.I. /‘hp. Chem. So/i& Vol. 48, No. II, pp. 1101-1113, 1987 (X)22-3697/87 $3.00 + 0.

00
Printed in Great Britain. 0 1987 Pergamon Journals Ltd.

STRESS-CORROSION CRACKING
K. SIBRADZKI
Department of Applied Science, Brookhaven National Laboratory, Upton, NY 11973, U.S.A.

and
R. C. NEWMAN
Corrosion and Protection Centre, UMIST, P.O. Box 88, Manchester M60 IQD, England

Abstract-We review stress-corrosion cracking (SCC) with an emphasis on recent developments in this
field regarding the transgranular form of cracking. Evidence is presented indicating that transgranular
SCC occurs via a series of discontinuous microcleavage events. Each event is typically 1 pm in extent and
is triggered by a thin film of several hundred nm in thickness which has formed around the crack tip owing
to an anodic process. This mechanism of SCC is called film-induced cleavage and we discuss its operation
for many metals including stainless steels, Cu-Al alloys, a-brasses, and pure copper. Analytical
calculations are presented which support the concept of film-induced cleavage.
The compositional dependence of SCC in Cu-AI and Cu-Zn alloys is shown to correlate exactly with
the compositional dependence of de-alloying the less noble metal element from these alloy systems. The
selective dissolution process is discussed within the general framework of percolation theory.
Keywordr: Corrosion, de-alloying, stress-corrosion cracking, fracture, dislocation, cleavage.

