Aramco Coe10602

Engineering Encyclopedia
Saudi Aramco DeskTop Standards
Corrosion Failures
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Engineering Development Program (PEDP) of Engineering Services.
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employees. Any material contained in this document which is not
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without the written permission of the Vice President, Engineering
Services, Saudi Aramco.
Chapter : Materials & Corrosion Control

File Reference: COE10602
For additional information on this subject, contact

S.B. Jones on 874-1969 or S.P. Cox on 874-2488
Materials & Corrosion Control

Corrosion Failures
CONTENTS
PAGES
INTRODUCTION....................................................................................................... 1
Corrosion Failures ........................................................................................... 1
FEATURES OF UNIFORM (GENERAL) CORROSION ......................................... 3
Uniform Corrosion Rates................................................................................. 4
Corrosion Allowance....................................................................................... 4
NACE Corrosion Data Survey ........................................................................ 5
TYPES AND FEATURES OF LOCALIZED CORROSION..................................... 6
Galvanic (Two-Metal) Corrosion .................................................................... 6
Stray Current Corrosion....................................................................... 9
Inspection for Galvanic Corrosion Failures ......................................... 9
Pitting ............................................................................................................ 10
Inspection for Pitting Corrosion Failures........................................... 13
Intergranular Attack....................................................................................... 15
Sensitization....................................................................................... 16
Weld Decay ....................................................................................... 17
Knife-Line Attack .............................................................................. 18
Inspection for IGA Failures ............................................................... 18
Crevice Corrosion.......................................................................................... 18
Under-deposit Corrosion.................................................................... 19
Corrosion Under Insulation................................................................ 19
Inspection for Crevice Corrosion....................................................... 19
Selective Leaching ........................................................................................ 20
Inspection for Selective Leaching...................................................... 21
FEATURES OF CORROSION THAT INVOLVES MULTIPLE
VARIABLES ............................................................................................................ 22
Environmental Cracking................................................................................ 22
Stress Corrosion Cracking............................................................................. 24

Corrosion Failures
Material Factors ................................................................................. 25

Environmental Factors ....................................................................... 25
Mechanical Factors ............................................................................ 26
Time................................................................................................... 26
General Features of Stress Corrosion Cracks..................................... 26
Stress Corrosion Cracking in Specific Materials ............................... 27
Inspection for SCC Failures............................................................... 38
Hydrogen-Induced Damage .......................................................................... 38
Hydrogen Embrittlement.................................................................... 39
Sulfide-Stress Cracking ..................................................................... 40
Hydrogen Blistering........................................................................... 41
Hydrogen-Induced Cracking.............................................................. 41
Inspection for Hydrogen Damage...................................................... 42
Liquid Metal Embrittlement .......................................................................... 43
Solid Metal Embrittlement................................................................. 43
Inspection for Liquid/Solid Metal Embrittlement Failures ................ 43
Microbiologically-Influenced Corrosion ....................................................... 44
Anaerobic Bacteria............................................................................. 44
Aerobic Bacteria ................................................................................ 44
Additional Forms of MIC .................................................................. 44
Inspection for MIC Damage .............................................................. 45
Erosion-Corrosion ......................................................................................... 45
Inspection for Erosion-Corrosion....................................................... 45
Corrosion Fatigue .......................................................................................... 46
Inspection for Corrosion Fatigue ....................................................... 46
Elevated Temperature Attack ........................................................................ 47
Oxidation ........................................................................................... 47
Inspection for Oxidation .................................................................... 49
Sulfidation ..................................................................................................... 50
Cyanide-Induced Corrosion ............................................................... 52

Corrosion Failures
Inspection for Sulfidation .................................................................. 52

Vanadium Attack........................................................................................... 52
Inspection for Vanadium Attack ........................................................ 53
Carburization ................................................................................................. 53
Metal Dusting .................................................................................... 53
Decarburization.................................................................................. 54
Inspection for Carburization .............................................................. 54
Hydrogen Attack ........................................................................................... 55
Inspection for Hydrogen Attack......................................................... 56
GLOSSARY ............................................................................................................. 57
ADDENDUM A: COMMON ENGINEERING MATERIALS ................................ 62
ADDENDUM B: EXCERPT FROM NACE CORROSION DATA
SURVEY................................................................................................................... 63
REFERENCES.......................................................................................................... 68

Corrosion Failures
INTRODUCTION
Corrosion Failures
Corrosion is the material deterioration that is caused by a chemical or electrochemical
reaction with the environment. Corrosion occurs in all phases of oil and gas production as
well as in refinery and petrochemical plant operations. When corrosion is uncontrolled,
failures occur. Corrosion is a leading cause of materials-related failures in the
petroleum/petrochemical industry. The purpose of this module is to discuss, with emphasis on
the features and characteristics of actual failures, the types of metallic corrosion that are
encountered in the petroleum/petrochemical industry.
Corrosion experts typically cite eight forms of corrosion. Additional forms are included in
subgroups of these eight forms of corrosion. Many of the forms are interrelated, and the eight
forms differ in various textbooks. In the analysis of corrosion failures, it is more useful to
divide the forms of corrosion into three major categories that can often be distinguished
during the initial field examination of failures:
Uniform Corrosion: Corrosion that occurs uniformly over all exposed surfaces
of the material.
Localized Corrosion: Corrosion that occurs preferentially in specific areas of

the material.
Corrosion that Involves Multiple Variables: Deterioration that results from the
interaction of corrosion with one or more factors, such as stress, velocity
effects, temperature, or bacteria. This category includes various forms of
environmental cracking.
A survey of the forms of corrosion that were experienced over a nine-year period revealed the
distribution that is shown in Figure 1.

Corrosion Failures
Localized
32
Uniform
35
68
Corrosion that Involves
Multiple Variables
Figure 1. Distribution of Corrosion Failures by Major Category
(Mobil Experience, 1980-1988)

Corrosion Failures
FEATURES OF UNIFORM (GENERAL) CORROSION

The most common example of uniform (general) corrosion is the atmospheric rusting of
ordinary steel. Constantly dry climates are not extremely corrosive; however, atmospheric
corrosion is accelerated in industrial environments where moisture and corrosive gases are
more likely to be found. The green patina on copper and bronze statues is an example of
corrosion where sulfur in the atmosphere formed copper sulfide. Other locations where
uniform corrosion is commonly found include marine, soil, boiler/heater (high temperature),
and process (chemical) environments.
The term uniform implies that corrosion is perfectly even along the entire metal surface.
Since some irregularity in the corrosion almost always occurs, many people prefer to use the
term general corrosion to describe this form of attack.
Uniform (or general) corrosion is illustrated schematically in Figure 2. In this case, the metal
is thinned, and although it is slightly roughened, the corroded surface is clean. Clean surfaces
are typical of acid forms of corrosion attack in carbon steels. In other materials, such as
aluminum alloys, clean surfaces suggest alkaline attack. Clean, uniformly thinned surfaces,
however, are not always indicative of general corrosion. As will be discussed later in this
module, mechanisms of corrosion that involve multiple variables such as erosion corrosion
also exhibit smooth, thinned surfaces.
Figure 2. Uniform (General) Corrosion

Uniformly corroded metals often retain a thick corrosion product layer on the exposed
surfaces, as illustrated in Figure 3. In this course, we will define corrosion product as the
material that is produced by the corrosion reaction. Corrosion products typically involve
oxidized forms of the metal or alloy.
Figure 3. Uniform Corrosion with Remaining Corrosion Product

Corrosion Failures
High temperature oxides [found above approximately 300 C (572 F)], or other corrosion
products, are commonly referred to as scale. Deposits are foreign materials that settle or
attach in the region that is under study. Deposits on the surface do not necessarily mean that
the underlying surface is corroded; however, in most cases deposits are a major accelerant of
corrosion. (Under-deposit corrosion will be covered later in this module.) Deposits may be
corrosion products from elsewhere in the system where corrosion is occurring, or they simply
may be the intrusion of foreign material such as sand. Where the deposits are not corrosion
products from the specific area of interest, their presence may be an indicator of corrosion in
another area, and such an indication would be important in the overall failure analysis.
The examination and analysis of corrosion products, scales, and deposits provide important
information for use in failure analyses. As will be demonstrated later in this course, chemical
composition, thickness, and morphological features of the corrosion product can be used to
identify the corrosion mechanism, rate of corrosion, and variations in in-service conditions.
Uniform Corrosion Rates
Uniform corrosion is one of the forms of corrosion attack with which it is most easy to deal.
Since corrosion rates are conveniently measured in the field or laboratory, it is easy to identify
problems early and implement solutions.
Metal loss is described in terms of mils per year (mpy) according to the following equation:
mpy = 3445 W
DAT
where
(1)
W = weight loss, mg
D = density of metal, g/cm3
A = area of specimen, cm2
T = exposure time, hr
Corrosion Allowance
Uniform corrosion rates are used to set the corrosion allowance (CA) for equipment in
corrosive service. As an example, consider a vessel with a typical design life of 10 years. For
carbon steel, the expected corrosion rate in the vessel environment is 10 mpy. A corrosion
allowance
of
2.5 mm (0.1 in) is chosen since 10 mpy X 10 years = 2.5 mm (0.1 in).

Corrosion Failures
In the performance of failure analyses, it is often prudent to back-calculate the expected

corrosion for comparison with actual corrosion. Often, it is found that the design conditions
were exceeded in actual operation due to increases in temperature, pressure, concentration of
corrodant, or throughput. Corrosion rates that are adjusted for these changes, may enable one
to determine the reasons for failure.
Example: Exchanger Shell Failure
An exchanger in mildly corrosive service (10 mpy) was designed for 10 years of operation
with a 12 mm (0.5 in) shell thickness and a CA of 2.5 mm (0.1 in). Failure of the shell
occurred after seven years. A review of the service history revealed that for the first two years
operating conditions followed the design conditions, but after this period the shell-side
product was changed to one with a corrosion rate of 75 mpy. Calculated thickness loss was as
follows:
2 years
5 years
X
X
7 years
10 mpy
75 mpy
= 0.020 in
= 0.375 in
= 0.395 in (10.0 mm)
The calculated corrosion of the vessel thus was found to be approximately two-thirds of the
wall thickness. A stress analysis of the vessel confirmed that failure at the operating
temperature and pressure would occur at approximately two-thirds of the original wall
thickness.
NACE Corrosion Data Survey
An extensive compilation of uniform corrosion rates is available in text and computerized
form from the National Association of Corrosion Engineers (NACE). In the absence of
specific corrosion test data, this compilation can be used in the analysis of failures to estimate
corrosion rates.
A sample selection and keys to the table are shown in the Addendum (Reference No. 6). The
format is semi-graphical; that is, corrosion rates are classified into four ranges and arrayed on
a temperature-composition plot. Selective attack such as pitting or stress corrosion cracking is
indicated by footnotes. The example that is shown indicates the increased corrosion resistance
of steels in dilute carbonic acid with increasing chromium content.
Because general corrosion usually is a slow process which can be detected easily, there are
few equipment failures caused by general corrosion. By comparison, the majority of
equipment failures from corrosion are due to localized corrosion.

