current and potential distributions are not simultaneously uniform.
and potential distribution have been developed and are available in As a result, interpretation of data obtained below the mass-transfer-
the open literature. limited current requires sophisticated mathematical models.
• Only standard machining is required to fabricate the electrodes and, • Even at high rotation speeds, a fraction of the disk operates under
once encased in the electrically isolating material such as epoxy or laminar flow. The nonuniform flow regime seen at high rotation speeds
PTFE, the surface is easily polished and is therefore reproducible. can result in potentially misleading differential mass-transfer effects.
• The system is easy to use. No pumps are needed because the flow • Maintaining low-resistance electrical connection to the rotating
pattern is induced by the rotation of the disk. electrode can be difficult.
• The system is easily adaptable to many solutions and • As for all systems using rotating coupons, a bearing-guided shaft is
hydrodynamic environments. needed to avoid wobble.
• Both electrochemical methods and mass loss can be used to

provide information on corrosion rates.
7.13.3.2.2. Rotating Cylinder.
The rotating cylinder technique is a popular tool for studying the erosion-corrosion behavior of metallic materials because it
provides a simple mean to conduct experiments in the turbulent flow regime and determine whether a given reaction is
influenced by mass-transport limitations in these conditions. As for the rotating disc, a rotating cylinder will cause swirling of
the fluid because of surface drag. The extent of the drag depends on the exact geometry, particularly the degree of baffling. A
favored experimental arrangement is one involving the presence of a concentric stationary outer cylinder around the inner
rotating cylinder (Fig. 7.54).50 Laminar flow only occurs at low rotational speeds, for example 10 rpm (revolutions per minute),
giving a critical Re values less than 200. This may be increased if the outer cylinder is also rotated.
Figure 7.54 System of cylindrical electrodes, whose inner can usually rotate.
Three flow regimes have been defined with series of LCDT measurements with 71-point electrodes located in a stationary outer
cylinder51:
1. At low rotational speeds flow is tangential and laminar (Fig. 7.55a).
Figure 7.55 Transition study on a rotating cylinder electrode using limited current density
measurements51: (a) laminar flow for Ta <412, (b) laminar plus vortex flow for Ta <800, (c) and (d)
transition between laminar and turbulent flow for Ta of 1000, (e) turbulent plus vortex flow for Ta
between 2000 and 15000, and (f) fully turbulent flow above Ta of 15000.
2. Above a critical Taylor number value flow regains laminar, but turbulent vortices develop giving superimposed radial and
axial motion (Fig. 7.55b through 7.55e).
3. Above a critical Re value true turbulence develops (Fig. 7.55f).
The Taylor number mentioned here is a dimensionless number that specifically characterizes the degree of vortices in a
rotating system. For the rotating system described in Fig. 7.54, the Taylor number is defined as Eq. (7.13):
(7.13)
The results summarized in Fig. 7.55 show the complexity of the local turbulence.
In some cases, the entire cylindrical assembly consists of the metal to be studied, which is machined into the form of a cylinder
that is immersed in the test environment and rotated inside a concentric mesh or foil counter electrode (Fig. 7.54). Another
approach is to have the metal coupon machined into an annulus and supported by an inert material such as epoxy or PTFE to
expose the outer cylindrical surface to the solution (Fig. 7.56). This later approach has the advantage that the coupon itself is
smaller, but it has the disadvantage that the current distribution below the limiting current is no longer uniform.41
Figure 7.56 System of cylindrical electrodes, whose inner contains a coupon machined into an
annulus and supported by an inert material.
The advantages and disadvantages of the rotating cylinder technique are listed inTable 7.10.41 As for the rotating disc, it is
recommended to use a bearing-guided shaft to minimize wobble. Vortices can also cause entrainment of air and associated
impingement of entrained bubbles onto the electrode surface. Reference electrode placement far from the cylinder electrode is
used in electrolytes of modest resistivity. Such placement allows use of the theoretical predictions for resistance, eliminates
uncertainties associated with reference electrode placement, and avoids disturbance to the flow pattern near the working
electrode.
Table 7.10 Advantages and Disadvantages of the Rotating Cylinder Technique for Corrosion Testing
• If the electrode is normal to all electrically isolating planes, • If the electrode is not normal to all electrically isolating planes, the current and
both the current and potential distributions are uniform. The potential distributions will not be uniform at the same time. Such non-uniformity
electrode behaves as an ideal one-dimensional surface that makes interpretation of results dependent upon application of fairly
can be modeled easily. sophisticated mathematical models.
• Hydrodynamic flow is well defined. Empirical correlations • Once encased in the electrically isolating material such as epoxy or PTFE, the
are used to obtain mass transfer, coefficients, and friction electrode surface can be difficult to polish.
factors in turbulent flow.
• The system is easy to use. No pumps are needed because • Maintaining low-resistance electrical connection to the rotating electrode can
the flow pattern is induced by the rotation of the cylinder. be difficult.
• Only standard machining is needed to fabricate the • As for all systems using rotating coupons, a bearing-guided shaft is needed to
electrodes. avoid wobble.
• The system is adaptable to many solutions and

hydrodynamic environments.
• Corrosion information can be provided by both

electrochemical methods and mass loss.
• Turbulent flow is achieved at relatively low rotation rates.
7.13.3.2.3. Rotating Cage.

The rotating cage technique was introduced in 1990 as a promising laboratory methodology to simulate pipe flow in the
laboratory by rotating the specimens at speeds up to 1500 rpm.52 Earlier version of this increasingly popular tests were carried
under the names of "stirred autoclave with rotating specimens," "strips exposed to a rapidly stirred solution," and more
commonly "rotating probes." Rotating cage experiments have also been reported as high-speed autoclave tests (HSAT) or
rotating probe experiments. Invariably, experiments using a rotating cage have been carried out under elevated pressure in an
autoclave.53
Figure 7.57 shows a schematic diagram of the rotating cage system for atmospheric pressure operation. The vessel can be
manufactured from a readily available material such as acrylic. At the bottom of the container, a Teflon base is snugly fitted. At
the center of the base, a hole is drilled, into which the lower end of the stirring rod is placed. This arrangement stabilizes the
stirrer and the coupons being tested. In the experiments described here, eight coupons were supported between two Teflon
disc mounted 8 cm apart on the stirring rod of the autoclave. Holes were drilled in the top and bottom Teflon plates of the cage
to increase the turbulence on the inside surface of the coupons. This experimental setup may be used at temperatures up to
70°C and rotation speeds up to 1000 rpm.53 Figure 7.58a and 7.58b shows respectively a side view and a top view of a rotating
cage assembly. The flow patterns in the rotating cage have been qualitatively divided into four zones54:
Figure 7.57 Schematic diagram of a rotating cage assembly.
Figure 7.58 (a) Side view (b) and top view, of a rotating cage assembly.
1. Homogeneous zone: The vortex length and width increase linearly with rotation speed (Fig. 7.59).53
Figure 7.59 Rotating cage with fully developed homogeneous zone.
2. Side-wall affected zone: The vortex length increases, but the width has reached the side and collides with the wall (Fig.
7.60).53
Figure 7.60 Rotating cage with side wall being the affected zone.
3. Turbulent zone: The vortex length penetrates into the rotating cage and creates turbulent flow (Fig. 7.61).53
Figure 7.61 Rotating cage in turbulent zone.
4. Top-cover-affected zone: The liquid level oscillates and rises to the top due to the backward movement of the fluid F
( ig.
7.62).53
Figure 7.62 Rotating cage when top cover is affected.
The flow patterns in the absence of rotating cage or in the homogeneous zone are similar to flow patterns observed with a
rotating cylinder for which the wall shear stress is expressed in Eq. (7.14).53
(7.14)
where ρ = fluid density
r = radius of a rotating cylinder or a rotating cage
ω = angular velocity
In the side-wall- and top-cover-affected zones, the wall shear stress is less than that calculated by Eq. (7.14), due to the
movement of fluids in the opposite direction. In the turbulent zone, on the other hand, the wall shear stress can be much higher
than that calculated by Eq. (7.14), due to the penetration of the vortex through the cage. In all zones, except in the top-cover-
affected zone, the solution is dragged toward the coupons, due to the vortex formation, increasing the wall shear stress at least
on the outer surface of the coupons. Figures. 7.63 and 7.64 show graphically the experimental conditions of rotation and
volume of liquid for which the homogenous zone has been observed when holes were aligned (Fig. 7.63) or not aligned (Fig.
7.64).53
Figure 7.63 Typical variations of fluid characteristics as a function of rotation speed and volume of
liquid with water as the fluid and holes aligned.
Figure 7.64 Typical variations of fluid characteristics as a function of rotation speed and volume of
liquid with water as the fluid and holes not aligned.
7.13.3.3. Flow Systems.