1. INTRODUCTION 1.2 Intergranular stress-corrosion cracking

1.1 Stress -corrosion cracking
Stress-corrosion cracking (XC) is defined as the
growth of cracks under the combined influence of a
non-cyclic tensile stress and a reactive environment.
Usually the environment is an aqueous solution, and
for the purposes of this review we shall restrict
ourselves to metals. All SCC failures have in com-
mon a macroscopic appearance of brittleness, in the
engineering sense that the ductility of the material is
impaired, but the degree to which they involve
microscopic cleavage or brittleness remains unclear.
The rate of SCC can vary from lo-” to 10-r m/s, but
normally lies within the range of 10-‘0-10-7m/s.
SCC is a formidable engineering problem, especially
in the nuclear power and chemical industries.
There are several processes that can contribute to
the growth of stress-corrosion cracks, including
anodic dissolution, film growth and hydrogen effects.
These have often been expressed as a “spectrum” of
behavior ranging from obvious anodic dissolution
control to obvious hydrogen embrittlement [l].
Examples of extreme behavior include the inter-
granular cracking of mild steels in nitrate solutions
(anodic dissolution) and the cracking of high-
strength, low-alloy steels in chloride solutions
(hydrogen embrittlement). The position of trans-
granular SCC in this spectrum has been unclear for
some time, but current thinking is converging to the
view that intergranular SCC is continuous and
transgranular SCC is a discontinuous brittle process
121.
1101
Intergranular SCC is often related to the existence
of some chemical heterogeneity in the grain bound-
ary, such as a segregated impurity element, that can
provide an electrochemically active path for the
corrosion process to occur. Normally a good
correlation can be obtained between the rate of
intergranular SCC and the rate of anodic reaction on
a bare metal surface [3]. There are a few cases of
intergranular SCC where the grain boundary corro-
sion rate is far too low to account for the observed
cracking rate: Newman et al. [4] identified the
existence of a substantial mechanical component in
the intergranular SCC of sensitized 304 stainless steel
which accounted for the unusually high cracking
rates they observed in their study, and similar
observations were reported in the Ni-P system by
Jones and Danielson [5]. In other systems inter-
granular SCC seems to be a continuous process
except where hydrogen is involved.
1.3 Tramgranular stress -corrosion cracking
Transgranular SCC invariably has a brittle,
cleavage-like appearance. The most well known and
important practical example is the chloride-induced
cracking of austenitic stainless steels, which has been
reviewed by Latanision and Staehle [6] and more
recently by Theus and Staehle [7j. Cracking has been
observed at all temperatures between 50” and 350°C
and all conceivable cracking mechanisms have been
proposed at one time or another. It has been known
for many years that hydrogen is produced in the
1102 and R. C. NEWMAN
K. SIERADZKI
cracks [8], but no conclusive role of hydrogen
embrittlement has been demonstrated. The sus-
ceptibility of stable austenitic steels adds consid-
erably to the difficulty of building a case for hydro-
gen embrittlement and an alternative brittle
mechanism is almost certainly required.
Hahn and Pugh [9], working with a stable
austenitic steel, found strong indirect evidence for
discontinuous crack growth on (100) surfaces in
increments of about 0.5 pm. They showed, by mark-
ing the fracture surface with load pulses, that the
crack remained in one position for a critical length
of time before a load pulse would cause it to
advance. Hydrogen diffusion was suggested as the
rate-controlling process, although more recently
Pugh [lo] seems less sure of the role of hydrogen. We
have developed an alternative line of reasoning based
on earlier evidence that a spongy layer is formed
within cracks in susceptible steels [1 11, and we have
shown that this is not an oxide but a de-alloyed
metallic layer consisting of an Fe+Ni alloy of con-
tinuously varying composition through its thickness
[12]. Chromium hydroxide is precipitated within
the pores of the layer, and this misled earlier
investigators into identifying the layer as an oxide. In
view of the evidence for de-alloying-controlled
cleavage in other systems (see Section 2), this finding
should help end the controversy regarding the role of
absorbed hydrogen in chloride SCC of austenitic
steels, since there is much other evidence against a
critical role of hydrogen (e.g. lack of correlation
between SCC and austenite stability; small effect of
temperature in the range of 1%3SOC). There are
many other f.c.c. metals and alloys which display
transgranular SCC in which the role of hydrogen can
be neglected on thermodynamic grounds. Perhaps
the most well known of these is the cracking of
alpha-brass, which occurs in a wide variety of
environments. Newman and Sieradzki [13] demon-
strated that this alloy cracks discontinuously in a
sodium nitrite solution. Periodic electrochemical
current transients were found to occur simulta-
neously with acoustic events to within at most 1 ms.
The sizes of the current transients were consistent
with the crack advance distances measured metal-
lographically and the number of transient events
corresponded to the number of crack arrest marks on
the fracture surface. There is also strong evidence for
discontinuous SCC in Au-G alloys [14] and in pure
copper [151.
1.4 Film -induced cleavage
This paper will focus on the transgranular form of
SCC. This is particularly appropriate in view of the
close relationship which we feel exists between trans-
granular SCC and other topics in fracture to be
addressed in this special issue, such as the
brittleductile transition. Sieradzki and Newman [ 161
have recently proposed a new model of transgranular
SCC based upon the concept of film-induced
cleavage, and this will be reviewed together with new
material on the special films that can nucleate
cleavage in ductile materials.
Over time-scales relevant to the SCC process, most
ambient temperature reactions between a metal and
its environment are limited to a surface or near-
surface effect. (Hydrogen absorption is an obvious
exception to this statement; however, as noted
earlier, hydrogen can often be ruled out as a cause
of SCC.) The reaction product is usually a thin
layer or film with different chemical, structural, and
mechanical properties with respect to the bulk metal
substrate. Some examples of relevant films are
oxides, chlorides, nitrides and porous metallic layers.
The concept introduced by Sieradzki and Newman
[16] is that thin films can induce microscopically
brittle (cleavage-like) behavior in intrinsically ductile
metals. Recent results of molecular dynamic simu-
lations supporting this notion are reviewed by Dienes
and Paskin [17]. The concept of film-induced
cleavage is further supported by analytical calcu-
lations [16, 18, 191 which define relationships which
must exist between film and substrate in order for
this mechanism to operate. The main film and
interfacial parameters affecting material behavior are
the following:
(a) lattice parameter misfit;
(b) elastic modulus mismatch;
(c) interfacial state of coherency;