Corrosion Failures
TYPES AND FEATURES OF LOCALIZED CORROSION

Galvanic (Two-Metal) Corrosion
Galvanic corrosion is an accelerated type of corrosion that occurs when dissimilar metals
contact each other to form an electrical couple. An electrolyte (water) environment is
necessary to complete the circuit. The electrochemical cell that is formed between the two
metals has a current flow that is similar to the current flow in a battery. In general, the less
noble metal is corroded, as shown schematically in Figure 4. Metal loss is typically more
severe near the metal-to-metal couple, with the result that there is a localized form of attack at
the junction.
Figure 4. Galvanic (Two-Metal) Corrosion

Corrosion Failures
The galvanic series (Figure 5) of engineering alloys is often used to predict galvanic
corrosion. The materials are listed according to their activity (electrical potential) when they
are immersed in seawater. The less noble, or more negative alloy in the series will corrode
faster. Greater distances between alloys result in a greater difference in their electrical
potential and an increased possibility of galvanic corrosion.
Galvanic Series in Seawater at 25 C (77 F)
Corroded end (anodic, or least noble)
Magnesium
Magnesium alloys
Zinc
Galvanized steel or galvanized wrought iron
Aluminum alloys
5052, 3004, 3003, 1100, 6053, in this order
Cadmium
Aluminum alloys
2117, 2017, 2024, in this order
Low-carbon steel
Wrought iron
Cast iron
Ni-Resist (high-nickel cast iron)
Type 410 stainless steel (active)
Type 316 stainless steel (active)
Lead
Tin
Copper alloy C28000 (Muntz metal. 60% Cu)
Copper alloy C67500 (manganese bronze A)
Copper alloys C46400, C46500, C46600, C46700 (naval brass)
Nickel 200 (active)
Inconel alloy 600 (active)
Hastelloy alloy B
Chlorimet 2
Copper alloy C27000 (yellow brass. 65 % Cu)
Copper alloys C44300, C44400, C44500 (admiralty brass)
Copper alloys C60800, C61400 (aluminum bronze)
Copper alloy C23000 (red brass, 85 % Cu)
Copper C11000 (ETP copper)
Copper alloys C65100, C65500 (silicon bronze)
Copper alloy C71500 (copper nickel, 30 % Ni)
Copper alloy C92300, cast (leaded tin bronze G)
Copper alloy C92200, cast (leaded tin bronze M)
Inconel alloy 600 (passive)
Monel alloy 400
Type 410 stainless steel (passive)
Incoloy alloy 825
Inconel alloy 625
Hastelloy alloy C
Chlorimet 3
Silver
Titanium
Graphite
Gold
Platinum
Protected end (cathodic, or most noble)
Figure 5

Corrosion Failures
Galvanic corrosion is often the result of poor design and selection of materials. The
appearance of galvanic corrosion includes localized corroded areas that are relatively free of
corrosion products. The amount of corrosion lessens with increasing distance from the metal
couple as illustrated in Figure 6. The extent of the corrosion from the couple depends on the
difference between the metals in the galvanic series and the conductivity of the electrolyte.
Corroded Zone
Brass Bolt
Aluminum
Copper
Copper
Steel
Corroded Zone
Figure 6. Examples of Galvanic Corrosion

(Reference No. 8)
Surface areas of the anodic and cathodic materials are an important factor in galvanic
corrosion. A large anode (active metal) coupled to a small cathode will result in only minor
corrosion; however, a small anode will corrode rapidly if it is surrounded by a large cathode.
Depending on their relative positions in the galvanic series, coated metals exhibit specific
galvanic-corrosion characteristics. Figure 7 shows that tin, which is cathodic to steel, protects
steel as long as the coating is intact. If perforation occurs, the underlying steel is galvanically
attacked. By comparison, the zinc on galvanized steel is anodic, and thereby results in a large
anode that sacrificially protects steel.

Corrosion Failures
Tin
Zinc
Steel
Steel
Figure 7. Galvanic Corrosion of Tin and Zinc-Coated Steel

Arrows indicate corrosive attack.
(Reference No. 9)
Stray Current Corrosion

This special form of galvanic corrosion occurs when stray currents from nearby electrical
equipment pass through conductive liquids or soil. The current tends to jump back and forth
from the corroding object, and it essentially forms a cathode where the current enters and an
anode where the current leaves. The result is accelerated corrosion at the anode.
Inspection for Galvanic Corrosion Failures
Do the following when inspecting possible cases of galvanic corrosion:
Look for localized attack that is adjacent to material interfaces.
Examine all parts of equipment that are in contact with the failed region.
Different metals should not be mixed.
Look for contamination from melted droplets, steel wool, or other foreign
materials that are in contact with corroded surfaces.
Check for possible stray currents.
Look for perforations in protective coatings, especially coatings that are

cathodic.
Check for a small anode-to-cathode ratio.
Check for dissimilar weld and base metals.
Determine the environment. Remember that the galvanic series pertains to a

seawater environment and that the galvanic series may not be useful in some
petroleum/petrochemical environments.
Dissimilar metal couples also can result in cracking due to hydrogen embrittlement. This
phenomenon will be covered later in this module.

Corrosion Failures
Pitting
Pitting is a localized corrosion process that results in sharply defined surface cavities or holes
in a metal as illustrated in Figure 8. The rate of attack inside a pit can be many times the rate
of general corrosion. Hence, pitting is often described as an autocatalytic process whereby the
reactions within the pit induce conditions that make the pitting process self-sustaining or
accelerating in rate. Since through-wall penetrations can occur in a relatively short time,
failures that are caused by pitting corrosion are more unexpected than are those failures that
are caused by general corrosion.
Figure 8. Pitting Corrosion
10

Corrosion Failures
A common mechanism that is used to describe pitting is the localized electrochemical cell. As
shown in Figure 9, the bottom of the pit is anodic, and forms metal ions. If the adjacent
surface is cathodic, the cell will produce hydroxyl ions. The increasing metal ion
concentration in the pit attracts cations in solution such as the chlorine ion, which reacts to
form acids that lower the pH and accelerate corrosion. Since reactions within the pit are often
independent of the surface conditions, pitting is often hard to stop. For example, chemical
cleaning or neutralizing the surface may not halt the acid formation and corrosion that is deep
within the pit.
Figure 9. Electrochemical Nature of Pitting Corrosion

(Reference No. 1)
Pitting corrosion begins at defects or discontinuities in the surface films on metals. Often, the
more passive metals, such as stainless steels, are more prone to pitting than are the less
passive metals, which tend to corrode more uniformly. Sometimes general corrosion and
pitting occur simultaneously, as illustrated in Figure 10. When numerous pits in close
proximity overlap, the condition is described as interconnected pitting or wastage.
Figure 10. Pitting and General Corrosion

11

Corrosion Failures
12

Corrosion Failures
Pitting of a metal is environment specific. For example, pitting of carbon and alloy steels
occurs in boiler feedwater piping due to dissolved oxygen and in oil field equipment due to
dissolved oxygen, carbon dioxide, or hydrogen sulfide. Aluminum alloys pit in chloride
environments, and the copper alloys (aluminum, brass, and cupronickel), pit in seawater that
is contaminated with sulfides. As a class, stainless steels are very susceptible to pitting in
chloride solutions; however, resistance varies somewhat with composition. The alloying
element molybdenum, added to make Type 316 stainless steel, is probably the most effective
addition for pitting resistance.
Inspection for Pitting Corrosion Failures
The American Society for Testing and Materials (ASTM) includes a Standard Practice (G-46)
for Examination and Evaluation of Pitting Corrosion. In addition to pit depth and density
measurements, variations in cross-sectional shapes of pits (Figure 11) are useful in analyzing
failures. Different environments produce different shapes of pits in different materials. For
example, stainless steels exposed to chlorides tend to develop sharp, deep pits, while cast iron
underground piping tends to develop shallow pits. Subsurface and undercut pits may explain
why large pits may have been missed during inspections. Preferential pitting that is related to
microstructural orientation can significantly influence the performance or failure of a part in
service. As will be discussed later, cross-sectional variations can also be used to distinguish
pitting corrosion from erosion or erosion-corrosion.
Figure 11. Variations in the Cross-Sectional Shape of Pits

13

Corrosion Failures
14

Corrosion Failures
Depending on the material, the environment, and other conditions of exposure, such as flow,
pits may or may not contain corrosion products. Features that should be noted in analyzing a
failure include pits that are filled with corrosion product that sometimes exhibit pitcaps or
nodules. For example, pitting of steels is accompanied by tubercles of increasing size as the
pH increases. Filled pits also provide well-preserved samples for chemical analyses. In certain
cases, thermal cycling of equipment containing tightly filled pits has caused cracks to initiate
from the bottoms of sharp pits and propagate to the point where the metal fails. Such cases
will be further explored under the subjects of stress corrosion cracking and thermal fatigue.
Intergranular Attack
Intergranular attack (IGA), or intergranular corrosion (IGC), occurs preferentially at or
adjacent to the grain boundaries of a metal. Usually, there will be only a slight attack on the
remainder of the grains. Intergranular attack is shown schematically in Figure 12. As
illustrated, IGA can occur uniformly or, more likely, in localized regions such as welds. In
some cases of IGA, metal loss occurs as the metal grains fall completely out of the sample;
however, in other cases, the grain boundaries are attacked deep below the surface without
drop-out. In the latter case although the material appears to be acceptable, the mechanical
properties (strength and ductility) of intergranularly attacked regions are severely degraded,
which results in unexpected failures.
Figure 12. Intergranular Attack
Intergranular attack can occur by either of two mechanisms. In some alloys, such as brass and
aluminum, precipitation of active second phases with poor corrosion resistance results in IGA.
Failures in this case could be attributed to an incorrect material heat-treated condition or to an
unexpectedly corrosive environment.
In the case of austenitic materials (stainless steels and some nickel alloys), IGA occurs when
the materials are sensitized. In this case, it is not the second phase (chromium carbide) that is
attacked, but instead the adjacent region, which is depleted of chromium, is attached. The
process of sensitization and resulting IGA are discussed below.
15

Corrosion Failures
Sensitization
Austenitic alloys, such as Type 304 stainless steel (Fe - 18Cr - 8Ni), depend largely on
chromium for corrosion resistance. In the normally used solution annealed condition,
chromium is homogeneously dispersed in the single-phase austenite solution. If the alloy is
heated in the range of approximately 427 C (800 F) to 816 C (1500 F), chromium carbide
precipitation occurs at the grain boundaries. As shown in Figure 13, the region that is adjacent
to the chromium-rich precipitates is depleted of chromium, and the depleted region is no
longer corrosion resistant or stainless. The material is sensitized.
Figure 13. Sensitized Grain Boundaries in Austenitic Stainless Steel

(Reference No. 1)
Sensitization of stainless steels does not significantly affect the mechanical properties or
corrosion resistance at elevated temperatures; however, environments that contain such
substances as nitric acid, which normally does not attack austenitic stainless steel, rapidly
corrode the depleted zones and leave deep ditches.
16

Corrosion Failures
Sensitization can be eliminated by the following:
Heating sensitized material to approximately 1050 C (1925 F) to dissolve the

chromium carbides, and cooling rapidly to avoid re-precipitation.
Lowering the carbon content of the alloy during melting so that less carbon will
be available to precipitate as chromium carbide. Examples include Types 304L
and 316L.
Adding carbide forming (stabilizing) elements during melting to tie up the

carbon so that it is unable to form chromium carbide. Stabilized stainless steels
include Type 321 (titanium stabilized) and Type 347 (niobium stabilized).
Weld Decay
When stainless steels are welded, a heat-affected zone (HAZ) forms adjacent to the weld.
Within the zone, temperatures pass through the sensitizing temperature range. Depending on
metal thickness and welding heat input, sensitization may occur if the temperature remains in
the range long enough. Subsequent service exposure can result in localized intergranular
attack known as weld decay. The IGA occurs in the HAZ, parallel to the weld as illustrated
in Figure 14.
Figure 14. Weld Decay of Austenitic Stainless Steel
17

Corrosion Failures
Knife-Line Attack
Stabilized stainless steels can undergo, as a result of welding, a special case of IGA that is
known as knife-line attack. In a region of the HAZ that is closer to the weld, the metal
temperatures can exceed 1230 C (2250 F), and thereby cause the stabilizing carbides (NbC
or TiC) to dissolve. If rapid cooling occurs and is followed by heating in the sensitizing range,
the material may be susceptible to IGA. The IGA occurs in a thin band that is close to the
weld.
Inspection for IGA Failures
Do the following when inspecting possible cases of IGA:
Inspect for localized attack at welds.
Look for a shiny, crystalline appearance in regions with metal loss. In some
cases, small crystals that dropped out of the corroded region may be found at
the bottom of tanks, etc.
Look for surface etching in regions without grain dropout.
Check fracture surfaces for brittle, intergranular appearance.
Crevice Corrosion
Crevice corrosion, which sometimes is referred to as gasket corrosion or concentration cell
corrosion, is a localized attack that occurs at crevice regions such as joints or gasket seals
(Figure 15). Corrosion occurs by a concentration cell mechanism. Stagnant conditions within
the crevice prevent the interchange of corrosive with the bulk environment outside the
crevice. As a result, oxygen in the crevice is depleted due to the corrosion reaction, and a
concentration gradient forms. The low-oxygen crevice region becomes the anode of the
concentration cell, and accelerated corrosion (typically 10 - 100 times the general corrosion
rate) occurs.
Figure 15. Crevice Corrosion
18

