6.

01
Stress Corrosion Cracking
H. E. HAºNNINEN
Helsinki University of Technology, Finland

6.01.1 INTRODUCTION 1

6.01.2 STRESS CORROSION CRACKING 3

6.01.2.1 Crack Initiation 3
6.01.2.2 Crack Growth 4
6.01.3 SCC MECHANISMS 4
6.01.3.1 Dissolution Mechanisms 5
6.01.3.2 Hydrogen-assisted Cracking Mechanisms 9
6.01.3.2.1 Decohesion mechanism 10
6.01.3.2.2 Deformation mechanism 10
6.01.3.2.3 Adsorption mechanism 11
6.01.3.2.4 Hydrogen pressure mechanism 11
6.01.3.2.5 Brittle hydride mechanism 11
6.01.3.2.6 Vacancy mechanisms 12
6.01.3.2.7 Summary 12
6.01.3.3 Adsorption Mechanisms 12
6.01.3.4 Film-induced Cleavage Mechanism 14
6.01.3.5 Surface Mobility Mechanism 14
6.01.3.6 Selective Dissolution (Dealloying)—Vacancy Creep Mechanism 15
6.01.4 SCC ENVIRONMENTS 15
6.01.4.1 Carbon and Low-alloy Steels 15
6.01.4.2 High-strength Steels 16
6.01.4.3 Stainless Steels 17
6.01.4.4 Nickel Alloys 18
6.01.4.5 Copper Alloys 20
6.01.4.6 Aluminum Alloys 21
6.01.4.7 Hexagonal Alloys: Titanium, Zirconium, and Magnesium 21
6.01.5 SCC ENVIRONMENTAL AND MECHANICAL CONDITIONS 22

6.01.6 STRESS CORROSION FIELD FAILURES 23

6.01.7 REFERENCES 25

6.01.1 INTRODUCTION crack growth here depends upon the stress

Stress corrosion cracking (SCC) is interpreted
to take place due to specific combinations of
susceptible materials in suitable corrosion en-
vironments under adequate stress, specifically
under constant stress, Figure 1. The equivalent
mechanism for crack growth under cyclic
stresses is called corrosion fatigue (CF), and
ratio. In particular, when the stress ratio is high,
CF becomes close to SCC; this type of loading
is called ripple loading, which often simulates
very well the loading situation during plant
operations. Strain-induced corrosion cracking
(SICC) is used especially in Germany as a
term for the situation, where cracking takes
place under increasing load, which may not

1
2 Stress Corrosion Cracking
Figure 1 Factors affecting EAC. Note that the specific conditions are required for cracking to occur (source
Speidel, 1984; reproduced by permission of Kluwer Academic Press).
necessarily increase monotonically, but also
some cyclic variations may be present as
typically in start-up and shut-down situations
of plants. Therefore, the last mechanism can be
considered to be a special case of corrosion
fatigue, when only a very small number of cycles
are present. This loading can be simulated by
the slow strain rate test (SSRT) technique,
where a specimen is tensile tested with a very
slow strain rate in the environment. All these
mechanisms can be described by a general term,
namely, environment-assisted cracking (EAC).
Ellis et al. (2000) have clarified the taxonomy
for EAC by comparing the definitions for
various EAC mechanisms and reduced by an
improved nomenclature the number of named
EAC phenomena from more than 25 to just 7.
The literature of SCC and related EAC
phenomena is immense, and a large number of
conferences have dealt with various topics such
as SCC (Rhodin, 1959; Westwood and Stoloff,
1965; Staehle et al., 1967, 1977; Scully, 1971;
Craig, Jr., 1976; Swann et al., 1977; Foroulis,
1979; Latanision and Fourie, 1977; Ugiansky
and Payer, 1977; Latanision and Pickens, 1983;
Gangloff, 1984; Gibala and Hehemann, 1984;
Goel, 1984; Dean et al., 1984; Jones and
Gerberich, 1986; Turnbull, 1986; Latanision
and Jones, 1987; Gangloff and Ives, 1990;
Lisagor et al., 1990; Bruemmer et al., 1992;
Magnin and Grass, 1993; Jones and Baer,
1996; Magnin, 1997; Kane, 2000; Jones, 2001),
hydrogen embrittlement (HE) (Bastien, 1972;
Bernstein and Thompson, 1973; Thompson
and Bernstein, 1975; Beachem, 1977; Bernstein
and Thompson, 1981; Azou, 1982; Interrante
and Pressouyre, 1982; Raymond, 1988; Moody
and Thompson, 1990; Thompson and Moody,
1996), and CF (Devereaux et al., 1972; Fong,
1979; Larsson, 1981; Crookes and Leis, 1983;
Van Der Sluys et al., 1997). In addition, there
are a number of more general series of
conferences on corrosion such as the Interna-
tional Congress on Metallic Corrosion, Frac-
ture; the International Conference on Fracture
and Fatigue; the International Fatigue Con-
ference; or topical conferences related to some
specific field such as Environmental Degrada-
tion of Materials in Nuclear Power Systems—
Water Reactors and IAEA Specialists Meet-
ings on Subcritical Crack Growth (Cullen,
1981, 1986, 1990; Cullen et al., 1985; Forsten,
1983), or ASME-PVP symposia, e.g., in the
nuclear energy field. The same is also true in
pulp and paper, petrochemical, and other
process industries. In the annual meetings of
the corrosion societies, e.g., National Associa-
tion of Corrosion Engineers (NACE) and
European Federation of Corrosion (EFC),
there are also specific sessions on EAC. In
addition to the conference proceedings, there
are some very useful extensive review reports
 Stress Corrosion Cracking
and textbooks on EAC related topics (Logan,
1966; Brown, 1977; Parkins, 1982; Ford, 1982;
Latanision and Fischer, 1983; Briant, 1985;
McIntyre and Dillon, 1985; Oriani et al., 1985;
Jones, 1992); a brief historical summary on
SCC by Newman and Procter (1990) is also
very instructive.
6.01.2 STRESS CORROSION CRACKING
SCC describes service failures in engineering
materials that occur by slow (e.g., 10
6 m s
1)
time-dependent environmentally assisted crack
growth when the necessary electrochemical,
mechanical, and metallurgical conditions exist.
The crack growth is a result of the combined
and synergistic interaction of mechanical stress
and corrosion reactions. In general, the stresses
required to cause SCC are small, often below
the macroscopic yield stress and they are
tensile in nature, either external applied or
residual fabrication stresses. Crack growth
occurs perpendicular to the principal tensile
stress direction. Crack branching is generally
thought to be a positive indication of SCC.
This is also an indication of constant crack
growth rate over a range of applied stress
intensities. Compressive stresses can be im-
posed to prevent SCC. Static loading is usually
considered to be responsible for SCC, but CF
and SICC are often considered to be subsets of
SCC. Stress corrosion cracks initiate at surface
flaws that either are pre-existing or are formed
during service by corrosion. The cracks grow
with very little macroscopic evidence of me-
chanical deformation in metals and alloys that
are normally very ductile. Crack growth can be
either transgranular or intergranular, and
sometimes mixed cracking can occur. Typi-
cally, fracture surfaces look very brittle and
close matching of the fracture surfaces is
commonly observed, indicating minor loss of
material by corrosion. SCC is mainly used to
describe failures in metallic alloys. However,
ceramics also exhibit environmentally assisted
crack propagation and polymers exhibit craze
cracking due to interaction of applied stress
and environmental reactions (Jones, 1987;
Chapter 6.06, this volume). Earlier it was
thought that pure metals were immune to
SCC, but nowadays it is known that they can
also be susceptible to SCC (Sieradzki and
Newman, 1985; Yu and Parkins, 1987; Aalto-
nen et al., 1998a). This summary will focus on
SCC of metallic materials and will not be
concerned with ceramics and polymers.
The environments that cause SCC are
usually aqueous solutions, but they can also
be condensed as layers of moisture, and even
water of crystallization of salts can induce
3
SCC. Typically, SCC of a metal alloy is a result
of the presence of some chemical species in
addition to water in the environment. For
example, SCC of austenitic stainless steels and
aluminum alloys is most commonly caused by
chloride ions, and ammonia is the most
common cause of SCC in copper alloys,
traditionally referred to as season cracking.
Variation in temperature, degree of aeration
(corrosion potential), and concentration of
ionic species may change an innocuous envir-
onment to cause SCC. Metallurgical conditions
of alloys may also affect markedly SCC
susceptibility. In Section 6.01.4 the most
common alloy–environment combinations that
result in SCC are briefly described. However,
the number of possible alloy–environment
combinations causing SCC is continuously
increasing.
In general, SCC is observed in alloy–
environment combinations that result in the
formation of a film on the metal surface, which
reduces the rate of general and uniform
corrosion (Jones, 1987). However, materials
like austenitic stainless steels and copper alloys
also show cracking in active corrosion condi-
tions (Hänninen, 1980), which naturally is not
their normal operating condition in practice.
These films may be passive, salt and tarnish
films, or dealloyed layers. Thus, SCC is of
greatest concern with the corrosion-resistant
alloys in aggressive aqueous environments. The
sequence of events involved in SCC is usually
divided into three stages: (1) crack initiation,
(2) steady-state crack growth, and (3) final
failure. Distinction between these stages is
often difficult, since the transition occurs in a
continuous manner. For example, the crack
initiation stage has been considered to change
to the crack growth phase when the size of the
crack is 20–50 mm, i.e., about one grain
diameter and greater (Ford and Andresen,
1995). The critical conditions for a SCC crack
to grow are the environmental, mechanical,
and electrochemical conditions of the incipient
crack. However, in the engineering sense,
initiation takes place when the cracks can be
detected by normal nondestructive methods,
i.e., crack size is 41–10 mm, dependent on
material and component geometry.
6.01.2.1 Crack Initiation
Stress corrosion cracks frequently initiate at
pre-existing surface features, such as grooves,
laps, burrs, weld defects, or a highly cold
worked surface layer resulting from fabrication
processes. Stress corrosion cracks also initiate
from corrosion pits (either formed at nonme-
tallic inclusions, e.g., MnS, or by breakdown of
4 Stress Corrosion Cracking
the passive film) that form during exposure to
the service environment when the electroche-
mical pitting corrosion potential is exceeded.
The change in the corrosion environment
within the pit is important, since pits can act
as occluded corrosion cells similar to cracks
and crevices. The transition between pitting
and SCC is particularly dependent on electro-
chemistry as well as on pit geometry (stress
concentration), local stress and strain rate at
the bottom of the pit. Crack initiation can also
take place by other forms of localized corro-
sion, e.g., by intergranular corrosion when the
grain boundary chemistry makes it possible. In
materials where stacking fault energy is low,
slip-dissolution may take place at emerging slip
planes on the surface. An additional form of
localized corrosion is corrosion tunnel/slot
formation, which, e.g., in the austenitic stain-
less steel surfaces, forms dealloyed (iron and
nickel are selectively dissolved) corrosion
sponge structures (Cr2O3-rich phase) (corro-
sion trenches). From these corrosion trenches,
very narrow (approaching atomic dimensions)
corrosion slots grow in /111S directions and
have {110} type plane walls which comprise the
microscopic fracture plane of austenitic stain-
less steel in chloride solutions under tensile
stress (Scamans, 1973; Silcock and Swann,
1979; Hänninen, 1980). Analytical Transmis-
sion Electron Microscopy (TEM) observations
(Bruemmer and Thomas, 2001; Lewis et al.,
2001) of SCC crack tips formed in high-
temperature water in Inconel alloy 600 and
AISI 304 and 316 stainless steels have con-
firmed the presence of Cr2O3 (predominant)
and Cr-rich spinel oxides at the interface with
the matrix. The formation of the Cr-rich oxides
at the crack tips is consistent with selective
dissolution (dealloying) and/or preferential
oxidation of Cr. No Cr-depleted layers were,
however, observed under the oxide films.
Formation of Cr-rich oxides also allows, by
hydrolysis reactions, to obtain high hydrogen
fugacity at the crack tip to make the hydrogen-
assisted cracking mechanisms viable. However,
it has not generally been possible to describe
very well the transition from initiation to crack
growth in any system, as yet.
When corrosion pits, corrosion trenches,
intergranular corrosion grooves, or surface
flaws actually become SCC cracks and the
cracks in turn start growing is very difficult to
measure experimentally, since the incipient
crack must fulfill the three important condi-
tions for SCC to occur: electrochemical,
mechanical, and chemical. Application of
fracture mechanics to this transition implies
that a certain defect size is necessary before
crack growth can occur, e.g., a threshold stress
intensity, KI SCC, value for any given alloy–
environment system must be exceeded. In
practice, the transition between initiation and
propagation usually occurs so close to the
surface that linear elastic fracture mechanics is
inapplicable and so the KI SCC concept finds
only limited application, e.g., in the case of
rather high strength alloys or to the arrest of
deep cracks in strongly decreasing residual
stress fields.
6.01.2.2 Crack Growth
When SCC cracks start to grow from pre-
existing flaws or localized corrosion sites, all
the mechanisms of crack growth are localized
at the crack tips, and it is not necessary for the
entire component to become embrittled, even
though hydrogen is often generated as a by-
product of the crack tip corrosion reaction and
crack growth may occur by an HE process.
There are a number of plausible mechanisms
that can describe SCC in a large variety of
materials. The mechanisms are most often
divided into dissolution or mechanical fracture
models. The mechanical models can further be
divided into ductile and brittle crack growth
models. Dissolution models include various
film-rupture and active path corrosion pro-
cesses such as slip-dissolution and corrosion
tunneling. Ductile mechanical models include
hydrogen-enhanced localized plasticity
(HELP) (Chapter 6.02) and adsorption-en-
hanced plasticity models. Brittle mechanical
models include tarnish rupture and film-in-
duced cleavage models as well as HE by some
decohesion mechanism, for example.
6.01.3 SCC MECHANISMS
The mechanistic knowledge of EAC crack-
ing is described here by combining the mechan-
istic information from various cracking
phenomena, SCC, HE, CF, and liquid metal
embrittlement (LME). It is generally recog-
nized that for understanding EAC an inter-
disciplinary approach is needed, i.e., in
addition to mechanics and materials science,
various aspects of electrochemistry, surface
science, physics, and analytical chemistry are
required. Fractographic and metallographic
studies reveal changes in the fracture mode,
the crack path, and the extent of plasticity and
microcracking around the cracks. The gener-
ally proposed possible mechanisms of EAC of
materials are shown in Figure 2. Generally, in
EAC either the slip-dissolution or hydrogen-
induced cracking mechanisms have been
favored as reasonable working hypotheses.
Under high-strain-rate conditions, when the
 SCC Mechanisms 5

