A Theory for the Propagation of

Stress Corrosion Cracks in Metals

David A. Vermilyea*
Corporate Research and Development, General Electric Company, Schenectady, N e w Y o r k 12301

ABSTRACT
A q u a n t i t a t i v e theory for the rate of propagation of stress corrosion cracks
in meta]s is presented and discussed. The theory is based on the film r u p t u r e
mechanism and is valid w h e n p h e n o m e n a at the crack tip control the propaga-
tion rate. The i m p o r t a n t parameters in the theory are the strain required to
r u p t u r e the passive film, the a m o u n t of corrosion before repassivation, and
the creep rate of material at the crack tip. P l a u s i b i l i t y of the theory is d e m o n -
strated for stainless steel and for a m a g n e s i u m alloy.

The objective of this paper is to present and discuss
a model which makes it possible to predict the rates
of propagation of stress corrosion cracks in metals in
terms of e x p e r i m e n t a l l y accessible characteristics of
the system. The theory is based upon the film r u p t u r e
mechanism (1, 2) and is applicable to situations in
which p h e n o m e n a at the crack tip control the propa-
gation rate. The theory accepts the generally held view
that during stress corrosion cracking metal strain and
corrosion are m u t u a l l y stimulative. S t r a i n accelerates
corrosion b y periodically causing film rupture, while,
as suggested by Hart (3), corrosion accelerates strain
by removing the most severely strain hardened m a t e -
rial in the immediate vicinity of the crack tip. F r o m
the point of view of the theory, adequate information
is not presently available about all of the system char-
acteristics, especially about the details of stress and
strain at the crack tip, in order to permit accurate rate
predictions. Nevertheless the theory provides a con-
ceptual f r a m e w o r k which is a m e n a b l e to f u r t h e r de-
velopment and identifies the r e l e v a n t m a t e r i a l char-
acteristics so that their influence on the process can
be discussed from at least a s e m i q u a n t i t a t i v e point of
view.
Theory
In order to predict crack propagation rates it is
necessary to d e t e r m i n e the values of L, E~, tL, and to.
Values for L, so, and tn can be obtained from t r a n s i e n t
experiments in which specimens covered with films
formed in a solution chosen to simulate the crack-tip
solution are strained while m a i n t a i n e d at the crack-
tip potential. If the specimen is strained slowly re can
be d e t e r m i n e d from the specimen strain at which a
m a r k e d c u r r e n t change occurs. Values for L and tL can
be obtained from the c u r r e n t t r a n s i e n t following a
sudden extension of the specimen.
The film r u p t u r e time, given b y tc -- tL, is found
from the creep strain vs. time behavior of the metal
and the value of the critical strain. The creep behavior
must be k n o w n for the m a t e r i a l present a distance L
ahead of the crack tip, that is, for the material at the
o~
D
M.J

Model.--The model is outlined in Table I.

The m e t a l is assumed to be homogeneous, isotropic, Z
and uniform, and the detailed atom motions involved $
in creep strain, i n c l u d i n g dislocation motion, are ig-
nored. The rate of crack propagation,,f", according to
this model is
,~ L \
= [1]
tc I !

Corrosion is assumed to proceed at a negligible rate

when the metal is passive.
Figure 1 portrays schematically the strain rate and
strain d u r i n g crack propagation. Following film r u p -
ture an a b r u p t increase in strain rate occurs because
the r e s t r a i n i n g influence of the surface film is removed.
During corrosion prior to repassivation a f u r t h e r strain
rate increase occurs as the most highly strained m a t e -
rial n e a r the crack tip is removed. A f t e r repassivation
the strain rate decreases because of the presence of
the surface film and because of strain hardening.
" Electrochemical Society Active Member.
K e y w o r d s : film r u p t u r e , creep.

Table h Model of stress corrosion cracking mechanism

I I |
to tL tc
Event Time
T~
1. Passive film ruptures t = to
Fig. I. Variations of crack tip strain and strain rate during stress
2. M e t a l corrodes to a d e p t h L t = tr~ corrosion cracking. Film rupture occurs at t = O; corrosion occurs
3. Repassivation occurs t = tL
4. Creep strain continues to tL; repassivation occurs at tL; creep continues to te at which
5. P a s s i v e f i l m r u p t u r e s a t a c r i t i c a l s t r a i n ec t = tc film rupture occurs again and the cycle repeats.

