A Unified Mechanism of Stress

Corrosion and Corrosion Fatigue Cracking

DENNY A. JONES

A mechanism of stress corrosion cracking (SCC) is outlined in which anodic dissolution at film rupture
sites relieves strain hardening and reduces the fracture stress at the crack tip. Experimental evidence
is cited to suggest that relief of strain hardening occurs by interaction of subsurface dislocations with
divacancies generated by the anodic dissolution. A transgranular crack propagates by accumulation of
divacancies on prismatic planes which then separate by cleavage under plane strain conditions at the
crack tip. At appropriate metallurgical and chemical conditions, anodic dissolution and/or divacancy
migration may be enhanced at grain boundaries, leading to an intergranular failure mode. Evidence
is also available to indicate that cyclic loading relieves strain hardening, Relief of strain hardening by
combined cyclic loading and corrosion accounts for the higher incidence of corrosion fatigue cracking
(CFC) without the requirement of any critical dissolved species. Data on fatigue of stainless steel at
elevated temperature in both vacuum and air provide additional support for the proposed mechanism.

I. INTRODUCTION One measure of repassivation kinetics is given by the strain-

A widely accepted mechanism of stress corrosion cracking
(SCC) under static tensile load has eluded experimentalists
and theoreticians for decades. Less effort has been devoted
to corrosion fatigue cracking (CFC) under cyclic load. The
relationship, if any, between SCC and CFC is presently
unclear. The purpose of the present paper is to describe a
mechanism to account for previously known and recently
revealed facts concerning these two forms of metal failure.
The keystone of the proposed mechanism is the experi-
mental evidence that anodic dissolution or corrosion relieves
strain hardening in many, if not most, metals and alloys. It
will be demonstrated that relief of strain hardening at the
crack tip surface reduces the fracture stress and facilitates
nucleation of brittle cracks. The rupture of passive films is
essential to concentrate the anodic dissolution at the crack
tip rupture sites. Cyclic loading has also been observed to
relieve strain hardening and increase plastic creep in many
alloys at ambient temperature. Crack tip relief of strain
hardening, caused by a combination of corrosion and cyclic
load, can account for CFC without any critical anion such as
C1- and for accelerated CFC at lower cyclic frequency.
Recent experimental evidence is reviewed in the initial
section of this paper to provide the necessary background,
followed by a description of the proposed mechanism and
finally by discussion of further experimental data which
support the mechanism. Whenever possible, results are cited
involving SCC of austenitic stainless steel in hot chloride
solutions, a system which has been the subject of extensive
investigation and exhaustive review.
II. EXPERIMENTAL BACKGROUND
A. Film Rupture
Many recent discussions ~-5 of the SCC mechanism have
emphasized film rupture and repassivation as key elements.
DENNY A. JONES is Professor and Chairman, Department of Chemical
and Metallurgical Engineering, University of Nevada-Reno, Reno,
NV 89557.
Manuscript submitted September 21, 1984.
ing electrode method originated by Hoar and co-workers. 6'7
A straining electrode is maintained at or near the original
corrosion potential with a potentiostat. Fresh surfaces
formed by plastic strain and consequent film rupture have
more active free corrosion potentials and are anodically
polarized when maintained potentiostatically at the original
corrosion potential. Such a test thus results in an anodic
current transient which is related to repassivation kinetics
and resistance to SCC.
Results of Jones et at. 8 using the straining electrode
method are shown in Figure 1. The ratio i*/i, potentiostatic
anodic current during straining i* divided by the anodic
current i without straining, is plotted in Figure 1 vs time,
which is proportional to strain in the constant strain rate test.
A significant increase in anodic current did not occur until
plastic deformation had developed above the elastic limit.
Plastic strain of the substrate alloy produced film rupture
resulting in high potentiostatic anodic currents on the
unfilmed surfaces. The highest current transients were
present for steel in air contaminated liquid anhydrous am-
monia which is known to cause SCC. Lower transients
resulted from nitrogen-contaminated ammonia, oxygen-
contaminated ammonia, and air contaminated ammonia in-
hibited with water, all of which are progressively lower in
their propensity to cause SCC.
The significance of the straining electrode test to the
mechanism of SCC is shown more clearly by the simplified
electrochemical analysis of Figure 2. 8 A specimen rapidly
strained to failure (Figure 2(a)) shows an active potential
shift from Eco~ to Estrain because film rupture creates film free
surfaces which have lower polarization. If straining is
stopped or if the specimen fractures, the specimen potential
rapidly returns to Eco~rby formation of new passive film over
the previous film rupture sites. In the usual SCC processes,
the strain rate is low, and repassivation keeps the unfilmed
anode quite small at the film rupture sites. Thus, the anode
sites are heavily polarized to near Eco~r (Figure 2(b)), and
changes in corrosion potential are undetectable during SCC.
However, the current density at the rupture site anodes is
very high, which accounts for initiation and growth of stress
corrosion cracks at these sites.