Flowing systems are popular for studying the effects of flow velocity on corrosion and erosion-corrosion because they more
closely reproduce actual operation conditions. Ideally the fluid would pass through the system once without being recirculated,
but such systems can be very expensive to operate and maintain. Most flowing systems use a recirculating flow loop. A
multitude of flow systems have been designed and operated to evaluate FAC and erosion-corrosion. These systems can be
divided in three broad categories:
1. Flow loops in which the tube material or a specific component typically used in service are used as coupons.
2. Flow systems using an orifice or a nozzle to enhance flow velocity.
3. Flow systems using jet impingement to focus the flow on a target surface.
7.13.3.3.1. Flow Loop.

The design parameters for a flow loop system can include a broad range of variables such as temperature, pressure, diameter
and length of test section, maximum flow velocity, and fluid properties such as density, viscosity, and heat capacity. The
advantages and disadvantages of the flow loop technique are listed in Table 7.11. The hardware to construct a flow loop
system should be selected to withstand the desired pressures and temperatures. Not all hardware designed to work in static
systems will work in flowing systems. Tables 7.12 and 7.13 provide some general guidance on the requirements of various
components of flow loop systems.41
Table 7.11 Advantages and Disadvantages of the Flow Loop Technique for Corrosion Testing
• Mathematical expressions for velocity profiles, • Flow loop systems are expensive and cumbersome to operate. Problems associated
mass-transfer characteristics, and current with equipment reliability may limit collection of long-term data.
distribution have been developed for this system.
• For a fully developed flow the shear stress is • The setup uses a pump in its operation, which can create problems with mechanical
uniform over the surface if the specimen being seals or packing seals and may invite leakage of oxygen into the system, although many
tested does not interfere with the flow pattern. problems may be avoided by using a magnetic drive pump.
• Placement of specimens parallel and

perpendicular to the flow field can allow study of The relatively easy entrainment of particles or air bubbles can greatly affect the
differential shear. measurements.
Interpretation of results can be complicated by nonuniform mass transfer.
The use of a flow loop increases the possibility for spills or floods. This is a
particularly important consideration when toxic, flammable, corrosive, or otherwise
difficult-to-handle fluids are used.
Table 7.12 Equipment Requirements for Flow Loop Systems: Data Acquisition, Instrumentation, Filters, and Heaters
Data acquisition and instrumentation: The number of instruments needed for computerized data acquisition is the same as that needed for a
manual system. The only changes relate to the type of instrument selected. For example, pressure transducers are used for computerized
acquisition whereas pressure gauges suffice for manual acquisition. Temperature and pressure transducers or gauges should be located
throughout the loop, especially in areas such as the liquid reservoir, the line of the pump discharge, throughout the test section, and, most
importantly, at the entrance and exit of the test section. Probes should be placed away from corrosion test cells in order to avoid disturbing the
flow near them. Flow meters should be installed at the entrance of the test section. If a turbine flow meter is selected, it is good practice to install
a mechanical flow meter parallel to the turbine flow meter so the meters can be checked against each other to ensure proper functioning. The pH
is monitored with an in-line pH probe that can be located in the liquid tank or at the entrance line to the test section. If pH is controlled, a pH
control system can be installed in the liquid tank. These systems consist of a pH probe, a controller, acid and caustic injection pumps, and tanks
containing acid and caustic solutions. For long-duration tests, it is good practice to install a pressure relief safety valve in the liquid tank, a high-
low-temperature shutdown switch in the liquid tank, a high-low-pressure shutdown switch in the liquid tank, a low-liquid-level shutdown switch fn
the liquid tank, and a vibration shutdown switch on or very near the pump.
Filters: In flow loop systems filters are frequently installed to remove particles from circulation. A full-flow strainer to remove large-size particles
can be placed directly in the liquid line before the test section. A partial-flow filter can be placed in a bypass loop to remove small particles. The
filter may use disposable cartridges that can be changed at the beginning of each test. Different sizes are available for removing different size
particles.
Heaters: The function of the heater is to achieve and maintain the desired temperature of the system. For flow loop systems, electric heaters are
usually easier to operate and install than gas heaters. Two types of heaters can be used: the immersion type or the band type. Immersion heaters
fit inside the liquid tank with the heating coils in direct contact with the solution. The advantages of this type of heater are that the heating of the
solution proceeds quickly and that a constant temperature is easily maintained. The disadvantages are that the material selected for the heating
coils must be resistant to possibly corrosive environments; the temperature at the surface of the coils is much greater than the desired system
temperature, so the material chosen for the particular operation can be very expensive; and the liquid reservoir has to be provided with a port for
installation of immersion heaters. Band heaters are located around the liquid reservoir. The advantages of using this type of heater are that they
are much less expensive than immersion heaters; they are easier to install because they do not require a special port for installation; and the
heater can be easily replaced without interrupting the test, an important advantage if the test is designed for a long period of time. The
disadvantages are that, because the heat has to dissipate through the reservoir wall, the rate of heat transfer for a given power input is smaller,
and materials problems associated with high wall temperatures are transferred to the reservoir wall.
Table 7.13 Equipment Requirements for Flow Loop Systems: Insulation, Liquid Reservoir, Mixing Tank, Pump, and Test Section
Insulation: Thermal insulation of the loop may be needed to maintain the desired system temperature.
Liquid reservoir: The purpose of this reservoir is to hold the desired volume of the testing solution at the desired system pressure and temperature.
The liquid reservoir is designed to hold at least 10 times the volume of the test section. Another important parameter is the ratio of the reservoir
volume to the specimen surface area. The reservoir is provided with ports to install the different instruments for safety and control of the
experiment. It is also provided with a drain at the bottom of the tank, an inlet for a bypass line and the return line from the test section, a port to
connect a line where the pressure relief valve may be installed, and a line for the gas inlet and vacuum for deaeration.
Mixing tank: The mixing tank can be an open tank in which the test solution is prepared and then introduced in the liquid reservoir for deaeration. If
a vacuum pump is used for deaeration purposes at the liquid reservoir, the pump can also be used to transfer the solution from the mixing tank.
Aeration may be needed for simulations of systems that would normally be open to ambient air.
Pump: Centrifugal pumps can be used for almost any service condition unless extremely low flow rates associated with excessive pressure drops
are used. Selection of the pump is based on the maximum flow rate desired and the maximum pressure drop in the test section. The power
requirements can be calculated given a desired velocity and the pressure drop experienced in the system. The main problem with centrifugal
pumps occurs at the seals. Mechanical and packing seals are typically used, and, if the material is not properly selected, undesirable leakage may
occur. Obtaining as much information as possible from the pump and seal manufacturers is important to ensure the proper selection of seals to
the system conditions. An alternative to the use of seals is the use of magnetic drive pumps. These pumps can be expensive, but the seals are not
a problem.
Test section: The test section can be designed to accommodate different geometries such as valves, elbows, straight tubing, coupling, tees, etc. If
a pump has already been selected, the test section is designed so that the total pressure drop across it does not exceed the pressure drop for
which the pump was selected. The test section is also provided with ports to install instrumentation. The instrumentation may characterize the
system, such as temperature and pressure gauges or transducers, flow meters, pH probes, etc., or may make corrosion measurements via mass
loss, electrochemical polarization scans, or electrochemical impedance spectroscopy. If temperature and pressure conditions and system
chemistry allow, it is useful to have viewing sections made of clear pipe. Viewing sections allow for identification of possible bubble entrainment
and solution contamination. Viewing sections can also allow for observation of scale formation and deposition. It is important to check with the
manufacturer regarding the material's chemical resistance, mechanical and electrical properties, creep, and thermal endurance before installing
any viewing section. If possible, tests can be performed to verify the manufacturer's information.
The lower limit for the laminar to turbulent transition is around Re values of 2000 when there are large disturbances in the flow
system. The flow will probably be turbulent when Re reaches values around 100,000 while the following classification of pipe
flow patterns was produced using LCDT measurements at a point electrode55:
a. At low Re flow was laminar with no current fluctuations.
b. At a Re of 2140 a slight wavy disturbance was observed in the measurements.
c. Intermittent patches or plugs of turbulent flow were observed at higher Re values (Fig. 7.65a).
Figure 7.65 Transitions in pipe flow obtained with limiting current density measurements at (a) Re
of 2340, (b) Re of 3740, and (c) 17300.
d. As Re increases the fraction of time the motion is turbulent known as the intermittency factor is increased.
e. At a Re number of 3740 the flow is completely turbulent (Fig. 7.65b).
f. Further increases in Re increase the frequency of the fluctuations in the LCD (Fig. 7.65c).
7.13.3.3.2. Nozzle or Orifice.