(d) degree of interfacial bonding;
(e) geometric shape of film surrounding crack
(determined by growth kinetics);
(f) porosity;
(g) intrinsic brittleness or ductility of the film.
In Section 3 we will show how suitable combina-
tions of some of these parameters can induce
cleavage-like behavior of intrinsically ductile solids.
The propagation and arrest of microcleavage events
are considered in Section 4.
We propose that the presence of a film at a crack
tip can modify the local deformation in such a way
as to initiate cleavage. In this respect we are con-
cerned with the film’s effectiveness in changing the
balance between cleavage and dislocation emission.
In Section 4 we shall also describe the physical
conditions under which a cleavage crack can propa-
gate a significant distance in a ductile metal before
coming to an arrest. Processes of this sort are not
rare and are not confined to SCC. For example, the
initiation of cleavage in carbon steel is just such a
process. McMahon and Cohen [20] observed that a
carbide served as the site of crack initiation, and
under appropriate conditions the crack propagated
through the carbideferrite interface into the ferrite.
In some cases the cracks arrested in the bulk of the
grain, but more often cracks were stopped at the
nearest grain boundary. If we imagine that a new
carbide is formed at the arrest position of the crack,
 Stress-corrosion cracking
then this would represent a process by which com-
plete fracture of the body could occur. The rate of
crack growth would depend upon the rate of for-
mation of the carbide, and if this were finite a form
of intermittent brittle (or cleavage-like) cracking
would result. In SCC the reaction of the metal with
the environment produces a film which is the ana-
logue of the carbide.
In the next section we will discuss the relationship
between de-alloying and transgranular SCC within
the general context of porous films. Our emphasis on
de-alloying (selective dissolution) arises because
some of the most clearcut transgranular SCC systems
involve rapid de-alloying on fresh surfaces. However,
other forms of transgranular SCC occur in pure or
nearly pure metals such as copper [l&21] or low-
alloy steel [22] where de-alloying is obviously not
involved. In these cases we proposed that other
forms of reacted layers can nucleate cleavage. These
can be oxides (copper in nitrite solution [IS]) or
nitrides (steel in anhydrous ammonia [22]). More
speculatively, we have suggested that a carbide or
carbon hardened layer is responsible for trans-
granular SCC of steel in CGCO,/H,O solutions
[23]. Finally, copper single crystals can be made to
crack in ammonia solutions were dissolution is
occurring to a low rate and no chemically distinct
film can be present [21]. Here, as discussed briefly in
the next section, a porous zone similar to a de-
alloyed layer is formed and may nucleate cleavage.
The film-induced cleavage concept has unified
many disparate pieces of information in the literature
on transgranular SCC. It used to be thought that an-
odic (metal oxidation or dissolution) processes could
account for the rate of cracking without mechanical
fracture, but in order to do so it was necessary to
postulate unrealistically high reaction rates and crack
tip strain rates. The brittle fractography was also a
difficulty. With film-induced cleavage the propor-
tionality of the cracking rate to the anodic reaction
rate can be explained, since the anodic reaction
produces the cleavage-initiating film [23]. However,
the improbable reaction rates and strain rates are no
longer required, since the anodic process is only
responsible for N 1% of the total crack advance, and
the fractography arises naturally from the micro-
cleavage process.
It is an open question as to whether transgranular
SCC could occur without cleavage. Most probably it
could not, as there would be too much chemical and
mechanical blunting of the crack. Certainly all trans-
granular SCC is cleavage-like, and in most cases
it is possible to detect crack arrest markings
corresponding to the individual cleavage events [2].
Transgranular embrittlement by hydrogen or liquid
metals sometimes shows similar markings on the
fracture surfaces, but can also reportedly grow in a
discontinuous fashion involving extensive micro-
plasticity [24]; no evidence exists for similar processes
in SCC.
P.C.S.
48,11--J
1103
2. THE RELATIONSHIP BETWEEN
DEALLOYING AND SCC
2.1 De -alloying
De-alloying (selective dissolution) occurs in solid
solutions or intermetallic compounds where there is
a large difference in reactivity between the com-
ponents. Good examples of alloys where de-alloying
might be expected are Cu-Al and Cu-Zn where
copper is the more noble element. Cracking in these
systems has long been known to display a marked
sensitivity to the alloy composition, and it has been
shown that no transgranular SCC occurs when the
solute (Zn or Al) content is less than about 20 at.%
[25]. The conventional view of this behavior is that
it relates to the effect of the solute content on the
stacking fault energy in these alloy systems. As the
solute content is raised the dislocation distribution
changes from cellular to planar, and this change
occurs at approximately the composition where these
alloys become susceptible to transgranular SCC.
However, the transition has now been shown to
correspond identically to the onset of de-alloying [26]
(see Section 2.2).
2.2 De-alloying and percolation
Recently, Sieradzki [27] has offered a new
explanation of the compositional dependence of
de-alloying in which the significance of the 20%
threshold becomes clear. The selective dissolution
process is believed to involve an atypical form of the
notion of percolation. Consider an A, B, _-x alloy
immersed in an aggressive aqueous solution in which
the less noble element (say A) is selectively dissolved
out. We believe that de-alloying can operate without
bulk solid-state diffusion of the more reactive com-
ponent if there are continuous connected pathways
of the A atoms throughout the structure of the solid.
The existence of such a connected cluster of A atoms
(termed an infinite cluster in percolation theory)
depends in a statistical manner on the composition
of the alloy and the geometric packing (crystal
structure) of the solid. In f.c.c. structures the site
percolation threshold occurs at approximately 20%,
so that in our A,B, _-x alloy we would predict that
x should be greater than 20 in order for selective
dissolution to progress more than a few monolayers.
The selective dissolution process is sustained by
the surface diffusion of the more noble component,
which allows the aggressive solution to penetrate
through to the connected paths of A atoms. If the
alloy components are sufficiently different in reac-
tivity, then the alloy parting limit will be quite close
to the site percolation threshold. The parting limit is
loosely defined as the limiting composition at which
a particular alloy system will be de-alloyed in a given
environment. The variation in the parting limit and
de-alloying tendency from one alloy system to an-
other due to the varying reactivities among the!
constituent elements in the alloys. Specifically, a
1104 K. SIERADZKIand R. C. NEWMAN
more reactive element will be able to dissolve from