METALLURGICALTRANSACTIONS A VOLUME 16A, JUNE 1985--1133

 Controlling potential at or near Eco~ during rapid straining
9. . . . PURE NH3
PURE NH3 + N2 results in a large anodic current iappat a large number of film
.... PURENH3 +AIR + H20~ rupture sites (Figure 2(c)). Thus, the anodic rupture sites are
..... PURENH3 + 02 / ~, -- 2000 heavily polarized, as in the usual stress corrosion process.
160 "
. . . . . . .
PURENH3 + AIR /
/ ~,
\ The applied anodic current is readily measurable and is
indicative of the film rupture microprocesses which occur
140 "'" ".*..
ELASTIC .""" I "".. ~, during usual SCC. Although film rupture is an essential part
,< of the SCC mechanism, these measurements do not give any
120 -- 1500 indication of the metallurgical processes which are involved
d
F- in crack initiation and propagation, Film rupture infor-
100 - - mation must be correlated with mechanical responses to
g
corrosion before the mechanism of SCC and CFC can be
o
d clarified.
m 80-- 1000 J
O

B. Creep Due to Anodic Dissolution and Corrosion

g
6(]1- - .':
z Film rupture results in high anodic dissolution at the rup-
i RUPTURE /"~r':: ture sites, according to the above analysis. Uhlig and co-
40 -- 9 .'" :. : -- 500 workers 9'l~ have amply demonstrated that anodic surface
: ~ ./ X .., : dissolution increases the ambient temperature primary creep
9

- ~....~ ! rate for both copper and iron. An example of their data is
20
shown in Figure 3, where an applied anodic current clearly
7 9 "--- . . . . . . . . ~ " "~ "f'~'" ~m
increased the creep rate, which then decreased to the origi-
nal rate when the current was stopped. In a similar way,
0[- I 1 , , , i, Smialowski and Kostanski ~zand Petit and Desjardins l~ have
0.1 0.2 0.3 0.4 0.5 06
observed that creep rate of austenitic stainless steel is in-
TIME, minutes
creased by corrosion in boiling MgC12 solutions. Anodic
Fig. 1--Anodic current transient on a straining steel electrode, liquid dissolution resulting from corrosion presumably increases
anhydrousammoniawith variousadditivesJ creep in these instances.

Ecorr Ecorr Estrain

E strain I

(a) F (b) i co..os,o

LOG CURRENT, i LOG CURRENT, i

P O L A R I Z A T I O N CURVES AT
f
STEADY STATE
Ecorr - ~ iiapp ~|~I
A N O D I C P O L A R I Z A T I O N CURVES
DURING PLASTIC STRAINING

E strain i CORROSION CURRENT AT STEADY STATE

i' TRANSIENT CORROSION CURRENT DURING

PLASTIC STRAINING

Idpl~ APPLIED ANODIC CURRENT TO M A I N T A I N

Ecorr POTENTIOSTATICALLY DURING
(c)
STRAINING
LOG CURRENT. i

POLARIZATION DIAGRAMS FOR: (A) RAPID STRAINING UNDER FREE CORROSION CONTROL,
(8) NORMAL SLOW STRAINING DURING STRESS CRACKING, (C) RAPID STRA~NTNG WITH
POTENTIAL M A I N T A I N E D P O T E N T I O S T A T I C A L L Y AT FREE CORROSION POTENTIAL E(x.,

