Corrosion Science 49 (2007) 81–91

www.elsevier.com/locate/corsci

Characterization and perspective of stress

corrosion cracking of austenitic stainless steels
(type 304 and type 316) in acid solutions
using constant load method
Rokuro Nishimura *

Department of Materials Science, Graduate School of Engineering, Osaka Prefecture University, 1-1,
Gakuen-cho, Sakai, Osaka 599-8531, Japan

Available online 30 June 2006

Abstract

The stress corrosion cracking (SCC) of the commercial austenitic stainless steels, type 304 and
type 316 has been extensively investigated as functions of applied stress, sensitizing temperature, sen-
sitizing time and the environmental factors such as pH, anion concentration, anion species (chloride
ions and sulfate ions), test temperature, applied potential and inhibitor concentrations of chromate
and molybdate by using a constant load method. We have found that the steady state elongation rate
obtained from corrosion elongation curve becomes a relevant parameter for predicting time to fail-
ure and also for criterion on assessment of whether SCC takes place or not. The value of tss/tf is also
found to become an indicator for assessment of whether SCC takes place or not. Furthermore, from
the results obtained, it is deduced that a unified SCC mechanism is qualitatively proposed to explain
both of transgranular SCC (TGSCC) and intergranular SCC (IGSCC), where the unified SCC mech-
anism is basically based on a film rupture- formation event at crack tips.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Austenitic stainless steels; C. Steady state elongation rate; C. Corrosion elongation curve; C. SCC
mechanism

*
Tel./fax: +81 72 254 9323.
E-mail address: nishimu@mtr.osakafu-u.ac.jp

0010-938X/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2006.05.011
82 R. Nishimura / Corrosion Science 49 (2007) 81–91

1. Introduction

In a series of papers [1–12], the SCC of the austenitic stainless steels (type 304 and type
316) was extensively investigated as functions of applied stress (r), sensitizing temperature,
sensitizing time, applied potential and environmental factors (pH, anion concentration,
anion species, inhibitor and test temperature) by using a constant load method. It was
found that a steady state elongation rate (lss/ms1) obtained from a corrosion elongation
curve (elongation vs. time) became a relevant parameter for the prediction of time to fail-
ure (tf) for the sensitized and the solution annealed specimens. In addition, the maximum
applied stress (rmax), the ratio of transition time (tss) to tf, the slope of the linear equation
between log tf and log lss, and the fracture appearance (transgranular or intergranular
mode) in the SCC-dominated region depended upon only the degree of sensitization. Then
the intergranular SCC (IGSCC) and transgranular SCC (TGSCC) were qualitatively
explained by a unified SCC mechanism based on a film rupture-formation event at crack
tips. In this paper, we would review the SCC behavior of the austenitic stainless steels in
acid solutions and propose a unified SCC mechanism to explain both of TGSCC and
IGSCC, whereas this paper is not concerned with hydrogen embrittlement (HE).

2. Characterization of SCC behavior

2.1. Corrosion elongation curve—three parameters of tf, tss and lss

An elongation versus time curve (called corrosion elongation curve) up to failure under
a constant applied stress condition is schematically presented in Fig. 1. The corrosion elon-
gation curve consists of three regions with an initial sudden rise of elongation; primary,
secondary and tertiary regions, which correspond to crack nucleation, steady crack prop-
agation and terminal crack propagation periods, respectively. From the curve, the three

Fig. 1. Schematic representation of corrosion elongation curve; tf time to failure, lss steady state elongation rate,
tss transition time.
 R. Nishimura / Corrosion Science 49 (2007) 81–91 83

parameters can be obtained; (1) the steady state elongation rate in the secondary region,
lss, (2) the transition time between the secondary and tertiary regions, tss, and (3) the time
to failure, tf. If the specimens are not fractured within a laboratory time scale (<107
second), lss becomes of the order of 1010 m/s and less.

2.2. Applied stress dependence of three parameters

Fig. 2 shows a schematic representation of the three parameters (tf, lss, tss/tf) versus
applied stress (r) relationships for the solution annealed specimens (type 304 and type
316) in the three different corrosive environments; mild, intermediate and aggressive; for
instance a neutral NaCl solution is mild for type 304 and type 316, a sulphuric acid is inter-
mediate for type 304 and mild for type 316, but a HCl solution is aggressive for type 304
and type 316. They consist of three regions that are dominated by stress, SCC and corro-
sion, respectively. The maximum applied stress (rmax) in the SCC-dominated region keeps
constant independent of the environmental factors, but depends predominantly on the
degree of sensitization as described later. The minimum applied stress (rmin) is largely
dependent on the combination between material and environment, and corresponds to a
threshold stress (rth) below which little SCC takes place. A value of tss/tf is always constant
in the SCC-dominated region, while those in the stress-dominated and corrosion-domi-
nated regions approach to unity with increasing or decreasing applied stress for any spec-
imens. This implies that the value of tss/tf becomes an indicator for whether SCC takes
place or not. The applied stress dependence of three parameters for the sensitized speci-
mens is basically the same as that for the solution annealed specimens.