Figure 2 Schematic presentation of possible effects of environment on fracture (source Lynch, 1983;
reproduced by permission of Taylor & Francis Ltd. (http://www.tandf.co.uk/journals)).

crack tip is continuously maintained in a bare
surface condition, the crack growth can be
identified atomistically with the bare surface
reaction rates for either dissolution or hydrogen
evolution reaction. Under normal strain rate
conditions, however, the crack tip surface is not
maintained continuously in a bare condition.
The crack growth is controlled by the oxide
rupture rate, the repassivation rate, and the
liquid diffusion rate at or near the crack tip
(Ford, 1982). Since these rate-determining
parameters may control both slip-dissolution
and hydrogen-induced cracking mechanisms, it
has been difficult to differentiate mechanisti-
cally between these two mechanisms. This has
resulted in a situation where some researchers
have chosen the slip-dissolution model and
others the hydrogen-induced cracking model as
a working hypothesis. Adsorption models have
been studied much less and brittle hydride
models are inadequate in many systems (with
the exception of those described in Chapter
6.03). In the following, the mechanisms are first
outlined generally concentrating on basic re-
quirements and attributes, but because the
proposed mechanisms are controversial, their
advantages and disadvantages are also dis-
cussed on the basis of the supporting evidence
for each mechanism—fractography, electro-
chemistry, etc.
6.01.3.1 Dissolution Mechanisms
The film rupture/anodic dissolution model,
which is also referred to as the slip-dissolution
model, has evolved from various ideas where
strain-assisted active crack paths are consid-
ered. It has been proposed that dissolution at
the film-free crack tip can be enhanced by the
strain concentration (e.g., Logan, 1966). This
has been supported by TEM observations of
stressed thin foils of austenitic stainless steels
showing that dissolution occurs preferentially
in regions of moving dislocations (Swann and
Embury, 1965; Smith and Staehle, 1967). It
was then demonstrated that the rate of film
formation on a rapidly strained, bared surface
correlated with the susceptibility to SCC,
Figure 3. With the help of repassivation rate
measurements, qualitative explanations for the
6 Stress Corrosion Cracking
Figure 3 Relationship between the average crack propagation rate and oxidation (dissolution and oxide
growth) kinetics on a straining surface for several ductile alloy/aqueous environment systems known to be
susceptible to SCC (source Parkins, 1979a).
influence of various loadings, environmental
and metallurgical variables on EAC have been
developed (Scully, 1980; Parkins, 1972, 1979a;
Ford, 1982). In general, if the repassivation is
too fast, no significant amount of dissolution
can occur, and if the repassivation rate is too
slow, chemical blunting of a crack is expected
to occur. The problems with dissolution
mechanisms are related mainly to transgranu-
lar SCC, where fracture surfaces are crystal-
lographically oriented and flat, matching
precisely on the opposite sides of the fracture
surfaces and indicating very little dissolution
during the crack growth. In many systems
transgranular SCC is discontinuous. Therefore,
film rupture/anodic dissolution models have
generally been accepted as viable mechanisms
of intergranular SCC in some systems (e.g.,
ferritic steels in carbonate–bicarbonate solu-
tions, or sensitized austenitic stainless steels in
high-temperature water), but are not generally
accepted as mechanisms of transgranular SCC
(Pugh, 1985).
A (semi-)quantitative explanation for EAC
in the low-alloy steel/high-temperature water
system has been formulated by Ford and
Emigh (1985). They calculated the maximum
theoretical environmental enhancement in
crack growth, which may be expected under
specific combinations of alloy, environment,
and loading conditions. In the slip-dissolution
model, crack growth occurs by oxide rupture at
the tip of the crack due to an increase of strain
in the underlying matrix or slip step emergence
(repeated rupture is caused by fatigue, or
creep-strain-induced rupture is caused by
sustained loading). In order to maintain a
sharp crack, the sides of the crack must be
passivated, even though the crack tip is in an
active condition. The crack growth rate is
related, by Faraday’s equation, to the oxida-
tion rate on the bared surface including both
dissolution and oxide growth. The environ-
ment-assisted component of the crack growth
is reinitiated by a further increment of matrix
strain, which ruptures the crack tip oxide again
after a time period, tf ð¼ ef =’ect Þ; where ef is the
fracture strain of the oxide and e’ct is the strain
rate in the metal matrix at the crack tip
affected by mechanical loading, creep rate,
and a contribution to the strain rate related to
the crack advance itself. The environment-
sensitive component of the time-dependent
crack growth, Vt, can then be represented by
M Qf
Vt ¼ e’ct ð1Þ
nrF ef
where M and r are, respectively, the atomic
weight and density values for the crack tip
metal, F is Faraday’s constant, and n is the
number of electrons/mol involved in the overall
oxidation process and Qf is the oxidation
charge density passed between oxide rupture
 SCC Mechanisms
events. Strong support for the slip-dissolution
model comes from the observation that crack
growth rates of many different alloy/environ-
ment systems are in direct proportion to the
experimentally determined dissolution rates
measured on straining electrodes (with a
continuous supply of bared metal surface due
to film rupture) under the mechanical and
chemical conditions expected at the crack tip,
Figure 3. Since the data cover a wide range of
systems and over three orders of magnitude in
crack growth rate, it has been thought that the
slip-dissolution model has a rather wide
applicability.
In various SCC studies, it has been observed
that the strain rate at the crack tip is a critical
parameter (Parkins, 1972, 1979b). Crack tip
strain rate generally includes both a time-
dependent component (creep strain rate) and a
time-independent component. A more general
approach would consider the total strain rate
with the specimen geometry and type of
loading. Estimates of crack tip strain distribu-
7
tions based on linear elastic fracture mechanics
both for static and dynamic cracks have been
presented, and they are summarized by Ger-
berich and Chen (1990) and Ford (1990).
At the crack tip, a dynamic equilibrium
between the continued creation of bared sur-
face and passivation occurs, Figure 4. Crack
growth may be produced either by emission of
dislocations from the crack tip or egress of
dislocations at the crack tip. However, the
probability of dislocations nucleated from
near-surface sources exactly intersecting the
crack tip is low and dislocation activity on slip
planes not intersecting the crack tip would
produce general strain and extensive crack tip
blunting (Lynch, 1983). Therefore the slip-
dissolution may only operate by emission of
dislocations from the crack tip.
Figure 5(a) shows schematically the envir-
onmentally enhanced crack growth in the low-
alloy steel/high-temperature water system,
when it is purely governed by a film rupture/
slip-dissolution model. In addition to the crack

Figure 4 Illustration of the factors of importance in the constant-charge criterion for SCC crack
propagation. Propagation will occur in the statically loaded case only if a dislocation source is activated by
the stress increment, Ds, caused by the crack advance, Lmin, at the crack tip. This latter amount will be a
function of the charge density increments caused by the individual oxide rupture events at the crack tip, the
periodicity between their occurrence, t1, and time, t2, during which plasticity is occurring (source Ford, 1982;
reproduced by permission of EPRI).
8 Stress Corrosion Cracking

Figure 5 Schematic variation of oxidation charge density and, hence, penetration with time following oxide
rupture at strained crack tip (a) and penetration with time following oxide rupture, where crack advance due
to environmentally assisted cleavage, an, acts in addition to that associated with oxidation of the bare metal
(b). Note the importance of periodicity of oxide rupture (ef =’ect ), and of oxidation rate on crack sides (Vs) in
maintaining propagation of a sharp crack (Vt) (source Ford and Emigh, 1985).