Corrosion Failures
Crevices, like galvanic couples, are design-related and account for a significant number of
equipment failures. Crevice corrosion occurs under washers, gaskets, nuts, bolt heads, and at
poorly fitted joints. In tubular heat exchangers, crevice corrosion occurs at the tube to
tubesheet crevice and between tubes and baffles.
Under-deposit Corrosion
This specific form of crevice corrosion occurs under deposits where corrosive contaminants
tend to concentrate and oxygen depletion occurs. Examples of these deposits are sludge on
tank bottoms, silt that results from untreated water and is deposited on cooler tubes during
low flow conditions, and scale that is deposited in the dead legs of piping. In steam
generators, deposits insulate tube surfaces and cause overheating and dryout. When
evaporation occurs, water contaminants such as caustic precipitate. Subsequent wetting results
in a highly concentrated solution that can be very corrosive.
Corrosion Under Insulation
This related form of corrosion is especially critical in the petroleum and petrochemical
industry. While corrosion under insulation does resemble crevice corrosion, the mechanism
for corrosion is usually somewhat different. Moisture and an adequate oxygen supply are
required for corrosion of steel under insulation. Failures under insulation result from use of
the wrong insulation materials for the application, poor weatherproofing, as well as improper
design for drainage. Since it is often inconvenient to remove insulation for inspections,
corrosion often continues until failure results. It is worth noting that in addition to localized
corrosion under insulation, austenitic materials experience a significant number of chloridestress corrosion cracking failures as discussed later in the course.
Inspection for Crevice Corrosion
Do the following when inspecting possible cases of crevice corrosion:
Inspect crevices and dead-leg regions.
Inspect under insulation, loose coatings, and packing materials.
Look for damage to, or absence of, vapor barriers and weatherproofing in
insulated components.
Determine if the service conditions exceed the insulating material limits.
Inspect under deposits and scale. Check localized areas where deposits are
likely to accumulate.
19

Corrosion Failures
Selective Leaching
The preferential removal (corrosion) of one element in an alloy is called selective leaching,
dealloying, or parting. The alloy constituents that are more corrosion resistant remain in a
porous structure with essentially the same geometry, but with severe loss of strength,
hardness, and ductility. The two general types of selective leaching, layer and plug, are
illustrated in Figure 16.
Layer
Plug
Figure 16. Selective Leaching
Common types of selective leaching that are found in the petroleum and petrochemical
industry are as follows:
Dezincification: Selective leaching of zinc in copper-zinc (brass) alloys.
Denickelification: Selective leaching of nickel in copper-nickel alloys.
Dealuminization: Selective leaching of aluminum in aluminum brasses or

bronzes.
Graphitization (Graphitic Corrosion): Selective leaching of iron in gray cast

irons.
Selective leaching mechanisms vary with material. One mechanism that is commonly used for
dezincification is the dissolution of copper and zinc, with the copper subsequently redeposited
at the site of attack in metallic form. A suggested mechanism for other alloys is the removal of
one alloying element, which selectively leaves behind all others.
Failures that are caused by selective leaching are often sudden and unexpected since the
dimensions of the failures do not change significantly. A color change is one visible indicator
of a selective leaching problem. Copper-base alloys where zinc, nickel, or aluminum have
leached away often display a dark orange metallic copper appearance.
Graphitic corrosion or graphitization of gray cast irons is a unique form of selective leaching.
The iron is leached away, leaving a porous structure of graphite, with some iron oxide,
silicon, and phosphorous. The porous structure is soft and easily cut with a knife.
Underground cast iron piping is particularly prone to graphitic corrosion.
20

Corrosion Failures
Inspection for Selective Leaching

Do the following when inspecting possible cases of selective leaching:
Examine for color changes in the area of the failure when copper alloys are
involved.
Test the hardness of gray cast iron that is suspected of graphitic corrosion.
Remember that selective leaching can occur at ambient temperatures in some

cases, and, in other cases, it can occur above an upper limit.
An example of a high temperature selective leaching failure is the denickelification and

dezincification of a bronze labyrinth seal for a high pressure steam turbine. The result of the
initial failure was extensive foreign object damage to the turbine rotor. The steam at the seal
location was approximately 482 C (900 F). Handbook data revealed that the Cu-Ni-Zn alloy
corrosion and strength loss were both excessive at the operating temperature. The inherent
loss of strength at temperature combined with weakness due to selective leaching resulted in
the failure. The bronze seal was replaced with a stronger, more corrosion-resistant material
(Ni-Resist: Fe-21Ni-2Cr ductile cast iron).
21

Corrosion Failures
FEATURES OF CORROSION THAT INVOLVES MULTIPLE VARIABLES

Corrosion that involves multiple variables include stress corrosion cracking (SCC), hydrogeninduced damage, liquid metal embrittlement (LME), corrosion fatigue, elevated temperature
attack, erosion corrosion, and microbiologically-influenced corrosion (MIC). For these types
of corrosion, a second variable (stress, bacteria, or high temperature) in addition to a corrosive
environment is necessary for failure to occur.
Corrosion that involves multiple variables includes environmentally-induced cracking, which
can be the most devastating form of failure for a vessel, pipeline, structure, or piece of
equipment. In most cases, the reaction rates for other forms of corrosion permit detection by
inspection. Environmental crack propagation, however, occurs at a relatively high rate, and it
often precludes detection. Furthermore, while other forms of corrosion commonly result in
localized failures such as pinhole leaks, environmental cracking is often catastrophic, with
large cracks that are analogous to brittle fracture. Since higher alloy materials are often the
most prone to environmental cracking, this form of corrosion can occur when it is least
expected in otherwise corrosion-resistant equipment.
Environmental Cracking
Environmental cracking may be defined as a cracking process that is caused by the synergistic
effects of stress and environment on a specific material. The phenomenon is best illustrated in
the popular Venn Diagram as shown in Figure 17. All three factorsstress, aggressive
environment, and susceptible materialare necessary for environmental cracking. If initiation
has not occurred, the removal of any one factor will often negate cracking.
Figure 17. Interaction of Material, Stress, and Environment
22

Corrosion Failures
Stress corrosion cracking, hydrogen-induced damage, and liquid metal embrittlement fit the
general definition for environmental cracking. Corrosion fatigue also fits the definition in
some cases.
Several theories have been advanced to describe environmental cracking, but none of the
theories can explain all the types. From an electrochemical point of view, stress corrosion
cracking is generally assumed to be an anodic process, while hydrogen-induced cracking is a
cathodic process.
Some of the popular environmental-cracking mechanisms are discussed below and illustrated
in Figure 18.
Figure 18. Schematic Illustrations of SCC Mechanisms
Slip-Dissolution (Film Rupture): Localized plastic deformation (slip) ruptures

the passive film and exposes bare metal that dissolves and results in crack
extension.
Film-Induced Cleavage: Stress causes a brittle crack to initiate in a brittle

surface film. The brittle crack continues to propagate into the ductile base metal
until arrest occurs.
Stress-Sorption: Weakening of the cohesive bonds between surface metal

atoms through adsorption of damaging species in the environment. The surface
energy of the metal is assumed to be reduced, and this reduction increases the
tendency for crack formation under tensile stress.
23

Corrosion Failures
Stress Corrosion Cracking

As mentioned previously, complex forms of corrosion typically account for one-half of the
total failures in the petroleum and petrochemical industry. Stress corrosion cracking usually
accounts for over one-half of the complex failures.
Stress corrosion cracking (Figure 19) is a form of environmental cracking that is caused by
the synergistic effects of a corrosive environment and sustained stress on a specific material.
Figure 19. Stress Corrosion Cracking
Conditions that are necessary for initiation and propagation of SCC are as follows:
Susceptible Material
Specific Aggressive Environment
Sustained Tensile Stress
Time.
The factors that are involved with the above conditions are discussed on the following pages.
24

Corrosion Failures
Material Factors
High purity metals are generally more resistant to SCC than are commercial metals and
alloys. The addition of even small quantities of solute or interstitial elements can significantly
increase the potential for SCC. Impurities that are concentrated in grain boundaries promote
intergranular cracking. Microstructures that are produced by various heat treatments also
influence the susceptibility to SCC. It is interesting to note that transitions in crack modes
(intergranular versus transgranular) can occur in the same environment, depending on the heat
treated condition for iron-chromium-nickel, high nickel, and brass alloys.
Environmental Factors
In most practical cases, water (moisture) is required for SCC. When exposure to water can be
absolutely ruled out for a given cracking problem, the possibility of SCC (but not other forms
of embrittlement) sometimes can be dismissed. When water is present, the possibilities of
stress corrosion cracking increase, especially when temperatures are above ambient and the
water contains contaminants.
Chloride solutions at the ppm level are often sufficient to crack austenitic stainless steels,
particularly when crevices and/or dryout promote concentration of the contaminating species.
Dissolved oxygen alone can also crack sensitized stainless steels at temperatures of
approximately 300 C (570 F). Some of the more interesting research in the field of SCC is
on the synergistic effects of contaminants such as chlorides, sulfates, and oxygen. A unique
form of intergranular SCC is pure water or Coriou cracking of nickel-base alloys in high
temperature, 315 C (600 F), deaerated, contaminant- free water. Surprisingly, a sensitized
microstructure is more resistant than an unsensitized microstructure for this form of SCC.
Temperature at the environment/material interface is another important factor for SCC.
General temperature ranges exist for different types of SCC. Cracking commonly occurs at
ambient temperatures. While chloride SCC of austenitic stainless steels has a threshold
temperature of approximately 60 C (140 F), SCC is often found at ambient temperatures in
equipment that is radiantly heated.
Additional environmental parameters that are known to affect SCC are as follows:
Pressure
pH
Electrochemical Potential
Solution Viscosity
Stirring or Mixing
25

Corrosion Failures
Mechanical Factors
Tensile stress, either applied or residual, is a requirement for SCC. For SCC to occur,
materials need not be stressed above the yield strength. In some situations, very low threshold
stresses (e. g., 10 % of the yield strength) are sufficient to cause cracking. While compressive
stresses from shot peening have been used to avoid SCC in some cases, control of applied
(operating) stress levels generally is not considered an effective method of preventing SCC.
Stresses that are sufficient to cause cracking can result from thermal processing, fabrication,
assembly, surface finishing, and localized stress risers. Surfaces with pits, defects, or other
stress risers tend to provide initiation sites for SCC.
Time
Another factor that is common to the various SCC mechanisms is time. Since an incubation
period is necessary before cracking initiates, SCC is sometimes referred to as delayed
cracking. The incubation period is dependent on the material/environment couple as well as
stress. Generally, the length of time for cracking to initiate is shorter for higher stresses. Once
cracks are initiated, propagation velocities for SCC are relatively slow as compared to LME.
Nevertheless, from a practical viewpoint, the speed of crack growth can be devastatingly fast.
General Features of Stress Corrosion Cracks
Various macroscopic and microscopic features that are related to SCC are used in failure
analyses. These features are as follows:
Macroscopic Features
Stress corrosion cracks are usually perpendicular to principal stresses in regions

of stress concentration; for example, cracking of steel vessels in caustic service
is typically perpendicular to (across) girth welds and parallel to longitudinal
weld seams.
Stress corrosion cracks are more likely on hardened surfaces or in heat affected
zones.
Stress corrosion cracks are often tighter than other failure modes.
Microscopic Features
Crystallographic features include transgranular and intergranular crack

propagation.
Other morphological features include singular and multiple cracks that may be
branched or unbranched. Some stress corrosion cracks typically initiate at the
bases of corrosion pits.
26

Corrosion Failures
Some forms of SCC characteristically exhibit cracks that are filled with oxide
(example: caustic cracking of steel) or corrosion products. An SCC failure
analysis is more conclusive if the causative contaminant can be identified, by
microanalysis, deep within the crack.
Fractographic indications of crack-propagation lines that resemble fatigue

striations are observed for SCC in some alloy/environment systems.
Stress Corrosion Cracking in Specific Materials

The environmental cracking susceptibility of various engineering materials in more common
environments is summarized in the table in Figure 20. Included is information for hydrogen
embrittlement (HE) and liquid metal embrittlement (LME), which are covered later in this
module. Due to the complex nature and uncertainties of environmental cracking, the table in
Figure 20 should not be considered all-inclusive. In some cases, an indication of susceptibility
to cracking in one ionic species (e.g., chlorides) may indicate susceptibility to other members
of the elemental group (e.g., halogens). Discussions on SCC characteristics for each material
follow.
Material
SCC
HE
LME
Steel
Annealed
OH-, NO3, CN- , CO=3, NH3
Hardened
OH-, Cl- , NH3
Cd, Cu, Pb, Sn, Zn