more highly co-ordinated surface sites at a given
electrochemical potential and this in turn can be
related to the difference between the corrosion
potential and its equilibrium metal-metal ion
electrode potential. Normally the site percolation
threshold sets a lower limit on the parting limit of the
alloy, but if one element is extremely reactive then
selective dissolution may proceed via second-nearest
neighbors leading to a slight lowering of the 20%
parting limit.
Dissolution of the reactive element from highly
co-ordinated sites permits exposure of more of these
atoms by surface diffusion of the noble atoms. Little
or no selective dissolution can occur near the per-
colation threshold if the dissolution of the reactive
element is restricted to low-co-ordination sites such
as kinks. To obtain de-alloying in such systems (e.g.
Au-Ag, Cu-Au, Fe-Ni-Cr) the concentration of the
more reactive component(s) must be increased to
about 70% [28]. This view of alloy corrosion is quite
different from the classical view developed by Pick-
ering and Wagner [29], which relies upon bulk
diffusion of the reactive component and has always
required unrealistic room temperature diffusivities of
metal atoms [30]. The percolation model of de-
alloying with surface diffusion accounts for all of the
experimental observations including the extremely
sharp parting limits which are inexplicable in terms
of bulk diffusion models.
2.3 De-alloying and SCC
Sieradzki et al. [26] have recently obtained data on
the selective dissolution and stress-corrosion behav-
ior of Cu-Zn and Cu-Al monocrystals tested in
1C.k
cu.-Al
1
1.
0. I 0.2
ATOM FRACTION OF Zn OR AI
Fig. 1. Dependence of the de-alloying charge density on
alloy composition for Cu-Zn and Cu-A1 alloys.
I
Cu-A
0. I
I
0.2
I1
0.: 3
ATOM FRACTION OF 7.n OR Al
Fig. 2. Effect of alloy composition on the thickness of the
de-alloyed layer produced in 18 s on Cu-Zn and Cu-Al
alloys.
de-oxygenated 15 M ammonia with 0.05 M cuprous
ions [Cu(NH,)t], added as Cu,O. The dependence of
de-alloying on solute concentration is shown in
Figs 1 and 2. The depth of de-alloying cannot be
calculated directly from the charge passed without a
knowledge of the concentration profiles produced.
However, in order to give an estimate of the depth
involved after 18 s of de-alloying, we have assumed
in Figs 1 and 2 that the de-alloyed layers are
completely depleted in the solute elements and all the
solute is replaced by an equivalent volume of poros-
ity. The results are in the 20-50 nm range and are
consistent with our earlier theoretical prediction of
200 atom layers for 7S30 brass [16]. The occurrence
of cleavage-like SCC was found to correspond iden-
tically to the parting limits found for de-alloying, as
shown in Figs 3 and 4. Based on the crack growth
rate and the spacing of the crack arrest markings, we
have shown that the crack is advancing about 1 pm
by cleavage after forming a de-alloyed layer about
20-50nm in thickness, i.e. the anodic process
accounts for only a few per cent of the total crack
growth. The results for the Cu-Al alloys show a
parting limit of approximately 14%, which indicates
that dissolution may be proceeding along chains of
Al atoms which are second-nearest neighbors
(second-nearest neighbor site percolation threshold
in the f.c.c. lattice is 13.6%). This is consistent with
the very high overpotential for dissolution of the
3 aluminum atoms in Cu-Al alloys.
2.4 Morphology de-alloyed layers
A very interesting porous microstructure results
 Stress-corrosion
I I I cleavage-like SCC under electrochemical conditions
-2
=I
,
- I/
1 0.1 0.2 0.2
I _e
ATOM FRACTION OF Zn
Fig. 3. Dependence of the de-alloying rate and average crack
propagation rate (using the longest crack) on Zn concen-
tration in Cu-Zn alloys.
from the de-alloying process. Assuming constancy of
volume within the corroded material, the solute
removed from the de-alloyed layer will be replaced
by an equivalent volume of porosity. Since the attack
follows pathways of initially connected material, the
porosity takes the form of a fine skeletal or branched
structure with numerous inter-connected pathways.
The branches initially have a diameter of a few nm,
but as the film grows in depth the skeletal structure
coarsens in a manner analogous to Ostwald ripening.
The driving force for the coarsening is the overall
reduction in the surface free energy and the kinetics
are controlled by the surface diffusivity.
Our electrochemical measurements of the de-
alloying kinetics [13, 16,261 indicate that only a few
hundred monolayers of film growth occurs during the
time interval (10-60 s) between microcleavage events.
We believe that during this time interval only a slight
degree of coarsening is possible. The porosity which
develops in such thin films has not yet been detected
owing to the very high spatial resolution required to
do so. Nevertheless it is possible to resolve the
porosity developed in thicker films; Fig. 5 shows the
porosity developed following the de-alloying of Ag
from a 80-20 Ag-Au alloy in 4 M perchloric acid for
8000 s. Figure 6 shows the porosity developed after
40,000 s. The size scale of the porosity has increased
by a factor of approximately 2 in 32,000s.
2.5 Role of porous layers in XC
We are convinced that a layer of fine-scale poros-
ity, formed by de-alloying, triggers the microcleavage
events during SCC in many alloy systems. A related
(though at first puzzling) observation is that an
oriented single crystal of copper can undergo
cracking 1105
for which no film is present, i.e. the copper is
undergoing active dissolution [21]. This is not to be
confused with earlier work on the cracking of copper
single crystals in sodium nitrite solution in which a
cuprous oxide film is known to form [15]. In the
film-free condition a fine-scale porosity developed on
the specimen surface, provided that it was under
dynamic strain and within an intermediate range of
strain rates (Fig. 7). The porosity is formed by a
selective dissolution process which occurs at
emergent points of mobile dislocations. At low
enough displacement rates the corrosive attack
reverts to the normal crystallographic etching pro-
cess.
We do not yet understand how a porous film
nucleates a microcleavage event. There seem to be
several possibilities:
(a) The porous layer could undergo high-speed
ductile tearing which could initiate microcleavage.
Hancock and Cowling [31] have discussed the occur-
rence of such a process on a more macroscopic scale
in steels.
(b) The mechanical behavior of the fine-scale me-
tallic ligaments comprising the porous layer may be
significantly different from that of the bulk material.
In sufficiently thin ligaments, dislocation sources may
not be present and the deformation mode may be
significantly altered. If the ligaments fail by homoge-
neous shear, a mesoscopic cleavage-like process in the
layer may ensue which may then continue into the
bulk metal owing to dynamic effects.
The mechanical properties of porous structures are
currently under study in our laboratory and we hope
‘1
i
l-&L_
C
0.1 0.2 0.;
ATOM FRACTION OF Al
Fig. 4. Dependence of the de-alloying rate and average crack
propagation rate (using the longest crack) on Al concen-
tration in Cu-Al alloys.
1106 K. SIERADZKIand R. C. NEWMAN