405

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 406 J. E l e c t r o c h e m . Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y
position of the crack tip after film r u p t u r e and re-
passivation.
The most difficult q u a n t i t y to d e t e r m i n e is u n -
d o u b t e d l y the film r u p t u r e time, because creep be-
havior, especially in response to sudden la r g e stress
transients at low temperatures, is poorly understood.
In addition, the distribution of stress and strain near
the crack tip in an elastic-plastic m e d i u m is not a m e n -
able to exact treatment, so that a p p r o x i m a t i o n s must
be m a d e in d e t e r m i n i n g crack tip conditions. The ch ar -
acteristics of stress corrosion cracks suggest that the
plastic strain n e a r crack tips is less than 0.2, for no
gross d ef o rm at i o n is visible f r o m the microstructure,
but more than 0.05, for the cracks are g e n e r a l l y sharp
and r ep r es en t l ar g e stress concentrators. A reasonable
assumption m i g h t be that the plastic strain near the
crack tip is 15%. Transient creep m e a s u r e m e n t s using
m a t e r i a l c o l d - w o r k e d 15% should then provide data
from which the film r u p t u r e time can be estimated.
Applications of the Theory
The l i t e r a t u r e does not p r e s e n t l y supply enough data
for an y system to m a k e an a d e q u a t e test of the theory.
The only useful data are for the creep strain vs. time
b e h a v i o r of stainless steel in boiling m a g n e s i u m
chloride, and for a m a g n e s i u m alloy at a m b i e n t t e m -
perature. A l t h o u g h the available data w e r e not origi-
nally obtained with th e objective of duplicating crack-
tip conditions, t h e y do at least give an o r d e r - o f - m a g n i -
tude idea about the rates involved. Values of L, ~c, and
tr are also not available. The best that can be done is
to d e m o n s t r a t e plausibility by assuming reasonable
values for ~c; assuming that tL is small compared to to;
and using the available creep data and stress corrosion
crack propagation rates to calculate values for L.
The f r a c t u r e strain, ~c, for a l u m i n u m oxide has been
reported by Cochrane and Block (4) to be 3 9 10-4; by
B r a d h u r s t and Leach (5) to be 3 9 10-3; by B r u m m e r
and Cocks (6) to be 10 -3 to 5 9 10-3; and by Gross-
k r e u t z (7) to be 1.5 9 10 -3 to 3 9 10-8. These a v e r a g e to
about 2 9 10 -8, and accordingly a v a l u e of 2 9 I0 -3 for ~c
will be used, the assumption being m a d e that the frac-
t u r e strain wo u l d be about the same for most oxides,
at least as to o r d er of magnitude.
Brauns and Ternes (8) r e p o r t e d that the creep
strain rate, ~, for an A I S I 304 stainless steel at the
t e m p e r a t u r e of boiling MgC12 obeyed the relationship
= kt - m [2]
in w h i c h m ~ 1.1 to 1.3 and k is a constant. F r o m their
data for 20 k g / m m 2 (28,300 psi) k = 1.45 9 10 -3. F r o m
Eq. [2] by integration, taking m = 1.2
= const -- 5kt -0.2 [3]
Assuming repassivation to be complete at 1 sec, Eq.
[3] gives 5 sec for the strain to reach 2 9 10 -8. A c c o r d -
ing to Brauns and Ternes the time to crack a 0.35 cm
test specimen at 20 k g / m m 2 and at a potential of --80
m V is 2 hr, so that the crack propagation rate is about
5 . 10 -5 cm/sec. F r o m Eq. [1] L ~_ 3" 10 -4 cm. At
E = --110 m V the failure time increased to about 200
hr, and the corresponding value of L w o u ld be 3 9 10 -6
cm. Brauns and Ternes also give values for the creep
strain rate at 10 k g / m m 2 and 30 k g / m m 2, and also
for the cracking time at those stresses. At 30 k g / m m e
the creep strain r a t e is about a factor of 2 g r e a t e r than
at 20 k g / m m 2, and the f a i lu r e t i m e at --80 mV is about
half that at 20 k g / m m 2. A t 10 k g / m m 2 the creep r a t e
is l o w e r by a factor of 3 and the failure time longer
by a factor of 5. A ll these data are consistent w i t h a
constant value of L at a given corrosion potential, and
the values deduced for L seem reasonable.
Logan (9) gave data for the c r e e p strain rate of m a g -
nesium alloy AZ31. A n analysis similar to that above
gives a v al u e of L of 10-2 cm, w h i c h at first glance
seems r a t h e r large. On the other hand the specimens
cracked in only a f e w minutes, and the cracks appeared
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A p r i l 1972
from the 10 • photographs to be r a t h e r wide. The value
of L of 10 -2 cm is at least conceivable. It is also pos-
sible that the v al u e assumed for ~c is too high, or that
the repassivation times are v e r y short so that creep
strain below one second is important.