2.3. Environment dependence of three parameters

By using a constant applied stress in the SCC-dominated region, the effect of the environ-
mental factors on SCC can be elucidated from the behavior of the three parameters. Fig. 3

Fig. 2. Schematic representation of the relationships between applied stress and three parameters for solution
annealed specimens under three different environment conditions; 1: stress-dominated region, 2: SCC-dominated
region and 3: corrosion-dominated region.
84 R. Nishimura / Corrosion Science 49 (2007) 81–91

Fig. 3. Time to failure and steady state elongation rate as a function of pH for the solution annealed type 304 and
type 316 n 0.82 kmol/m3 chloride solution at 353 K under a constant applied stress of 437 MPa.

shows a representative example of tf and lss obtained as a function of pH for type 304 and
type 316 specimens under a constant applied stress of 437 MPa. The SCC susceptibility of
type 304 and type 316 specimens decreases with increasing pH and is not observed at or
above a certain pH, which means a critical pH at the constant applied stress. Above the crit-
ical pH with little SCC susceptibility, the order of lss becomes 1010 m/s and less. The value of
tss/tf keeps constant irrespective of pH, whenever SCC takes place. Similar results are
obtained on test temperature, anion concentration, inhibitor concentration (chromate and
molybdate), chloride concentration in sulphuric acid solution and so on.

2.4. Effect of sensitization

The applied stress and environment dependences of the three parameters for the speci-
mens with the different degrees of sensitization are basically the same as those of the solution
annealed specimens described in the previous sections, where the specimens were sensitized
as functions of sensitizing temperature (800–1300 K, sensitizing time: 24 h) and sensitizing
time (0–1.08 Ms, sensitizing temperature: 923 K). However, the differences in the SCC
behavior between the sensitized and solution annealed specimens are summarized as follows:

(1) rmax in the SCC-dominated region increases with increasing the degree of sensitization
in 0.82 kmol/m3 HCl solution compared to that for the solution annealed specimens,
 R. Nishimura / Corrosion Science 49 (2007) 81–91 85

whereas it decreases at or around the severest degree of sensitization in 0.82 kmol/m3

H2SO4 solution at a test temperature 353 K, but increases at 323 K as well as that in the
HCl solution.
(2) rmin in the SCC-dominated region varies with the degree of sensitization in the
H2SO4 solution, but not in the HCl solution.
(3) The value of tss/tf in the SCC-dominated region increases with increasing the degree
of sensitization in the HCl and H2SO4 solutions compared to that for the solution
annealed specimens.
(4) The fracture appearance of the specimens changes from transgranular mode through
a mixture of transgranular and intergranular to intergranular mode with increasing
the degree of sensitization.
(5) The SCC susceptibility shows a small difference between the solution annealed and
the sensitized specimens irrespective of the degree of sensitization in the HCl solu-
tion, while the difference in the SCC susceptibility between them in the H2SO4 solu-
tion increases largely with increasing the degree of sensitization, and
(6) Sulphate ions become more aggressive than chloride ions for the severest sensitized
specimens.

These differences between the solution annealed and sensitized specimens would be
induced by the formation of Cr carbides and Cr depletion zone through sensitization,
where the amount of Cr carbides and the degree of Cr depletion depend upon sensitizing
temperature and sensitizing time.