Fig. 5. The morphology of a 8&20 Ag-Au alloy de-alloyed Fig. 6. The morphology of a 80-20 Ag-Au alloy de-alloyed
in 4 M perchloric acid for 8000 S. in 4 M perchloric acid for 40,000 s.

to have some of these issues resolved in the near radius of a dislocation in the film, (b) the shear
future. modulus of the film, (c) the surface energy of the film
In the next section we consider film properties and (d) the surface or interfacial energy associated
other than porosity which may allow for the devel- with fracture in the substrate. Here we assume that
opment of film-induced cleavage. These parameters the film-metal interface presents no barrier to dis-
may be expected to dominate the situation for films location motion; however, in the usual situation it
of little or no porosity. will strain harden the near-crack-tip region. This case
will be considered in Section 3.2.
Consider a crack coated with a film loaded in
3. ANALYTICAL MODELING OF FILM longitudinal shear as illustrated in Fig. 8. The force
EFFECTS
In this section we will consider the manner in which
a thin film surrounding a crack can induce brittle
behavior of an intrinsically ductile metal. The par-
ameters which we investigate are the elastic modulus
mismatch and the lattice parameter misfit between
film and substrate. The basis of our approach is the
analysis developed by Rice and Thomson [32] in their
study of the stability of an atomically sharp crack in
a solid against blunting by dislocation emission.

3.1 Elastically hard jilms

An elastically hard film is considered to be a film
with a shear modulus greater than that of the
substrate. Consider a film-free crack in a metal which
under sufficient loading is unstable to dislocation
nucleation, i.e. the crack tip can spontaneously emit
dislocations. Sieradzki [33] has discussed how the
presence of an elastically hard film surrounding the
crack can alter the stability of the crack tip. The
main effect results from the modification of the image Fig. 7. The porous morphology developed during tensile
testing of a monocrystal of copper in a 15 M ammonia
force owing to the presence of the hard film. The solution with 0.3 g/l dissolved copper powder. The strain
following parameters enter into determining the rate was 1 x IOm5s-l and the tensile axis was 2” off (1 lO>
dislocation nucleation criteria: (a) the core cut-off This sample underwent severe SCC.
 Stress-corrosion cracking 1107

and is given by

f,= -fi$ (3)

where

u = e312to 12,

1
-= sin e cos fp,
Co’
and &, is the core cut-off for the dislocation in the
film. The critical distance, t,, at which a straight
dislocation is in unstable equilibrium is given by the
condition f,,, =f, +f, +f; = 0.

Fig. 8. Geometry of the dislocation crack configuration

loaded in longitudinal shear. +if
,n2-(r/h)Z
1
k”

1=o,
&s,y,b
2y h2”_

per unit length of dislocation due to the applied load

--- - 1-
2
rFI + [
7K0’<2+LXr x5 0
(4)
is given by
provided that l, < k.
Figure 9 shows the results of calculations for 5,
using values appropriate for iron (yFe= 1.975 J/m’,
Kmb
=-cos8/2sincp
bFe= 2.49 x lo-rOm pLFe= 6.92 x 10” Pa) for
(2np)“Z different values of ;he ratio p,/p, and varying film

=-%y,b
1 thickness h. The results predict brittle behavior for

nt1W’
[
(1)
values of h greater than 2 and ratios of pfflpL,greater
than 3.5. As the value of 2y, is reduced the range of
stability of an atomically sharp crack in the p,/p, - /I
where field is increased. If weak interfaces exist in the solid
in close proximity to the crack tip, elastically hard
G =Q,, 5 =plb films would tend to promote fracture of the solid at
such interfaces.
and
3.2 Ductile films
1 Suppose that the film which forms over a metal as
- = cos e/2 sin rp.
0 a result of a corrosion process is intrinsically ductile.
We are interested in determining whether or not the
Here b,,, = b sin cp, 2y, represents the work required deformation mode of the film could be altered by the
to reversibly separate an internal interface, and p is film-substrate system in such a way as to result in
the shear modulus. The subscripts f and s refer to the initiation of a cleavage cracking mode. In general
film and substrate respectively. the film will have a lattice parameter, a,, different
The image force on a screw dislocation in a film from that of the bulk substrate metal, a,. The lattice
surrounding a crack is given by [33] misfit and the film thickness combine to determine
the nature of the interface and the coherency strains.

h=$ -++;“g,n2_:;,h)2
1
(2) ’
The lattice misfit is given as

where
and h is the film thickness in units of b.
The force due to the ledge left behind during
formation of the dislocation results from the normal
component of the Burgers vector to the crack plane,
3.2.1 Cleavage nucleation by coherent ductile films
of positive misfit. Sieradzki and Newman [16] have
discussed how a crack surface and a planar surface
differ in the manner in which coherency strains are
accommodated. For a/ c a,, coherency strains within
the film are tensile while on the substrate side of the
interface they are compressive. This situation allows
the interface to serve as a barrier to dislocation
1108 and R. C. NEWMAN
K. SIERADZK~

yin,= I .975 J-t-ri*

h=80
// h=50
h=30

h=IO

h=5

1::
h=2

' I.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0

Fig. 9. Results of calculations for yint = 1.975J/mZ.Values of l, less than 2/3 indicates ductile behavior.