Discussion
The parameters o~ the m o d e l . - - T h e critical strain, ~c,
will depend on the n a t u r e of t h e film which forms and
on its homogeneity, and hence in t u r n p r i m a r i l y on the
al l o y but also possibly on the solution composition.
F i l m r u p t u r e probably nucleates at flaws, and hence
the n a t u r e and distribution of p r eci p i t at e particles in
the m et al will be important. If the reaction product e x -
hibits considerable plasticity, stress corrosion c r a c k -
ing m a y be impossible.
The value of L will be influenced by the metal, the
solution (a possible role for inhibitors), and especially
the potential. If the potential is low enough (cathodic
protection) t h e value of L will be too small for crack
propagation. A m i n i m u m v al u e for L can be computed
as follows. It is necessary for corrosion to result in a
change n, in the crack tip strain of at least ~c. ~e is
given by
~, ----Co -- ,(p+L) [4]
w h e r e co is the crack tip strain and ,(p+L) is the strain
at t h e crack tip after corrosion to the depth L. Tetel-
m an and M c E v i l y (10) state that the plastic strain
varies a p p r o x i m a t e l y as x - 1 , so that
pro
,~ = [5]
X
in which ex is the strain at distance x and p is the radius
of c u r v a t u r e at the crack tip. Using Eq. [5] to find
e(p+L) gives
p+L
Setting ne --~ ~c and solving for L gives
cr
L ~--, (p + L) [7]
co
and a m i n i m u m v al u e for L is given by
pro
Lmin = - - [8]
eo ~ ec
Taking Ec = 10 -3, co = 10 - I , p = 10 - 4 gives L m i n =
10 -6 cm, while if ~r = 10-8, ~o = 10-2, p = l0 -3 the
v al u e of Lmin is about 10 -4 cm. Note that L m a y be
associated w i t h the striations often observed on stress
corrosion f r a c t u r e surfaces, and that the v al u e obtained
for L can be confirmed f r o m a m e a s u r e m e n t of the
spacing of such striations. A casual p er u sal of t he
l i t e r a t u r e shows striation spacings of about 0.03 to
1 ~m.
The repassivation time, tr, will be influenced b y the
metal, the potential, and especially by t h e solution
composition. Aggressive species like chlorides m a y
cause a large increase of tL.
F o l l o w i n g film r u p t u r e the creep rate w h i c h d e t e r -
mines the time to cause cracking, tc, is influenced by
t h e stress, the m e t a l composition, and by L. The effect
of stress is p a r t i c u l a r l y i m p o r t a n t and is discussed be -
low. Metal composition d e t e r m i n e s the detailed t r a n -
sient creep response to a stress change. A n e x a m p l e
of an i m p o r t a n t m e t a l composition effect is r ep r es e nt e d
by the possibility of strain aging. S t r a i n aging should
play a v e r y i m p o r t a n t role in stress corrosion cracking
for two reasons. In a strain aging alloy a large va l ue
of • m a y be r e q u i r e d to start plastic deformation, and
the ensuing t r an si en t creep m a y be sharply curtailed
so that stress corrosion cracking m i g h t not occur. The
role of L in d e t e r m i n i n g the creep rate arises from the
fact that a large L results in l a r g e r i n c r e m e n t s of
 Vol. 119, No. 4 P R O P A G A T I O N OF S T R E S S C O R R O S I O N C R A C K S
stress and strain following crack advance, so that a
large L should result in faster creep.
Roles of temperature and stress.--The t e m p e r a t u r e
will influence the creep rate and the corrosion process.
A n increase in t e m p e r a t u r e would always be expected
to increase the creep rate, and u s u a l l y would increase
the value of L. In special cases an increase in t e m p e r a -
ture m a y decrease L and decrease the rate of stress
corrosion cracking. For instance, a higher t e m p e r a t u r e
m a y increase the rate of repassivation more than it
increases the rate of corrosion prior to repassivation.
The stress dependence of the creep rate can be ex-
pressed by the equation
= const 9 ~a [9]
where a is a constant (the strain rate exponent) which,
for low homologous temperatures, has values of about
5-10. A smaller dependence of the creep rate on applied
stress m a y be expected in stress corrosion cracking,
however, since an increase in applied stress will pro-
duce a proportionately smaller increase in the stress
at the crack tip where plastic strain has occurred. A
h i g h - p o w e r dependence of crack propagation rate on
stress can be expected w h e n stress corrosion cracking
occurs with crack tip stresses which are just above the
yield stress, i.e., at low applied stresses, a n d w h e n
the strain rate e x p o n e n t is high. On the other hand
there m a y be a value of strain rate exponent above
which stress corrosion cracking does not occur at all.