Fig. 2--Electrode kinetic analysis of straining electrode,s

l134--VOLUME 16A, JUNE 1985 METALLURGICAL TRANSACTIONS A

 4.35 I I I I I I
4.30
4.25
g oo~' c u r r e n t off
o
u.i
4.20
)() .~
4.15 ~
,~r c u r r e n t on
qT~l l J I i 1 I
40 50 60 70 80 90 110
Time, minutes
Fig. 3 - - E f f e c t of anodic dissolution on creep in pure copper. 9
Revie and Uhlig 9 have proposed that anodic dissolution
forms a supersaturation of subsurface vacancies, which
form divacancies which in turn have sufficient mobility to
interact with dislocations near the surface, relieve strain
hardening, and accelerate creep. A mechanism of va-
cancy generation during corrosion, shown schematically in
Figure 4, follows the treatment of Pickering and Wagner. 14
Anodic metal dissolution may be considered analogous to
metal evaporation. The most energetically favorable path is
from a kink site at position 1 until eventually the atom
reaches an adsorbed site and leaves the surface. However,
any anodic overvoltage (excess driving force) will favor
dissolution directly from ledge sites (e.g., position nos. 2
to 8) which are more prevalent than kink sites. For example,
a ledge-site atom at position no. 5 can migrate directly to an
adsorbed position as shown in Figure 4. If a subsurface
atom jumps into the vacant ledge site at position no. 5,
a vacant lattice site is created just below the surface.
A considerable supersaturation of subsurface vacancies can
be created by such a mechanism, favoring formation
of divacancies which have sufficient mobility to affect
mechanical behavior. Mechanisms whereby divacancies
may affect mechanical properties are discussed later in this
paper.
C. Creep Due to Cyclic Load
Evans and Parkins ~5 have recently observed that cyclic
loading in air extends ambient temperature plastic defor-
mation in manganese steel beyond the primary creep stage
observed under constant load. Figure 5 shows that after
primary creep had exhausted under constant load, the strain
(creep) rates increased markedly when a cyclic load was
superimposed. Others j6 previously observed attenuation of
work hardening and consequent accelerated ambient tem-
perature creep under cyclic deformation in copper, alumi-
num, and cadmium. These workers 16 attribute accelerated
creep to bulk generation of vacancies which promote dis-
location climb and consequent relief of strain hardening.
D. SCC Due to Strain
In recent years continuous slow tensile strain has been
found to have a highly accelerating influence on SCC. Iv In
METALLURGICAL TRANSACTIONS A
I I I I
Fig. 4 - - S c h e m a t i c mechanism of dissolution from kink and ledge sites on
a crystal surface.
l I 1 I 20~
120 100 130 140 150
S t r e s s at s t a r t of c y c l i c l o a d i n g 3 4 8 M N / r n 2
Prior s t r a i n 0.12
0 016
Time
Fig. 5 - - E f f e c t of cyclic load on creep of C-Mn steel. ~
constant strain rate testing, a critical controlled strain rate is
imposed on a tensile specimen until it fractures. The exact
value of the critical strain rate to cause SCC depends on the
alloy but is usually about 10 6 s 1 for iron, aluminum, and
copper base alloys. Above the critical strain rate, film for-
mation cannot keep pace with film rupture due to the rapid
mechanical strain, and the test specimen fails by ordinary
cup-and-cone ductile rupture. Below the critical strain rate,
the film formation rate may be sufficiently rapid that the
film is not continuously ruptured, and ductile failure is again
observed. However, in some instances, repassivation rates
may be very slow and SCC still prevails even at very low
strain rates, as in Figure 6.
A typical example of results from slow strain rate testing
is shown in Figure 6 Is for Type 316 stainless steel exposed
to hot concentrated MgCI2 solutions. In glycerine at the
same temperature, the load vs deformation plot shows a
large deformation at failure with the expected ductile frac-
ture. Exposure to the corrosive solution during slow strain-
ing produces low ductility SCC.18
It is important to note in Figure 6 that brittle SCC is
accompanied by a lower stress to cause any given strain.
The yield strength is unaffected, but the subsequent strain
hardening before failure is diminished by the concurrent
effects of corrosion during SCC. Consider a tensile bar,
subjected to slow constant strain rate, as being composed
entirely of numerous contiguous axial elements of equal
cross sectional area. Under uniform stress, each element
bears the same portion of the total load. The bar specimen
is under strain control during constant strain rate testing.
That is, strain is the independent variable, and the stress
changes to accommodate the imposed strain. If at some time
any element(s) deforms more rapidly with less required
load, less total load and apparent engineering stress is re-
quired to maintain uniform strain in the bar.
VOLUME 16A, JUNE 1985--1135
C
^[0 9 C steel in NO~
"o 1~);.~_.~ 9 C steel in OH
o ]:; 9 F e r r i t i c s t e e l in MgCI 2
T E } Csteel in CO:~/HCO~
u) ~ 18/8 st. steel in MgCI 2
E 0 C steel in C01C02/H20
E X AI-7 Mg in NaCI