Nozzles and orifices inserted in a flow system upstream of test surfaces can provide severe hydrodynamic conditions and
accelerate corrosion. They are thus a useful tool for studying the effects of varying hydrodynamic factors on corrosion as well
as being relevant to practical situations. Both heat-transfer data (HTD) 56 and mass-transfer data (MTD), using LCDT,57 have
shown that the maximum mass-transfer rate may be described by Eq. (7.15)49:
(7.15)
where Reo is defined as a relation between the orifice diameter (do ) and the diameter (d) of the tube itself in Eq. (7.16).
(7.16)
The flow enhancement over fully developed pipe values, which is expressed in Eq. (7.16), occurs at approximately two tube
diameters downstream of the orifice. The enhancement will be reduced slightly if mass transfer is taking place prior to the
orifice. The enhancement itself can be obtained by dividing the correlation equation for the maximum mass-transfer
downstream of an orifice by that for fully developed flow. After simplification this becomes Eq. (7.17):
(7.17)
where Shfd is Sh for a fully developed turbulent pipe flow.
A systematic compilation of the HTD and MTD results has yielded a single expression of the mass-transfer enhancement as a
function of distance from an orifice [Eq. (7.18)]49:
(7.18)
Values of the coefficients Ax and Bx at different tube diameters from the orifice are given in Table 7.14 for the HTD56 and
MTD 57 results, and Fig. 7.66 illustrates the enhancement of mass-transfer downstream of an orifice modeled withEq. (7.18) for
which average values of Ax and Bx in Table 7.14 are used.
Figure 7.66 Enhancement of mass-transfer downstream of an orifice modeled with Eq. (7.18) for
which average values of Ax and Bx are used.
Table 7.14 Values of Constants in Equation for Mass-Transfer Profiles of Orifices
(Distance from orifice) (x/d) (HTD) Ax (HTD) Bx (MTD) Ax (MTD) Bx
HTD = heat-transfer data; MTD = mass transfer data.
0.5 2.72 0.057 2.12 0.073
1.0 3.67 0.051 3 0.049
1.5 4.52 0.059 3.75 0.062
2.0 4.7 0.066 4.2 0.072
2.5 4.5 0.068 4.17 0.079
3.0 4 0.067 3.74 0.078
3.5 3.15 0.065 2.92 0.073
4.0 2.45 0.064 2.25 0.069
4.5 1.72 0.063 1.62 0.064
5.0 1.45 0.062 1.27 0.063
5.5 1.22 0.059 0.98 0.062
6.0 1 0.058 0.77 0.062
6.5 0.82 0.056 0.6 0.062
7.0 0.67 0.055 0.45 0.062
7.13.3.3.3. Impinging Jet.