Ho ,
H2S
Cd, Cu, Pb, Sn, Zn, In, Li
Stainless Steel
Austenitic
OH-, Cl-
Al, Cd, Cu, Pb, Zn
Austenitic (Sens.)
OH-, Cl- , S2O6 , steam
Al, Cd, Cu, Pb, Zn, Hg
Ferritic
OH-, Cl-
Martensitic
OH-
Copper Alloys
NH3, NO3 , steam, SO2
Nickel Alloys
OH-, HF + O
Aluminum Alloys
Cl- , Ox, agents
Titanium Alloys
Cl- , HNO3
Ho ,
H2S
Ho
H2S
Methanol
Hg, Sn, Pb, Bi, Na

Hg, Pb, S
Hg, Na, Sn, Zn, Ga, In
Cd, Pb, Sn, Zn
* Based on various empirical data.
Figure 20. Environmental Cracking of Engineering Materials*
27

Corrosion Failures
Carbon and Low Alloy Steels - The most common cases of SCC in carbon and low alloy
steels result from caustics, nitrates, and ammonia. Stress corrosion cracking in sodium
hydroxide (NaOH) solutions occurs at temperatures above approximately 150 C (300 F) in
applications such as boilers, where concentration or dryout occurs. This type of SCC
historically was called caustic embrittlement. Caustic cracking is ordinarily intergranular and
branched. Traces of oxide are often observed deep within the cracks. Low carbon steel also
has been reported to crack transgranularly in potassium hydroxide (KOH) at temperatures as
low as 33 C (91 F). Caustic SCC can be mitigated by the lowering of the pH of the solution,
the addition of inhibitors, the anodic or cathodic protection of the steel, and stress relief of
welds.
The intergranular SCC of mild steels in various nitrate solutions is well documented. Cracking
has been reported at temperatures as low as ambient after several months exposure. In some
ways, nitrate SCC is the converse of caustic cracking; as the environment becomes more
acidic, the potential for SCC increases. The addition of caustic to nitrate solutions can retard
cracking, just as the addition of nitrates to caustic solutions can retard caustic SCC. Inhibitor
additions, the increase of the pH of the environment, and welds that relieve stress are three
approaches for mitigating nitrate SCC. While cathodic protection may be beneficial for the
retarding of nitrate SCC, anodic polarization is harmful.
Stress corrosion cracking of steels in ambient temperature ammonia (NH3) is an anomaly with
respect to other types of aqueous SCC. Failures occur when air is mixed with anhydrous
ammonia. Cracking is intergranular in carbon steels and both intergranular and transgranular
in high strength steels. The addition of a small quantity of water to the ammonia is a widelyused method for eliminating ammonia cracking of steels. Stress relieving is also beneficial.
Austenitic Stainless Steels - Austenitic stainless steels are subject to SCC in chloride,
polythionic acid, and caustic solutions. Optical micrographs of the three types of SCC are
shown in Figure 21.
Figure 21. Stress Corrosion Cracking in Austenitic Stainless Steels

28

Corrosion Failures
29

Corrosion Failures
Chloride Stress Corrosion Cracking - The susceptibility of austenitic stainless steels to SCC
in chloride solutions is widely known. Nevertheless, numerous failures occur each year,
particularly in the case of the 300-Series grades. The role of nickel in the chloride SCC of
austenitic stainless steel is illustrated in Figure 22. Minimum SCC resistance occurs at
approximately 8 % nickel, which makes Type 304 (8 - 10.5 % Ni) the type that is most prone
to attack. Other 300-Series stainless steels such as Type 321 (9 - 12 % Ni), Type 347 (9 13 % Ni), Type 316 (10 - 14 % Ni), and Type 309 (12 - 15 % Ni) offer very marginal
improvement in chloride SCC resistance. Ferritic (Fe-Cr) stainless steels, as well as higher
nickel alloys, generally are resistant to chloride SCC.
1000
Cracking
Minimum Time
to Cracking
100
Time to
Failure
(hr)
No Cracking
10
- Did Not Crack in 30 Days
1
20
40
60
80
Nickel, (%)
Figure 22. The Effect of Nickel Content on SCC of Austenitic Materials

(Tests conducted in boiling MgCl2 . )
30

Corrosion Failures
Chloride SCC occurs when the five following conditions are present:
Chloride ion
Oxygen
Tensile stress
Moisture at a pH less than 7.
Temperature above 60 C (140 F).
The results of a survey that included 136 cases of chloride SCC at 109 locations is shown in
Figure 23. Interestingly, some failures were reported at or below 1 ppm chloride.
Figure 23. Chloride SCC of Austenitic Stainless Steels - MTI Survey Data (Reference
No. 12)
31

Corrosion Failures
Chloride stress corrosion cracks are typically transgranular and branched; however, sensitized
material can crack intergranularly in high-temperature water that contains oxygen. The
synergistic role of oxygen and chloride is illustrated in Figure 24. In the complete absence of
oxygen, chloride levels as high as 1000 ppm may be tolerable, but in highly oxygenated
water, 0.0l ppm chloride could cause SCC. The type of metallic cation in the chloride solution
also affects SCC susceptibility; for example, magnesium and ferric chlorides are more
aggressive than sodium chloride.
1000
SCC - All Heat Treatments
304
SCC No SCC
Annealed
Dissolved O2 , g/m (ppm)
100
Sensitized
250 - 300 C
10
SCC
Sensitized
Only
0.1
Tentative
SCC - Safe Area
0.01
0.001
0.01
0.1
10
100
1,000
10,000
CI Concentration, g/m3(ppm)
Figure 24. Synergistic Effect of Chlorides and Oxygen on the

SCC of Type 304 Stainless Steel
(M. O. Speidel, ARPA Handbook on Stress Corrosion Cracking, to be published.)
The control of chloride SCC is often very difficult, especially on heat transfer surfaces or in
crevices where chloride concentration can occur. Localized boiling can cause concentration
and cracking at practically any bulk water chloride concentration. Since very low stresses can
cause SCC, often the only recourse is to change materials. In some cases, removal of oxygen
and/or the increase of the solution pH can effectively mitigate cracking.
32

Corrosion Failures
Polythionic acid stress corrosion cracking (PSCC) - Cracking that is due to sulfur
compounds was first recognized as a problem in catalytic reformers in the 1950s. This form of
attack involves intergranular cracking of sensitized austenitic materials at ambient conditions.
Three environmental conditions are necessary to form polythionic acids oxygen (air),
moisture, and a source of sulfur (H2S, SO2, S, or FeS).
Austenitic stainless steels are often used because of their resistance to high-temperature
sulfidation; however, thin iron sulfide films do form in service. The film that is formed at high
temperatures is porous and tends to be more susceptible to polythionic acid formation than
sulfide films that are formed at lower temperatures or in aqueous media. When equipment is
opened to the atmosphere, formation of polythionic acid (H2SxO6 in Eq. 2) can result in PSCC
due to residual stresses.
FeS + H2O
H2SxO6 + FeO
(2)
Austenitic stainless steel equipment often is neutralized before exposure to the atmosphere.
NACE Standard RP-01-70, Protection of Austenitic Steel in Refineries Against Stress
Corrosion Cracking by Use of Neutralizing Solutions During Shutdown covers alkaline
washing of stainless steel equipment.
Usually only sensitized materials are susceptible to PSCC. Unfortunately, service
temperatures are often high enough to sensitize unstabilized grades of stainless steel. The use
of properly heat treated stabilized grades (Types 321 and 347) can prevent PSCC. It is worth
noting that higher nickel alloys such as Alloy 800 are very susceptible to PSCC when the
alloys are sensitized.
33

Corrosion Failures
Caustic Stress Corrosion Cracking - Continual concerns over chloride SCC often leave
caustic SCC to be overlooked. All austenitic stainless steels are susceptible to caustic
cracking. Both transgranular and intergranular cracking have been observed. The temperature
and concentration limits for caustic SCC of various alloys are shown in Figure 25.
350
600
Failure (One Day)
Unsensitized
Temperature, C
250
Unsensitized
304
200
400
Sensitized
304
300
150
Failure (100-300 Days)
100
50
0
500
200
Tentative Safe SCC Limit
10
20
30
40
300
100
50
60
Concentration of Sodium Hydroxide, Wt. %
Figure 25. Temperature and Concentration Limits for Caustic SCC

of Types 304, 316, 321, and 347 Stainless Steel
(Reference No. 12)
Ferritic, Martensitic, and Duplex Stainless Steels - Ferritic stainless steels are susceptible
to SCC in chloride and caustic solutions, but these steels are affected to a lesser degree than
are austenitics. Unless the alloy contains significant amounts of nickel or copper, SCC in
service occurs very rarely.
Martensitic, maraging, and precipitation hardening stainless steels are susceptible to SCC in
the hardened condition. These alloys are especially susceptible to hydrogen embrittlement,
and distinguishing SCC from HE is usually difficult. Cracking can occur in nonspecific
environments. For example, cracking has been reported in ambient temperature fresh water.
Any environment that is corrosive enough to cause hydrogen evolution can cause cracking
when the alloys are in the fully hardened condition. Cracking of these materials is usually
intergranular.
34

Corrosion Failures
Duplex stainless steels are mildly susceptible to chloride stress corrosion cracking. The fact
that cast austenitic stainless steels contain ferrite, which makes them essentially duplex,
accounts for their improved assistance to chloride SCC as compared to wrought materials.
Hardenable duplex grades are susceptible to hydrogen embrittlement.
Copper Alloys - Copper alloys are susceptible to SCC in ammonia, nitrates, steam, and moist
sulfur dioxide. Stress Corrosion Cracking may also occur in amines at low concentrations,
and in caustic in the case of high zinc alloys.
Ammonia SCC is the most common cause of copper alloy heat exchanger tube failures in
many plants. The number of ammonia SCC failures has actually decreased in recent years,
mostly because copper alloys have been replaced by more resistant materials such as titanium
alloys.
A classic example of ammonia SCC is the season cracking of brass as illustrated in Figure 26.
As shown in the accompanying optical micrograph, cracking is typically intergranular and
branched. Cracking can be transgranular in alloys that contain more than 40 % zinc and in
some other copper alloys.
Figure 26. Season Cracking of Brass

Tube 1 - Cracked in Mercurous Nitrate Test
Tube 2 - Cracked in 3 Days in Ammonia Vapor
35

Corrosion Failures
The conditions that are necessary for ammonia SCC of copper alloys include the following:
Ammonia
Oxygen
Tensile stress
Moisture.
Carbon dioxide especially accelerates the cracking process. Anhydrous ammonia does not
crack copper alloys; however, it is almost impossible to keep ammonia free of air and
moisture during shipment and storage.
The corrosion products that form under the above conditions frequently are dark blue, dark
brown, or black with only a small amount of the metal being corroded. The visual corrosion is
often associated with a special SCC mechanism (the tarnish rupture model) that is related to
film-induced cleavage. Depending on the stress level, solution concentration, and alloy
susceptibility, failures may develop within a few hours or after several years. Some of the
variables affecting ammonia SCC of copper alloys are as follows:
Susceptibility increases with increased cold work
Time to failure decreases with increased temperature
Time to failure decreases with increased stress
Time to failure decreases with increasing grain size
Time to failure is a minimum at pH = 7
Threshold stresses are usually very low.
The possibility of ammonia SCC in brass can be minimized by eliminating any of the four
conditions that are necessary for attack to occur. Although not often achievable, the removal
of ammonia, oxygen, or moisture from the environment will mitigate cracking. Annealing the
material will also mitigate cracking.
36