2 1 ~N H
lOZl~ ~,, Brass
r in ~ 7 /
h-
lie
/" I=MgCI2, =6.4,10-5/s
10C
A 2=MgCI2, =6.4,10-6/s
\ 3=MgCI2, =6.4 o10-7/s
ao 1()"=

0 1 2 3 4 5 6 7 8 9 10
l, Deformation (ram)
Fig. 6 - - Slow strain rate test results on Type 304 stainless steel in boiling
MgCI2 solution, t8
6 ~Oe~
~

"l i, Ill[
/2/.
, I i ililii i I il lllll ! i ,illill i , i

16 3 102 1-01 100

In the absence of corrosion, each element undergoes a
sequence of elastic deformation, plastic deformation, strain
hardening, and finally fracture. In the presence of a corro-
sive environment, interior elements are unaffected, but the
exterior elements are weakened inasmuch as lower stress
is required to achieve the same strain compared to the
noncorrosive case. Because the yield strength is relatively
unchanged in Figure 6, the major effect on the exterior
elements by corrosion is a decrease in strain hardening.
Accompanying this decrease is a decrease in the fracture
stress, as evidenced by the common observation of minute
surface cracks shortly after yield in a stress corrosion envi-
ronment. The fact that corrosion apparently alleviates strain
hardening has considerable significance in later descriptions
of the mechanism of SCC and CFC.
Parkins 'v''9 found that if carbon steel were stressed and
retained at a noncracking electrochemical potential for a
period of time before potential was switched into the crack-
ing potential range, no cracking resulted. The explanation
given was that strain rate had exhausted to the point that it
was below that necessary to rupture films and initiate crack-
ing. Cracking did result if the potential was switched into
the cracking range immediately after the load was applied,
when the strain rate was still substantial.
III. MECHANISM
A. Stress Corrosion Cracking (SCC)
Figure 1 illustrates some universal characteristics of SCC
in most systems. An oxidizer is required (dissolved oxygen
in Figure 1), and SCC occurs on an otherwise passive sur-
face. However, a critical species (nitrogen in Figure 1) must
also be present which apparently hinders repassivation of
rupture sites by competitive adsorption leading to SCC. In
aqueous systems dissolved oxygen is also often the pas-
sivating species and chloride is required for SCC of aus-
tenitic stainless steel. In any event, a passive surface film is
requisite for SCC. Without the oxidizer (passive film), the
critical species causes only general corrosion and no SCC.
These facts are readily explained by film rupture which thus
seems to be a necessary element in any mechanism of SCC.
Crack propagation in most versions of the film rupture
model is presumed to occur by dissolution of the film-free
Average Current Density on Straining Surface A.cm-2
Fig. 7--Correlation betweencrack growth rate and anodic dissolution rate
on the strained surface.5
material at the crack tip where stress concentration con-
tinuously ruptures the passive film as it reforms. In support
of this concept, Parkins 5'2~ demonstrated a proportionality
between crack growth rates and anodic current density of a
straining electrode surface, as shown in Figure 7. The model
has been criticized, 4 because resultant anodic dissolution
rates are not sufficiently high to account for the known rates
of crack propagation in some systems, especially those in-
volving brass and austenitic stainless steel. Proportionality
between crack velocity and anodic dissolution of a straining
electrode does not guarantee that the crack actually grows by
anodic dissolution. Instead, anodic dissolution may control
some subsequent consecutive process which actually causes
the fracture. Furthermore, fractography of crack surfaces
generally shows brittle cleavage or intergranular failures
with no obvious evidence of electrochemical dissolution. By
similar reasoning, a "brittle component ''2' has been postu-
lated to account for the crack propagation. However, the
source of the brittle component has not been elucidated
thus far.
The central thesis of this paper is that a brittle component
of SCC may be explained by observed corrosion induced
relief of strain hardening (Figure 3) which is localized at the
crack tip. A crack may be thought to initiate and propagate
as follows: an area of localized plastic strain develops on the
surface at an emergent slip band consisting of a cluster of
slip lines. In this area of local slip, the local stress must
exceed the yield strength ~rys. In the absence of corrosion
(e.g., in air), the metal in this local area strain hardens and
the local stress increases to ~ri, the true fracture stress,
initiating a crack. The same sequence follows at the tip of
the growing crack and can be more easily pictured in
Figure 8. Stress is concentrated at the crack tip causing
plastic deformation, and the crack propagates into the lead-
ing volume of plastic strain. The radius of the cylindrical
plastic volume is rp. Yielding just begins at a distance 2rp
ahead of the crack tip at a stress O'ys. Strain hardening in-
creases within the plastic volume until fracture occurs at the
crack tip at o-i.

