En,vkwin~

Froctun

Mechunks

Vol. 16. No. I, pp. I15-127. 19X?

wI3-7944/82/010115-13$03.00/0
Pergamon Press Ltd

Printed in Great Britain

INVESTIGATION OF STRESS CORROSION CRACKING

OF LOW-ALLOY STEEL IN WATER
WU-YANG
Department

of Metal

CHU,

Physics,

CHI-MEI

Beijing

HSIAO

University

and SHI-QUN

Ll

of Iron and Steel Technology.

China

Abstract-For
four low-alloy
steels with a wide range of tensile strength, the dynamical processes of the
nucleation and propagation of stress corrosion cracking (XC)
in water with various polarization
conditions
and in a 0.1 N K:Cr:OT solution were traced with an optical microscope.
The results show that if the tensile
strength of the steel is higher than a critical value that is different in different polarization
conditions and K,
Kr\~r,
the plastic zone in front of a loaded crack tip is enlarged with time, i.e. the delayed plastic
deformation
occurs in all the environments
used. The nucleation and propagation of SCR will proceed when
this delayed plastic deformation
develops to a critical condition. Neither anodic and cathodic polarization
nor the inhibitor can change the feature of the delayed plasticity and the nucleation and propagation of SCC
in water.
In all the environments
used, K IXC is increased and da/df is decreased with the decrease in the strength
of the steel. Krscc is increased and da/df is decreased vvith the anodic polarization
and the addition of the
inhibitor, but the cathodic polarization
has the opposite effect.

INTRODUCTION
of stress corrosion cracking (SCC) of low-alloy stell in water has been
thoroughly investigated. But there are still some contentions [ l-31.
Using the polished modified WOL type constant defection specimen, we have successfully
traced the dynamical process of the nucleation and propagation of SCC of ultra-high strength
steel in water[4]. In the present work, the nucleation and propagation of SCC in water were
investigated with this metallographic shadowing technique for four low-alloy steels with a wide
range of tensile strength. The influence of an odic polarization, cathodic polarization and the
inhibitor on the process of the nucleation and propagation of SCC has been investigated. The
KIscc and da/dt of all the four steels in various environments were measured. The influence of
various heat treatments on the K rscc and daldt has been studied.
Based upon these results, a new mechanism of SCC in aqueous solution has been
proposed.
THE

MECHANISM

EXPERIMENTALPROCEDURES
The chemical compositions and strength of the steels are listed in Table 1.
All the specimens were of the modified WOL type whose thickness is 20 mm. Owing to the
decrease in K, with the increase in the crack length of the constant deflection specimen, the
K,scc and daldt can be measured with one specimen[5]. In order to trace the dynamical
processes of the nucleation and propagation of SCC with an optical microscope, the polished
precrack specimens were loaded and then put into various aqueous solutions with their polished
surfaces remaining in air. Because of the capillary effect, the crack tip of a polished surface was
still filled with water, and the nucleation and propagation of SCC could be followed with time.
Copper was cathode in the condition of anodic polarization and magnesium was anode in the
condition of cathodic polarization. The polarization voltage was 1.0 V. The inhibitor used was
0.1 N KzCrz07 aqueous solution.
The fracture surfaces of SCC in various environments were investigated with SEM.
Table

I. Composition

of the steels (Wt. %)

Steel

Si

Mn

Cr

Ni

MO

30CrMnSiNi:
30CrMnSi
40CrNiMo
ZG-18 Cast

0.29
0.30
0.38
0.24

I.1 I
1.18
0.22
0.65

I.15
0.95
0.64
0.87

0.005
0.006
0.007
0.005

0.028
0.019
0.012
0.018

I .07
0.91
0.69
1.27

1.57
1.59
-

1.19
0.54

EFM Vol 16. No I-H

II5

WU-YANG

116

CHU

et al.