Corrosion Failures
Changing the alloy content is another method for reducing the susceptibility to ammonia
SCC. As the zinc content of brass is reduced, the SCC susceptibility is also decreased. If a
lower zinc content alloy is otherwise acceptable for a given application, the possibility of SCC
failure can be greatly reduced by its use. The table in Figure 27 ranks the SCC resistance of
several copper alloys.
Relative Susceptibility of Copper Alloys to Ammonia SCC
Class 1
Very Low Susceptibility
Class 2
Low Susceptibility
Class 3
Intermediate Susceptibility
Class 4
High Susceptibility
Cupro-Nickel 90-10
Cupro-Nickel 70-30
ETP Copper
DLP Copper
DHP Copper
Red Brass
Commercial Bronze
Aluminum Bronze
Silicon Bronze
Phospor Bronze
Nickel Silver
Leaded Brass
Naval Brass
Admiralty Brass
Yellow Brass
Manganese Bronze
Aluminum Brass
Muntz Metal
Cartridge Brass
Figure 27. Relative Susceptibility of Copper Alloys to Ammonia SCC
Nickel Alloys - Nickel and its alloys are relatively resistant to SCC; Alloy 600 is virtually
immune to chloride SCC. Intergranular caustic SCC can occur in high temperature [300 C
(575 F)] water. Fluorides crack Monel Alloy 400 in the presence of oxygen or oxidizing
species, and various cases have been reported in HF Alkylation Units. Nickel-chromiummolybdenum alloys such as Hastelloy C-276 and Alloy 625 are often used for their SCC
resistance in various chemical environments.
Aluminum Alloys - High-strength aluminum alloys with greater than 6 % magnesium or
12 % zinc are susceptible to SCC in ordinary atmospheric and aqueous environments.
Moisture, temperature, chlorides, and other contaminants accelerate cracking. Cracking is
usually intergranular. Commercially pure and lower-strength alloys are not susceptible to
SCC. The corrosion rate of aluminum alloys in caustic is so great that SCC is precluded.
Titanium Alloys - Titanium alloys are resistant in most cases to SCC in environments such as
boiling magnesium chloride and sodium hydroxide solutions. Stress corrosion cracking does
occur in fuming nitric acid and hot, dry chloride salts. In chlorine and hydrogen chloride
environments, SCC can occur when both oxygen and water are present. When sharp cracks or
notches are present, cracking of some titanium alloys can occur in seawater; however,
commercially pure grades of titanium that are generally used in industrial applications are
quite resistant to SCC in chloride solutions.
37

Corrosion Failures
Inspection for SCC Failures

When inspecting possible SCC failures, it is helpful to visualize the Venn Diagram in
Figure 17 and ask are the conditions for SCC satisfied? In other words, is the specific
material known to be susceptible to SCC in the given environment, and does the failed region
contain sufficient tensile stresses?
Related factors that often play roles in failure analyses are as follows:
An aqueous phase must be present for SCC. Process streams that are free of
water will not stress corrosion crack unless moisture enters during a shutdown,
for example.
Specific material/environment couples have threshold temperature limits for

SCC. SCC failures are less likely to occur below the threshold temperature.
Specific material/environment couples have pH ranges for SCC. For example,

mild acid solutions are necessary for chloride SCC of austenitic stainless steel,
while caustic SCC requires strongly alkaline solutions.
Stress corrosion cracking failures typically have a brittle appearance. When the failed part
contains a multitude of cracks, stress corrosion cracking is the most probable failure mode.
During the inspection of possible SCC failures, it is most important to look for consistencies.
For example, macroscopic features, microscopic features, fractographic features, temperature
ranges, chemical analyses, and pH should all be indicative of the specific type of SCC
cracking.
Hydrogen-Induced Damage
Hydrogen causes several types of metal degradation. Hydrogen embrittlement, sulfide stress
cracking, hydrogen blistering, and hydrogen-induced cracking are lower temperature types
that are covered in this section. Hydrogen attack, which occurs at high temperatures in steels,
is covered in the Elevated Temperature Attack section. The types of hydrogen-induced
damage that are covered in this section pertain primarily to steels, but other engineering alloys
that form hydrides, such as titanium, also experience hydrogen embrittlement.
38

Corrosion Failures
Hydrogen Embrittlement
Hydrogen embrittlement, which is caused by the absorption of atomic (nacent) hydrogen, is
the loss of toughness or ductility in a metal. When carbon and low-alloy steels are exposed in
corrosive environments, atomic hydrogen is generated by cathodic reduction. While hydrogen
molecules are too large to pass into the metal, atomic hydrogen readily diffuses through the
metal lattice, becomes entrapped, and interferes with the normal process of deformation under
load. This form of embrittlement typically occurs at temperatures of -100 C to +120 C (148 F to 248 F). In addition to corrosion processes, acid cleaning (pickling), electroplating
processes, and poor welding procedures can embrittle steels.
Hydrogen gas environments do not embrittle steels at low temperatures because hydrogen is
in molecular form. At temperatures above approximately 150 C (300 F), appreciable
dissociation to atomic hydrogen occurs and diffusion into the metal can occur. Hydrogen that
leaves the metal is approximately the same as hydrogen that enters; however, when the steel is
cooled rapidly, some atomic hydrogen remains trapped in the steel and this entrapped
hydrogen results in embrittlement. Baking hydrogen out of steels at temperatures of 175 C to
200 C (347 F to 392 F) or higher is commonly performed for de-embrittlement.
Hydrogen embrittlement results in degraded, but not necessarily failed metal. For example,
baking can restore ductile properties before failure occurs. Failures occur by cracking when
the embrittled metal is subjected to stress. Shock loading almost always results in cracking;
however, residual stresses can sometimes be sufficient to cause cracking. An example of the
latter is the delayed hydrogen cracking failures that result in welds that are made through the
use of moist weld rods. In this case, the water that is heated during welding dissociates and
forms atomic hydrogen that enters the metal. Upon cooling, residual stresses cause hydrogenembrittlement cracking.
Hydrogen-embrittlement cracking is also referred to as hydrogen-assisted cracking, hydrogenstress cracking, and hydrogen-stress corrosion cracking. Different terms are used by different
experts to denote specific characteristics. For example, hydrogen-assisted cracking and
hydrogen-stress cracking are often used to describe hydrogen embrittlement in the absence of
a corrosion reaction, and hydrogen-stress corrosion cracking refers to cracking with active
corrosion.
Generally, higher strength (hardenable) steels and weldments are most prone to embrittlement
cracking failures. Cracking may be either intergranular or mixed mode. Most often, failures
occur from a singular crack with no branching.
39

Corrosion Failures
Sulfide-Stress Cracking
Sulfide-stress cracking (SSC) is a special case of hydrogen embrittlement in which high
strength or high hardness steels crack under stress. Sulfide-stress cracking results from
cathodic charging that is caused by corrosion in sulfide environments. Sulfide-stress cracking
can occur in materials with over 200 BHN hardness, and is sometimes considered as a type of
stress corrosion cracking. This type of cracking is found most commonly in weld heat
affected zones.
NACE standard MR0175-93 presents the material requirements for resistance to SSC.
Parameters considered to affect SSC are as follows:
1)
chemical composition, strength, heat treatment, and microstructure of the

material
2)
hydrogen ion concentration (pH) of the environment
3)
hydrogen sulfide concentration and total pressure
4)
total tensile stress (applied plus residual)
5)
temperature
6)
time
Sour environments commonly are defined as fluids that contain water and greater than
0.34kPa (0.05 psia) hydrogen sulfide partial pressure. More specifically, MR0175-93 defines
critical H2S levels as follows:
Sour Gas: SSC susceptibility if the gas being handled is at a total pressure of
448 kPa (65 psia) or greater and if the partial pressure of H2S in the gas is
greater than 0.34 kPa (0.05 psia). Systems operating below 65 psia total
pressure or below 0.05 psia H2S partial pressure are outside the scope of this
standard.
Sour oil and multiphases: SSC susceptibility when

1)
the gas:oil ratio is over 5,000 SCF:bbl (barrel of oil)
2)
the gas phase contains a over of 15% H2S
3)
the partial pressure of H2S in the gas phase is over of 69 kPa (10 psia)
4)
the surface operating pressure is over of 1.8 MPa (265 psia)
5)
when pressure exceeds 265 psi, refer back to sour gas rules
40

Corrosion Failures
Figures for determination of critical SSC environments are provided in Addendum B. When it
is determined that a critical environment exists, the requirements for materials must be
followed according to MR0175-93.
Hydrogen Blistering
Hydrogen blistering occurs when atomic hydrogen diffuses into steel and recombines to form
molecular hydrogen (H2) at metallurgical defects such as planar inclusions or laminations.
The molecular hydrogen that is formed cannot diffuse, and it creates extremely high pressures
as more and more atomic hydrogen diffuses to the defect. The blister that forms eventually
becomes visible on the metal surface. When the blister forms close to the surface, the surface
exhibits a typical blister. When the blister forms more deeply below the surface, near the
middle of the thickness, the surface may exhibit a bulged appearance.
Blistering typically occurs in carbon and other low alloy, unhardened steels. Hardened steels
usually crack instead of blistering. Blistering is often found at the interface in clad vessels.
Hydrogen-Induced Cracking
Hydrogen-induced cracking (HIC), which is also referred to as stepwise cracking, occurs in
carbon and low alloy steels that are exposed to wet hydrogen sulfide environments. The
mechanism for HIC is related to the mechanism for blistering. Small blisters form at planar
inclusions and grow at varying depths through the thickness of the steel. Cracking initiates at
the tips of the blisters, and stepwise crack propagation between blisters on adjacent parallel
planes occurs, as shown in Figure 28. A series of steps eventually reaches the surface of the
steel, and pressure is relieved.
Figure 28. Hydrogen-Induced Cracking (HIC)
Hydrogen-induced cracking appears visually as small surface blisters with associated cracks.
The mode of cracking is usually transgranular, but it can be intergranular or mixed mode. HIC
is typically found in older, dirtier steels. Elongated manganese sulfide inclusions are
commonly associated with the cracking. Newer, cleaner steels, and steels with sulfide shape
control are less prone to HIC.
41

Corrosion Failures
Since hydrogen-induced cracking is driven by internal pressure in blisters, high pressures in

the vessel or pipeline are not required. Stress oriented hydrogen-induced cracking (SOHIC) is
a related form of HIC that occurs when the steel is stressed significantly. In this case, the
blisters are stacked perpendicularly to the applied stress (Figure 29). The end result of SOHIC
is through-thickness cracking. Whereas HIC may be found by inspection before leakage or
failure occurs, SOHIC more often results in failure before surface evidence is apparent.
Figure 29. Stress-Oriented Hydrogen-Induced Cracking

(Reference No. 17)
Inspection for Hydrogen Damage

Do the following when inspecting possible cases of hydrogen embrittlement:
Check for previous chemical cleaning, electroplating, or welding operations

where atomic hydrogen may have been generated.
Inspect for surface blisters.
Check for delaminations in bonded steel.
Determine the environment and the likelihood of atomic hydrogen existing at

the service temperature.
Check for galvanic couples or nearby corroding surfaces. Cases have been
observed where high strength stainless steel fittings were embrittled by nearby
carbon steel corrosion.
42

Corrosion Failures
Liquid Metal Embrittlement

Liquid metal embrittlement (LME), which is also called liquid metal cracking, is a form of
environmental cracking in which a normally ductile solid metal under stress cracks in a brittle
manner due to contact with a specific liquid metal. Cracking may be spontaneous or delayed.
Several characteristics of LME are similar to SCC, and variations of the stress-sorption
cracking model often are used to describe the LME mechanism. As in the case of SCC, LME
cracking can be intergranular or transgranular, depending on the embrittled metal and liquid
metal embrittler. Whereas SCC usually occurs in an aqueous environment, LME does not
necessarily involve moisture.
The number of liquid metal/solid metal couples that are susceptible to LME are numerous.
Some of the common couples are included in Figure 20. At elevated temperatures, molten
cadmium, copper, lead, tin, and zinc have caused problems in steel process equipment. For
example, welding on copper clad vessels has led to cracking. Another example occurred when
an alloy steel motor shaft was overheated and caused tin babbit sleeve bearings to melt. Shaft
failure resulted from LME.
Stainless steels are particularly susceptible to LME that is caused by molten aluminum. Nickel
alloys can be embrittled by molten nickel sulfide formed from sulfur contamination. Copper
and aluminum alloys are especially susceptible to LME by mercury. Mercury in the process
streams at LNG plants has caused several cases of cracking of aluminum process equipment.
Solid Metal Embrittlement
Cracking of a metal that is exposed to specific embrittlers at temperatures below the melting
point of the embrittler is called solid metal embrittlement (SME). Although this form of
embrittlement is not recognized as a problem in most industrial processes, it can play a role in
certain failures. For example, cadmium-plated high strength steel bolts can fail at
temperatures above 230 C (450 F), which is below the melting point for cadmium (321 C
[610 F]). Titanium alloys are also susceptible to SME due to the presence of solid cadmium.
Leaded steel parts have failed below the melting point for lead due to SME.
Inspection for Liquid/Solid Metal Embrittlement Failures
Do the following when inspecting possible cases of liquid or solid metal embrittlement:
Examine for brittle fracture appearance.
Check fasteners for plating with embrittlers such as cadmium.
Determine if temperatures at the failure were sufficient to cause melting