1136-- VOLUME 16A, JUNE 1985 METALLURGICAL TRANSACTIONS A

 o stainless steel yields an rp of 0.0033 inch (0.084 ram).
~ _ - R
Od
~ ...... I . . . . . . . . . .
/ \1
If - I~x
/
//
4 2rp 9
Fig. 8 - - S t r e s s and strain behavior at a crack tip. Not to scale. R: di-
vacancy penetration distance relieving strain hardening and reducing frac-
ture stress from 05 to o~.
In the presence of a corrosive solution, surface displace-
ments are sufficiently large that the passive film is rup-
tured, causing a large anodic current transient at the rupture
site. If some critical species such as C1- is present to retard
repassivation for a sufficient time, continued anodic
dissolution will generate additional divacancies, which
penetrate a distance R (Figure 8), further relieve strain hard-
ening, and initiate a crack. A crack will initiate because the
fracture strain is lowered by the relief of strain hardening
from ~rs to o-/, as shown graphically in Figure 8. Experi-
mental evidence for a reduction of strain hardening and
lowering of ~rI during SCC was shown previously in
Figure 6. Strain hardening is relieved in the plastic volume
ahead of the crack tip just as it is on the outer surfaces of a
slow strain rate tensile specimen.
It has been observed that SCC cracks initiate on {111} slip
planes in austenitic stainless steel, a'= The mechanism may
be slip-step dissolution 4 with slip increased by relief of strain
hardening due to enhanced dislocation climb from corrosion
induced divacancies. Transgranular SCC propagates on pris-
matic planes; {110}, {210}, {100} are mentioned most often. 22
Slip-step dissolution at an emerging {lll} slip plane 4 can
account for initiation, but further suggestions of complex
slip on the non-close packed prismatic planes during SCC
propagation 4'23 are unconvincing.
A triaxial stress state (plane strain condition) will inhibit
plastic deformation in the crack tip region once an active
crack has initiated. Thus, SCC cracks are brittle with very
little plastic deformation ahead of the growing crack even in
very thin cross section. Plane strain conditions require that
a crack grows under the Mode I displacement, in which the
crack surface grows in a plane perpendicular to the applied
tensile stress. 24 Therefore, additional evidence of plane
strain conditions at the tip of an SCC crack is the fact that
SCC cracks almost invariably follow in a plane perpendicu-
lar to the tensile component of applied stress. Further sup-
port for plane strain conditions at the crack tip may be found
from a calculation of the plastic zone radius rp which is
given at crack arrest by 25
rp = \ O.v---'-f/
where Kr,,.,. is the critical stress intensity for SCC crack
growth and o'~, is the yield stress. Substituting estimated
values of Ki,,, " 10 ksi ~nn and O'ys = 40 ksi for austenitic
METALLURGICAL TRANSACTIONS A
Thus, the low value of Km.c requires a very low value of rp,
and plane strain conditions prevail during SCC, even in very
thin cross sections.
It may be noted that Davidson and Lyle 26 made electron
channeling measurements at the SCC crack tip on the sur-
face of a stainless steel specimen, where plane stress condi-
I tions prevail. Their measurements of plastic zone size were
I
I in good agreement with plane stress predictions which were
I
s Ef about a factor of 3 larger than expected for plain strain
conditions.
Figure 8
The prismatic {100}, {210}, {110} planes have the common
characteristics of low indices and low atomic density. An fcc
crystal will be weakest in cleavage across such planes, be-
cause fewer bonds are present on the low atomic population.
Divacancies charged into the plane strain region at the crack
tip can cause a cleavage-like fracture when enough ran-
domly inhabit those prismatic planes which are oriented
nearly normal to the tensile stress. The migration of di-
vacancies and consequent relief of strain hardening are con-
fined to only a few thousand angstroms ahead of the crack
tip surface within the plastic zone. Calculations are given
later in the Discussion section. The depth, R, of divacancy
accumulation is very small compared to plastic zone, rp, and
the schematic plot of stress vs distance, x, in Figure 8 is not
drawn to scale. The divacancies cannot induce any signifi-
cant further plastic deformation in this crack tip material
because the surrounding material is already strain hardened
to near the fracture stress of O~r.Thus a lowering of fracture
stress to o-j as shown in Figure 8 can result only in brittle
cleavage fracture on prismatic planes.
Fracture may occur simply by displacement of atomic
bonds on the plane by vacancies, or the net tensile stress
may become high enough to actually cause a cleavage frac-
ture after a sufficient concentration of vacancies have accu-
mulated on the plane. A brittle cleavage fracture suggests
a decreased fracture strain which is observed experimen-
tally (Figure 6) and which is postulated in the schematic
stress-strain curves of Figure 8. If film rupture and/or di-
vacancy migration rate is favored at grain boundaries, then
the cleavage fracture would be intergranular rather than
transgranular.
Such cleavage fracture never occurs, of course, in the
absence of plane strain conditions, when plastic deformation
can develop on the multitude of slip systems in fcc crystals.
The relief of strain hardening by corrosion or anodic dis-
solution is evidenced by plastic deformation or creep in the
absence of plane strain, as shown in Figure 3.
B. Corrosion Fatigue Cracking (CFC)
By an analysis similar to that above, cyclic loading can
promote brittle crack growth. Cyclic loading above o-r~ in
the crack tip plastic zone would relieve strain hardening,15
reduce the fracture stress, and nucleate a crack as in
Figure 8. The mechanism of crack initiation and growth
would again involve accumulation of vacancies on either
crystal planes or at grain boundaries in the crack tip region,
the vacancies being generated in the plastic zone by cyclic
loading, as postulated by others. 16
Although supporting data are unavailable, it is not unrea-
sonable to suppose that below a certain stress level in ambi-
ent temperature air, cyclic loading is no longer effective in
VOLUME 16A, JUNE 1985--1137
attenuating strain hardening and promoting creep as it does
in Figure 5. Thus, cracks cannot grow, and a fatigue limit
results in ferrous alloys. When corrosion is superimposed,
the relief of strain hardening is increased above the apparent
minimum, eliminating the fatigue limit observed in usual