growth due to oxidation, an extra mechanical
component of crack growth can be included,
e.g., according to a concept (originally devel-
oped for Cu alloys in tarnishing conditions and
not associated with absorbed hydrogen as may
be the case here) of Sieradzki and Newman
(1985), associated with a rapid fracture of
crack tip oxide and penetration of this ‘‘clea-
vage’’ crack into the underlying ductile matrix.
Figure 5(b) shows schematically the effect of
this additional cleavage component, an, on the
crack growth. The extent of this component is
believed to be in the range of 0.1–1 mm for
ductile alloys (for low-alloy steel a value of
0.1 mm was used). When the measured oxida-
tion rate transients are used to produce the
oxidation charge density/time relationships
shown schematically in Figure 5(a), the theo-
retical crack growth rate/crack tip strain rate
relationships for the film rupture/slip-dissolu-
tion model are obtained. Figure 6 shows the
results for two different crack tip conditions
(low- and high-sulfur conditions). A e’nct power-
law relationship for crack growth rate is
predicted with limitations at high and low
strain rates. At crack tip strain rates
410
2 s
1, the crack growth rate is limited by
the dissolution rate on a continuously bared
surface, whereas at low strain rates a limit is set
by the criterion that the crack tip must
propagate faster (Vt) than the dissolution rate
on the adjacent crack sides (Vs), if a sharp
crack is to be maintained. In Figure 6 three Vt/
Vs ratios of 1, 5, and 10 are shown. Ford and
Emigh (1985) assumed that the crack blunting
will become dominant if the Vt/Vs ratio is less
than 5. Also, an example of theoretical crack
growth rate/crack tip strain rate relationship
for the situation where crack growth occurs by
the above-mentioned cleavage model is shown
in Figure 5(b) in which the crack grows
discontinuously a distance, an ( ¼ 0.1 mm),
every (ef =’ect ) seconds. The chosen an value is
arbitrary, and if, e.g., the fractographically
observed typical brittle striation spacings, 1–
5 mm, are equated to the cleavage events, the
EAC crack growth rates would increase
correspondingly. Ford and Emigh (1985) came
to the main conclusion that the film-rupture/
slip-dissolution model predicts a Vt vs. e’nct
relationship (n ¼ 0.3–0.5, obtained from bared
surface dissolution current decay experiments)
with the constants in that relationship depend-
ing on the localized conditions at the crack tip
(e.g., sulfur concentration). Alternatively, the
environmentally enhanced cleavage model
would predict a Vt vs. e’1:0 ct relationship with
an undefined effect of crack tip conditions on
the relationship constants.
The film rupture/anodic or slip-dissolution
mechanism presented above is based on a
simplified behavior of slip at the crack tip. A
 SCC Mechanisms 9

Figure 6 Theoretical crack growth rate/crack tip strain rate relationships for low-alloy steel in stagnant
deaerated water at 2881C, in which either 1.16  10 ppm or o0.5 ppm sulfur is created and maintained in
crack tip enclave. In addition to the predictions of the film rupture/slip-dissolution model, those of an
environmentally assisted cleavage model are also shown, in which it is assumed that the cleavage distance is
0.1 mm (source Ford and Emigh, 1985).