3. Perspective of SCC mechanism

3.1. A parameter for prediction of time to failure

The relationship between log lss and log tf in the SCC-dominated region becomes a good
straight line under a constant applied stress condition (environment: variable) and under a
constant environment condition (r: variable) regardless of the environmental factors (pH,
test temperature, anion concentration and so on) and metallurgical factors (materials such
as type 304, type 316 and type 310, sensitizing temperature and sensitizing time). Fig. 4
shows a representative example of the relationships between log tf and log lss obtained as
functions of various environmental factors at a constant applied stress of 437 MPa for
the solution annealed type 304 and type 316 specimens. The relationships become the good
straight lines with a slope of 1 regardless of the environmental factors and the materials
(type 304 and type 316). On the other hand, although the results are not shown, the rela-
tionship between log lss and log tf as a function of applied stress under the same environ-
mental conditions becomes also a good straight line, but its slope is 2 for the solution
annealed specimens independent of the environmental factors. However, their slopes were
found to decrease with increasing the degree of sensitization. Hence, we get the following
empirical equations for the type 304 and type 316 specimens,
log lss ¼ A  log tf þ C a ð1 < A 5 2Þ r : variable; environment : constant ð1Þ
log lss ¼ B  log tf þ C b ð0:5 < B 5 1Þ r : constant; environment : variable ð2Þ
where the slopes, –A and –B, depend on the degree of sensitization, although the
solution annealed specimens have A = 2 and B = 1, Ca is a constant depending on the
86 R. Nishimura / Corrosion Science 49 (2007) 81–91

Fig. 4. The relationships between log tf and log lss for the solution annealed type 304 and type 316 specimens as
functions of pH, test temperature and chloride concentration in chloride solutions under a constant applied stress
of 437 MPa.

environmental factors and the degree of sensitization, and Cb a constant depending upon
applied stress and the degree of sensitization. The above linear equations imply that lss
becomes a relevant parameter for predicting tf for the specimens with and without sensiti-
zation, because the lss can be obtained at a time within 10–20% of tf from the corrosion
elongation curve.

3.2. Estimation of critical (threshold) value for SCC

First of all, we consider a threshold stress (rth) below which no SCC takes place. The
applied stress dependence of the three parameters for type 304 and 316 showed the three
regions (stress-dominated, SCC-dominated and corrosion-dominated regions) at various
environments. Therefore, we can conclude that the minimum applied stress (rmin) in the
SCC-dominated region corresponds to rth at each environment. Even if the specimens were
fractured at an applied stress less than rth, the value of tss/tf is different from that in the
SCC-dominated region. By the value of tss/tf we can distinguish between SCC and mechan-
ical fracture. On the other hand, from Section 3.1, when lss becomes of the order of 1010
m/s and less, tf becomes of the order of 107 s and more, which is concluded to be beyond the
laboratory time scale. This means that the order of lss becomes a criterion for assessment of
whether or not SCC takes place. By using this criterion, the critical values, below or above
which little SCC takes place, of the environmental factors such as pH, test temperature,
 R. Nishimura / Corrosion Science 49 (2007) 81–91 87

Fig. 5. The relationship between a reciprocal of critical test temperature and a logarithm of chromate
concentration for solution annealed type 304 in 0.82 kmol/m3 H2SO4 solution including 0.3 kmol/m3 NaCl under
a constant applied stress of 388 MPa.

chloride concentration, inhibitor concentration and so on can be estimated at a certain con-

stant applied stress. Fig. 5 shows a representative example of the relationship between a
reciprocal of the critical test temperature and the logarithm of chromate concentration,
where the critical test temperatures were obtained from the test temperature dependence
of the three parameters at various chromate concentrations under a constant applied stress
of 388 MPa in 0.82 kmol/m3 H2SO4 solution including 0.3 kmol/m3 NaCl. The relationship
becomes a good straight line, which indicates that the critical test temperature at a given
chromate concentration is determined from the linear relationship under the same experi-
mental condition Thus, a similar linear relationship is found to be obtained for a relation-
ship between a critical value of a certain environmental factor and the other one.

3.3. A proposal of a unified SCC mechanism

3.3.1. A concept of the unified SCC mechanism: film rupture-formation event

The term ‘‘unified’’ is used in a sense that TGSCC and IGSCC can be explained with
the same concept, that is, a film rupture-formation event, which would take place by devel-
opment of an additional local stress at crack tips with a help of corrosion (dissolution and
film formation) in addition to a local stress caused by applied stress. The austenitic stain-
less steels, type 304 and type 316, that are ductile materials, have a brittle fracture appear-
ance, whenever TGSCC and IGSCC take place. In order for the brittle fracture to take
place, a dislocation movement in the grains, which can occur over several grains and more,
needs to be inhibited by an obstacle. For the solution annealed and sensitized specimens of
88 R. Nishimura / Corrosion Science 49 (2007) 81–91

type 304 and type 316, a film formed at crack tips and on the other surface serves as the
obstacle of the dislocation movement. In the case of the sensitized specimens, Cr carbides
formed along the grain boundaries also serve as the obstacle as well as the film and hence
the dislocation movement would be limited within one grain. For that reason, grain
boundary sliding (GBS) would, therefore, be significantly predominant for the sensitized
specimens instead of the dislocation movement in the grains.
In order that film rupture occurs, an additional local stress at or around crack tips
(radd) must be generated for TGSCC and IGSCC in addition to a local stress caused by
applied stress (rapp), where a net local stress (rtip) consists of rapp and radd. When the rtip
reaches a critical fracture stress (rF), the film rupture is considered to take place.