fatigue testing of ferrous alloys. The combined relief of
crack tip strain hardening by cyclic load and corrosion
would account for the more frequent occurrence of CFC
than SCC. Also, periodic tensile stress serves to continually
activate film rupture sites, 27 and a specific ion such as C1-
is not necessary in CFC.
C. Summary of the Mechanism
The proposed mechanism may be summarized in a series
of consecutive steps listed below.
(1) Film rupture when mechanical stress is applied to an
alloy in the passive state exposed to a corrosive solution.
(2) Retarded repassivation of rupture sites caused by com-
petitive adsorption of a critical dissolved species for SCC
(C1- for austenitic stainless steel), or by repeated cyclic load
for CFC.
(3) Anodic dissolution at rupture sites intensified by cou-
pling to large adjoining passive surfaces.
(4) Vacancy formation at the rupture sites from anodic
dissolution.
(5) Divacancy.formation from a supersaturation of surface
vacancies followed by migration to critical lattice sites. Di-
vacancies may be formed at internal bulk vacancy sources to
function in the same way during CFC.
(6) Initiation of surface cracks" by film rupture and slip
dissolution on close packed planes with enhanced slip due
to dislocation climb induced by reaction with divacancies
which have migrated from the surface,
(7) Brittle crack propagation under plane strain conditions
by cleavage-like fracture due to accumulation of divacancies
on prismatic planes.
The cycle is repeated on film free brittle crack surfaces,
omitting the initiation step no. 6, as a crack continues to
grow. Figure 9 shows the growth cycle at a crack tip sche-
matically, again omitting the initiation step.
IV. DISCUSSION
A. Stress Corrosion Cracking
Beavers and Pugh 28 have observed prismatic {110} SCC
fracture surfaces in fcc brass and have also concluded that
a simple cleavage mechanism is operative. Restrictions on
cross-slip in the plastic zone also seem necessary, since
alloys of higher stacking fault energy (Cu-Zn with < 15 pct
Zn, Cu-Ni) are generally immune to transgranular S C C . 29
Still more recent work 3~ on SCC of hcp magnesium has
revealed prismatic {2203} cleavage facets on the crack sur-
faces. Hydrogen embrittlement is considered 28'3~ to be a
likely cause of cleavage in both cases. For brass, however,
there is no evidence of embrittlement under cathodic hy-
drogen charging. 29 For austenitic stainless steel, hydrogen
charging stops propagating SCC cracks. 31 Thus, corrosion-
induced divacancy accumulation on prismatic planes ap-
pears to be a reasonable alternative mechanism for cleavage
during transgranular SCC.
l138--VOLUME 16A, JUNE 1985
STEPS in SCC MECHANISM
1. Film r u p t u r e by m e c h a n i c a l s t r e s s
2. R e t a r d e d r e p a s s i v a t i o n by c o m p e t e t e t i v e a d s o r p t i o n of
c r i t i c a l species, e.g. CI-
3. Anodic d i s s o l u t i o n by coupling to surrounding p a s s i v e s u r f a c e s
4, Vacancy f o r m a t i o n from rapid dissolution
5. D i v a c a n c y formation and migration
6. C r a c k initiation (Omitted from diagram)
'7. Crack p r o p a g a t i o n by c l e a v a g e due to a c c u m u l a t i o n of
d i v a c a c i e s on prismatic planes, e.g. {100~
Fig. 9 - - S c h e m a t i c diagram summarizing steps in the proposed mecha-
nism of SCC and CFC.
Corrosion induced divacancies have also been implicated
as the cause of dealloying of brasses. ~4 SCC crack surfaces
on brass have shown evidence of dealloying,32 which offers
still further evidence that divacancies play a role in the
SCC mechanism, In this connection, Forty 33 some time ago
proposed that interaction of vacancies produced by de-
zincification with dislocations may be responsible for SCC
in brass. More recent information reviewed here suggests
that divacancies can be generated by the corrosion process
itself even in pure metals. Nevertheless, Forty's suggestions
seem both pertinent and prophetic at this time.
It should be noted from Figure 8 that the present theory
requires localized relief of strain hardening within a matrix
of strain hardened material in the plastic zone ahead of the
crack tip. If strain hardening were absent in the plastic zone,
the fracture stress cr/ would be identical to the reduced
fracture stress @. The material would be very ductile (per-
fectly plastic) and brittle SCC would be impossible. This
explains the fact that SCC is most often observed in alloys;
pure metals are not usually affected. In the absence of alloy-
ing elements, most pure metals do not strain harden exten-
sively. Although vacancies are generated by corrosion in
pure metals, 9 the necessary strain hardened condition is ab-
sent, and SCC does not occur readily in pure metals. A
notable recent exception is the observation of SCC in pure
hcp magnesium. 3~ The limited number of slip systems in
hcp polycrystals 34 allows sufficient strain hardening which
can be imitated in bcc and fcc only in the presence of alloy-
ing elements.
In a given alloy system, the susceptibility to SCC usually
increases as the tensile strength increases. Increased strain
hardening as it affects ultimate tensile strength presumably
enhances susceptibility to SCC. A measure of strain hard-
ening is the difference ~ r f - cry, between the fracture and
yield stresses in Figure 8. A larger difference c r j - Cry,
gives a larger capacity for reduction to cry. High yield
strength of itself is not a necessary criterion. For example,
highly alloyed austenitic stainless steels have relatively
METALLURGICAL TRANSACTIONS A
low yield strength, but are highly susceptible to SCC in
hot chlorides. Yet, these same alloys are notoriously diffi-
cult to machine because of their high rate of work (strain)
hardening.
The diffusion of divacancies can sustain experimentally
observed crack velocities. The root mean distance R that
divacancies can diffuse ahead of a crack tip in time t is given
by 35
R = 2.45(Dt) 1/2 [2]
for an fcc lattice, where D is the diffusivity of divacancies.
The rate of diffusion can be obtained by differentiation:
dR
- - = 1.23D1/2 t 1/2 [3]
dt
A preliminary estimate of D = 10 ~2 cm 2 per second, as
used by Pickering and Wagner 14 for divacancies in brass,
seems reasonable for most metals and alloys at ambient or
slightly elevated temperature. Logarithmic plots of these
equations using this value of D are shown in Figure 10.
Superimposed are crack velocity levels from Figure 7 of
--2 • 10 -3 mm per second for carbon steel in nitrate solu-