Impinging jets are another method of growing popularity to provide focused-flow acceleration. Three types of impinging jets
have been used to accelerate erosion and erosion-corrosion, namely, free jet, submerged jet, and jet-in-slit (Fig. 7.67).58 Free jet
is commonly used in conventional liquid impingement tests in which the liquid jet strikes at right angles with the specimen
surface in air.59 Submerged jet is a jet submerged in water that can provide a wide range of testing conditions as will be
demonstrated in a few examples described later. In the jet-in-slit, jet is injected into a narrow gap forcing the test liquid through
a local depressurization capable of causing cavitation. The average radial flow rate distribution of the submerged jet is
intermediate between the free jet and the jet-in-slit.
Figure 7.67 Three types of impinging jets used to evaluate the erosion, erosion-corrosion, and
cavitation resistance.
The following example illustrates the main differences produced by the three types of impinging jets on yellow brass specimens
with a 3% sodium chloride test solution maintained at 40°C. A series of tests with specimens 16 mm in diameter was carried
out with jet nozzles having an inside diameter of 1.6 mm and a 0.8-mm gap between the nozzle and specimen. The flow rate of
the test liquid was 0.4 L/min, thus producing a fluid velocity at the nozzle outlet of 3.3 m/s with a Re of 8100 at that point. The
weight loss measured after 24 hours was 9.7, 10.0, and 11.3 mg for respectively the free jet, submerged jet, and jet-in-slit.
Inspection of surface and cross section of the specimen after the tests showed that extreme corrosion was seen with the
submerged jet and jet-in-slit as shown in Fig. 7.68. The cross section was measured with a surface roughness meter, so that
the longitudinal direction is magnified 100 times with respect to the transverse direction.58
Figure 7.68 Sketches of surface and cross sections of specimens tested for 24 hours with
impinging jets and sodium chloride solution.
The pressure radial distribution for these three jets was measured, and the results obtained for each nozzle are shown inFig.
7.69. The dotted line in this figure indicates the nozzle inside radius. For each of the three jets, Δ
P peaked close to the inside
nozzle radius and fell going toward the periphery of the specimen. It can be noted that ΔP of the jet-in-slit was zero at r = 2.6 mm
and became negative thereafter. The fact that the shear stress falls to zero at a certain point and then takes a reverse sign
indicates that the flow is separated at that point, producing a vortex downstream.58
Figure 7.69 Distribution of local pressure for three types of impinging jets.
The advantages and disadvantages of the submerged impinging jet technique are listed inTable 7.15.41 The flow patterns for
this system have been extensively studied with detailed mathematical analyses, mostly focused on the stagnation and wall jet
regions (Fig. 7.70).41 The stagnation region is observed directly beneath the jet. Under these conditions, a stagnation point
exists at the intersection of the central axis with the specimen and the flow is symmetric about the axis. Because the flow is
axisymmetric, only the flow and fluid properties in the radial plane normal to the specimen need to be considered.60
Figure 7.70 Schematic representation of the flow regions produced by a submerged impinging jet.
Table 7.15 Advantages and Disadvantages of the Impinging Jet Technique for Corrosion Testing
• The fluid flow is well characterized. The hydrodynamic shear for the • Uniform mass-transfer characteristics are observed only in the
impinging jet system in the stagnation region is a linear function of radial stagnation region for impingement normal to the flow. These
position and can be determined indirectly for measurement of mass- characteristics are not observed for other impingement angles or
transfer-limited currents. outside the stagnation region.
• Mass transfer to the disc is uniform if the entire disc lies within the • For cases in which mass transfer limits corrosion, the mass-
stagnation region. This uniformity prevents establishment of differential transfer-limited current distribution is not necessarily uniform.
oxygenation cells and aids in the interpretation of experimental results.
• The electrode is both stationary and flat, which allows the use of in situ • The system invites entrainment of particles and/or air bubbles that
determination of film thickness by ellipsometry, for example. may not be desirable.
• Shear-induced erosion-corrosion can be studied with fewer experiments • The impinging jet setup uses a high-pressure pump in its
than with rotating electrodes. operation.
• The use of a flow loop increases the possibility for spills or floods.
This is a particularly important consideration when toxic, flammable,
corrosive, or otherwise difficult-to-handle fluids are used.
Within the stagnation region, the axial velocity is independent of radial position. The flow in this region therefore resembles a
rotating disc in that the surface is uniformly accessible to mass transfer. Further from the centerline, a boundary layer develops
that is called the wall jet region. Mass transfer generally depends on both the jet to plate distance (H/d) and the radial position
on the plate (x/d) as expressed by Eq. (7.19)49:
(7.19)
7.13.4. High-Temperature/High-Pressure Testing

Autoclave corrosion tests are a convenient way to simulate service environments where high temperatures and pressures are
common. There are many HT/HP environments of commercial interest, which include those in industries such as petroleum,
nuclear, chemicals, aerospace, and transportation where reliability, serviceability, and concerns for corrosion are paramount.61
Corrosion coupons may be placed in the aqueous phase, vapor space, or at phase interfaces depending on the specific interest
involved. Additionally, it is also possible to conduct electrochemical tests in HT/HP vessels. If multiple liquid phases are
present, it can be necessary to stir or agitate the media or test vessel to produce mixing and conditions whereby the corrosion
test specimens are contacted by all of the phases present.
Special magnetic and mechanical stirrers are available that can be used to produce movement of the fluid to produce a mixing
of the phases. In some cases where contact of the specimens with both liquid and gaseous phases is important in the
corrosion process, it may be necessary to slowly rotate or rock the test vessel to produce the intended results.
7.13.4.1. Static Tests.

7.13.4.1. Static Tests.
The simplest type of HT/HP corrosion test is conducted in a sealed and static pressurized test vessel (Fig. 7.71). The test
vessel would typically contain a solution and a vapor space above the solution. In static corrosion tests, the only form of
agitation of the test environment is convection produced by heating of the solution. The solution itself can be anything from a
single liquid to water-based solutions containing various dissolved salts such as chlorides, carbonates, bicarbonates, alkali
salts, and other constituents or mixtures. The liquid and gas phases will be determined by the amount and vapor pressures of
the constituents in the test vessel, as well as by the test temperature. In general, the degree of difficulty and amount of expense
required for these tests increase with increasing test pressure and temperature.
Figure 7.71 Double-vessel system with two 5-L pressure vessel bodies, two end flanges, and three
seal rings for evaluation of high temperature (340°C at 35 MPa or 540°C at 25 MPa) hydrogen
attack, or hydrogen-induced disbonding. (Courtesy of InterCorr International, Inc.)
7.13.4.2. Refreshed and Recirculating Tests.

7.13.4.2. Refreshed and Recirculating Tests.
The depletion of volume of corrosive environment in HT/HP tests is a serious limitation that may be overcome by the
introduction of fresh environment either continuously or by periodic replenishment of the gaseous and liquid phases being
depleted by the corrosion processes. The volume of corrosive fluid to specimen surface area ratio is a critical factor that should
be maintained to no less than 30 cm3 per centimeter square of tested surface area.
The need for agitation is particularly required when multiple liquid phases are present. Special magnetic and mechanical
stirrers are available that can be used to produce movement of the fluid (Fig. 7.72). Magnetic or mechanical stirring can also be
employed to spin the specimens in the test environment or alternatively a high-velocity flow system can be employed to induce
cavitation or erosion damage on the specimens.
Figure 7.72 Custom-designed 150-L vessel, C276 (N10276), construction for exposure of large-
scale plate specimens to wet H2S, magnetic stirring attachment with motor and control, and
pressure-balanced Ag/AgCl reference electrodes. (Courtesy of InterCorr International, Inc.)
7.13.4.3. Factors Affecting HT/HP Test Environments.

7.13.4.3. Factors Affecting HT/HP Test Environments.
For simple HT/HP exposure tests involving either aqueous or nonaqueous phases, the total pressure is usually determined by
the sum of the pressures of the constituents of the test environment that will vary with temperature. Where liquid constituents
are being used for the test environment, the partial pressure is usually taken to be the vapor pressure of the liquid at the
intended test temperature. In some cases, higher test pressures can be obtained by pumping additional gas into the test vessel
using a special gas pump. Alternatively, hydrostatic pressurization may be employed whereby there is no gas phase in the test
vessel and the pressure is increased by pumping additional liquid into the test vessel in a controlled manner. The importance of
partial pressure in HT/HP corrosion testing is that the solubility of' the gaseous constituents in the liquid phase is usually
determined by its partial pressure, which explains why the effect of some gaseous corrosives is often magnified by high
pressures.
7.13.4.4. Special HT/HP Corrosion Test Conditions.