more careful analysis of slip would indicate
that this kind of situation with alternating slip
step dissolution would result in a fissure rather
than a tight crack (Cullen et al., 1985). Also the
chosen dissolution anisotropy values, 5 and 10,
are very small for sustaining a tight stress
corrosion crack. Thus, much more anisotropic
dissolution would be needed for this mechan-
ism to occur and be able to explain the brittle,
cleavage-like fracture surface morphology in
transgranular SCC. The above model has
especially been used for quantitative prediction
of crack growth of intergranular SCC of
sensitized stainless steels in high-temperature
water using for the crack growth rate a power
law relationship:
da
Vt ¼ ¼ A’enct ; ð2Þ
dt
where A and n are constants that depend on the
material and environment composition at the
crack tip and are related to the oxidation
reaction rates, or current densities. The model
is specifically able to predict the crack growth
rate of sensitized stainless steels in high-
temperature water obtained in different types
of the tests as well as the effects of corrosion
potential on cracking (Ford et al., 1987;
Andresen, 1992; Ford and Andresen, 1995).
6.01.3.2 Hydrogen-assisted Cracking
Mechanisms
At the crack tip, conditions of potential, pH,
and anion content are such that both slip-
dissolution and hydrogen-assisted cracking
mechanisms are thermodynamically and kine-
tically viable in most of the systems where SCC
takes place. The crack tip conditions are often
created by the formation of an occluded
corrosion cell inside the crack (e.g., oxygenated
at the crack mouth and deoxygenated at the
crack tip). The crack tip chemistry may be
largely modified by the dissolution of metalloid
inclusions (e.g., dissolution of MnS that
produces H2S and HS- species) and precipitates
or segregations in the small volume of solution
at the crack tip. Both mechanisms are depen-
dent on oxide rupture, passivation, and liquid
diffusion rates, since these factors affect the
charge transfer per unit time in the slip-
dissolution model and the hydrogen adatom
coverage and hydrogen evolution rate in
hydrogen-assisted cracking models. The oxide
rupture event was used as the rate-determining
step in the slip-dissolution mechanism. This
same event is naturally very important in
hydrogen-assisted cracking models, since it
affects directly hydrogen entry into the metal.
In the case of HE, numerous other rate-
determining parameters are also possible,
depending on the exact mechanism considered.
Therefore, calculations of the maximum crack
growth rate (as presented above for the slip-
dissolution model) based on hydrogen-assisted
cracking models have been hampered by lack
of quantitative knowledge of events such as
hydrogen coverage at the crack tip, hydrogen
diffusion ahead of the crack and possible
dislocation transport phenomena including
trapping and subsequent diffusion away from
10 Stress Corrosion Cracking
the supersaturated sites, as well as specific
details of the dislocation activity and inter-
atomic rupture event.
In the following, hydrogen interactions in
metals, i.e., hydrogen-assisted fracture pro-
cesses and hydrogen transport are briefly
summarized with reference to possible mechan-
isms of EAC of metals (see also Chapters 6.02
and 6.03).
6.01.3.2.1 Decohesion mechanism
The oldest of the HE mechanisms is the
hydrogen-enhanced decohesion (HEDE) me-
chanism, which proposes that high, localized
concentrations of hydrogen can weaken the
interatomic cohesive forces at or ahead of
crack tips. As a result, tensile separation of
atoms (decohesion) occurs in preference to slip
(Troiano, 1960; Oriani, 1972; Gerberich and
Chen, 1975). In this mechanism, hydrogen is
thought to accumulate at regions of high
triaxial stress ahead of the crack tip at a
distance of about twice the crack tip opening
displacement (CTOD). High concentrations of
hydrogen can occur also within a few atomic
distances of crack tips or at several tens of
nanometers ahead of cracks where dislocation
shielding effects result in higher stress. When
sufficiently large local hydrogen concentrations
over some critical length are formed, the bond
strength between metal atoms can be weakened
by hydrogen effects on electron-charge density.
Crack growth can then occur along cleavage
planes or intergranularly along grain bound-
aries weakened by segregation of metalloid
impurities, or by separation of particle–matrix
interfaces. Decohesion mechanism can also be
thought as a continuous crack growth by bond
rupture at the crack tip. Hydrogen-enhanced
bond rupture occurring ahead of the crack tip
at stress concentration points produces micro-
cracks, which then link up with the main crack,
possibly with some degree of plastic tearing of
ligaments, giving rise to discontinuous crack
growth. Otherwise, the HEDE mechanism
should produce atomistically flat fracture
surfaces because of limited dislocation activity.
6.01.3.2.2 Deformation mechanism
Hydrogen can reduce the local stress re-
quired for dislocation motion (Beachem, 1972).
This can cause localized softening due to solute
hydrogen, which has been explained to occur
by the presence of hydrogen atmospheres
around both mobile dislocations and obstacles
in the plastic zone ahead of the cracks. These
hydrogen atmospheres are thought to shield
dislocations from repulsive interactions by
their rapid reconfiguration in response to
changing elastic stress fields. This phenomenon
is now called the HELP mechanism. The
HELP mechanism has been supported by
direct in situ high-voltage transmission electron
microscopy (HVEM) observations, which
show increases in dislocation (edge, screw,
and mixed dislocations) activity (velocity and
dislocation source operation), when hydrogen
is present, and extremely localized crack tip
plasticity (Birnbaum, 1990; Birnbaum and
Sofronis, 1994; Birnbaum et al., 1997a,
1997b; Ferreira et al., 1998). The dislocation
spacings in the pile-ups and the extent of cross-
slip were also observed to decrease. The thin
foil observations supporting the HELP me-
chanism have been criticized, since other effects
such as generation of stresses due to nonuni-
form hydrogen distributions and reduction of
oxide films may affect the dislocation activity.
In bulk specimens, decrease of flow stress
(softening) and strain localization have some-
times been observed, but hardening is observed
more often than softening. The operation of
this mechanism can result in lower stress
intensity for crack growth, but it has not been
possible to prove that HELP is responsible for
HE in bulk specimens (in plane-strain condi-
tions). The HELP mechanism can operate only
in temperature and strain rate regimes where
hydrogen atmospheres can keep up with the
dislocations. In nickel base alloys, e.g., this is
possible between –80 and þ 2001C. At lower
temperatures, hydrogen diffusivity would be
too slow and at higher temperatures the
Cottrell atmospheres of hydrogen will evapo-
rate (Smuk et al., 1999). The effective upper
temperature for ferritic steels is similar to that
of nickel alloys. For more brittle cracking the
role of a reduced flow stress is not as apparent,
unless the effect is related to hydrogen trans-
port in the vicinity of the crack tip. At present
no detailed mechanism of how HELP results in
brittle cleavage-like fracture has been pro-
posed. It has also been recognized that any
reduction in interatomic cohesion will also
reduce the shear stress necessary to move
dislocations. Thus, the decohesion and defor-
mation mechanisms are difficult to test unequi-
vocally since cracking can be formulated in
terms of reduced normal stress across the
lattice planes or in terms of reduced shear
stress for flow.
For intergranular SCC of Ni–Cr–Fe alloys
in high-temperature water, Hall and Symons
(2001) have developed a phenomenological
hydrogen-assisted creep fracture (HACF)
model based on hydrogen embrittled grain
boundaries.
 SCC Mechanisms
6.01.3.2.3 Adsorption mechanism
Adsorbed hydrogen lowers the surface en-
ergy of the metal and, according to the Griffith
criterion for crack growth, facilitates crack
growth at a lower fracture stress level (Petch,
1956). Plasticity effects were not addressed in
the early development of this mechanism,
which reduces it to a special case of the
decohesion mechanism, when the crack growth
is reversible (Oriani, 1972). The adsorption-
induced surface energy reduction may, how-
ever, be very important in internal interfaces
(particle/matrix interfaces and segregated grain
boundaries), where it affects interface separa-
tion, hydrogen recombination, and interaction
with other locally accumulated species such as
sulfur (Rice, 1976).
Lynch (1979, 1983, 1988, 1997, 2002) has
proposed that hydrogen adsorption at the
crack tip (i.e., hydrogen on the surface and in
the first few atomic layers) weakens the
interatomic bonds, which results in dislocation
emission from the crack tip. Dislocation
emission from the crack tips always produces
crack advance opposite to the operation of
dislocation sources near the crack tips, which
causes only blunting of the crack since
dislocation egress occurs also behind the crack
tip. This mechanism is called adsorption-
induced dislocation emission (AIDE). Crack
growth due to AIDE occurs primarily by
alternate slip at crack tips with contributions
from general plasticity and void formation
ahead of the cracks. Void formation ahead of
the cracks also resharpens the crack tips
keeping the crack opening angle small. Frac-
ture surfaces are macroscopically parallel to
low-index crystallographic planes (bisecting the
angle between the slip planes of {111} or {112}
in f.c.c. and b.c.c. metals, respectively). This
would result in crack fronts parallel to /110S
directions on {100} planes, which is normally
observed, e.g., in cleavage-like fracture surfaces
of single crystals of nickel and iron–silicon.
The AIDE mechanism is also supported by the
high crack-growth velocities observed in nickel
and nickel-based superalloys in gaseous hydro-
gen, where hydrogen diffusivities are low. In
these cases, hydrogen diffusion ahead of the
crack can be precluded. Possible dislocation
transport of hydrogen also cannot result in
hydrogen atmospheres around other disloca-
tions and obstacles directly ahead of the crack
tip. Close similarities between LME, where
only adsorption can take place, and HE also
support the AIDE mechanism. In addition,
observations of immediate inhibition of crack
growth in Fe–Si single crystals by addition of
oxygen to gaseous hydrogen suggest that
11
cracking is due to a surface or very-near-
surface effect. Unresolved questions related to
AIDE are the often observed discontinuous
crack growth behavior in a number of systems
and the necessary further effect on dislocation
motion in the metal.
6.01.3.2.4 Hydrogen pressure mechanism
Formation of high-pressure molecular hy-
drogen within the metal in internal voids and
cracks has been proposed to exert an internal
stress which lowers the apparent fracture stress
(Zapffe and Sims, 1941). This mechanism is not
thought to be a general one, since brittle crack
growth can occur under hydrogen partial
pressures well below 1 atm (Hirth and Johnson,
1976). However, if hydrogen transport by
mobile dislocations is a major component of
the fracture process, then significant quantities
of hydrogen can be transported to some sites in
the metal, leading to development of a
localized, nonequilibrium, high fugacity of
hydrogen. Even though the rapid transport of
hydrogen by dislocations can occur, it would
probably not concentrate hydrogen along
planes or at particles directly ahead of the
crack tip plane, but along the slip planes
deviating from the fracture plane. Significant
internal hydrogen pressures (of the order of
105 bar) can affect ductile fracture behavior,
e.g., through their effect on void growth rate.
Therefore, the brittle, cleavage-like fracture
mode cannot be explained by this model.
6.01.3.2.5 Brittle hydride mechanism
For hydride-forming materials, such as zirco-
nium, niobium, and magnesium (Chapter 6.03),
it has been well established that HE can occur
by repeated formation and fracture of brittle
hydrides in the stress fields at the crack tips
(Birnbaum, 1979, 1990). The hydride mechan-
ism occurs only in the temperature and strain
rate range where hydrogen has time to diffuse to
the crack tips and at temperatures where the
hydride phase is stable. Brittle hydride mechan-
ism in HE has been considered to be possible in
Ni, Pd, Mg, Ti, Zr, and their alloys as well as in
the group Vb metals (Nb, V, Ta), since stable
hydrides have not in general been identified in
connection with cracking. Fujita (1977) has,
however, proposed that hydrogen in iron
accumulates into plate-shaped clusters in a
way which is enhanced by stress. Clustering
occurs most readily under high triaxial stress.
The hydrogen platelets are unstable and are
therefore difficult to observe experimentally
and, as of early 2000s, there has been no
experimental evidence for this mechanism.
12 Stress Corrosion Cracking
6.01.3.2.6 Vacancy mechanisms
The increase in vacancy concentration in the
presence of hydrogen has recently been re-
vealed experimentally in many f.c.c. and b.c.c.
metals and their alloys, including various steels
(Iwamoto and Fukai, 1999; Birnbaum et al.,
1997a, 1997b, Nagumo et al., 2001). The excess
vacancies formed due to hydrogen and plastic
deformation can be stabilized by formation of
vacancy–solute complexes with hydrogen. The
condensation of excess vacancies can lead to
the formation of microvoids, which may also
promote local shear instability, i.e., shear
localization due to void formation. Excess
vacancies may play an important role in the
HELP mechanism, where they can facilitate
dislocation climb around obstacles; in this way
vacancies, instead of hydrogen, enhance the
localized plasticity. Nagumo et al. (2001) have
formulated a vacancy agglomeration model for
HE where formation and stabilization of large
vacancy clusters having high hydrogen binding
energies are considered to play the primary role
in HE of high-strength steels due to microvoid
formation. Thus, this mechanism will result in
shear instability and more or less ductile
cracking inside the shear bands, except when
the vacancy generation takes place at the crack
tip that facilitates dislocation emission at that
location.
6.01.3.2.7 Summary
Hydrogen may play an important role in the
SCC of steels, aluminum, titanium, magne-
sium, nickel as well as intermetallic alloys when
hydrogen can be generated at crack tips. As
shown above, there is some dispute as to the
location of the critical region of hydrogen
damage and none of the hydrogen cracking
mechanisms is sufficiently general to be used
quantitatively for particular cases of EAC in a
way similar to the slip-dissolution mechanism.
Moreover, an examination of the proposed
mechanisms suggests that hydrogen can exhibit
many effects on fracture behavior and the
different proposed mechanisms may operate
simultaneously. For example, AIDE predomi-
nates for cleavage-like transgranular and
dimpled intergranular fractures, HEDE pre-
dominates for brittle intergranular fractures,
and HELP may contribute especially for shear
band fractures.
6.01.3.3 Adsorption Mechanisms
Adsorption of surface-active species other
than hydrogen has been proposed to reduce the
fracture stress in various embrittlement phe-
nomena. In adsorption-related mechanisms,
the influence of adsorption is limited to one
or two atomic distances from the surface of the
metal. Adsorption can thus only influence the
tensile strength (s) and the shear strength (t) of
the interatomic bonds at the crack tip, Figure
7. A crack can grow rapidly by cleavage or
slowly by slip, depending on whether the
tensile fracture stress for the interatomic bond
or the shear stress to cause slip in a favorable
slip system is achieved first. Hence, as the ratio
s/t decreases, cleavage becomes more probable
and, conversely, shear failure becomes more
likely as the ratio increases (Westwood et al.,
1967). Hence, this criterion is inapplicable in
cases where ductile and ‘‘brittle’’ fracture
occurs by slip and the distribution of slip
around the crack tip determines the fracture
behavior.
Adsorption can promote crack growth by
facilitating tensile-decohesion as stated earlier
for the case of hydrogen, when chemisorption
of an environmental species on the crack tip
reduces the surface energy term, gs, in the
equilibrium Griffith relationship and thereby
reduces the local fracture stress of the metal
lattice. Such an argument has been used for
HE, LME, and for the effects of specific anions
in aqueous solutions, where the adsorbed atom
coverage is dependent on the electrode poten-
tial (Uhlig, 1979). However, in ductile materials
the plastic work will be at least an order of
magnitude greater than the surface energy.
Therefore, adsorption is best discussed in terms
of its effects on interatomic bond strengths
rather than in terms of its effects on surface
energy. Lynch (1983, 2002) explains that
adsorption reduces the shear strength of
interatomic bonds and thereby facilitates nu-
cleation of dislocations at crack tips, although
the mechanism by which this occurs is unclear.
Theoretical shear strengths for ductile materials
Figure 7 Environment/metal interaction model
(source Westwood et al., 1967; Figure reprinted by
permission of ASM International).
 SCC Mechanisms
are much lower than theoretical tensile
strengths and, hence, adsorption-induced crack
growth probably involves dislocation emission
rather than tensile decohesion. Inhibition of
dislocation nucleation by adsorption would
lead to crack growth by tensile-decohesion
rather than slip, but would probably not
produce subcritical crack growth. Surface layer
effects on the mechanical behavior of metals
(relaxation of surface layer stresses, plastic
deformation, strain hardening, yield point
phenomena, ductility, fatigue, creep, and
SCC) have been reviewed in detail by Kramer
(1983).
Lynch (1979) has proposed a CF fracture
mechanism where chemisorption of environ-
mental species intensifies localized slip at the
crack tip instead of over a more generalized
slip field, which results in the extensive blunting
observed in the absence of the environment,
Figure 8. The crack growth occurs by slip
process at the crack tip only on planes
intersecting the crack tip. In fatigue, during
unloading, slip occurs behind the crack tip so
that part of the fracture surface produced
during the previous loading is deformed by
reverse slip and the crack tips are resharpened.
Slip during unloading generally concentrates
just behind the crack tip with less deformation
farther from the crack tip. Ductile striations
are produced in a manner similar to brittle
striations. The difference in spacing and profile
of the two types of striations arises because the
extent of blunting during loading differs: the
blunter crack tip profile produced in inert
environments concentrates slip just behind the
crack tip to a greater extent during unloading.
The detailed appearance of striations depends
13
on a variety of factors (e.g., R-ratio, DK,
orientation of slip planes with respect to crack
plane, ease of dislocation egress at fracture
surfaces, etc.). Environment affects dislocation
egress, which explains why well-defined stria-
tions are sometimes not observed since oxide
films, e.g., can impede dislocation egress. In the
case of fatigue, sharp cracks can propagate
along crystallographic planes. However, in a
tension test (e.g., SSRT test), this mechanism
necessarily leads to crack blunting. Lynch
(1979) also proposed that to a large extent
crack growth in inert environments probably
occurs by egress of dislocations at crack tips,
while in embrittling environments cracks prob-
ably grow predominantly by nucleation and
movement of dislocations from the crack tips.
In aqueous environments where oxide films are
forming at crack tips, chemisorption on the
metal surface cannot occur, and rupture of the
oxide film is necessary before crack growth
promoted by chemisorption is possible. Thus,
cracking can be discontinuous because compet-
ing reactions (such as repassivation) tempora-
rily prevent adsorption and cause crack arrest.
Here chemisorption is the rate-limiting step
and the degree of embrittlement is a function of
surface coverage of adsorbed species.
There are also SCC systems where hydrogen
adsorption/absorption are unlikely to be in-
volved, but other adsorbed species may possi-
bly weaken the interatomic bonds at crack tips
and thereby facilitate dislocation emission or
decohesion. Adsorption mechanisms may be
possible during, e.g., SCC of zirconium alloys
in iodine vapor and of titanium alloys in
carbon tetrachloride, where interactions other
than adsorption of halogens seem unlikely.