EXPERIMENTAL RESULTS
The KIscc and da/dt in various heat treatments are listed in Table 2 for four low-alloy
steels. The variation of the Klsci with the strength and microstructures of the steel
3OCrMnSiNi~is shown in Fig. I from which it can be seen that the K Isc(.of tempering bainite is
higher than those of temperated martensite and bainite that was not tempered for the same
strength level. Table 2 shows that the KIscc of sample No. 5 which has a larger grain size
(ASTM No.5)is higher than that of sample No. 1 whose grain size is ASTM No. 9.
The variations of the average Klsc.t, and dajdt of all the four steels in various environments
Table

NO

Steel

3OCrMnSiN~~

4
!
6
I
8
9

10
II
I?

30CrMnSi

40CrNiMo
ZG-18

Cast

13
14
I5
I6
1:
1%
19
20
21
22

2. The KI\(

and da/dt

Heat Treatment

OQ., 200C
OQ., 270C
OQ., 350C
OQ., 500C
OQ.. 200C
28SC ISO.
360C ISO.
310C ISO.
310C ISO..
ISO.,
ISO..
ISO.,
ISO..
ISO..
ISO..
00..
OQ.,
OQ..
OQ..
OQ.,
OQ.,
200C

Temp.
Temp.
Temp.
Temp.
Temp.

400C
Temp.
450C Temp.
SOoC Temp.
550C Temp.
600C Temp.
650C Temp.
700C Temp.
400C Temp.
49sC Temp.
200C Temp.
450C Temp.
500C Temp.
550C Temp.
ISO.

of four low-alloy

T.S.
IMPa)

Kiycc IMPam?
0.C
A.P.

1760
1750
1670
l?&l
1740
1610
1350
l%O

16.0
18.7
37.5
20.0
17.8
23. I

I560
1440
1300
1230
10%
980
900
1420
i 270
IRIO
1400
1320
1180
1580

23.4
31.6
55.2
80.6
no**
no
nc,
38. I
89.2
is.1
45.5
61.0
no
22.4

I LX

1X.6

steels

C.P.

80

30.4
--

32. I
XL:!

IS.5
14.7

I.0
7.
7.)
6.0
1.X

0.7

66.7
no
no
44.3
11.0
22.0
36.6
54.0
44.3

no
no
17.1
69.0
no
-

?
\
i,

of the &SK

0.4
0.1
no
no
no
0.9
0.1
1 I.6
I.5
0.5
no

no
no
no

4.3
_0.9
no

O.C. = open circuit;

1 Quenched and temper

Isothermal
310C IS0 and temp

2000

1500
TS,
of different

structures

MPo
Nith the strength

C.l

---~

IO00

Fig. I. Variation

x.0
21.0
60.0

--

OQ. = 900C oil quenched; OQ? = 1200C oil quenched; no ** = SCR did not occur:
polarization:
C.P. = cathodic polarization;
da/dt is an average value.
IO@ --

diz/dr <x1 mm/min)

O.C.
A.P.

of 3OCrMnSiNil

steel.

n,ns
no
no
_I.7
35.6
2.5
1.4
0.3

A.P. = anodic

Stress corrosion

cracking

of low-alloy

117

steel in water

with the tensile strength of the steels are shown in Figs. 2 and 3 respectively. As expected, the
K,scc is decreased and the daldt is increased with the increase in the strength of the steels for
various environments.
Cathodic polarization decreases the Krscc and increases the da/dt,
anodic polarization increases the K rscc and decreases the da/dt for the same tensile strength of
steels. The inhibitor of 0.1 N KzCrz07 aqueous solution increased the KIscc for steel
40CrNiMo(No.
18) from 15.1 to 27.2 MPadm and decreased the da/dt from 11.6 x IO- to
1.7 X IO- mm/min.
When the tensile strength of the steels was lower than a critical value (e.g. 1090 MPa for
30CrMnSiNi? and 1180 MPa for 40CrNiMo), XC in water would not occur. The cathodic
polarization could decrease the critical value, e.g. from 1090 to 980 MPa for 30CrMnSiNL
(2) The nucleation and propagation
of SCC in water
The process of the nucleation and propagation of SCC in water with anodic polarization is
shown in Fig. 4 for ultra-high strength steel (No. 8). There was a small plastic zone in front of
the loaded crack tip (Fig. 4.1) that did not change if it was put in air after being loaded. But
when it was put into water with its surface remaining in air, the size of the plastic zone was
continuously enlarged with the time, i.e. delayed plasticity was generated (Fig. 4.2). After the
closure of the delayed plastic zone, a discontinuous stress corrosion cracking was nucleated at
its tip B (Fig. 4.3). After 34 hr, there was a second delayed plastic zone in front of crack B and
the plastic deformation of the plastic zone continuously
enlarged. In the dark field metallograph, the slip lines inside the plastic zone appear as light ripple lines, but the cracks appear
as a brown black narrow line. These processes were repeated (Figs. 454.7).
These discontinuous cracks grew and joined each other during the progress of the delayed plasticity (Fig.
4.7).
The process of the delayed plasticity and SCC in open circuit and cathodic polarization are
shown in Figs. 5 and 6 respectively for the same sample (No. 8).
When the strength of steels and K, were greater than a critical value, the same sequences of
the delayed plasticity and cracking were also observed for other ultra-high strength steels, such
as 30CrMnSiNi? (Nos. 1, 2, 3, 5 and 6), 40CrNiMo (No. 18) and ZG-18 cast steel (No. 22).