It has been known for decades that atomic hydrogen can produce embrittlement in many metallic materials. Under high-
hydrogen environment pressure or electrochemical reaction, or both, atomic hydrogen can penetrate structural materials where
it can react destructively with the metal (see Chap. 5 for more details).
There has been much interest in conducting hydrogen-induced cracking (HIC) tests in aqueous media that can produce atomic
hydrogen on the surface of materials as a result of corrosion or cathodic charging. When aqueous hydrogen charging is
involved, pressure is usually not a major factor. However, as in the case of steels exposed to aqueous environments containing
hydrogen sulfide, the atomic hydrogen is produced as a result of sulfide corrosion. The severity of the mass-loss corrosion and
hydrogen charging is directly dependent on the amount of hydrogen sulfide dissolved in the aqueous environment. Special
multiphase autoclave assemblies have been constructed to allow in situ corrosion monitoring under high-temperate flowing
conditions (Fig. 7.73).
Figure 7.73 HP/HT flow loop for evaluation of velocity-accelerated corrosion and chemical
treatment. A 5-L N10276-lined reservoir, three independently controlled N10276 flow loop sections
and magnetic stirring attachment with motor and speed control (a); higher pressure version of (a)
that can go up to 14 MPa and 200°C for evaluation of velocity-accelerated corrosion and chemical
treatment (b). (Courtesy of InterCorr International, Inc.)
7.14. SURFACE CHARACTERIZATION TECHNIQUES
From an engineering materials viewpoint, the impact of corrosion on a system is mostly a surface phenomenon, and the
scientists and engineers interested in fundamental corrosion processes have always been among the first to explore the utility
of surface analysis techniques. Surface analysis is used for microscopic chemical and physical probes that give information
about the surface region of a sample. The probed region may be the extreme top layer of atoms, or it may extend up to several
microns beneath the sample surface, depending on the technique used. These techniques have been increasingly successful in
shedding light on many facets of corrosion mechanisms.
Surface analysis techniques are fundamentally destructive, because they generally require that the sample be placed in an
ultrahigh vacuum to prevent contamination from residual gases in the analysis chamber. A rule of thumb is that up to an atomic
layer per second can be formed at pressures of 10−4 Pa if each collision of a gas molecule results in its sticking to the
surface.62 Because surface analysis is an extremely specialized field, it has its own nomenclature; the reader is referred to
ASTM E673, Terminology Relating to Surface Analysis. Table 7.16 presents a representative list of various techniques with their
fundamental principles, and Table 7.17 identifies the types of information and resolution that they can produce.30 The following
list gives some of the common acronyms used to describe some of the surface analysis techniques:
Table 7.16 Surface Analytical Techniques with Typical Applications and Signal Detected
Analytical Typical applications Signal detected

technique
Auger Surface analysis Auger electrons from near-surface atoms
High-resolution depth profiling
FE Auger Surface analysis, microanalysis, microarea depth profiling Auger electrons from near-surface atoms
AFM/STM Surface imaging with near atomic resolution Atomic scale roughness
micro-FTIR Identification of polymers, organic films, liquids Infrared absorption
XPS/ESCA Surface analysis of organic and inorganic molecules Photoelectrons
HFS Hydrogen in thin-films (quantitative) Forward scattered hydrogen atoms
RBS Quantitative thin-film composition and thickness Backscattered He atoms
SEM/EDS Imaging and elemental microanalysis Secondary and backscattered electrons and x-
rays
FE SEM High-resolution imaging of polished precision cross sections Secondary and backscattered electrons
FE SEM (in lens) Ultrahigh-resolution imaging with unique contrast mechanism Secondary and backscattered electrons
SIMS Dopant and impurity depth profiling, surface, microanalysis Secondary ions
Quad SIMS Dopant and impurity depth profiling, surface analysis, microanalysis, Secondary ions
insulators
TOF SIMS Surface microanalysis of polymers, organics Secondary ions, atoms, molecules
Table 7.17 Surface Analytical Techniques with Detection Characteristics
Analytical Elements Organic information Detection limits Depth Imaging/mapping Lateral resolution
technique detected resolution (probe size)
Auger Li-U — 0.1–1 at% <2 nm Yes 100 nm
FE Auger Li-U — 0.01–1 at% 2–6 nm Yes <15 nm
AFM/STM — — — 0.01 nm Yes 1.5–5 nm
micro-FTIR — Molecular groups 0.1–100 ppm — No 5 μm
XPS/ESCA Li-U Chemical bonding 0.01–1 at% 1–10 nm Yes 10 μm–2 mm
HFS H, D — 0.01 at% 50 nm No 2 × 10 mm
RBS Li-U — 1–10 at% (Z<20) 2 mm Yes
0.01–1 at%
(20<Z<70)
0.001–0.01 at%
(Z>70)
SEM/EDS B-U — 0.1–1 at% 1–5 μm Yes 4.5 nm (SEM)

(EDS)
FE SEM — — — Yes 1.5 nm
FE SEM (in — — — Yes 0.7 nm

lens)
SIMS H-U — ppb–ppm 5–30 nm Yes 1 μm (imaging),
30 μm (depth
profiling)
Quad SIMS H-U — 1014–1017 at/cc <5 nm Yes <5 μm (imaging)
30 μm (depth
profiling)
TOF SIMS H-U Molecular ions to mass <1 ppma, 10 8 at 1 monolayer Yes 0.10 μm
10,000 cm−2
Auger electron spectroscopy (AES)
Electron spectroscopy for chemical analysis (ESCA)
Field-emission Auger electron spectroscopy (FE Auger)
Scanning Auger microscopy (SAM)
Scanning probe microscopy (SPM)
Scanning tunneling microscopy (STM)
Secondary electron microscopy (SEM)
Secondary ion mass spectrometry (SIMS)
Time-of-flight (TOF)
Ultraviolet photoelectron spectroscopy (UPS)
X-ray photoelectron spectroscopy (XPS)
Some of these techniques require ultrahigh vacuum for the analysis of interfaces and others do not. They all involve irradiating
the interface with a beam of photons, electrons, or ions and analyzing the reflected beam to determine the chemical nature of
the interface. For any of these techniques, the conditions of the film must not change drastically during the measurement. Many
of the techniques used to probe surfaces use a beam of ions to strike the surface and knock off atoms of the sample material.
These atoms are ionized, and are identified and measured using a mass spectrometry technique. Other techniques strike the
surface with electrons (AES, EDS) or x-rays (ESCA) and measure the resulting electron or photon emissions to probe the
sample. Measurements of the way high-energy helium nuclei bounce off a sample can be used as a sensitive measure of
surface-layer composition and thickness (RBS). Surface structure on a microscopic scale is observed by using electron
microscopes (SEM), optical microscopes, and atomic force or scanning probe microscopes (AFM/SPM). One common way of
characterizing surface analysis techniques is by tabulating the incoming and outgoing particles. These techniques can be
classified according to whether they utilize photons, electrons, or ions.63
Surface analysis is mainly used in two separate modes. One is in surface science, where the goal is to investigate the root
causes of the problem and the mechanisms that are occurring in a system. Usually a model system is picked to eliminate as
many confounding variables as possible in order to get a system about which firm conclusions can be drawn. Often, many
different techniques will be used on the same problem in order to illuminate as many facets as possible of the problem. The
other mode is failure analysis. The goal here is to determine which of the failure modes is most significant for a particular
failure. The samples are real and hence nonideal. This analysis mode is often used to identify the elements present, their
distribution pattern, and their oxidation state.62
AES and XPS are probably the two surface analysis techniques that have found the greatest use in corrosion-related work. One
of the first applications of surface analysis techniques to corrosion was an examination of the composition of the passive film
on stainless steel. This investigation was undertaken to rationalize the substantial improvement in resistance to pitting and
acid solutions that is found when Mo and/or Si are present in stainless steels. The AES results obtained in these early studies
challenged the generally accepted explanation of the mid-1970s that the beneficial effects of Mo and Si were due to their
enrichment of the passive film. In fact, the AES results indicated that Mo and Si were depleted in the film. There are basically
two approaches in using surface-sensitive techniques to elucidate the mechanistic details of the interfacial processes and
determine the molecular nature of the surface products, that is, ex situ and in situ techniques. To investigate the interfacial
processes at the metal/liquid interface, one has to resort to in situ techniques; however, one can use both in situ and ex situ
techniques for the characterization of the interphase.
7.14.1. General Sensitivity Problems