motion. If the barrier is strong enough, the near-tip value of the stress intensity for the film. The main
strain hardening will transform the dislocation emit- contribution to _Y comes from dislocation-crack
ting crack into a cleaving crack. The geometric interactions and in the stress-corrosion problem
blunting which the crack tip undergoes during the there are four primary sources of dislocations:
hardening process is inconsequential to the trans-
formation process. Paskin et al. [34] have suggested (1) The grown-in structure present in the annealed
that the geometric blunting of a crack by several crystal. These dislocations are geometrically homoge-
lattice spacings has a negligible effect on the near-tip neous and will not contribute to the shielding term.
stress fields and so the cleavability of the solid. This (2) Dislocations produced under load at sources
is because at an atomic level the crack tip other than crack tip. If the sources are driven by the
configuration affecting the near-tip stresses is deter- crack tip stress field the antishielding components of
mined by the lattice crystal structure. the dislocation are attracted toward the tip and the
In general, coherent films of positive misfit will shielding components are forced away from the tip.
induce a stress intensity, k,,which will tend to open For sources located on the substrate side of the
the crack. Sieradzki and Newman [16] have shown film-substrate interface the antishielding dislocations
that the induced stress intensity is given by will tend to accumulate at distances of approximately
twice the film thickness from the crack tip. The
k/= 2~,(1 - vZ)f.t1’2, (5) contribution of these to 9 is balanced by shielding
dislocations resulting from the arrest process as
where t is the film thickness. In order for the crack discussed in (3). Within the film itself the absolute
to experience stresses induced by the film, t should number of active dislocation sources is low (owing to
be greater than the microscopic crack tip opening the thinness of the film in SCC) so that this con-
displacement. The total stress intensity, k,,acting on tribution to LZ’can be neglected.
the crack is given by (3) In Section 4 we discuss the production of
dislocations at the crack tip during the crack arrest
kr=k,+K+g, (6) process. The shielding portion of these dislocations
will dominate geometrically in the immediate region
where K is the stress intensity resulting from the surrounding the crack which is to become the film.
applied loads and _.Yis the stress intensity resulting The spatial arrangement of these dislocations is
from the shielding effects. The fracture condition determined mainly by the dynamics of the crack
may be expressed as k, > k/c, where k/Gis the Griffith arrest process. Their structure is frozen in by the
 Stress-corrosion cracking
corrosion process and will not vary substantially
during static loading.
(4) The crack tip embedded in intrinsically ductile
material serves as the dominant dislocation source
during static loading. Dislocations produced here
shield the crack from the externally applied stress.
We shall assume that the external loading is such
as to maintain k, at a value equal to k/G [equation
(6)]. Dislocations nucleated at the crack tip will
pile-up at the film-substrate interface located a
distance h (h = t/b) from the tip. The pile-up will
exert a force on an incipient dislocation opposing
nucleation. As the pile-up grows it becomes in-
creasingly difficult for the crack tip to nucleate the
next dislocation. Eventually the local k required to
nucleate the (N + 1)th dislocation is greater than k$
and the emitting crack undergoes a transition to a
cleaving crack. Lin and Thomson [35] have also
discussed the occurrence of such a transition. Re-
ferring to Fig. 10, the number of dislocations in the
pile-up, N, required to cause the deformational mode
transition is given by the condition that the sum of
the forces acting on the incipient (N + 1)th dis-
location is zero, i.e.
Ftotal=o
= k/,(b/8nt,)“* sin rp cos (p/2 cos rp
-pb/4n<j-a,b +pbb/2x
x 5 (5i/5j)"*(tj- tile'. (7)
i=l
t#j
The first term is the force on a dislocation at cj (in
units of b) resulting from the crack tip stress field.
The second term is the image force on a dislocation
at t;, and the third term is the frictional force. The
fourth term is the force on a dislocation at <,
produced by all the dislocations at &, i #j.
SLIP
CRACK LINE
Fig. 10. The geometry of dislocation,
1109
Equation (7) is solved for N using an iterative
algorithm. The position, 5, that the first dislocation
emitted from the crack takes up is equal to the film
thickness, h, unless friction is too great to allow the
dislocation to reach the film-substrate interface. The
force at 4 = &,, the position of the incipient dis-
location (assumed equal to the core cut-off distance
of a dislocation in the film), is continually examined.
When F(&) = 0 a dislocation is nucleated there and
moves away, eventually taking up a position deter-
mined by equation (7). Finally, after N dislocations
have been nucleated, F(&) remains negative and no
further nucleation is possible for k, < k/c. At this
point cleavage in the film becomes possible. In this
analysis we have neglected the contribution of the
ledge terms.
Using parameters appropriate for a-brass we have
evaluated equation (7) for the number of dislocations
N, required to affect a deformational mode transition
as a function of the film thickness, h. The results are
shown in Fig. 11. If N is greater than the interfacial
barrier can withstand, interfacial integrity breaks
down and ductile behavior ensues. If the interface
can support a pile-up of N dislocations, a cleavage
crack is nucleated. The maximum number of
dislocations that a film of thickness h and misfitfcan
withstand is given approximately by [16],
N,_ =f .h. (8)
Using equations [7j and [8], coherent film parameters
for microscopic cleavage in a-brass are summarized
in Fig. 12.
3.2.2 Cleavage nucleation by incoherent$lms. Equi-
librium considerations indicate that the maintenance
of coherency becomes difficult as the product f .h
increases [36]. Most films will lose coherency with the
substrate by forming a network of misfit dislocations.
These misfit dislocations can harden the near-tip
region in a manner similar to dispersion hardening.
PLANE
CLEAVAGE PLANE -
crack and film-substrate boundary.
1110 K. SIE~UDZKI
and R. C. NEWMAN

where

l/8 = sin 4 cos(f$/2) cos *.