(LME), or high enough to otherwise embrittle by SME. Also, determine if
molten metal may have dripped from another hot location.
43

Corrosion Failures
Microbiologically-Influenced Corrosion
Microbiologically-influenced corrosion (MIC), which is also referred to as biological
corrosion or microbiological corrosion, is considered a complex form of corrosion, since
attack is the indirect consequence of the presence of microbes. Corrosion can occur due to
corrodants that are produced by microbes or due to under-deposit attack that is related to the
presence of microbes. Subsurface regions and water systems are prone to MIC. Most often,
MIC causes localized attack such as pitting or under-deposit corrosion.
Anaerobic Bacteria
Anaerobic bacteria are sulfate-reducing types of bacteria that cause corrosion, but the bacteria
do not require oxygen to exist. They reduce relatively noncorrosive sulfate ions to corrosive
sulfide ions according to the equation:
SO4-2 + 4H2
S-2 + 4H2O
(3)
Sulfate-reducing bacteria are commonly found underground in oxygen-starved regions such

as wet clay. The sandy soils of Saudi Arabia generally provide better resistance to anaerobic
bacteria than do soils in other parts of the world. Steel that is corroded as a result of anaerobic
bacteria produces iron sulfide as a corrosion product.
Aerobic Bacteria
Bacteria that exist in aerobic conditions oxidize sulfur to corrosive sulfuric acid according to
the equation:
2S + 3O2 + 2H2O
2 H2SO4
(4)
Sulfur oxidizing bacteria are found in low pH environments where sulfur is present. Locations
include oil fields and regions with sewage.
Additional Forms of MIC
Iron bacteria form ferric hydroxide and cause localized attack of steels. Corrosion products
frequently appear as tubercles on steel surfaces, with localized corrosion underneath. Other
bacteria oxidize ammonia and carbon dioxide respectively to corrosive nitric acid or carbonic
acid. Several microorganisms simply attach to exposed metal surfaces and result in underdeposit corrosion. A special group of slime formers are commonly found in oil fields.
44

Corrosion Failures
Inspection for MIC Damage

MIC failures resemble other localized corrosion failures, such as pitting and under-deposit
attack. Probable locations are stagnant regions of systems such as tank bottoms and filter
beds. Unusual smells, slime, sludge, and black water, all of which are indicative of bacteria,
may suggest MIC. Sulfur species that are detected in deposit or water analyses may also
indicate MIC. The acquisition and biological analysis of actual bacterial samples requires
special procedures that will be further covered in COE 106.06 and COE 106.07. This type of
corrosion, even with laboratory investigation, is extremely difficult to verify. For the most
part, MIC damage is identified by default when no other corrosion mechanism can be
definitely determined.
Erosion-Corrosion
Erosion is surface wear that is caused by the impingement of particles or fluids. Erosion will
be covered along with other forms of wear in COE 106.03. Erosion corrosion is accelerated
erosion that is caused by corrosive fluid. The total metal loss from erosion-corrosion can be
several times the metal loss from erosion or corrosion alone. Most metals are susceptible to
erosion-corrosion under specific conditions. Passive films often play an important role in
erosion-corrosion. As long as the film remains intact, resistance to erosion-corrosion is
maintained. When the film is broken, rapid attack can occur. Carbon and low-alloy steels
generally perform acceptably in hydrocarbon streams that contain hydrogen sulfide because
of the tenacious iron sulfide film that is formed. If the film is broken down by cyanide or by
another corrodant that attacks the film, rapid corrosion occurs.
Liquid erosion-corrosion failures exhibit grooves, ditches, rounded holes, horseshoe-shaped
attack, and other forms of metal loss that are associated with flow patterns. It is often difficult
to distinguish erosion from erosion-corrosion, since both of them result in clean surfaces in
regions of high velocity, impingement, or turbulence. In many cases, conclusions are
intuitive, based on prior experience of, for example, the corrosion rates under stagnant
conditions or the erosion rates in noncorrosive streams with similar flow conditions.
Inspection for Erosion-Corrosion
Do the following when inspecting possible erosion-corrosion failures:
Examine failed region for flow patterns such as grooving and lack of adherent
corrosion product.
Compare corrosion rate data from stagnant tests and general erosion resistance
of materials, if available.
Examine the failed region for excessive fluid velocities, impingement, and
turbulence.
45

Corrosion Failures
Corrosion Fatigue
Corrosion fatigue occurs as a result of the combined action of a cyclical stress and a corrosive
environment. Purely mechanical fatigue failures will be examined in COE 106.03. The critical
parameter for fatigue failure is fatigue strength, which is the maximum stress that can be
sustained by a metal for a specified number of cycles without failure. The fatigue strength of a
metal can decrease when cycled in the presence of a corrodant. An aggressive environment
can affect crack initiation, crack propagation, or both. It is worth noting that LME cracking is
also accelerated by cyclical stress.
Corrosion pitting and intergranular attack are sometimes initiation sites for corrosion fatigue.
Subsequent corrosion-fatigue cracking may be intergranular or transgranular. Sometimes
corrosion products cause a wedge-opening effect, which causes crack growth. When crack
propagation is caused by a wedge-opening, straight singular cracks are observed. In other
cases, some crack branching may be evident.
As with erosion-corrosion, corrosion fatigue is often difficult to discern from purely
mechanical fatigue. The surfaces of cracks that are produced by mechanical fatigue often
exhibit fatigue striations, which will be examined later. Corrosion often destroys telltale
fatigue striations; however, corrosion often occurs after cracking rather than as part of the
cracking process.
Inspection for Corrosion Fatigue
Do the following when inspecting possible corrosion fatigue failures:
Examine for corrosion products within the cracks.
Check for pits, intergranular attack, or other localized forms of corrosion that
may have contributed to crack initiation.
Look for singular, or widely spaced cracks that are unbranched or only slightly
branched.
Investigate for possible cyclical stressing.
46

Corrosion Failures
Elevated Temperature Attack

The types of corrosion that are covered in this section are those types that occur at
temperatures above approximately 260 C (500 F). Most of the types actually occur at much
higher temperatures.
Oxidation
Generally, oxidation refers to any corrosion process that results in an oxide corrosion product.
High temperature forms of oxidation that occur in petroleum and petrochemical facilities
typically involve oxidation by hot gases that contain air, oxygen, or other oxygen sources
such as carbon dioxide, as well as oxidation in boiler water and steam.
Much of the processing of oil occurs at elevated temperatures. While the hydrocarbon process
streams are not oxidizing environments, heating is performed by combustion with air, and
external surfaces oxidize. The engineering alloys that are used for processing equipment have
maximum temperatures above which they readily oxidize in service. Approximate maximum
metal temperatures for selected engineering alloys are given in the table in Figure 30. Note
that steam oxidizes more severely than air.
47

Corrosion Failures
Maximum Metal Temperature, C (F)

Alloy
Composition
Carbon Steel
Clean Combustion
Atmosphere
Steam
425 (800)
Brass
70 Cu - 30 Zn
700 (1290)
Fe - Cr Alloys
1.25 Cr - 0.5 Mo
595 (1100)
565 (1050)
2.25 Cr - 1.0 Mo
635 (1175)
610 (1125)
5.0 Cr - 0.5 Mo
650 (1200)
620 (1150)
7.0 Cr - 0.5 Mo
675 (1250)
9.0 Cr - 1.0 Mo
705 (1300)
Type 410 SS
12.0 Cr
760 (1400)
Type 304 SS
18.0 Cr - 8.0 Ni
845 (1550)
Type 310 SS
25.0 Cr - 20.0 Ni
1040 (1900)
Alloy 800
20.0 Cr - 32.0 Ni
1095 (2000)
650 (1200)
815 (1500)
Figure 30. Maximum Metal Temperatures for Resistance to Oxidation
The ability of metals to resist oxidation depends largely on the added alloying elements and
consequently on the formed oxides. Dense, tightly adhering oxides, such as chromium oxide
(Cr2O3), are protective, while voluminous, incoherent oxides offer no protection from further
oxidation. In failure analyses, the oxides are often studied in detail to determine various
characteristics and compositions as well as to distinguish oxides from other forms of
corrosion such as sulfidation or carburization. Internal oxidation occurs when oxygen diffuses
below the surface of the metal and preferentially oxidizes specific alloy constituents. This
form of attack is less predictable or detectable, and it often results in premature failures.
48

Corrosion Failures
Overheating is probably the most common cause of failure for heater tubes. Failure modes are
either oxidation or, more likely, creep (covered in COE 106.03). Oxidation rate curves as
shown in Figure 31 are useful for determining tube temperatures. For example, if 25 mils of
scale (oxide) are found on a tube after one year of operation, and the volume of oxide is
assumed to equal that of metal loss (corrosion), the operating temperature for 25 mpy can be
read from the chart.
Figure 31. Oxidation Rate Curves for Selected Alloys

(Oxidation rates in Steam)
(Reference No. 19)
Thermal cycling can cause oxides that normally adhere tightly to crack and spall off of heater
tubes. Each time spalling occurs, bare metal oxidizes until a sufficient protective scale is
formed. Exfoliation is a term that is used to describe preferential corrosion that is generally
along grain boundaries and parallel to the metal surface. Differential expansion of corrosion
products at grain boundaries causes spalling of layers of metal and creates a leafy appearance.
Exfoliation is often associated with cyclical operation.
Oxides are usually more voluminous that the base metal. Extremely high compressive forces
can occur when oxides form in confined spaces. Corroding carbon steel tubesheets have been
known to crush tubes or crack tubesheets due to the oxide growth in crevices that is formed
by rolled-in tubes.
Inspection for Oxidation
Do the following when inspecting possible oxidation failures:
49

Corrosion Failures
Determine, if possible, operating temperature. It is possible that temperatures

were simply too high for the alloy (Figure 30).
Determine, if possible, if unusual cycling has repeatedly occurred during

operation.
Check for excessive scaling and spalling.
Analyze scale to confirm oxide. Note that magnetite (Fe3O4) is magnetic;

therefore, a magnet test can provide a simple clue to scale identity.
Sulfidation
Sulfidation is the high temperature reaction of a metal with sulfur species to form metallic
sulfides. Whereas oxidation occurs in combustion and boiler environments, sulfidation occurs
on the process side. The common source of sulfur in petroleum processing is hydrogen sulfide
(H2S). Sulfidation proceeds according to the following equation:
Fe + H2S
FeS + H2
(5)
50

Corrosion Failures
Sulfidation begins at approximately 260 C (500 F) and reaches a maximum at

approximately 427 C (800 F). The effect of temperature and hydrogen sulfide concentration
on the sulfidation rate is exemplified in Figure 32 for a low alloy steel and an austenitic
stainless steel. Lower corrosion rates for the austenitic stainless steel indicate why stainless
steels are often used for sulfidation resistance.
Figure 32. Sulfidation rates of low alloy (0.5 Cr) steel

and austenitic stainless (18 Cr - 8 Ni) steel.
In some ways, sulfidation is analogous to oxidation. Under certain conditions both scales are
protective; as the scale thickens, the corrosion rate decreases. Sulfidation is generally more
destructive than oxidation because the protective sulfide scales are more friable and tend to
spall off more than do oxide scales. Sulfidation is also sensitive to erosion effects in high
velocity streams. Nickel alloys have poor sulfidation resistance; therefore, corrosion of nickel
alloys by sulfidation is much more likely to occur than is corrosion by oxidation.
51