7.14.1. General Sensitivity Problems
The problems of sensitivity and detection limits are common to all forms of spectroscopy. In its simplest form, the question of
sensitivity boils down to whether it is possible to detect the desired signal above the noise level. In virtually all surface studies,
sensitivity is a major problem. Consider the case of a sample with a surface of size 1 cm 2 with typically 1015 atoms in the
surface layer. In order to detect the presence of impurity atoms present at the 1% level, a technique must be sensitive to 10 13
atoms.30 Contrast this with a spectroscopic technique used to analyze a 1-cm3 bulk liquid sample, typically containing 1022
molecules. The detection of 1013 molecules in this sample would require 1 part per billion (ppb) sensitivity, a level provided by
only a few techniques.
Assuming that a technique of sufficient sensitivity can be found, another major problem that needs to be addressed in surface
spectroscopy is distinguishing between signals from the surface and signals from the bulk of the sample. To ensure that the
surface signal is distinguishable (shifted) from the comparable bulk signal, either the detection system must have sufficient
dynamic range to detect very small signals in the presence of neighboring large signals or the bulk signal must be small
compared to the surface signal; that is, the vast majority of the detected signal must come from the surface region of the
sample. It is the latter approach that is used by the majority of surface spectroscopic techniques; such techniques can then be
said to be surface-sensitive.
7.14.2. Auger Electron Spectroscopy

AES is the most commonly used surface technique on metal samples because of the following advantages62:
High surface sensitivity
Acceptable detectability for many corrosion problems
Simultaneous detection of all elements (except hydrogen and helium)
Very good small-area analysis (mapping)
Ability to probe deeper into the surface by sputter profiling
Analysis time not excessively long
Readily available instrumentation
The Auger process gives electrons of characteristic energy for each element, which are determined by the differences in energy
of the orbital involved. In addition to the Auger electrons, there are also much more plentiful secondary electrons with a broad
energy distribution that overlies the characteristic peaks. To highlight the characteristic peaks, differentiation is performed on a
plot of the number of electrons emitted by the sample versus the energy of those electrons. This results in a spectrum that
ignores the more plentiful background (secondary) electrons and emphasizes the characteristic electrons that are used to
identify the elements present. In some cases, the exact peak shape and energy can be used to identify the oxidation state of the
elements present.62
One of the attractions of Auger analysis is that it is quite surface-sensitive, because an Auger spectrum typically represents
information about the composition of the top 0.5 to 2 nm of the surface, depending upon the sample analyzed and the analysis
conditions. Although Auger electrons can be generated at depths of several micrometers into the sample, the Auger electrons
must be able to escape to the surface without undergoing an inelastic collision in order to be detected. Compilations of
elemental spectra and charts of atomic number versus electron energy are available to help assign peaks. Modern data
processing (background subtraction, peak fitting to standard spectra) has made it possible to correctly resolve many peak-
identification problems caused by peak overlap.62
7.14.3. Photoelectron Spectroscopy

7.14.3. Photoelectron Spectroscopy
Photoelectron spectroscopy utilizes photoionization and energy-dispersive analysis of the emitted photoelectrons to study the
composition and electronic state of the surface region of a sample. Traditionally, when the technique has been used for surface
studies, it has been subdivided according to the source of exciting radiation into
XPS, which uses soft (200 to 2000 eV) x-ray excitation to examine core levels
UPS, which uses vacuum UV (10 to 45 eV) radiation from discharge lamps to examine valence levels
Photoelectron spectroscopy is based upon a single photon-in/electron-out process, and from many viewpoints this underlying
process is much simpler than the Auger process. In XPS the photon is absorbed by an atom in a molecule or solid, leading to
ionization and the emission of a core (inner-shell) electron. By contrast, in UPS the photon interacts with valence levels of the
molecule or solid, leading to ionization by removal of one of these valence electrons. The kinetic energy distribution of the
emitted photoelectrons can be measured using any appropriate electron energy analyzer, and a photoelectron spectrum can
thus be recorded. An alternative approach is to consider a one-electron model along the following lines.
The realization that the energy of the ejected photon could be used to determine the chemical state of an atom gave rise to the
name ESCA (electron spectroscopy for chemical analysis). Because x-ray photons are necessary to generate the appropriate
electrons, the technique is also called x-ray photoelectron spectroscopy (XPS). XPS shares the Auger characteristic of good
surface sensitivity, because this is driven by the same need for the electrons to be able to reach the detector unscathed. It is
possible to vary the depth of analysis in both techniques by varying the tilt angle with regard to the detector. This technique is
used more extensively in XPS, where it is often called angle-resolved depth profiling. XPS also has the very important advantage
that it can obtain chemical state information on most atoms.62
For each and every element, there will be a characteristic binding energy associated with each core atomic orbital; that is, each
element will give rise to a characteristic set of peaks in the photoelectron spectrum at kinetic energies determined by the
photon energy and the respective binding energies. The presence of peaks at particular energies therefore indicates the
presence of a specific element in the sample under study, and the intensity of the peaks is related to the concentration of the
element within the sampled region.30
7.14.4. Rutherford Backscattering

7.14.4. Rutherford Backscattering
Rutherford backscattering (RBS) is based on collisions between atomic nuclei. This technique is named after Lord Ernest
Rutherford, who in 1911 was the first to present the concept of atoms having nuclei. It involves measuring the number and
energy of ions in a beam that scatters back after colliding with atoms in the near-surface region of a sample at which the beam
has been targeted. With this information, it is possible to determine atomic mass and elemental concentrations versus depth
below the surface. RBS is ideally suited for determining the concentration of trace elements that are heavier than the major
constituents of the substrate. Its sensitivity for light molecular masses and for the makeup of samples well below the surface
is poor.30
When a sample is bombarded with a beam of high-energy particles, the vast majority of the particles are implanted into the
material and do not escape. This is because the diameter of an atomic nucleus is on the order of 10−6 nm while the spacing
between nuclei is on the order of 0.2 nm. A small fraction of the incident particles do undergo a direct collision with a nucleus of
one of the atoms in the upper few micrometers of the sample. This collision does not actually involve direct contact between
the projectile ion and the target atom. Energy exchange occurs because of Coulomb forces between nuclei in close proximity to
each other. However, the interaction can be modeled accurately as an elastic collision using classical physics.30
The energy measured for a particle backscattering at a given angle depends upon two processes. Particles lose energy as they
pass through the sample, both before and after a collision. The amount of energy lost is dependent on the material's stopping
power. A particle will also lose energy as the result of the collision itself. The collisional loss depends on the masses of the
projectile and the target atoms. The ratio of the energy of the projectile before and after collision is called the kinematic factor.30
The number of backscattering events that occur from a given element in a sample depends upon two factors: the concentration
of the element and the effective size of its nucleus. The probability that a material will cause a collision is called its scattering
cross section.
7.14.5. Scanning Probe Microscopy (SPM/AFM)