tion and 3 x 10 6 mm per second for carbon steel in
carbonate/bicarbonate solution both at about 75 ~ For the
carbon steel in carbonate/bicarbonate, a film rupture event
would have to occur about every 10 seconds at a crack
increment of 1000 ,~ in order to maintain the growth rate of
3 x 10 -6 mm per second. The estimated 1000 A increment
length is still below the minimum resolution of the usual
SEM fractographs which show brittle cleavage or inter-
granular surfaces with no obvious indications of discon-
tinuous crack propagation.
To maintain the high crack velocity of carbon steel in
nitrate, Figure 10 shows that the crack increment would be
only between one and two angstroms, equal to or less than
the dimension of the unit cell of the crystal lattice. This
questionable result may be due to an estimate of divacancy
diffusivity which is too low for the disordered structure of
grain boundaries at the SCC temperature of 75 ~ Each
order of magnitude increase of D would increase the neces-
sary crack increment by a factor of ~ = 3.16. Further-
more, an added component of the crack increment may
come about by very rapid mechanical cleavage on the grain
boundaries beyond simple displacement of atoms on those
surfaces by vacancies.
To account for the large difference in velocity of inter-
granular SCC of carbon steel in the carbonate/bicarbonate
and nitrate environments (Figure 7), one must assume that
more rapid repassivation in carbonate/bicarbonate sup-
presses anodic dissolution at rupture sites and maintains
crack velocity at low values. And, in fact, rates of re-
passivation may indeed control crack velocity rates in most
instances. The purpose of the calculations summarized in
Figure 10 is to demonstrate that rates of divacancy diffusion
are sufficient to sustain measured rates of SCC. Other pro-
cesses may actually control the velocity.
It may be expected that the activation energy (and tem-
perature dependence) for divacancy diffusion in the bulk
crystal will be higher than in the disordered grain boundary.
Thus, one can predict that intergranular SCC may be preva-
lent at lower temperatures, but transgranular SCC at higher
temperatures when bulk becomes higher than grain bound-
M E T A L L U R G I C A L TRANSACTIONS A
i
~- Crack -3
, ~ g r o w t h rate, 2 x 1 0 mm/sec.
10 :. t carbon s t e e l
~ t r a t e solution
~10-' ""..~0 o
"6
,3~,0..C~ . . . . . . .
d
~10-~
D
g
10-6 in C 0 3 / H C O 3 solution
10-7 "~---C~- 5 ------L------~ --'~- ~----~--~------ I ....
10 5 10-4 10 3 10 2 10-1 1 10 102 103
Time. see.
Fig. 10--Distance and rate of divacancy diffusion as function of time
estimated from Eqs. [1] and [2] assuming D = 10-~ cm2/sec.
ary diffusivity. The prediction is confirmed by Takano 36 who
observed intergranular SCC of austenitic stainless steel at
128 ~ and transgranular SCC at 143 ~ in MgC12 solutions.
Figure 7 suggests that in general crack growth rate is
proportional to the current density of a straining electrode of
the same alloy. The conventional explanation is crack propa-
gation by electrochemical dissolution at the crack tip rupture
sites. However, generation of divacancies by this same elec-
trochemical dissolution better explains more rapid, brittle
transgranular crack propagation rates in brass and austenitic
stainless steel. The proposed mechanism involves an elec-
trochemical dissolution step, as does the conventional film
rupture mechanism. 1-5 However, the proposed mechanism
does not require that the dissolution rate match the crack
propagation rate. The dissolution rate may be considerably
below the crack propagation rate due to a mechanical cleav-
age component of crack growth, and dissolution features
would be unobservable.
It has been observed that the crack interior may have a
different electrolyte composition than the bulk electrolyte.
For example, the pH in cracks of austenitic stainless steel
has been measured as low as 2 or 3. 37 Such effects probably
aggravate the galvanic effects between crack tip and sur-
rounding surfaces since more acid solutions often lead to
more active potentials. Also, solute concentration such as
C1- in cracks may further retard the rate of repassivation at
crack tip film rupture sites.
Above 300 ~ nickel Alloy 600 has been observed to
exhibit SCC in pure pressurized water. 38 In this case, the
elevated temperature may increase the alloy reactivity suf-
ficiently to retard repassivation even in the absence of any
dissolved species. Thermal relief of strain hardening may
also be high enough to contribute to the cracking mechanism
at this temperature. Lee and Vermilyea 39 observed inter-
granular cracking of sensitized nickel Alloy 600 during
slow strain rate (1.65 x 10 -6 S l) testing in helium in the
absence of corrosion at 370 ~ Significantly, they sug-
gested that embrittlement of grain boundaries could be
caused by a mechanism other than one simply involving
precipitated grain boundary carbides.
B. Corrosion Fatigue Cracking (CFC)
Potentiostatic current transients on cyclically strained
carbon steel 27 suggest that film rupture is prevalent during
VOLUME 16A, JUNE 1985--1139
corrosion fatigue. A conclusion from this work was that
chloride affects the repassivation kinetics in alkaline solutions
rather than the dissolution rate at the rupture sites.
Furthermore, in pH 8-11 solutions containing CI-, the
maximum current of the transient increased for consecutive
strain cycles, suggesting that cyclic stress increases the
activity and/or number of rupture sites. This information
together with the cyclic creep data of Figure 5 indicates that
the mechanism of CFC should involve relief of strain
hardening by combined cyclic loading and anodic dissolution
at film rupture sites, as previously described. Hydrogen
embrittlement is not a probable factor, since Duquette and
Uhlig 4~ were able to suppress CFC in a similar sys-
tem by applied cathodic potential. Unfortunately, similar
current-transient data are not available for austenitic stainless
steel. Austenitic stainless steel is subject to CFC, however,
in dilute chloride solution even at room temperature. 4~
Therefore, it does not seem unreasonable to suppose that
a similar mechanism applies for stainless steel, or any film
covered metal.
It is worthwhile to examine the effect of elevated
temperature on fatigue behavior, since temperature should
relieve strain hardening much like anodic dissolution. Sidey
a n d C o f f i n 42 report that a positive sawtooth (slow-fast) stress
wave (,~-,4) and tensile hold times produce accelerated fatigue