Corrosion Failures
Cyanide-Induced Corrosion
A special case of accelerated sulfidation attack occurs in refineries where cyanides are formed
from nitrogen in the crude. Cyanides destroy the sulfide scale, and expose the base metal to
rapid sulfidation attack.
Inspection for Sulfidation
Do the following when inspecting possible sulfidation failures:
Determine if operating temperatures were within the expected range for

accelerated sulfidation.
Check for sulfur and sulfide attacking agents such as cyanides in the process
stream.
Check for excessive spalling of sulfide layers.
Analyze to confirm sulfide scale.
Note that some sulfides are similar to oxides in that they are mildly magnetic.
Vanadium Attack
Many crudes contain a stable organic compound of vanadium that remains in residual fuel oil.
When burned, the vanadium is oxidized to vanadium pentoxide, V2O5. Aided by sulfur in the
fuel oil as well as by other impurities such as sodium and potassium, the vanadium pentoxide
forms low melting phases on iron or nickel surfaces. As a result, severe metal loss can occur.
In steels, liquid phases can form at temperatures as low as 566 C (1050 F).
Vanadium attack exhibits thick scale layers on components such as heater tubes. The scale
may have a beaded external surface appearance. Often the scale spalls to reveal localized
regions of metal loss with features similar to pitting or acid attack. Sometimes the pitted
regions will exhibit features that resemble melting. Analysis of the scale usually will reveal
significant quantities of sulfur and vanadium, and the analysis possibly will reveal traces of
sodium or potassium.
It is not unusual for heaters to operate for several years without corrosion problems and then
suddenly experience accelerated corrosion due to introduction of vanadium-containing fuel.
Slight temperature increases can result in exceeding the melting temperature for the vanadium
pentoxide phase. All iron-base alloys are susceptible to vanadium attack. A cast 50 Cr - 50 Ni
alloy offers the best resistance to this type of attack.
52

Corrosion Failures
Inspection for Vanadium Attack

Do the following when inspecting possible cases of vanadium attack:
In the case of steels, check metal temperatures to determine if temperatures are

above approximately 566 C (1050 F). Vanadium attack of nickel alloys
occurs at higher temperatures. Heater and boiler components such as tube
supports operate at higher temperatures than do tubes, and, therefore, these
components are particularly prone to vanadium attack.
Confirm the presence of vanadium in the scale and/or the fuel oil.
Carburization
Carburization is an environmentally-related problem in high temperature petrochemical and
refinery equipment. Carbon in the process stream diffuses at high temperatures into the metal
and results in carbide formation. Iron carbide (Fe3C) forms in carbon and low alloy steels. The
result is low temperature embrittlement and enhanced creep fissuring in regions such as
welds. (Embrittlement and creep will be discussed in COE 106.03.) Chromium carbides form
in stainless steels and result in embrittlement and increased oxidation. Oxidation attack is also
accelerated due to the depletion of chromium from the matrix by the preferential formation of
chromium carbides. The greatest attack occurs when metal surfaces are simultaneously or
intermittently exposed to carburizing and oxidizing environments. The resulting metal loss
visually resembles oxidation failures. Carburization-related corrosion attack of stainless steel
heating elements and heater tubes that is caused by simultaneous carburization and oxidation
is referred to as green rot.
Internal carburization can be determined metallographically. As a general rule, tubes that are
carburized through one-half the wall thickness are prone to failure from thermal shock. The
carburized regions of the tube are magnetic in some cast high alloy austenitic steels.
Metal Dusting
Metal dusting is an accelerated form of carburization that occurs in austenitic alloys at
temperatures that range from 482 to 816 C (900 to 1500 F) in strongly reducing
atmospheres, such as those that contain large amounts of hydrocarbon gasses. Alternating
(oxidizing/reducing) atmospheres promote metal dusting.
The specific mechanism by which metal dusting occurs is not well understood. Under normal
conditions, the attack is highly localized and occurs in apparently random areas. Metal
dusting often appears as random pitting on the ID surfaces of heater tubes. Rates of attack can
exceed
1 mil/hr (0.6 mm/day).
53

Corrosion Failures
Metal dusting is an intergranular form of attack. Carburization at grain boundaries results in

grain fallout. The term metal dusting originated from the fine granular corrosion product
that falls out of the attacked regions. The attack often appears as random pitting. Loose,
magnetic coke is often associated with the attacked regions. Metallographic cross sections
typically show a thin layer of intergranular carbides near the surface and intergranular
carbides that penetrate deeper into the metal.
Decarburization
Decarburization can occur when carbon diffuses out of steel on the steam side of boiler tubes.
Decarburized regions have lower mechanical properties when compared to normal steel.
Fortunately, steam-induced decarburization only occurs in thin surface layers and does not
generally result in failures. Internal decarburization is a consequence of hydrogen attack,
which will be covered in the next section.
Inspection for Carburization
Do the following when inspecting possible carburization failures:
Examine apparent brittle failures for possible carburization, since carburized

tubes often fail due to thermal shock. Metallographic examination is required to
confirm carburization.
Check for cyclic oxidizing/reducing operating conditions.
Examine for metal dusting features in austenitic materials in stagnant,

carbonaceous gas atmospheres.
Determine if operating temperatures are within ranges for carburization attack.
54

Corrosion Failures
Hydrogen Attack
Hydrogen attack is the form of hydrogen-induced damage that occurs at temperatures above
221 C (430 F). As previously discussed in the subsection on hydrogen embrittlement,
dissociated hydrogen atoms can diffuse through the metal lattice at high temperatures. When
diffusing atomic hydrogen reaches defects (voids, inclusions, and oxides), it can react with
oxygen, in the case of copper alloys, or with carbon, in the case of steels, to form water or
methane, respectively:
Copper:
2H2 + O2
Steel:
2H2 + C
2H2O
CH4
(6)
(7)
or
2H2 + Fe3C
CH4 + 3Fe
(8)
Both water and methane formations create high pressures that cause internal fissures or
cracks. The internal fissures result in degraded mechanical properties. This phenomenon is
called hydrogen sickness in the case of copper alloys, and, more commonly, hydrogen attack,
in the case of steels. Since the water or methane molecules are too large to diffuse out of the
metal, the resulting damage is permanent.
An illustration of the reaction sites for methane formation in steel is shown in Figure 33. The
fissures and cracks decrease mechanical properties of the steel. In addition, the carbon that is
involved in methane formation is removed from the steel and this removal of carbon results in
a decarburized metal matrix with very poor mechanical properties.
Figure 33. Sites for Methane Formation (Hydrogen Attack) in Steel
55

Corrosion Failures
Hydrogen attack is dependent on temperature, the amount of hydrogen that is present, and the
carbon content of the steel. Alloying steel is the best means of preventing hydrogen attack.
Molybdenum is the principal alloying element since molybdenum carbide is more stable than
iron carbide and, therefore, more resistant to methane formation. Temperature limits for
various alloys are plotted versus hydrogen partial pressure on Nelson Curves. These curves
are based on data that was tabulated by G. A. Nelson in 1949, and they are illustrated in the
Addendum at the end of this module.
Inspection for Hydrogen Attack
Do the following when inspecting possible hydrogen attack failures:
Examine for cracking that suggests mechanical property loss (e.g., overload).
Extensive surface corrosion is not expected in hydrogen environments.
Determine the temperature and the hydrogen partial pressure for the failed
material.
Use nondestructive ultrasonic attenuation or radiography to test the failed area

for indications of hydrogen attack. Hydrogen attack often requires optical
metallographic (destructive) examination for positive confirmation. Detection
of both fissures and associated decarburization will conclusively indicate
hydrogen attack.
56

Corrosion Failures
GLOSSARY
aerobic bacteria
Bacteria that oxidize sulfur species to sulfuric acid to cause

corrosion.
anaerobic bacteria
Bacteria that reduce sulfate to sulfide, do not require air or

oxygen in order to exist, and cause corrosion.
atmospheric corrosion
Corrosion of unprotected materials that are exposed to

atmospheric conditions, primarily moist air.
atomic hydrogen
Uncharged atoms of hydrogen that can diffuse through

metals. Sometimes called nascent (newly formed) hydrogen.
carburization
Elevated temperature diffusion of carbon into metals, which

usually results in the formation of carbides. Metal loss and
embrittlement are typical results of carburization.
caustic embrittlement
An obsolete term that is used to describe the caustic stress

corrosion cracking of carbon steel.
corrodant
Chemical (environmental) species that cause corrosion of a

material.
corrosion that involves

multiple variables
Deterioration that results from the interaction of corrosion

with one or more factors, such as stress, velocity effects,
temperature, or bacteria.
corrosion allowance
Extra thickness that is added to equipment to compensate for

expected corrosion over design life.
corrosion attack
(or simply Attack)
A term that is often used to describe severe or acute

corrosion.
corrosion fatigue
Accelerated fatigue that results from the combined action of a

cyclical stress and a corrosive environment.
corrosion product
Material that is produced by a corrosion reaction. Corrosion

products are often found on or in the vicinity of the corroded
surface.
corrosion under insulation
Corrosion of equipment surfaces that are covered by

insulation. Common corrosion problems include localized
corrosion of carbon steels and stress corrosion cracking of
austenitic materials.
57

Corrosion Failures
cyanide-induced corrosion
A complex corrosion process wherein cyanides attack

protective sulfide scales on metals, and thereby acclerate
sulfidation.
dealuminization
Selective leaching of aluminum in aluminum brasses or

bronzes.
decarburization
Diffusion of carbon from steel, that results in a carbon-free

(ferrite) matrix with low mechanical properties.
denickelification
Selective leaching of nickel in copper-nickel alloys.
deposits
Foreign materials, which may be either corrosion products

from elsewhere in the system or contaminants, that settle or
attach in the area of interest.
dezincification
Selective leaching of zinc in copper-zinc (brass) alloys.
environmental cracking
Cracking processes that are caused by the synergistic effects

of stress and environment on a specific material.
Environmental cracking includes stress corrosion cracking,
hydrogen-induced damage, and liquid metal embrittlement.
erosion-corrosion
Accelerated erosion that is caused by corrosive fluid.
erosion
Surface wear that is caused by the impingement of particles

or fluids.
exfoliation
Preferential corrosion that is parallel to the metal surface.

Differential expansion of corrosion products at grain
boundaries causes spalling of layers of metal.
fatigue
Metal failure that results from cyclical stresses below the

yield strength.
galvanic corrosion
(two-metal corrosion)
Accelerated corrosion of a less noble metal in contact with a

more noble metal.
graphitic corrosion
Selective leaching of iron in gray cast irons.
green rot
Carburization-related corrosion attack of stainless steel

heating elements that is caused by simultaneous carburization
and oxidation.
hydrogen-assisted cracking
Stepwise cracking of carbon and alloy steels that are exposed
58

Corrosion Failures
(HAC)
to wet hydrogen sulfide environments.
hydrogen attack
High temperature damage that is caused by atomic hydrogen

diffusion into the metal lattice and the resulting formation of
methane gas at defects. This damage can result in internal
fissuring.
hydrogen blistering
Low temperature blistering or bulging of steel that is caused

by high pressure molecular hydrogen. The high pressure
molecular hydrogen is a result of the recombination of atomic
hydrogen and internal defects.
hydrogen embrittlement
The loss of toughness or ductility in a metal caused by

absorption of atomic hydrogen.
hydrogen-induced cracking Stepwise cracking of steels that are exposed to wet hydrogen
(HIC) (hydrogen blister sulfide.
cracking [HBC], stepwise
cracking [SWC])
hydrogen-induced damage
Degradation of a metal or alloy (usually steel) by exposure to

hydrogen-containing environments.
hydrogen sickness
Hydrogen attack in copper alloys whereby water formation

causes fissuring.
interconnected pits
Surface condition where multiple pits grow together, and

result in a corrosion attack that resembles general corrosion.
intergranular attack (IGA)

(intergranular corrosion
[IGC])
Preferential corrosion at, or adjacent to, the grain boundaries

of a metal.
internal oxidation
Preferential oxidation below the surface of a metal.
knife-line attack
A narrow band of intergranular corrosion that is adjacent to a

weld in stabilized stainless steel. High heat from welding
dissolves carbides and subsequently results in sensitization in
a thin band during cooling.
liquid metal embrittlement