7.14.5. Scanning Probe Microscopy (SPM/AFM)
In the early 1980s, two IBM scientists, Binnig and Rohrer, developed a new technique for studying surface structure, scanning
tunneling microscopy (STM). This invention was quickly followed by the development of a whole family of related techniques
that, together with STM, may be classified in the general category of SPM techniques. Of these later techniques, the most
important is undoubtedly atomic force microscopy (AFM).30 The development of these techniques has without doubt been the
most important event in the surface science field in recent times, and has opened up many new areas of science and
engineering at the atomic and molecular level. All of the SPM techniques are based upon scanning a probe (typically called the
tip in STM, because it literally is a sharp metallic tip) just above a surface while monitoring some interaction between the probe
and the surface. The interaction that is monitored is
In STM, the tunneling current between the metallic tip and a conducting substrate that are in very close proximity but not
actually in physical contact
In AFM, the van der Waals force between the tip and the surface; this may be either the short-range repulsive force (in
contact mode) or the longer-range attractive force (in noncontact mode)
For the techniques to provide information on the surface structure at the atomic level, the position of the tip with respect to the
surface must be very accurately controlled (to within about 0.01 nm) by moving either the surface or the tip.
If the tip is biased with respect to the surface by the application of a voltage between them, electrons can tunnel between the
two, provided that the separation of the tip and the surface is sufficiently small; this gives rise to a tunneling current. The
direction of current flow is determined by the polarity of the bias. If the sample is biased −υε with respect to the tip, electrons
will flow from the surface to the tip, while if the sample is biased +υε with respect to the tip, electrons will flow from the tip to
the surface.
The name of the technique arises from the quantum mechanical tunneling-type mechanism by which the electrons can move
between the tip and the substrate. Quantum mechanical tunneling permits particles to tunnel through a potential barrier which
they could not surmount according to the classic laws of physics; in this case, electrons are able to traverse the classically
forbidden region between the two solids. In this model, the probability of tunneling is exponentially dependent upon the distance
of separation between the tip and the surface; the tunneling current is therefore a very sensitive probe of this separation.
Imaging of the surface topology may then be carried out in one of two ways:
1. Inconstant-height mode, the tunneling current is monitored as the tip is scanned parallel to the surface.
2. In constant-current mode, the tunneling current is maintained constant as the tip is scanned across the surface.
If the tip is scanned at what is nominally a constant height above the surface, there is actually a periodic variation in the
separation distance between the tip and the surface atoms. At one point the tip will be directly above a surface atom and the
tunneling current will be large, whereas at other points the tip will be above hollow sites on the surface and the tunneling current
will be much smaller. In practice, however, the normal way of imaging the surface is to maintain the tunneling current constant
while the tip is scanned across the surface. This is achieved by adjusting the tip's height above the surface so that the tunneling
current does not vary with the lateral tip position. In this mode, the tip will move slightly upward as it passes over a surface
atom and, conversely, move slightly in toward the surface as it passes over a hollow.
7.14.6. SAM and SEM

7.14.6. SAM and SEM
The two forms of electron microscopy that are commonly used to provide surface information are secondary electron
microscopy (SEM), which provides a direct image of the topographical nature of the surface from all the emitted secondary
electrons, and scanning Auger microscopy (SAM), which provides compositional maps of a surface by forming an image from
the Auger electrons emitted by a particular element.30
7.14.6.1. SEM.
As the primary electron beam is scanned across the surface, electrons with a wide range of energies will be emitted from the
surface in the region where the beam is incident. These electrons will include backscattered primary electrons and Auger
electrons, but the vast majority will be secondary electrons formed in multiple inelastic scattering processes (these are the
electrons that contribute to the background and are completely ignored in Auger spectroscopy). The secondary electron current
reaching the detector is recorded, and the microscope image consists of a "plot" of this current I against probe position on the
surface. The contrast in the micrograph arises from several mechanisms, but first and foremost from variations in the surface
topography. Consequently, the secondary electron micrograph is virtually a direct image of the real surface structure.62
The attainable resolution of the technique is limited by the minimum spot size that can be obtained with the incident electron
beam, and ultimately by the scattering of this beam as it interacts with the substrate. With modern instruments, a resolution of
better than 5 nm is achievable. This is more than adequate for imaging semiconductor device structures, for example, but is
insufficient to enable many supported metal catalysts to be studied in any detail.
Although not a true surface technique, SEM-EDS (energy dispersive spectrometer) often provides useful information concerning
surface corrosion mechanisms. The ubiquitous nature, low cost, and ease of use of this technique cause it to be used as a tool
in many failure analyses involving corrosion. Because its analysis depth is much larger (approximately a micrometer) than that
of the true surface techniques, it is not necessary to analyze samples that are high-vacuum compatible. As a result, almost no
sample preparation is needed for many different kinds of samples.
The sample is scanned with a high-energy (typically 5–30 keV) electron beam in a raster pattern that causes the ejection of a
number of particles, including secondary electrons, backscattered electrons, and x-rays. Secondary electrons (with energies <
50 eV) are detectable only if they are generated in the top surface of a sample; this causes the secondary electron output to be
responsive to topographical detail and therefore gives an image that is remarkably similar to that seen with an optical
microscope. Added advantages are greater magnification and depth of field. The contrast in backscattered electron images is
mainly dependent on atomic number, so these images provide rough elemental distribution information.62
Element identification is provided by analysis of the characteristic x-rays that are emitted with an energy dispersive
spectrometer. Quantification can be quite good if appropriate standards are used. The x-ray detector can be set to detect and
count only x-rays that have energies within a narrow range. This output can then be used to generate elemental distribution
maps, or line scans. Newer detectors with ultrathin windows can easily detect all elements with an atomic number of 5 (boron)
or greater.
7.14.6.2. SAM.
With this technique, the incident primary electrons cause ionization of atoms within the region illuminated by the focused beam.
Subsequent relaxation of the ionized atoms leads to the emission of Auger electrons characteristic of the elements present in
this part of the sample surface. As with SEM, the attainable resolution is ultimately limited by the incident beam characteristics.
More significantly, however, the resolution is also limited by the need to acquire sufficient Auger signal to form a respectable
image within a reasonable time period, and for this reason the instrumental resolution achievable rarely approaches 20 nm.
7.14.7. Secondary Ion Mass Spectroscopy