The outwardly directed component of this force on

the slip plane is

1 kb
(10)

As shown in Fig. 13, p = r cos 0 + t and r = l/2,

where 1 is the spacing between misfit dislocations
given by

(11)

Using these substitutions, eqn [lo] may be written as

I cos e
I I
de. (12)
0 5 IO 15 [cos e + (2t/Z)]“2
NUMBER OF DISLOCATIONS TO INITIATE CLEAVAGE
Integrating we obtain
Fig. 11. The results of numerical calculations using equation
(7) and values appropriate for a-brass. The results indicate
the number of dislocations required to shift the balance 1(2t/l), (13)
from ductile to brittle behavior in a-brass as a function of
the thickness of a ductile de-alloyed layer surrounding the
crack tip. where the integral

This effect is possible for films of positive and

negative misfit.
Z(2t /I) =
s +n/2 COST
_n,2 [COS e + (2tp)p

is expressible in a standard form as a sum of elliptic

de

We examine the situation by assuming that all of

integrals of the first and second kind.
the coherency strain is accommodated by a network
The inwardly directed component of the line ten-
of misfit dislocations. The relevant question is
sion may be expressed as [37]
whether or not a dislocation formed at the crack tip
can be transmitted through the dislocated interface at
a k value less than kfG. Qb2 2-v ln8r (14)
4w ( l-v > e2y0 ’
The crack geometry is illustrated in Fig. 13. Our
approach is to consider the balance between the crack
Combining equations (14) and (15) yields an expres-
tip force and the line tension of the curved dis-
sion for the value of k required to push a dislocation
location. We assume that if the crack tip force is
sufficient to allow a dislocation to reach the saddle
point configuration (semicircular geometry) it will be
nucleated and pass into the substrate. Under these
circumstances the interface may even serve as a
source of dislocations (via Frank-Read multi-
0.05
l--T--l
plication). On the other hand, if the k value required
to push a dislocation into the saddle point conlig-
uration is greater than kfG cleavage crack nucleation
is possible.
The crack is under mode I loading. The stress field [ 0311 i yherent\\ 1
produced by the applied load yields a normal force on
a dislocation segment of length ds given by