If the strain rate e x p o n e n t is very large then the film
r u p t u r e induced application of a stress i n c r e m e n t to
material just ahead of the crack tip will result in a
very large creep rate. I n consequence n e a r l y all the
deformation following film r u p t u r e m a y ensue before
repassivation occurs, with the result that the total re-
m a i n i n g creep strain is insufficient to r u p t u r e the film
again. I n short, not only the m a g n i t u d e of the strain
transient but also its detailed t i m e - d e p e n d e n c e deter-
mine w h e t h e r the crack can progress. It should espe-
cially be noted that if the total strain t r a n s i e n t follow-
ing repassivation is less t h a n ec stress corrosion crack-
ing by this m e c h a n i s m is impossible.
The influence of cold work, strain hardening, and
grain boundaries.--Cold work should have an influence
on the rate of stress corrosion cracking through its
influence on the creep rate and because some grains
will be left in residual tension. Small a m o u n t s of cold
work m a y increase the dislocation density and creep
rate, while large a m o u n t s of cold work m a y produce
dislocation structures in which few free dislocations
are available and in which t r a n s i e n t creep m a y be v e r y
small.
The strain h a r d e n i n g e x p o n e n t will be i m p o r t a n t in
d e t e r m i n i n g the distribution of stress and strain near
the crack tip. If the material strain hardens relatively
little, there will be a gradient of strain b u t little
gradient of stress n e a r the crack tip. W h e n corrosion
allows the tip to advance the same stress will therefore
act on a m a t e r i a l which is plastically strained a smaller
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407
a m o u n t and creep will occur. For materials which strain
h a r d e n m a r k e d l y there will be gradients of both stress
and strain near the crack tip, so that after crack ad-
vance not only will the material at the new crack tip
be plastically strained less t h a n it was before crack
advance but also the stress acting on that m a t e r i a l will
be greater than before the advance of the crack. Ac-
curate predictions r e q u i r e more detailed knowledge of
these gradients, but it m a y be that materials which
strain h a r d e n m a r k e d l y are more susceptible to stress
corrosion cracking because crack advance results in
faster creep t h a n in those materials which do not strain
h a r d e n much.
Grain boundaries could influence stress corrosion in
several ways. First, strain is likely to be greater near
the grain boundary, which m a y also be the site of n u -
merous dislocation pile-ups. Second, the composition
at the grain b o u n d a r y m a y differ from the b u l k com-
position. Third, the grain b o u n d a r y m a y contain pre-
cipitate particles which change ec. There are therefore
several reasons to expect that stress corrosion cracking
should be p r e d o m i n a n t l y i n t e r g r a n u l a r . On the other
hand, for several reasons slip at low stresses m a y
often be easier w i t h i n the b u l k of the grains t h a n near
the grain boundaries. Then providing L is large enough
to give an adequate crack advance per film r u p t u r e
event so that the n e w creep rate can be large the m a -
terial m a y be susceptible to t r a n s g r a n u l a r cracking.
Acknowledgment
Conversations with L. F. Coffin, Jr., M. E. Indig,
E. W. Hart, D. Lee, H. W. Schadler, H. D. Solomon,
and C. S. Tedmon, Jr. contributed in an i m p o r t a n t w a y
to the development of the ideas incorporated into this
paper.
Manuscript submitted Aug. 6, 1971; revised m a n u -
script received Nov. 1, 1971.
A n y discussion of this paper will appear in a Dis-
cussion Section to be published in the December 1972
JOURNAL.
REFERENCES
1. F. A. Champion, "Symposium on I n t e r n a l Stresses
in Metals a n d Alloys," p. 468, Inst. of Metals,
London (1948).
2. H. Logan, J. Res. Nat. Bur. Std., 46, 99 (1952).
3. E. W. Hart, Proc. 14th Sagamore A r m y Materials
Research Conference, p. 210, Syracuse U. Press
(1966).
4. N. J. Cochrane and R. J. Block, This Journal, 117,
225 (1970).
5. D. H. B r a d h u r s t and J. S. L. Leach, ibid., 113, 1245
(1966).
6. S. B. B r u m m e r and F. H. Cocks, Gordon Research
Conference (Corrosion), 1970.
7. J. C. Grosskreutz, This Journal, 116, 1232 (1969).
8. E. B r a u n s and H. Ternes, WerkstolTe Korrosion, 19,
1 (1968).
9. It. Logan, "The Stress Corrosion of Metals," p. 234,
J o h n Wiley & Sons, New York (1966).
10. A. S. T e t e l m a n and A. J. McEvily, Jr., "Fracture
of S t r u c t u r a l Materials," J o h n Wiley & Sons,
New York (1967).