7.14.7. Secondary Ion Mass Spectroscopy
Secondary ion mass spectroscopy (SIMS) is the third of the three most common surface analysis techniques. In SIMS, the
sample is irradiated with a primary ion beam (normally argon), the impact of which sputters away the surface atoms, some as
neutrals and others as ions. Those atoms which become ionized are then detected in a mass spectrometer, where their
masses are measured.
SIMS is the most sensitive of all the commonly employed surface analytical techniques. This is because of the inherent
sensitivity associated with mass spectrometric-based techniques. There are a number of different variants of the technique30:
Static SIMS, used for submonolayer elemental analysis
Dynamic SIMS, used for obtaining compositional information as a function of depth below the surface
Imaging SIMS, used for spatially resolved elemental analysis
These variations are all based on the same basic physical process, and it is this process that is discussed here, together with a
brief introduction to the field of static SIMS. In SIMS, the surface of the sample is subjected to bombardment by high-energy
ions; this leads to the ejection (or sputtering) of both neutral and charged (±) species from the surface. The ejected species may
include atoms, clusters of atoms, and molecular fragments.
In traditional SIMS, it is only the positive ions that are mass-analyzed. This is primarily for practical ease, but it does lead to
problems with quantifying the compositional data, because the positive ions are but a small, nonrepresentative fraction of the
total sputtered species. It should be further noted that the displaced ions have to be energy-filtered before they are mass-
analyzed (i.e., only ions with kinetic energies within a limited range are mass analyzed). The most commonly employed incident
ions used for bombarding the sample are argon ions (Ar+), but other ions have been used in some applications.30 The mass
analyzer is typically a quadrupole mass spectroscopy analyzer with unit mass resolution, but high-specification TOF analyzers
are also used and provide substantially higher sensitivity and a much greater mass range (albeit at a higher cost).
In static SIMS (SSIMS), the aim is to obtain sufficient signal to provide compositional analysis of the surface layer without
actually removing a significant fraction of a monolayer, that is, to be able to analyze less than 1014 atoms or molecules, or
approximately 10% of a monolayer, for a 1-cm2 sample. The technique is then capable of providing information about the
topmost single atomic layer of the surface. In dynamic SIMS, which is more common, a high-energy ion beam removes layers of
the surface. The beam is so energetic that little chemical information is retained, because the vast majority of any molecular
species is fragmented. Although destroying the surface obviously prevents its reexamination, it is not a total disadvantage,
because it allows depth profiling to occur naturally.
Some of the advantages of SIMS are that it has a very low detection limit and that it can detect all elements. These advantages
make it able to address many problems that neither AES nor XPS is suitable for. Reasonably small (micrometer or smaller) spot
sizes allow elemental mapping. A major disadvantage of SIMS is that there is a very great range of ionization rates for different
elements. Furthermore, the rates will vary depending upon the other species present (matrix effects). A beam of either positive
or negative ions can be used as the exciting beam, with very different response factors. The biggest differences are found with
the very electronegative halogens and the electropositive alkali metals. 62
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17. Hladky, K., Callow, L. M., and Dawson, J. L., Corrosion Rates from Impedance Measurements: An Introduction, British
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18. de Levie, R., Electrochemical Response of Porous and Rough Electrodes, New York, Wiley-Interscience, 1967.
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20. Roberge, P. R., Analyzing Electrochemical Impedance Corrosion Measurements by the Systematic Permutation of Data
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23. Davis, G. D., Raghu, S., Carkhuff, B. G., Garra, F., Srinivasan, R., and Phillips, T. E.,Corrosion Health Monitor for Ground
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25. Eden, D. A., Electrochemical Noise—The Third Octave. Corrosion 2005, Paper 351, 2005. Houston, Tex., NACE International.
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29. Cottis, R. A., Al-Awadhi, M. A. A., Al-Mazeedi, H., and Turgoose, S., Measures for the Detection of Localized Corrosion with
Electrochemical Noise, Electrochimica Acta, 46:3665–3674 (2001).
30. Roberge, P. R., Handbook of Corrosion Engineering, New York, McGraw-Hill, 2000.
31. Cottis, R. A., and Turgoose, S., Corrosion Testing Made Easy: Electrochemical Impedance and Noise, Houston, Tex., NACE
International, 1999.
32. Klassen, R. D., and Roberge P. R., Self Linear Polarization Resistance. Corrosion 2002, Paper 330, 2002. Houston, Tex., NACE
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33. Eden, D. A., Electrochemical Noise, in Revie, R. W. (ed.), Uhlig Corrosion Handbook, New York, John Wiley & Sons, 2000.
34. Bosch, R. W., Hubrecht, J., Bogaerts, W. F., and Syrett, B. C., Electrochemical Frequency Modulation: A New Electrochemical
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39. Tomoe, Y., Miyata, K., Ihara, M., Masuda, K., and Efird, K. D., Evaluation of Corrosion Resistance of Metallic Materials for DGA
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40. Efird, K. D., Flow-Induced Corrosion, in Revie, R. W. (ed.),Uhlig's Corrosion Handbook, New York, Wiley-Interscience, 2000, pp.
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41. State-of-the-Art Report on Controlled-Flow Laboratory Corrosion Tests. NACE Publication 5A195, 1995. Houston, Tex., NACE
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42. Papavinasam, S., Revie, R. W., Attard, M., Bojes, A., Donini, J. C., and Michaelian, K.,Rotating Cage—Top Ranked Methodology
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43. Poulson, B., and Robinson, R., The Use of a Corrosion Process to Obtain Mass Transfer Data, Corrosion Science, 26:265–280
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44. Wang, H., Hong, T., Cai, J-Y., Dewald, H. D., and Jepson, W. P., Enhancement of the Instantaneous Mass-Transfer Coefficient
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[1] A ZRA is a current-to-voltage converter that produces a voltage output proportional to the current flowing between its input terminals
while imposing a "zero" voltage drop to the external circuit.

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7.

7.2. LABORATORY-CONTROLLED TESTS

7.2.1. Tests of the Metal

7.2.2. Tests of Fabricated Items

7.3. FIELD TESTS

Figure 7.3 Seawater erosion-corrosion test rig. (Courtesy of Corrpro Companies.)

Figure 7.4 Tidal wave test rack. (Courtesy of Corrpro Companies.)

7.4. TEST OBJECTIVES

7.5. PROCUREMENT OF TEST MATERIALS

7.5.1. Commercial Alloys

7.5.2. Nonstandard Alloys

7.5.3. Metal Form

7.6. SPECIMEN PREPARATION

7.6.1.1. Visual Examination.

7.6.1.2. Depth of Attack.

7.6.1.3. Weight Loss or Gain.

7.6.1.4. Loss in Tensile Properties.

7.6.1.5. Stress Corrosion Cracking Tests.

7.6.1.6. Corrosivity of the Test Environment.

7.6.1.7. Suitability to Other Test Purposes.

7.6.2. Specimen Identification

7.6.3. Replicate Specimens

1. The uniformity of the material tested

2. The accuracy in preparing the test specimens

3. The stability of test conditions

1. The accuracy needed (statistical evaluation)

3. The known reproducibility of the test

4. The number of variables investigated

7.6.4. Machining of Specimens

7.6.5. Simulated Machining of Specimens

7.6.6. Degreasing and Final Measurements

7.7.1. Control of the Metal

7.7.2. Control of the Test Environment

7.8. SPECIMEN ARRANGEMENT FOR CORROSION TESTS

3. The corrosive environment should be equally accessible to all specimens.

7.9. EFFECTS OF VARIABLES

7.9.2. Solution Concentration

7.9.5. Ultraviolet Light

7.9.6. Microbial Effects

7.10.2. Interim Inspections

7.10.3. The Unexpected

7.10.4. Concluding the Test

1. Shortage of test space

2. Backlog of other programs

3. Requests by those who need information

7.11. POSTTEST APPRAISALS

1. Visual examination before cleaning

2. Photographs before cleaning

3. Careful collection of corrosion products for chemical or other analyses

4. Saving test solutions for chemical study

7.11.2. Analyses of Products and Solutions

7.11.3. Cleaning the Specimens

1. Not remove any metal

2. Remove all adherent corrosion products

3. Facilitate the program of evaluation that will follow

Original weight: 30.0186

Final weight: 27.3243

Weight loss 2.6943

Original weight: 531.6