Figure 8 Schematic illustrations of fatigue crack growth mechanism and formation of striations in: (a)
embrittling environments and (b) inert environments. Nucleation and growth of microvoids and cracks ahead
of the main crack tip in the highly strained (shaded) areas occur during loading in many cases (source Lynch,
1979; Copyright ASTM International. Reprinted with permission).
14 Stress Corrosion Cracking
Fracture surfaces consist of cleavage-like,
intergranular, and fluted transgranular areas
similar to those observed in SCC of titanium
alloys in aqueous environments or due to LME
in mercury, where adsorption of hydrogen or
metal atoms, respectively, is most probably
responsible (Lynch, 2002).
6.01.3.4 Film-induced Cleavage Mechanism
Originally, film-induced cleavage was ob-
served after surface dezincification of a-brass in
ammonia, where dealloying and vacancy injec-
tion induce brittle fracture through several
micrometers in the unattacked substrate
(Forty, 1959). This observation was later
confirmed by Pugh (1985). Subsequently, it
was proposed that brittle fracture of the
surface film could induce cleavage fracture in
the substrate. After the brittle film has cracked,
the crack passes the film/matrix interface
without losing its velocity and continues to
propagate in a brittle manner in the ductile
matrix until finally the crack blunts and arrests,
after which the process repeats itself (Sieradzki
and Newman, 1985). Thus, with this model it is
possible to explain crack arrest markings, the
cleavage-like fracture surface and discontinu-
ous crack growth. The hypothesis that a brittle
crack can propagate after it has entered the
ductile defect-free matrix over distances much
greater than the film thickness is the major
problem of this model. Nanoporous metallic
layers produced by dealloying seem to be very
effective in triggering a crack with high velocity
into the matrix. These layers are both brittle
Figure 9 A schematic picture of the concepts underlying the enhanced surface mobility model for SCC
(source Galvele, 1995; reproduced by permission of Kluwer Academic Press).
and epitaxial and very strongly bonded to the
matrix. In addition to Cu-rich sponge films on
a-brass, Ni-rich films may form on Fe–Cr–Ni
alloys by active selective dissolution. Intergra-
nular fracture can also be generated by deal-
loyed layers in certain gold alloys (Au–Cu and
Au–Ag). This model needs special conditions
to be operative and has not been proven to
operate with more common oxide films. The
fracture surfaces suggest that cracking may still
occur by slip. Cleavage in ductile materials is
not expected to be possible.
6.01.3.5 Surface Mobility Mechanism
The surface mobility model of Galvele (1995)
is based on the transport of the atoms (possibly
combined with ions or molecules from the
environment) from the crack tip by surface
diffusion from their high-stress locations to new
sites on the less-stressed crack sides of the
advancing crack; thus, the crack advances by
one atom spacing after each movement, Figure
9. Crack growth results from the capture of
vacancies by the stressed lattice at the crack tip.
The crack growth rate is controlled by the
movement of adatoms on the fracture surfaces.
Adatoms are removed later by dissolution or by
surface vacancies. Environment can affect the
surface diffusion rate by consumption of the
adatoms or through the effect of surface films/
compounds on surface diffusivity. A predictive
equation for crack growth rate as a function of
the surface self-diffusion coefficient, the char-
acteristic diffusion length, the volume of a
vacancy, the elastic surface stress at the crack
 SCC Environments
tip and temperature has been proposed. The
model has been applied both to SCC and LME
and seems to have some predictive power even
though the treatment of the diffusion process is
greatly simplified.
6.01.3.6 Selective Dissolution (Dealloying)—
Vacancy Creep Mechanism
The role of vacancies in the mechanism of
EAC has been recognized as important
through various observations. It is proposed
that active dissolution of the metal surface in
acidic environment (Pickering and Wagner,
1967), selective dissolution of the alloy surface
(Sieradzki and Newman, 1985), growth of the
passivating oxide film (McDonald, 1992), and
hydrogen absorption to the metal (Birnbaum
et al., 1997a, 1997b) are accompanied by
vacancy generation in the surface layer of the
metal. Continuous generation of vacancies can
cause changes in dislocation behavior contri-
buting to deformation of the metal, i.e., creep
properties have been observed to change
(Revie and Uhlig, 1974). In the case of
externally unstressed materials, deformation
as indicated by deflection, has been observed
(Jaenicke et al., 1964) during one-sided oxida-
tion experiments with thin strip specimens.
Selective anodic dissolution of Zn in brass
exposed to tap water was shown to supply
excessive amounts of vacancies to the substrate
(Aaltonen et al., 1998a, 1998b). In a bimetallic
sample made of silver deposited with copper,
diffusion at the Cu/Ag interface has been
observed when the copper side was subjected
to anodic dissolution in 1N H2SO4 solution
(Jones, 1985). These observations have encour-
aged a more detailed study of the role
vacancies in SCC systems where dealloying
and selective oxidation occur during oxide film
growth processes.
Selective dissolution—vacancy creep (SDVC)
model has been proposed for Inconel alloy 600
in high-temperature water conditions (Aalto-
nen et al., 1996). The model was based on the
idea that vacancies are injected into the metal as
a result of the oxidation process and that their
accumulation in the near-surface layers and
subsequent diffusion in the bulk causes sig-
nificant changes in the defect structure of the
bulk metal. Vacancies can interact with dis-
locations in the plastic zone, enhancing plastic
flow locally at the crack tip, which can facilitate
cracking by localized shear. Vacancy clustering
leads to void formation ahead of the crack tip,
which also enhances localized shear instability.
This is expected to lead to passive film break-
down at the crack tip and repeated selective
dissolution, vacancy injection, and localized
15
deformation. The cation vacancies forming at
the film/solution interface are thought to be
transported through the oxide film to the film/
metal interface, where they are injected into the
metal lattice and interact with existing disloca-
tions. Further development of this model was
based on the observations during the oxidation
of pure copper, where it was shown that
continuous deformation occurred in the under-
lying metal matrix. This is now considered to
occur by vacancy-enhanced dislocation source
operation at the interface of the film and the
substrate, e.g., by Bardeen–Herring mechan-
ism. Thus, vacancy production at the crack tip
due to oxidation can be compared to the earlier
AIDE process and hydrogen-induced vacancy
stabilization phenomenon. Vacancy production
in metals and continuous plastic deformation of
thin samples during one-sided oxidation has
been confirmed in recent studies of copper in
conditions causing SCC (Aaltonen et al., 1998a,
1998b, 2002). However, more work is needed to
explain the brittle, cleavage-like fractography
and the rapid fracture after dealloying even in
the absence of environment and also discontin-
uous cracking.
6.01.4 SCC ENVIRONMENTS
The type of loading, materials, and environ-
ments that cause SCC are quite well defined. In
the following, a short summary of the most
common material–environment systems is gi-
ven where SCC occurs. Also, the electroche-
mical, metallurgical, and mechanical
conditions for SCC to occur are outlined and
the present mechanistic understanding is sum-
marized.
6.01.4.1 Carbon and Low-alloy Steels
Carbon and low-alloy steels (ferritic-pearlitic
and quenched and tempered steels) exhibit
SCC in hot nitrate, hydroxide, ammonia,
alkanol amine, chloride, and carbonate–bicar-
bonate solutions, where cracking typically is
intergranular along prior austenite grain
boundaries. Transgranular cracking occurs in
high-temperature water and in environments
containing H2S, and in H2. The strength level
(hardness) of the steel has the greatest influence
on SCC resistance; in general, the resistance
decreases as strength increases in various
environments. The effect of steel composition
has been studied extensively (e.g., Carter and
Hyatt, 1977; Giraldi, 1992), but practical
situations are usually complex because compo-
sition can greatly influence heat-treatment
response, strength, and welding properties that
also affect SCC.
16 Stress Corrosion Cracking
For ferritic carbon and low-alloy steels, it is
instructive to consider the locations of the
potential-pH value domains for cracking in
different known SCC systems in the range of
environments and temperatures between 201C
and 2881C, Figure 10. The SCC domains
together with the calculated equilibrium po-
tentials for reactions between Fe2O3 and
Fe3O4, between Fe3O4 and Fe, as well as for
hydrogen discharge at 901C (an average
temperature for several different systems) are
presented. Each SCC domain is associated with
the calculated Fe3O4/Fe2O3 line and in all these
systems Fe3O4 is observed to form under
conditions where SCC occurs. SCC can also
be associated with other phases such as FeCO3
in carbonate–bicarbonate solutions and
Fe3(PO4)2 in phosphate solutions. At high
potentials, where Fe2O3 forms alone, cracking
is generally ductile in SSRT tests. However, in
this respect, the nitrate environment and high-
temperature water are exceptions. In these two
systems, cracks initiate from corrosion pits and
within the pits Fe3O4 forms despite the external
surfaces being covered by Fe2O3 films. There is
usually a correlation between crack initiation
and the pitting corrosion potential when
cracking occurs from pits. Inside the pits and
cracks marked changes in environment and
potential may occur, but there are also systems
where these changes are small (Parkins, 1990).
SCC of carbon and low-alloy steels in
aqueous chloride, ammonia, hydrogen sulfide,
sulfuric acid, and hydrogen gas environments
has generally been rationalized in terms of HE
mechanisms, because additives known to pro-
mote hydrogen entry into the steel accelerate
SCC. In nitrates, an active path type of anodic
Figure 10 Potential and pH value ranges for SCC of ferritic steels in various environments, together with the
pH-value-dependent equilibrium potentials for reactions involving Fe, Fe2O3, Fe3O4, and H/H þ (source
Congleton et al., 1985).
dissolution mechanism is generally proposed
for cracking. Similarly, in hydroxide and
carbonate solutions, cracking occurs only
within a very narrow electrochemical potential
range close to active current peak, where steel
surface is considered to be partially covered by
a protective magnetite film. Cracking is also
generally thought to occur through an anodic
dissolution mechanism in high-temperature
water, although there has been no conclusive
evidence.
6.01.4.2 High-strength Steels
In high-strength steels (hardness 440 HRC)
susceptibility to intergranular SCC is particu-
larly prevalent. Environments that normally
cause minimal corrosion, even moist air,
promote SCC in these steels. Most commonly,
environments promoting SCC contain chlor-
ide. HE is generally accepted to be the
predominant SCC mechanism in these cases
(e.g., Kerns et al., 1977; Marsh and Gerberich,
1992), since cathodic polarization has only a
minor effect on SCC susceptibility (as deduced
from KI SCC measurements), but at higher
loading a strong influence on crack growth
rate is generally observed. The most harmful
environments are those containing cathodic
poisons, such as As, Se, Te, and S, which
prevent hydrogen recombination to molecular
hydrogen and, thus, increase hydrogen absorp-
tion by the steel. The most common cathodic
poison in practice is H2S. Other anions
promoting SCC are phosphate, sulfate, and
nitrate. High-strength steels are also suscepti-
ble to SCC in organic compounds. Any
environment capable of producing hydrogen
 SCC Environments
by any chemical reaction may cause SCC in
high-strength steels.
The kinetics of SCC in hydrogen gas differs
at low temperatures from that at high tem-
peratures, exhibiting a maximum susceptibility
temperature, which is dependent on the
strength level of the steel. Increase of the
strength level promotes higher crack growth
rates and causes a shift of maximum crack
growth rate to a higher temperature. The