0.0
dF = (a&) dr I IO IO2 IO3 IO4
FILM THICKNESS IN MONOLAYERS

1 kb Fig. 12. The misfit as a function of film thickness required

=_- (9)
/3 (8np)~~2 *, for crack initiation in coherent and incoherent ductile films.
 Stress-corrosion cracking
DISLOCATION
CRACti LINE
Fig. 13. The geometry of dislocation, crack and incoherent interface with misfit dislocation spacing 1.
through a film of thickness h with an interfacial
dislocation spacing 1:
where 1 = i/b. Owing to the r-L’z stress dependency
at fixed k and I, the closer the interface is to the tip
the easier it will be for the crack tip to push a
dislocation through the interface. Hardening is facil-
itated by small 1 and large h. If &, > kfG cleavage
crack nucleation is possible.
We have evaluated equation (15) as a function of
film thickness and misfit using parameters appropri-
ate for a-brass, and the results are shown in Fig. 12.
Examination of this figure indicates that very thin
(~50 monolayers) ductile film on brass can initiate
cleavage only if it remains coherent and has the
required misfit. For thicker films a deformational
mode transition may occur for proper combinations
of misfit and film thickness regardless of the state of
coherency between film and substrate. We assume
that even if coherency is lost the integrity of the
interface is such so that a high degree of bonding
exists between film and substrate.
4. CRACK ARREST
4.1 General considerations
In previous sections we considered a number of
ways in which films surrounding cracks could initiate
cleavage-like crack propagation in intrinsically
ductile metals. In this section we take up the question
of how far the cleavage crack can penetrate into the
ductile matrix. This issue is obviously related to the
brittleductile transition which is known to occur for
a variety of materials as a function of temperature
and strain rate. As a simplification we assume that
the crack will not undergo a decrement in velocity
traversing the film-substrate interface.
There is some experimental [38] and theoretical
[39] evidence indicating that dislocation generation at
the moving crack tip is concomitant with the cleav-
age process. In the simulations described by Dienes
and Paskin [17], the moving crack stops for an
1111
-f3p-
t
%i:
instant immediately following the dislocation nucle-
ation event. As the dislocation moves away from the
crack tip the cleavage cracking continues. It is
interesting to point out that if this crack were loaded
quasi-statically it would continually emit dislocations
and blunt. In the case discussed by Dienes and
Paskin (Figs 16 and 17 of their paper) cleavage
cracking continues owing to purely dynamic effects.
As the dislocation is emitted from the moving crack
the local k falls below k, for the material and the
crack momentarily stops its forward motion. Even
though the crack tip has stopped its forward motion,
the local displacement rate of atoms in the vicinity
of the tip remains extremely high; on the order of
0.2 vL. Thus the crack is shock loaded and its motion
is re-initiated once the dislocation-crack interactions
permit. We believe that the cracking behavior de-
scribed here typifies the cleavage-like crack advance
which occurs during the SCC process.
Crack arrest can occur in semi-brittle or ductile
metals for a variety of reasons:
(a) restraining effect of unbroken ligaments con-
necting the surfaces;
(b) encounters with pre-existing or deformation-
generated defects;
(c) crack bifurcation;
(d) exhaustion.
The restraining effect of ligaments is generally
considered to be the most significant in arresting
macroscopic cleavage cracks [40]. For the micro-
scopic cleavage situation in SCC the effect of liga-
ments seems limited for three reasons:
(1) In some cases (e.g. brass) the ligaments are
themselves extremely crystallographic and are only at
most tens of nanometers in height.
(2) Owing to time retardation effects, only a small
portion of the ligament can assume a role in arresting
the crack.
(3) The crack arrest markings observed micro-
scopically are continuous across many steps of
widely varying height, which tends to suggest an
arrest process intrinsic to the dynamic crack itself.
1112 K. SIERADZKI
We expect that in some cases crack arrest will occur
at defects such as slip bands. If this were the case,
then as the defect density increases the cleavage or
crack jump distance should decrease to an approxi-
mately constant distance limited by the maximum
defect density attainable. Alternatively a crack trav-
elling at high enough velocity may bifurcate, leading
to rapid arrest.
4.2 Estimation of crack arrest distance
As an estimate to the upper limit of the crack jump
distance in SCC, we have analyzed an arrest process
resulting from exhaustion. Consider a dynamic crack
which has just crossed the film-substrate interface. It
carries with it a kinetic energy [41]
where 1 is the crack length, E is Young’s modulus,
eG the nominal Griffith stress for a crack of initial
length l,,, and K is an undetermined constant. The
quasi-static assumption made by Mott in deriving
this expression has been criticized by a number of
researchers [42]; however, Freund [43] has remarked
on the general validity of Mott’s description and the
only difficulty comes from defining the value of K
which determines the terminal velocity. Here we
adopt a value of K corresponding to the terminal
velocity taking on the value of the Rayleigh wave
velocity IJ~. When the moving crack emits a dis-
location it loses an amount of energy equal to 1441
Eb2
‘,,I
ED=8~(l+p)b2 ro’
where
82 = (1 - U;/u’,)“‘,
Fig. 14. The crack jump distance as a function of the velocity of the crack as it leaves the film.
and R. C. NEWMAN
r, is the core cut-off radius of the dislocation, and r
is the smallest relevant macroscopic sample dimen-
sion. Applying the conservation of energy
A( W - U) = A( T + ED + Es), (18)
where W is the work done during the crack jump by
the external loading, U is the strain energy stored in
the system (U = nut 1=/E), and Es is the surface free
energy term (Es = 27,). We will ignore the Es term
and also a force times distance work term done by the
crack on the dislocation [16]. These terms contribute
a negligible amount to the energy balance in com-
parison to ED.
The work, W, done by the external load during a
microcleavage event will always be zero owing to the
following argument. At the instant the crack starts to
move in a cleavage mode elastic waves radiate from
the tip and move out toward the external boundaries.
The amount of time required for the external load to
sense the crack motion is given by, t = r/uL x 10 ps
(rL is the longitudinal sound velocity). The total crack
jump time, t*, is given by the v,/x where v, is the
crack velocity and x is the crack jump distance.
Assuming that the microcleavage crack moves at
speeds of at least 0.1 uL, t* z 10 ns for typical values
ofx-lpm, t* is x3 orders of magnitude smaller
than t which means that by definition W = 0 for such
a microcleavage process. Similar arguments regard-
ing microcleavage apply for the restraining effects of
ligaments.
Substitution into eqn (18) yields the following
expression for the change in crack velocity, au,, per
characteristic crack advance distance, 61,
(17)
&J, = -
x ($~ln~)~6N], (19)
CRACK GROWTH,pm
 Stress-corrosion cracking 1113

where 6N is the number of dislocations emitted
during a crack advance of 61. We assume that a single
dislocation is emitted per unit crack advance (equal
to b). Equation (19) can be used to estimate the
extent of a microcleavage event as a function of the
initial crack velocity. We have solved this equation
iteratively using values appropriate for brass, and the
results are shown in Fig. 14 for an initial crack length,
I, = 10m3m.
5. CONCLUSIONS
We have discussed how the film-induced cleavage
mechanism has unified many disparate pieces of
information in the literature on transgranular-SCC,
and provided a new framework within which many
forms of environmental embrittlement may be inter-
preted. The compositional dependence of noble metal
alloys has been shown to be directly related to the
susceptibility of a particular alloy to selective dis-
solution, which in turn depends upon the percolation
of the less-noble metal element. Analytical calcu-
lations are presented which support the concept of
film-induced cleavage in f.c.c. metals. Finally, we
discuss the process of crack arrest and show that
arrest from an exhaustion mechanism is consistent
with experimental results.
Acknowledgement-This research was performed under the
auspices of the U.S. Department of Energy, Division of
Basic Energy Sciences, under Contract No. DE-ACOZ-
76H00016.
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