and intergranular fracture in austenitic and ferritic alloys at
elevated temperature in vacuum. Similar results are given by
Barsom 4:~for CFC of a 12 Ni-5Cr-3 Mo steel in 3 pct NaC1 at
6 cpm. Again, the positive sawtooth (slow-fast) waveform
produced CFC, while the negative sawtooth (fast-slow) did
not. Any waveform involving a finite rise time of stress
(slow-fast, sinusoidal, triangular) accelerated CFC. Square
wave with a 10-second hold time (6 cpm) did not produce
CFC. Longer tensile hold times of 1, 3, and 5 minutes have
produced CFC of titanium in salt water. 44
The mechanism of these CFC effects is obscure because the
data are incomplete for any given system. However, the
similar enhancement of fatigue by both temperature and
corrosion suggests that both may have a kindred metallurgical
source. Dislocation climb due to enhanced vacancy
concentration and mobility seems a likely factor at high
temperature. In any case, the mechanism must be
metallurgical, since the degrading effects of a slow-fast
waveform were observed even in vacuum. 42 This suggests
further that waveshape effects in CFC may also have a
metallurgical source, that is, a metallurgical change (injected
divacancies) at the crack tip caused by surface reactions.
Barsom 43 has attributed environmental cracking in his
12 Ni-5Cr-3Mo steel (187 ksi tensile strength) to hydrogen
embrittlement. This conclusion cannot be accepted without
question, because Lee and Uhlig 45were able to stop CFC of
AISI 4140 steel of Rc44 (210 ksi tensile strength) by ca-
thodic protection. Cathodic protection did not result in hy-
drogen embrittlement of this same steel until heat treated to
Rc52 (240 ksi tensile strength). There seems to be a real
possibility that the frequency and waveform effects on CFC
observed by Barsom are due not to hydrogen embrittlement
but instead to a mechanism such as the one suggested here
involving film rupture and relief of strain hardening. One
can speculate that a rising tensile load stimulates divacancy
diffusion and consequent relief of strain hardening while a
falling load does not.
ll40 VOLUME 16A, JUNE 1985
Sidey and C o f f i n 42 observed even stronger waveform ef-
fects on fatigue in air as compared to vacuum. They attrib-
uted this effect to the high temperature environment, i.e.,
"oxidation fatigue" similar to corrosion fatigue. In view of
the preceding discussions, it is tempting to suggest that the
environmental effect may be attributable to vacancies gener-
ated by oxidation which then interact with subsurface dis-
locations to alter strain hardening. Electron microscopic
evidence of vacancy generation by high temperature oxi-
dation has been documented, 46 giving still further indication
that relief of strain hardening by vacancies (or divacancies)
has widespread application. Microvoids formed by vacancy
coalescence at grain boundaries during high temperature
oxidation showed 47 a remarkable influence on subsequent
mechanical properties. The effect was rather similar to that
shown in slow strain rate testing (Figure 6), in which reduc-
tion of both strength and ductility resulted from surface
corrosion reaction. Vacancy effects during oxidation were
permanent and independent of strain rate 47 because vacancy
density and mobility were sufficient to cause irreversible
formation of microvoids.
V. CONCLUSIONS
A concise list of steps in the proposed mechanism is
presented immediately preceding the Discussion section and
pictured schematically in Figure 9. The major conclusions
derived from this work are listed below.
1. Film rupture is a critical element in any mechanism of
environmentally assisted fracture. An overlooked factor
may be the high anodic current density which results
from galvanic coupling between bare surfaces at rupture
sites and surrounding film-covered passive surfaces.
2. During SCC some critical dissolved species such as C1-
must generally be present to retard the rate of repassi-
ration and maintain anodic dissolution. During CFC,
cyclic loading fills this function, a critical species is
not necessary, and CFC is a more frequent occurrence
than SCC.
3. Considerable experimental evidence is available to indi-
cate that anodic dissolution at the rupture sites promotes
(a) relief of strain hardening at surface slip bands during
crack initiation and (b)brittle cleavage on prismatic
planes or at grain boundaries in the plane strain region
adjacent to the crack tip during crack propagation.
4. The agent causing these effects may be divacancies which
are generated by anodic dissolution and which have suffi-
cient mobility to react with subsurface dislocations and
accumulate on cleavage planes. Diffusion calcula-
tions suggest that divacancies can migrate fast enough to
account for measured rates of crack propagation.
5. The assumption of divacancy relief of strain hardening
clarifies several metallurgical facts relating to SCC:
cleavage-like transgranular crack surfaces on prismatic
planes, transitions between intergranular and trans-
granular modes of cracking, resistance of pure metals,
and susceptibility of low strength highly strain harden-
able alloys.
6. Fatigue at elevated temperature in vacuum and fatigue at
lower temperature during corrosion may share similar
failure mechanisms. In both cases cracking is often accel-
erated by lower frequency and longer tensile hold time.
METALLURGICAL TRANSACTIONS A
 Thermally generated vacancies cause dislocation rear-
rangements at elevated temperature. Corrosion induced
divacancies may perform the same function during corro-
sion fatigue at lower temperature.
7. "Oxidation fatigue" in gases at high temperature has
many of the same characteristics of corrosion fatigue at
lower temperatures in aqueous solutions. Evidence of
vacancies from high temperature oxidation has been ob-
served by electron and optical microscopy.
8. The evidence is considerable that the mechanism of SCC
and CFC involves relief of strain hardening at the crack
tip by corrosion induced divacancies. This evidence has
been drawn from divergent alloy and corrosion systems.
Further work is needed to verify the generation of di-
vacancies and relief of strain hardening by corrosion in
a number of alloy systems which exhibit both SCC
and CFC.
ACKNOWLEDGMENTS
Discussions with Dr. B. E. Wilde, Ohio State University,
and Dr. V. K. Sethi, Kentucky Center for Energy Research,
Lexington, KY, have greatly stimulated and clarified the
author's thoughts on this work.
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VOLUME 16A, JUNE 1985--1141