(liquid metal cracking)
Spontaneous or delayed cracking of a stressed metal that is

exposed to specific embrittling liquid metals.
localized corrosion
Corrosion that occurs preferentially in specific areas of the

material.
59

Corrosion Failures
metal dusting
Accelerated
materials.
microbiologically-influenced
corrosion (MIC) (biological
corrosion, microbiological
corrosion)
Forms of corrosion that involve multiple variables and that

are associated with the presence of microbes.
molecular hydrogen
Molecules of hydrogen (H2) that are too large to diffuse

through metals.
morphological features
Usually microscopic features that are related to the structure

and form of a material.
Nelson Curves
Curves that show the operating limits for various steels to

avoid decarburization and fissuring in hydrogen service.
noble metal
A metal whose potential is positive relative to the hydrogen

electrode. In the galvanic series, noble metals are those metals
that are closer to the cathodic, or protected, end.
oxidation
A corrosion process that generally occurs at elevated

temperatures and results in an oxide corrosion product.
patina
Corrosion product that is found on materials after long-term

atmospheric exposure. Most notably, the green film that is
exhibited on copper and bronze statues.
pitting corrosion
Localized corrosion that is characterized by sharply defined

surface cavities or holes through a metal.
scale
High temperature corrosion products, such as oxides, that are

found on boiler tubes.
selective leaching
(dealloying; parting)
Preferential corrosion of one element in an alloy.
sensitization
Precipitation of chromium carbides in the grain boundaries of

austenitic materials. The adjacent regions are depleted of
chromium, and they corrode intergranularly in an otherwise
noncorrosive environment.
solid metal embrittlement
Cracking of a stressed metal that is exposed to specific

embrittlers at temperatures below the melting point of the
embrittler.
intergranular
carburization
of
austenitic
60

Corrosion Failures
spalling
Breaking or flaking away of surface layers of oxides, sulfides,

or other surface coatings. Differential stresses that are created
during cooling often cause the surface layers to pop off.
stray current corrosion
Corrosion that is caused by stray currents from nearby

electrical equipment.
stress-corrosion cracking
A form of environmental cracking that is caused by the

synergistic effects of a corrosive environment and sustained
stress on a specific material.
stress-oriented hydrogeninduced cracking (SOHIC)
Cracking of steels that is perpendicular to an applied stress

and is caused by wet hydrogen sulfide.
sulfidation
The high temperature reaction of a metal with sulfur species

to form metallic sulfides.
sulfide-stress cracking
(hydrogen-stress cracking,
hydrogen-embrittlement
cracking)
Special case of hydrogen embrittlement where high strength

or high hardness steels crack under stress in sulfide solutions.
tubercles
Corrosion products that appear as mounds over regions of

localized attack.
under-deposit corrosion
Accelerated corrosion which occurs under deposits. The

deposits provide crevices for crevice corrosion.
uniform corrosion (general

corrosion)
Corrosion that occurs uniformly over all exposed surfaces of

the material.
vanadium attack(fuel ash, High temperature corrosion that occurs as a result of low
melting phases and is formed from vanadium in fuel oils.
hot ash, oil ash corrosion)
wastage
Localized corrosion that usually extends deeply beneath the

surface of the sample over a specific area. Wastage is
sometimes used to describe uniform corrosion or
interconnected pits.
weld decay
Intergranular corrosion in the heat affected (sensitized) region

of welded stainless steel.
61

Corrosion Failures
ADDENDUM A: COMMON ENGINEERING MATERIALS

Fe Alloys
Carbon Steel
(10XX, A516)
Alloy Steels
(13XX-98XX, Cr-Mo Steels)
Stainless Steels
(12 Cr, 400-Series)

(18 Cr-8 Ni, 300-Series)
(Duplex Alloys; PH Grades)
Cast Irons
(2.0 - 6.7 wt.% Carbon)
Brasses
(Cu-Zn)
Bronzes
(Cu-Sn, Cu-Si, Cu-Al)
Cupronickels
(90 Cu - 10 Ni, 70 Cu - 30 Ni)
Inconels
(Alloys 600, 625, X-750)
Monels
(Alloys 400, K-500)
Hastelloys
(Alloys B-2, C-22, C-276, G-3, G-30, X)
> 99 wt.% Aluminum
(1XXX)
Alloys
(2XXX - 9XXX)
Unalloyed
(Grades 1, 2, 3, 4, 7)
Low-Alloyed
(Grades 7, 11, 12)
Alloys
(Alpha, Beta, Alpha-Beta)
Cu Alloys
Ni Alloys
Al Alloys
Ti Alloys
62

Corrosion Failures
ADDENDUM B: EXCERPT FROM NACE CORROSION DATA SURVEY

Reference No. 6
63

Corrosion Failures
Key to Data Tables
Matrix Key
F
500
260
400
204
300
149
200
93
100
38
-18
Throughout the data tables in this

book, data points representing
average penetration per year (key
below) are plotted on the matrix
enlarged here. The horizontal grid
represents temperature. The vertical
grid represents concentration.
20 40 60 80 100
% concentration in H2O
Key to Footnotes
1. Pitting
2. Stress Corrosion Cracking
3. Crevice Attack
Key to Data Points

Average Penetration Rate Per Year
Code
Mils
Inches
<2
0.002
50
<20
0.020
508
20-50
X
>50
0.020-0.050
0.050
508-1270
1270
64

Corrosion Failures
65

Corrosion Failures
66
NOTES:
1. After approximately 9-18 years' service, eight occurrences of
hydrogen attack have been reported in C-0.5Mo steels
operating below the 1922 0.5Mo curve in catalytic reforming
units. These steels experienced hydrogen attack under
conditions in which extensive decarburization or carbon
migration to grain boundaries was not documented or reported
prior to 1980. Further use of 0.5Mo steel in catalytic reforming
units to resist internal fissuring should be evaluated rigorously
until information is available to explain this phenomenon.
2. The curve for 0.5 Mo steel can apply to either C-0.5Mo or Mn0.5Mo steels.
Copyright 1967 by G.A. Nelson. Reproduction rights granted by author to API.

This figure has been revised by API in 1969, 1977, and 1982
a.
b.
c.
5.
4.
3.
Austenitic stainless steels are generally not decarburized in

hydrogen at any temperature or hydrogen pressure.
Effect of trace alloying elements (up to 1000 pounds per
square inch absolute [6.90 megapascals] hydrogen partial
pressure and below 1000 F [538 C]):
Mo has four times the resistance of Cr to hydrogen attack.
Mo is equivalent to V, Ti, or Nb up to 0.1 percent.
Si, Ni, Cu, P, and S do not increase resistance.
The limits described by these curves are based on
experience with cast steel as well as annealed and
normalized steels at stress levels defined by the ASME
Boiler and Pressure Vessel Code, Section VIII, Division 1.
Operating Limits for Steels in Hydrogen Service to Avoid Decarburization and FissuringReference No. 22
ADDENDUM C
Corrosion Failures
67
Temperature, C
Temperature, F

Corrosion Failures
REFERENCES
1.
Fontana, M. G. Corrosion Engineering, Third Edition, McGraw-Hill Book

Company, New York, NY, USA, 1986.
2.
Dillon, C. P. Corrosion Control in the Chemical Process Industries, McGrawHill Book Company, New York, NY, USA, 1986.
3.
American Society for Metals (ASM), Corrosion, Metals Handbook, Vol. 13,
Ninth Edition, Metals Park, Ohio, USA, 1987.
4.
E. D. D. During, comp. Corrosion Atlas - A Collection of Illustrated Case

Histories, Vols. 1 and 2, Second Edition, Elsevier Science Publishers B. V.,
Amsterdam, The Netherlands, 1988.
5.
Wyatt, L. M., Bagley, D. S., Moore, M. A., and Baxter, D. C., An Atlas of
Corrosion and Related Failures, MTI Publication No. 18, Materials Technology
Institute of the Chemical Process Industries, Incorporated, St. Louis, Missouri,
USA, 1987.
6.
National Association of Corrosion Engineers (NACE), Corrosion Data Survey,

Metals Section, Sixth Edition, Houston, Texas, USA, 1985.
7.
National Association of Corrosion Engineers (NACE), NACE Basic Corrosion

Course, Fourth Printing, Houston, Texas, USA, 1973.
8.
H. H. Uhlig, ed., The Corrosion Handbook, John Wiley and Sons, Inc., New
York, NY, USA, 1948.
9.
National Association of Corrosion Engineers (NACE), Process Industries

Corrosion, Houston, Texas, USA, 1975.
10.
American Society for Testing and Materials (ASTM), Metals Test Methods
and Analytical Procedures, 1986 Annual Book of ASTM Standards, Sect. 3,
Vol. 03.02, Wear and Erosion; Metal Corrosion, Philadelphia, Pennsylvania,
USA, 1991.
11.
O. Bauer and O. Vogel, Mitt. Mat. Pruf. Amt., Berlin, Germany, 1918.
12.
D. R. McIntyre, Experience Survey Stress Corrosion Cracking of Austenitic

Stainless Steels in Water, MTI Publication No. 27, Materials Technology
Institute of the Chemical Process Industries, Inc., Columbus, OH, USA, 1987.
13.
J. A. Sedriks, Corrosion of Stainless Steels, John Wiley & Sons, New York,
NY, USA, 1979.
68

Corrosion Failures
14.
D. R. McIntyre and C. P. Dillon, Guidelines for Preventing Stress Corrosion

Cracking in the Chemical Process Industries, MTI Publication No. 15,
Materials Technology Institute of the Chemical Process Industries, Inc.,
Columbus, OH, USA, 1985.
15.
C. P. Dillon, Guidelines for Control of Stress Corrosion Cracking of NickelBearing Stainless Steels and Nickel-Base Alloys, MTI Manual No. 1,
Materials Technology Institute of the Chemical Process Industries, Inc.,
Columbus, OH, USA, 1979.
16.
D. Warren, Materials Performance, Vol. 26, No. 1, p. 38, 1987.
17.
R. D. Merrick, Materials Performance, Vol 28, No. 2, p. 53, 1989.
18.
W. Rostoker, J. M. McCaughey, and H. Marcus, Embrittlement by Liquid

Metals, Reinhold Publishing Corp., New York, NY, USA, 1960.
19.
P. M. Brister and G. N. Emmanuel, Steels for Elevated Temperature Service,

United States Steel Corporation, Pittsburgh, PA, USA, 1965.
20.
D. N. French, Metallurgical Failures in Fossil Fired Boilers, John Wiley &

Sons, New York, NY, USA, 1983.
21.
National Association of Corrosion Engineers (NACE), NACE Standard

MR0175-93, Item No. 53024, "Standard Material Requirements - Sulfide Stress
Cracking Resistant Metallic Materials for Oilfield Equipment," Houston, Texas,
USA, 1993.
22.
American Petroleum Institute (API), Steels for Hydrogen Service at Elevated

Temperatures and Pressures in Petroleum Refineries and Petrochemical
Plants, API Publication No. 941, Washington, DC, USA, 1983.
23.
H. M. Herro and R. D. Port, The Nalco Guide to Cooling Water System Failure
Analysis, McGraw-Hill, Inc., New York, NY, USA, 1993.
69

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Engineering Encyclopedia

Saudi Aramco DeskTop Standards

Chapter : Materials & Corrosion Control

For additional information on this subject, contact

Materials & Corrosion Control

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Materials & Corrosion Control

Material Factors ................................................................................. 25

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Materials & Corrosion Control

Inspection for Sulfidation .................................................................. 52

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Materials & Corrosion Control

Localized Corrosion: Corrosion that occurs preferentially in specific areas of

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FEATURES OF UNIFORM (GENERAL) CORROSION

Figure 2. Uniform (General) Corrosion

Figure 3. Uniform Corrosion with Remaining Corrosion Product

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Materials & Corrosion Control

In the performance of failure analyses, it is often prudent to back-calculate the expected

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Materials & Corrosion Control

TYPES AND FEATURES OF LOCALIZED CORROSION

Figure 4. Galvanic (Two-Metal) Corrosion

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Protected end (cathodic, or most noble)

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Figure 6. Examples of Galvanic Corrosion

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Materials & Corrosion Control

Figure 7. Galvanic Corrosion of Tin and Zinc-Coated Steel

Stray Current Corrosion

Look for localized attack that is adjacent to material interfaces.

Check for possible stray currents.

Look for perforations in protective coatings, especially coatings that are

Check for a small anode-to-cathode ratio.

Check for dissimilar weld and base metals.

Determine the environment. Remember that the galvanic series pertains to a

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Materials & Corrosion Control

Figure 8. Pitting Corrosion

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Materials & Corrosion Control

Figure 9. Electrochemical Nature of Pitting Corrosion

Figure 10. Pitting and General Corrosion

Materials & Corrosion Control

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Figure 11. Variations in the Cross-Sectional Shape of Pits

Materials & Corrosion Control

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Figure 12. Intergranular Attack

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Materials & Corrosion Control