behavior is, however, often considerably dif-
ferent in aqueous solutions compared to that in
gaseous hydrogen. Below the maximum crack
growth rate temperature, an Arrhenius rela-
tionship is observed for the crack growth rate
in aqueous environments (apparent activation
enthalpy 33–38 kJ mol
1). The rate-controlling
step may be the effective hydrogen diffusion in
the bulk metal including the binding energy,
e.g., to dislocations or the iron oxide formation
including generation of hydrogen on the sur-
face. At higher temperatures, the rate-control-
ling process has also been thought to be
associated with surface reactions or the binding
energy related to collection of hydrogen at the
crack nucleation sites. In hydrogen gas envir-
onments, the crack growth rate temperature
dependence of high-strength steels in apparent
activation energy values are much lower
(6–8 kJ mol
1), i.e., close to that of the true
lattice diffusivity of hydrogen in iron.
The HE-susceptible steels include high yield
strength quenched and tempered, ausformed,
cold-worked fine pearlite and maraging steels.
In general, maraging steels have better SCC
resistance than other types of steels on the
same strength level. Quenched and tempered
steels are especially prone to temper embrittle-
ment due to impurity elements (Sb, Sn, As, and
P) segregation to grain boundaries, but also the
overall composition of the steel is very
important. Thus, in the case of intergranular
cracking, the compositional variations and
reactions at grain boundaries are important
as well as the grain size. The better SCC
resistance of maraging steels cannot be ex-
plained in terms of general corrosion resistance
and, therefore, hydrogen trapping behavior is
probably the key factor. Decreased trapping
leads to a decrease in hydrogen buildup for
embrittlement. This can be achieved by refined
microstructures containing fine martensite
structures, finer carbides and increased disloca-
tion densities obtained, e.g., by an austemper-
ing treatment.
The exact mechanism of HE causing SCC in
the high-strength steels is not quite clear. Since
high-strength steels are inherently sensitive to
SCC, these steels should be separated from the
environment if at all possible. Of these high-
17
strength materials, maraging steels exhibit the
best resistance as indicated above. Neverthe-
less, whichever type of steel is used, the yield
strength level should not be specified to be
greater than the minimum required.
6.01.4.3 Stainless Steels
Stainless steels are iron-based alloys, which
contain a minimum of 11% Cr needed to
ensure passivity and a very low rate of general
corrosion. Stainless steels may have austenitic,
ferritic, martensitic, or duplex microstructures.
In addition, there are precipitation-hardening
special stainless steel grades. The SCC suscept-
ibility of stainless steels depends on alloy
composition, microstructure, and thermal his-
tory (e.g., sensitization). Different stainless
steel grades can be susceptible to SCC in
different or common environments. For ex-
ample, austenitic stainless steels crack typically
in chloride and hydroxide environments, du-
plex stainless steels typically exhibit SCC in
chloride and sour gas environments that
contain chloride and hydrogen sulfide, whereas
ferritic and martensitic stainless steels may be
susceptible to HE under both anodic and
cathodic conditions, with anodic dissolution
probably contributing to the initiation of
cracking by pitting corrosion. There is no
agreement on the mechanism of SCC in these
systems and, in general, SCC is described in
terms of the environment that causes SCC, i.e.,
‘‘chloride SCC,’’ ‘‘caustic SCC,’’ ‘‘sulfide
SCC,’’ ‘‘polythionic acid SCC,’’ ‘‘high-tem-
perature water SCC,’’ or ‘‘irradiation-assisted
SCC’’ (Sedriks, 1992).
SCC of austenitic stainless steels has been
widely studied and the effects of composition
of steel, stress level, effects of microstructure
(various phases (d-ferrite, s-phase, a0 - and e-
martensites and others), sensitization (carbides
and nitrides), grain size and cold work) as well
as environmental variables have been evalu-
ated in detail (e.g., Theus and Staehle, 1977;
Hänninen, 1979; Hehemann, 1985; Newman
and Mehta, 1990; Sedriks, 1992). Similarly, the
SCC susceptibility of ferritic and martensitic
stainless steels (Truman, 1981; Spaehn, 1990)
and duplex stainless steels (Tseng et al., 2003)
has been thoroughly examined. In particular,
the effects of nickel content and sensitization of
these steels on SCC susceptibility have been
studied in various environments and a detri-
mental effect of nickel has been revealed in the
range of standard stainless steel grades. How-
ever, higher nickel contents (430% Ni) gen-
erally increase markedly the SCC resistance of
stainless steels. Sensitized stainless steels be-
come susceptible to intergranular SCC,
18 Stress Corrosion Cracking
whereas in non-sensitized stainless steels crack-
ing is predominantly transgranular with
branching. Exceptions do occur and non-
sensitized steels may also crack intergranularly.
Temperature is a very important variable in
determining the occurrence of SCC in chloride
solutions; in near-neutral solutions, chloride
SCC does not occur in nonsensitized austenitic
stainless steels below B501C, but in aggressive
low-pH conditions SCC can occur even at
ambient temperature. Stress corrosion crack
initiation in chloride solutions occurs by
localized corrosion trench formation (selective
localized dissolution) or pitting and crevice
corrosion processes result in acidification at the
crack tip by hydrolysis of dissolved metal ions
in the presence of acidic anions. Also, increase
of the electrochemical potential increases
cracking susceptibility, whereas decrease of
the electrochemical potential reduces the sus-
ceptibility until cathodic protection is achieved
below the critical potential, Ecrit. This critical
cracking potential can be compared to protec-
tion potentials for pitting and crevice corro-
sion. The possible threshold values for
temperature and corrosion potential depend
strongly on stress level, chloride and alloy
composition as well as on time and are
therefore always considered suspect.
The presence of d-ferrite in austenitic stain-
less steels generally improves SCC resistance in
chloride solutions by blocking the crack
growth across the austenite matrix. A signifi-
cant improvement is achieved in duplex stain-
less steels, where almost 50% d-ferrite is
typically present. The yield strength of duplex
stainless steels is high and therefore the
commonly measured threshold stresses and
stress intensities for SCC in duplex stainless
steels compared to austenitic stainless steels are
also much higher. The optimum ferrite content
has been shown to be at B40% and, in general,
when the total alloying content increases, the
chloride SCC resistance of duplex stainless
steels also increases. Duplex stainless steels
resist SCC better than austenitic stainless
steels, even though the individually synthesized
phases both crack very rapidly. This is because
the ferrite phase protects the austenite phase
cathodically, and the austenite phase protects
the ferrite phase mechanically by deforming
first in normal duplex stainless steels. In duplex
stainless steels cathodic protection prevents
chloride SCC.
Other common environments causing SCC
in austenitic stainless steels are caustic solu-
tions. In strong caustic solutions above 1001C,
transgranular SCC is possible and sensitization
is detrimental at lower caustic concentrations
where intergranular SCC takes place. SCC of
sensitized and nonsensitized stainless steels in
high-temperature water, especially in boiling
water reactor (BWR) applications such as in
weld heat affected zones, has become, since the
1970s, a major SCC corrosion problem (Gor-
don, 1980; Scott, 1985; B. M. Gordon and G.
M. Gordon, 1987). For predictive modeling of
intergranular SCC of sensitized austenitic
stainless steels, a quantitative and predictive
slip-dissolution/film rupture model was devel-
oped (Ford et al., 1987). Several mitigation
measures have been developed for intergranu-
lar SCC in BWR applications related to
material, stress, and water chemistry of the
BWR coolant (B. M. Gordon and G. M.
Gordon, 1987). Polythionic acid (H2SxO6,
where x ¼ 3, 4, or 5) causes intergranular
SCC in sensitized austenitic stainless steels in
the petrochemical industry. This problem can
be mitigated by reducing the degree of sensi-
tization and by changing the shutdown condi-
tions of the plants. Also, both anodic and
cathodic polarization can be used for prevent-
ing polythionic acid SCC, since it occurs in a
narrow potential range. In addition to sulfide
and polythionic acid, SCC of sensitized stain-
less steels can occur in the presence of other
sulfur species, such as thiosulfate, thiocyanate,
and sulfate solutions.
6.01.4.4 Nickel Alloys
Nickel and nickel-based alloys are often used
because of their good SCC resistance, but SCC
can also occur under certain combinations of
environment, microstructure, and stress. Pre-
dominantly intergranular SCC occurs in high-
temperature water (aerated or deaerated), in
acidic and basic solutions, in various sulfur-
containing environments and in gaseous hydro-
gen (Jones and Bruemmer, 1990; Sridhar and
Gragnolino, 1992). There are a number of
different kinds of nickel-based alloys for
various applications, such as Cu–Ni alloys for
seawater applications, Ni–Cr–Mo alloys for the
chemical industry, Ni–Fe–Cr alloys for the
power generation industry and precipitation-
hardenable nickel-based alloys such as alloy X-
750 and 718 for various high-strength applica-
tions. The most often studied nickel-based alloy
is Alloy 600, which shows mainly intergranular
SCC. The high-strength precipitation-harden-
able nickel-based alloys seem to exhibit an
enhanced cracking susceptibility as compared
to the solid-solution alloys. In these alloys a
variety of intermetallic phases form during
aging, such as g0 (Ni3(Al, Ti)), g00 (Ni3(Al, Nb),
Z(Ni3Ti), D(Ni3Nb) and Laves (Fe2Ti) phases
which strengthen the materials. Only the g0
phase has been suggested to enhance directly
 SCC Environments
the SCC process; its dissolution is proposed to
produce local hydrogen which enhances HE.
Much more attention has been paid to inter-
granular carbide precipitation (M7C3 in alloy
600 and M23C6 in more complex alloys), which
affects SCC in high-temperature caustic and
deaerated water environments. In oxidizing
aerated high-temperature water conditions
and in acid sulfate environments, sensitization
caused by Cr-depletion on grain boundaries,
controls SCC. In hydrogen gas environments,
intergranular impurity segregation (S, P, Se, Te,
Bi, Sb, and Pb) may also be important,
especially sulfur segregation.
Nickel-based alloys are resistant to SCC in
concentrated chloride solutions up to high
temperatures (the critical temperature is de-
pendent mainly on Ni content and not on Cr or
Mo contents). They are susceptible to SCC in
high-temperature, high-purity water even in
deaerated conditions, although a number of
impurities enhance SCC. Staehle (2001) has
collected the published experimental SCC data
obtained in various high-temperature water
environments and presented the known condi-
tions of SCC in a potential pH diagram, Figure
11. SCC is associated with active–passive
19
transition in the potential range above the
Ni–NiO equilibrium, where film repair kinetics
is low. Here again, the passive film formation is
important for SCC to occur. The SCC condi-
tions presented here, as in Figure 10 for low-
alloy steels, apply mainly to the conditions of
crack initiation and less to the chemistry
conditions at the growing crack tip, which
may be only slightly influenced by the external
bulk environment. SCC of nickel-based alloys
also occurs in concentrated acids and alkali
solutions. Additionally, hydrogen uptake may
occur in nickel-based alloys and, therefore
hydrogen-assisted crack growth is possible. In
nickel-based alloys, hydrogen-assisted crack
growth has been observed at ambient tempera-
ture up to B1001C in a number of hydrogen
charging conditions.
Both slip-dissolution/film rupture type ano-
dic and hydrogen-assisted crack growth me-
chanisms have been proposed for SCC of
nickel-based alloys depending on the alloy/
environment system. In general, high-strength
nickel-based alloys are expected to suffer from
some form of hydrogen-assisted cracking
mechanism. However, the new SDVC mechan-
ism may also become important, since the