rtip ¼ rapp þ radd ðfilm rupture at rtip ¼ rF Þ ð3Þ

Just after film rupture, rtip drops to rapp (= constant under a constant applied stress
condition) and then increases by increase in radd during film formation up to rF, that
is, rapp 5 rtip 5 rF. The radd for the solution annealed specimens is generated by an inter-
action between the film formed and the dislocation movement with the formation of a dis-
location pile-up, where in this case radd is denoted as rdis. On the other hand, the sensitized
specimens cannot form such a dislocation pile-up, since the dislocation movement is lim-
ited within one grain because of the existence of Cr carbides. Therefore, the radd for the
sensitized specimens is presumed to cause by an interaction between the film and grain
boundary sliding (GBS), where radd is denoted as rgbs.
A net local elongation (ln) consists of the elongation related to film rupture (lr) and the
elongation caused by GBS or dislocation movement during film formation (lf) up to the
next film rupture; ln = lr + lf. An average elongation rate per one film rupture- formation
event, Dln/Dt, is connected to lss: lss / Dln/Dt, where Dln and Dt are the net local elongation
caused and the time during one film rupture-formation event. A corrosion current density
(js) at crack tips is composed of a film formation current density (jf) and dissolution cur-
rent density (jd); js = jf + jd, where jf contributes to an inhibition of the dislocation move-
ment and GBS, while jd to the enhancement of the dislocation movement and GBS
through injection of defects into the dislocation pile-up [13]. A time variation of js (jf or
jd) during one film rupture-formation event is provided as follows; js / j0(t/t0)k and jf
or jd / j0(t/t0)m, where t is the time during the film rupture-formation event, and j0, t0,
k and m are the constants, but depend on environments, materials and the degree of
sensitization.

3.3.2. TGSCC and IGSCC mechanisms

In the case of TGSCC, the inhibition of the dislocation movement in the grains takes
place by the films formed at crack tips under a constant applied stress condition and as
a result rdis is generated with the dislocation pile-up, during which rapp holds constant.
An increasing rate of rtip, drtip/dt, during one film rupture-formation event was taken into
consideration in terms of the number of the pile-up dislocation (ntip), the length of the pile-
up dislocation (Ltip) and a concentrated tensile stress according to Tetelman and McEvily
[14] and consequently was expressed as follows,
1=2
drtip =dt / ðs  si ÞðL tip =rÞ jd =zF ðTGSCCÞ ð4Þ
 R. Nishimura / Corrosion Science 49 (2007) 81–91 89

where Ltip is also composed of Lapp caused by r and Ldis formed during film formation, s is
the shear stress (r = 2s), si is the friction stress and r is the length from the tip of the pile-
up, which corresponds to a film thickness at crack tips.
On the other hand, IGSCC takes place for the sensitized specimens, but not for the
solution annealed specimens, except hydrogen embrittlement. We consider GBS instead
of the dislocation movement, since its movement cannot extend over a next grain because
of the existence of Cr carbides at grain boundaries. A rate of sliding displacement (S = nb)
by GBS, dS/dt, is associated with jd, which is connected to dn/dt by injection of defects
into grain boundaries,
dS=dt ¼ bdn=dt / jd =zF ð5Þ
where n is the number of dislocations in each pile-up on grain boundaries, b is the Burgers
vector, z is the average valence of dissolved metal ions and F is the Faraday constant. In
addition, a rate of rtip, drtip/dt, is considered to be proportional to dS/dt and s (shear
stress: r = 2s in the case of a uni-axial tensile stress) [15],
drtip =dt / sdS=dt / sjd =zF ðIGSCCÞ ð6Þ
From Eqs. (4) and (6), it is found that drtip/dt for TGSCC and IGSCC is proportional
to only the common parameters such as s and jd.