Figure 11 (a) Potential and pH value ranges for various modes of SCC of nickel-based alloy 600 in sensitized
and mill-annealed conditions at 280–3501C in aqueous solutions based on the experimental data:
LPSCC ¼ low-potential SCC, HPSCC ¼ high-potential SCC, AkSCC ¼ alkaline SCC, AcSCC ¼ acidic SCC,
SN ¼ sensitized, MA ¼ mill-annealed, P ¼ pure water, C ¼ contaminated. (b) SCC modes relative to Ni/NiO
equilibrium: CuSCC ¼ SCC in mildly acidic sulfate solutions containing CuO, AcSCC ¼ low-pH SCC,
ClSCC ¼ SCC in chloride solution acidified with H3BO4, DSSCC ¼ SCC in doped (with various impurities)
steam environment, PbSCC ¼ SCC in dilute Pb-containing environment, ASSCC ¼ SCC in slightly alkaline
(pH 8) environment with alumina and silica, S
ySCC ¼ SCC in alkaline solutions where S2O2
3 is present
(source Staehle, 2001; reproduced by permission of TMS – Minerals, Metals and Materials Society).
20 Stress Corrosion Cracking
experimental findings clearly show that local
grain boundary sliding occurs by a creep
mechanism in conditions where SCC takes
place (Was et al., 2001). Hydrogen uptake can
also be considered to result in vacancy genera-
tion and therefore cause enhanced local creep.
6.01.4.5 Copper Alloys
SCC of brass occurs typically in moist air,
where a condensed moisture layer collects
ammonia and oxygen on the copper surface.
In the condensed film, a high concentration of
cupric complex ions forms rapidly. Tarnish film
formation starts quickly and has been found to
consist of Cu2O. Most research on SCC of
copper alloys is conducted in these conditions.
Other environments, such as sulfates, nitrates,
nitrites, chloride containing species, and even
pure water, have also been identified as causing
SCC of copper alloys. In addition to brass,
other copper alloys including pure copper (in
nitrite and acetate solutions) are also suscep-
tible to SCC. Environmental conditions causing
SCC in copper alloys have been reviewed in
detail (Bertocci et al., 1990; Beavers, 1992).
SCC conditions for a-brass exposed to various
nonammoniacal environments superimposed
on the Cu–H2O potential–pH diagram are
presented in Figure 12. It can be seen that, in
various anion domains, cracking always has a
tendency to occur where Cu2O film is likely to
form, thus revealing the importance of Cu2O
films in the SCC mechanism of copper alloys.
This is comparable to the role of Fe3O4 film in
SCC of low-alloy steels, Figure 10. In general, it
has been demonstrated that anodic polarization
from the free corrosion potential of copper
Figure 12 Potential and pH value ranges for SCC of copper alloys in various environments, together with the
equilibrium potentials for various reactions (source Parkins, 1990; Copyright ASTM International. Reprinted
with permission).
alloys enhances SCC, while cathodic polariza-
tion retards SCC. At noble potentials, general
corrosion becomes important, too. Tempera-
ture dependence of SCC in copper alloys
appears to follow an Arrhenius type behavior.
It has been demonstrated that pure copper
displays transgranular SCC in nitrite solutions
in the same potential range as for copper alloys.
In brasses, dealloying is involved in transgra-
nular SCC, but the cracking produced by some
of the environments indicated in Figure 12 is
intergranular. Therefore, the mechanism of
copper alloys must include both the effects of
Cu2O film and dealloying. Dealloying is not
possible in pure copper and therefore rupture of
a dealloyed layer does not explain transgranu-
lar cracking of pure copper. It has been
demonstrated (Aaltonen et al., 1998a, 1998b)
that during oxidation of pure copper in
conditions causing SCC, substantial injection
of vacancies into the base metal takes place.
Vacancy injection has already been proposed
(Forty, 1959) in a pioneering work on brass.
Thus, the conditions on the surface of pure
copper may resemble those in dealloying of
brass. Jones (1985) has proposed a mechanism
for how this vacancy-rich layer may crack in a
brittle manner. First, injected divacancies en-
hance dislocation mobility and slip and reduce
strain hardening, allowing dislocation climb. As
the divacancies accumulate ahead of the crack
tip, they populate the prismatic low-index
planes. The cleavage stress across such planes
is reduced due to weakening of the atomic
bonds by superabundant vacancies. This inter-
esting proposal still awaits final verification.
The mechanism of intergranular SCC
in copper alloys is considered to occur by a
 SCC Environments
slip-dissolution/film rupture mechanism.
Transgranular SCC, which occurs discontinu-
ously and has a brittle cleavage-like appear-
ance of the fracture surfaces, however, is
thought to take place by discontinuous clea-
vage (along {110} planes) possibly triggered by
an epitaxial film such as oxide or dealloyed
layer at the crack tip. HE is not considered as a
possible mechanism, since hydrogen discharge
on Cu–Zn in aqueous ammonia is very
unlikely. However, there is no consensus that
there are two different mechanisms for trans-
granular and intergranular cracking.
6.01.4.6 Aluminum Alloys
Aluminum is a thermodynamically reactive
metal and owes its excellent corrosion resis-
tance to the barrier (passive) oxide film,
composed of two layers in normal atmospheres,
that is strongly bonded to its surface. If
damaged, the film reforms immediately in most
environments. The oxide film is stable in the pH
range of B4–8.5, and beyond these values
aluminum corrodes in aqueous solutions, yield-
ing Al3 þ or AlO
2 ions, since aluminum oxides
are soluble in many acids and bases. SCC of
aluminum alloys and the related corrosion
phenomena have been reviewed in detail, e.g.,
by Holroyd (1990) and Jones (1992). In
aluminum alloys, the amount of second phases
present varies from nearly zero to B20%.
These phases are generally intermetallic com-
pounds and precipitate preferentially on grain
boundaries. The electrode potentials of these
phases are well known and they can either be
anodic or cathodic to the matrix, thus markedly
affecting the corrosion properties of aluminum
alloys. Intergranular corrosion occurs in alu-
minum alloys because of local potential differ-
ences between the grain boundaries and
adjacent grains. The anodic path along the
grain boundaries varies in different alloys: in
2xxx alloys it is a narrow copper solute-
depleted intergranular zone, in 5xxx alloys
anodic Mg2Al3 phase forms a continuous path
along the grain boundaries, in copper-free 7xxx
alloys it consists of continuous anodic Zn- and
Mg-bearing phases on the grain boundaries,
and in copper-alloyed 7xxx alloys it is the Cu-
depleted band along the grain boundaries. The
controlling metallurgical features along the
grain boundaries are the precipitate phase
composition, size and spacing, precipitate-free
zone along the grain boundaries, solute profile
across the grain boundaries and intergranular
segregation. Therefore, intergranular corrosion
is strongly involved in SCC of aluminum alloys
together with pitting corrosion, which is im-
portant during the crack initiation phase and in
21
forming a local occluded corrosion cell for
creating a locally acidified occluded environ-
ment. In general, only aluminum alloys, which
contain appreciable amounts of soluble alloy-
ing elements, such as Cu, Mg, Si, and Zn, are
sensitive to SCC. SCC of aluminum alloys is
almost exclusively intergranular and, as indi-
cated above, it is generally thought that the
grain boundaries form an anodic path for SCC
crack growth under the combined influence of
stress and environment. Therefore, SCC of
aluminum alloys may be prevented by cathodic
protection or with a suitable heat treatment
making the microstructure less sensitive to
SCC.
Water and water vapor are the key environ-
mental factors affecting SCC of aluminum
alloys although halide ions greatly enhance
SCC. Chloride solutions are the most impor-
tant and common environments for SCC of
aluminum alloys. In general, SCC susceptibil-
ity is greater in neutral solutions than in
alkaline solutions and still greater in acidic
environments.
The basic theories of SCC of aluminum
alloys are related to two models: (1) cracking
by highly localized anodic dissolution on grain
boundary regions under the combined influ-
ence of stress and environment or (2) cracking
promoted by hydrogen adsorption or ingress
into the aluminum alloy. Since crack growth in
these alloys is predominantly discontinuous, it
seems that the crack growth mechanism cannot
be solely controlled by a continuous anodic
dissolution mechanism at the stressed crack tip.
6.01.4.7 Hexagonal Alloys: Titanium,
Zirconium, and Magnesium
A common feature of materials having a
hexagonal close-packed (h.c.p.) crystal struc-
ture is that they all adopt very negative (active)
potentials, when bare metal is exposed to
aqueous environments. Therefore, hydrogen
uptake is very important for their SCC
resistance. Titanium and zirconium form very
stable hydrides (exothermic occluders of hy-
drogen), whereas magnesium hydride (MgH2)
will decompose rapidly at temperatures above
2801C. Also, the solubility of hydrogen in Mg
is lower than that in Zr and Ti. However, the
electrochemical potential of Ti and Zr alloys in
the presence of passive film is relatively high
(Hardie, 1990).
Ti alloys exhibit excellent SCC resistance in
most of the environments, but there are,
nevertheless, some environments in which
SCC occurs, such as anhydrous methanol (also
other alcohols and organic solvents), hot salts,
N2O4 (and some other strong oxidizers), and
22 Stress Corrosion Cracking
sometimes even in salt water/seawater and
high-temperature sweet and sour concentrated
brines (Schutz, 1992). In most susceptible
aqueous conditions, anodic and cathodic po-
larization tends to inhibit SCC and increase
KI SCC value of Ti alloys. An SCC susceptibility
maximum is observed in halide solutions in a
narrow potential range. In halide solutions,
crack initiation takes place through active
corrosion trenches where rapid repassivation
does not occur. These active surface sites
initiate crack growth, which takes place either
by some anodic dissolution mechanism or by a
hydrogen-assisted cracking phenomenon. This
may occur through local precipitation of brittle
titanium hydride ahead of the advancing crack
tip and crack extension by cleavage fracture
through the hydride phase (Birnbaum, 1979,
1990).
SCC of Zr alloys occurs only in limited
conditions, such as oxidizing chloride solutions
containing Fe3 þ or Cu2 þ , CH3OH þ halides,
concentrated HNO3, halogen vapors, and
liquid mercury and caesium. SCC of Zr alloys
can be intergranular, transgranular, or mixed,
depending on the specific conditions (Yau,
1992). Similar considerations on SCC mechan-
ism apply to Zr alloys as for Ti alloys.
Titanium and zirconium alloys are suscep-
tible to SCC in methanol in both the liquid and
vapor phases. Susceptibility is mainly confined
to methanol but some other low-molecular-
weight alcohols may also affect some of the
highly susceptible alloys. This intergranular
mode of cracking requires the presence of trace
levels of halides or halogens, such as Cl
, Br
.
Water is an inhibitor of cracking in this case.
SCC of wrought and cast magnesium alloys
occurs in atmospheric conditions and in
distilled water as well as in many other
environments. The only environments that do
not cause SCC in Mg alloys are those that are
noncorrosive to Mg or those that are highly
corrosive where general corrosion dominates.
Pure Mg is not susceptible to SCC, but its
alloys are; Al-containing alloys show the high-
est susceptibility, the sensitivity increasing with
increasing Al content. Zinc also increases the
SCC susceptibility and commonly used Al- and
Zn-containing Mg alloys have the greatest SCC
susceptibility. Cracking can be either transgra-
nular (usual case) or intergranular and, as in
the case of aluminum alloys, the crack path
seems to be connected to localized preferential
corrosion caused by some cathodic phases in
the microstructure. Transgranular SCC is
related to cathodic FeAl precipitates, and
intergranular SCC is related cathodic Mg17Al12
precipitates. Cathodic polarization has gener-
ally been observed to reduce SCC susceptibil-
ity, with some exceptions. Anodic polarization
always increases SCC susceptibility. Transgra-
nular SCC is highly crystallographic following
either cleavage or twinning planes, and cracks
show significant branching. Almost all SCC
mechanisms have been proposed for Mg alloys
including the brittle hydride model based on
observations of a stress-induced MgH2 hydride
phase (Miller, 1992).
6.01.5 SCC ENVIRONMENTAL AND
MECHANICAL CONDITIONS
Several different environmental parameters
are known to influence the rate of SCC crack
growth in aqueous solutions. These include (1)
temperature, (2) pressure, (3) solute species,
their concentration and activity, (4) pH value,
(5) electrochemical potential, and (6) flow rate
including stirring and mixing. Changing of any
of these parameters may alter the rate-control-
ling steps of cracking, either accelerating or
retarding crack growth. It is even possible to
arrest crack growth by changing the environ-
mental reactions, e.g., by external potential
control. The environment at the crack tip is
often formed by an occluded corrosion cell
reaction (e.g., an oxygen concentration cell)
and its chemistry can differ significantly from
the bulk solution. Often only small changes,
e.g., in the amount of trace impurities in the
bulk environment are sufficient to cause dra-
matic changes in crack growth rate, especially
in nominally pure water environments. In
addition to the environmental parameters,
SCC is influenced also by (1) magnitude of
the applied stress or stress intensity factor and
strain rate, (2) stress state (plane stress, plane
strain, or multiaxial stress), (3) loading mode at
the crack tip, (4) alloy composition including
impurity and tramp elements, (5) metallurgical
condition (strength level, slip mode, second
phases present and their composition, grain
size, grain boundary segregations, and residual
stresses), and (6) crack geometry (length,
width, aspect ratio, and crack opening/crack
tip closure). (Jones, 1987)
Stress corrosion crack initiation at the
smooth surfaces typically shows a threshold
stress (sth) that varies from 20% to more than
100% of the yield stress (sy), depending on the
metal and the environment. In practice, re-
sidual stresses are the main cause of SCC in
industrial systems. The higher the tensile stress
the shorter is the time to failure and, although
at low stress levels, time to cracking may be
long, there is in general no practical minimum
stress below which cracking will not occur,
given sufficient time in a critical environment.
However, from an engineering point of view it
 Stress Corrosion Field Failures
is generally accepted that SCC cracks initiate
when the stress exceeds a threshold stress, and
propagate when the stress intensity factor is in
excess of a threshold value, KI SCC, below
which the crack growth rate becomes insignif-
icantly small. Above this value, crack growth
rates increase and often exhibit a plateau over a
wide range of K values. The threshold and
plateau values depend strongly on the metal-
lurgical condition of the material and on the
environment and temperature as well as
pressure. In many systems SCC occurs when
the temperature exceeds a critical value. For
example, austenitic stainless steels in chloride
environments suffer from SCC at room tem-
perature at very acidic pH value (B0–1), above
40–501C in mildly acidic pH value (3–4) and
above 80–1201C in near neutral environments.
Typically KI SCC values lie between 10 and
25 MPa m1/2, but even lower values are found,
e.g., for austenitic stainless steels in boiling
chloride solutions. Stress corrosion cracks are
usually initiated by some form of localized
corrosion (Jones, 1987; Newman, 1995; Mag-
nin and Combrade, 1993). For example, in
chloride-induced SCC of austenitic stainless
steels or aluminum alloys, cracks start from
areas of pitting, intergranular corrosion, or
crevice corrosion that create the stress concen-
tration and low pH value required for crack-
ing. In SCC of C–Mn and low-alloy steels,
intergranular corrosion occurs at segregated
zones rich in carbon, nitrogen, or phosphorus,
which provides a stress concentration to
achieve a critical value of KI SCC. However, in
high-temperature water applications SCC has
often initiated directly from surfaces without
obvious localized corrosion or formation of a
nucleation phase where cracks have initially
grown at very low stress intensity factors,
below the usually anticipated KI SCC values
(Andresen et al., 2001).
SCC was earlier stated to be dependent on
local rupture of the passive films, but in fact
SCC does not easily occur in a true passive
state. Instead, there is usually some form of
local instability in the passive state present
when SCC occurs. There are a number of
electrochemical conditions that can lead to
SCC, Figure 13. At the active–passive transi-
tion (1) SCC occurs, e.g., in C–steel in aqueous
hydroxide, nitrate, or carbonate–bicarbonate
solutions and is normally intergranular and
related to grain boundary segregation. Close to
pitting corrosion potential (2), chloride-in-
duced SCC occurs in stainless steels, aluminum
alloys, or titanium alloys. In these conditions,
passivity is lost and more or less active
conditions are present at the crack tip due to
acidification in the crack, which also results in
23
hydrogen generation at the crack tip (Latani-
sion et al., 1979). Dealloying occurs in Cu–Zn,
Cu–Al, Au–Cu, and Au–Ag alloys and at
localized corrosion sites on passive alloys such
as stainless steels and as a result of surface
dealloying without forming any oxide. Forma-
tion of specific types of surface films that are
neither oxides nor dealloyed layers may play an
important role in SCC of steel in anhydrous
ammonia and in Zr/I2 and high-strength steel/
Cl2 systems. In the active state (3), hydrogen-
induced SCC occurs in high-strength steels and
in H2S-containing environments for medium-
strength steels. SCC mechanisms are mainly
based on local disruption of the passive state
and the film rupture/repassivation with suit-
able repassivation kinetics. Also, systems like
a-brass in near-neutral ammonia solutions
require a critical pH value. Thus, knowing
the conditions for cracking allows mitigation
by preventing the precursor corrosion condi-
tions from occurring.
Andresen et al. (2001) has discussed on SCC
of low-alloy and stainless steels in hot-water
conditions, emphasizing the above discussion
on possible regions of immunity or threshold
values, such as stress intensity, corrosion
potential, metallurgical condition (e.g., degree
of sensitization, amount of cold work, hard-
ness, etc.), temperature, pH value, critical
species concentration, etc. In high-temperature
water conditions, detailed well-controlled stu-
dies of austenitic stainless steels and nickel-
based alloys often show very low SCC crack
growth rates in conditions that were pre-
viously believed to represent immunity. This
suggests that there are no genuine threshold
values, but there is a continuity in the response
surface. Observations that SCC can occur
outside a supposedly limited region of suscept-
ibility are very often based on accelerated and
sometimes inadequate testing. Additionally,
the probabilistic nature of SCC plays an
important role in real plant conditions. These
comments do not only apply to hot-water
systems but also to other systems where long
lifetimes are required.
6.01.6 STRESS CORROSION FIELD
FAILURES
SCC field failures of light water reactor
(LWR) pressure boundary components have
caused significant forced outages with asso-
ciated high cost for repairs and replacement
power as well as significant personnel radiation
exposures and occasional safety hazards. Most
of the components and materials used in
nuclear power plants have been affected by
24 Stress Corrosion Cracking