Fig. 6. Schematic representation of time dependence of the net local stress (rtip) during the film rupture-
formation events at various constant applied stresses (applied stress: 1 > 2 > 3) under a constant environmental
condition.
90 R. Nishimura / Corrosion Science 49 (2007) 81–91

3.3.3. Behavior of rtip during film rupture- formation event

We consider the two cases of the experimental conditions to estimate the behavior of
drtip/dt during the film rupture- formation events.
Case (1) r = variable, but environment = constant.
Provided that the time dependence and magnitude of jd after film rupture are constant
independent of r, drtip/dt increases with increasing r. This means that the time, Dt, for rtip
to reach rF decreases with increasing r as schematically shown in Fig. 6. In other words,
the increase in r lessens the contribution of radd to rtip because of rF = constant. If rapp is
equal to or exceeds rF, rtip has little contribution of radd to lead to fracture, which corre-
sponds to that in the stress-dominated region. On the other hand, if rapp is equal to or
becomes below rth (threshold stress), which corresponds to rmin in the SCC-dominated
region, the contribution of radd to rtip to lead to fracture becomes very large. Hence the
increase in radd plays an important role in fracture. In this case, Dt, for rtip to reach rF
takes a long time and hence general corrosion becomes predominant instead of crack
propagation, that is, the reduction in cross sectional area by corrosion (fracture) or little
reduction in cross sectional area by the formation of passive film (no fracture), which cor-
responds to that in the corrosion-dominated region.
Case (2) r = constant, but environment = variable.
In this case, drtip/dt is subjected to only jd. The time dependence and magnitude of jd
depend upon the aggressiveness of environments. The SCC results already obtained show
that as the aggressiveness increases, the SCC susceptibility increases. This means that
drtip/dt increases with increasing the aggressiveness, which leads to the decrease in Dt. This
is schematically shown in Fig. 7. When the aggressiveness becomes very small, it would

Fig. 7. Schematic representation of time dependence of the net local stress (rtip) during the film rupture-
formation events at various environments under a constant applied stress condition, where rT is the threshold
stress below which no SCC takes place.
 R. Nishimura / Corrosion Science 49 (2007) 81–91 91

take a very long time for rtip to reach rF, which indicates that the materials have little SCC
susceptibility under such an environment condition.

4. Conclusions

(1) The characterization of the SCC behavior of type 304 and type 316 was described by
the behavior of the three parameters (lss, tf and tss) as functions of applied stress, the
environmental factors (test temperature, anion concentration, pH, inhibitor and so
on), sensitizing temperature and sensitizing time.
(2) The maximum applied stress (rmax), and the minimum applied stress (rmin) corre-
sponded to the maximum stress and the threshold stress at which SCC takes place
or not.
(3) The value of tss/tf in the SCC-dominated region became a good indicator for the
judgment of whether SCC takes place or not, although the value depended upon
the degree of sensitization.
(4) The steady state elongation rate, lss, became the relevant parameter for prediction of
time to failure tf.
(5) The unified SCC mechanism was proposed to explain IGSCC and TGSCC.

References

[1] R. Nishimura, K. Kudo, Corrosion 45 (1989) 308–316.

[2] R. Nishimura, Corrosion 46 (1990) 311–318.
[3] R. Nishimura, Corrosion 49 (1993) 796–801.
[4] R. Nishimura, Corros. Sci. 34 (1993) 1463–1473.
[5] R. Nishimura, Corros. Sci. 34 (1993) 1859–1868.
[6] R. Nishimura, K. Yamakawa, Nucl. Eng. Des. 182 (1998) 165–173.
[7] R. Nishimura, Sundjono, Corrosion 56 (2000) 361–370.
[8] R. Nishimura, I. Katim, Y. Maeda, Corrosion 57 (2001) 853–862.
[9] R. Nishimura, I. Musalam, Y. Maeda, Corros. Sci. 44 (2002) 1343–1360.
[10] R. Nishimura, A. Sulaiman, Y. Maeda, Corros. Sci. 45 (2003) 465–484.
[11] R. Nishimura, Y. Maeda, Corros. Sci. 45 (2003) 1847–1862.
[12] R. Nishimura, Y. Maeda, Corros. Sci. 46 (2004) 343–355.
[13] B. Gu, W.-Y. Chu, L.-J. Qiao, C.-M. Hsiao, Corros. Sci. 36 (1994) 1437–1447.
[14] A.S. Tetelman, A.J. McEvily Jr, Fracture of Structural Materials, John Wiley & Sons, USA, 1967, pp. 185–
186.
[15] H.E. Evans, Mechanisms of Creep Fracture, Elsevier, Amsterdam, 1984, p. 169.