Figure 13 Schematic polarization curve and potential ranges, where SCC can occur. SCC occurs most likely
in the regions of passivity either adjacent to the active peak (e.g., alkaline environments) or in the range of
breakdown potential (e.g., hot chloride solutions) and at lower potentials hydrogen evolution can contribute
to hydrogen-assisted cracking (source Staehle, 2001; reproduced by permission of TMS – Minerals, Metals
and Materials Society).

SCC (see, e.g., Scott, 1985; Hänninen et al.,
1987; Danko, 1987; Jones, 1993; Kilian and
Roth, 2002; and also Chapter 1.09). Materials-
related failures in large components do not
occur often, but when they do occur, outages
may extend for many months, causing major
capacity factor losses. The most costly issues of
SCC in nuclear components have been inter-
granular SCC of stainless steel coolant piping in
BWRs and corrosion damage of alloy 600 tubes
in steam generators and reactor pressure vessel
head penetrations in pressurized water reactors
(PWRs) (Jones, 1993). Also many high-strength
material parts in various applications have
shown SCC in reactor environments.
The stainless steel components inside the
pressure vessel are also potentially susceptible
to intergranular SCC. Here cracking occurs
under neutron and gamma irradiation and is
called irradiation-assisted SCC (IASCC) (An-
dresen et al., 1990; Scott, 1994). In most cases,
the internals affected by IASCC have been
easily replaced without major capacity factor
losses, although there have been significant
maintenance costs. IASCC in core shroud and
its support structures in BWRs are much larger
concern for the future.
SCC is a major problem in the pulp and paper
industry. Common cases of failures are CF in
duplex stainless steel components, such as
suction rolls, and SCC of various austenitic
stainless steel components of paper machines.
SCC also occurs in all kinds of heat exchangers
and is a common failure mechanism. In pulp
mills, continuous digesters of low-carbon steels
suffer from SCC in sulfur-containing caustic
conditions. Stainless steels in white and black
liquor pipelines, storage tanks, evaporators,
etc., are frequently suffering from SCC. Black
liquor recovery boilers are the key components
of the pulp mill and their SCC problems are
frequent, especially in compound tubes em-
ployed in the furnace and also in the other parts
of the boilers. Similarly, SCC occurs in various
parts of fossil fuel and municipal waste burning
power plants, e.g., in deaerators, reheaters and
superheaters, condensers, steam turbines, and
generators (e.g., generator rotor retaining rings).
SCC is an important form of corrosion in the
chemical processing industry, since it often
occurs unexpectedly and can cause expensive
outages, as in the nuclear industry. Typical cases
are cracking in various heat exchangers, SCC
under thermal insulation, and SCC connected
to other localized corrosion forms such as
crevice corrosion and pitting corrosion. Carbo-
nate cracking in piping at refinery catalytic
cracking units and intergranular SCC in alkanol
amine solutions in hydro-desulfurization plants
are interesting examples. Polythionic acid SCC
occurs in stainless steel parts of these hydro-
cracking and hydro-desulfurization processes.
Oil and gas production is a field where very
aggressive hydrogen sulfide–chloride environ-
ments are present up to high temperatures,
which makes the selection of structural mater-
ials very challenging (Rhodes, 2001).
In the transportation industry, SCC is well
known, especially in aircraft industry, where
high strength and light structures are of
 References
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commonly show SCC as can be expected with
high-strength components. In automotive ap-
plications, increasing use of Al and Mg alloys
is accompanied by concerns about the SCC
performance of these alloys.
SCC occurs also in our infrastructure.
Examples of SCC include, e.g., transgranular
SCC of nonsensitized austenitic stainless steels
at ambient temperature in atmospheres above
indoor swimming pools where cracking has
occurred in ceiling support rods. Copper alloys
crack in water supply systems in valves and
fittings. Cracking in various marine atmo-
spheres is also common, especially in high-
strength structural materials. External inter-
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conditions, respectively, and has been respon-
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gas pipelines. The SCC list is expanding
continuously and new material–environment
combinations susceptible to SCC are certain to
emerge in the future.
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Comprehensive Structural Integrity
ISBN (set): 0-08-043749-4
Volume 6; (ISBN: 0-08-044153-X); pp. 1–29