1000

1 Anodlc polartzatlon
* Cathodic
polamatlon
0 K, Cr, 0, solution
?

Open clrcult
Anodlc polarization
lCathod~c
polarlzatlon
3 K,Cr,O, solution

_.-___
loo0

1200

I400
TS,

I600

l8cYJ

IL

1000

MPo

Fig. 2.
Fig. 2. Variation

of the KISC

,
I200

1400

T %

MPa

I600

leoo

Fig. 3.

c of

four low-alloy

steels in various

environments

with the tensile

strength

of

the steels.
Fig. 3. Variation

of the daldt

(average

value) of four low-alloy

steels in varions
tensile strength of the steels.

environments

with

the

118

WU-YANG

CHU

et ai.

For lower strength steels, the progress of the delayed plasticity and SCC were somewhat
different as shown in Fig. 7 for 40CrNiMo (No. 19) in open circuit condition. There was an
initial plastic zone in front of the crack tip after loading (Fig. 7.1). The size of the plastic zone
was continuously enlarged with time (Fig. 7.2), i.e. delayed plasticity was generated. When this
delayed plasticity developed into a critical condition, SCC occurred and propagated along the
path near the border of the delayed pIasti~~elastic region (Fig. 7.3). These processes were
repeated and the crack tips formed at different times were marked with ,A, B, C and D
respectively in Fig. 7.
The process of the delayed plasticity and SCC in anodic and cathodic polarization are
shown in Figs. 8 and 9 respectively for the same sample (No. 19).
The same sequences of the delayed plasticity and SCC were also obseri<ed for other lower
strength steels, such as 3OCrMnSiNi~ (Nos. 4, 11 and 12), 40CrNiMo (Nos. 20 and 21) and
30CrMnSi (Nos. 16 and 17).
The process of SCC in 0.1 N K?Cr& solution for ultra-high strength steel (No. 18) is shown
in Fig. 10. Comparing all these figures, we shall see that neither anodic and cathodic
polarization nor KZCrZ07solution can change the feature of the nucleation and propagation of
SCC for steels used. Therefore, the mechanism of SCC in water is not affected by polarization
or inhibitor such as 0.1 N K2Cr207,
Our experiment showed that the delayed plasticity could also occur in Hz gas or in
specimens which had been charged with hydrogen electrolytically and this delayed plasticity
caused by hydrogen was just the necessary condition for hydrogen induced delayed cracking
(Figs. 11 and 12).
AI1these delayed plasticity and delayed cracking phenomena were observed on the surface
of the specimen. Does the interior of the specimen behave the same as the surface of the
specimen? The change of SCC with the depth from the surface has been investigated. Figure
5.4 indicated that SCC had not yet occurred inside the delayed plastic zone between discontinuous cracks B and C and in front of the last crack D. Removing the surface by polishing
layer by layer, no cracks were observed in these regions until 0.1 mm had been removed, as
shown in Fig. 5.5. After a layer of 0.3 mm had been removed, the crack propagated to H instead
of D, but no crack appeared between the discontinuous cracks E and F, F and H (Fig. 5.6).
This result implies that there existed a delayed plastic zone between the discontinuous cracks
and SCC nucleated also discontinuously by the mechanism of the delayed plastic deformation
in the interior of the specimen.
Is it possible for SCC to nucleate in the interior of the specimen and then cause the delayed
plastic deformation on the surface of the specimen ? After electrolytical charging, the WOL
specimen was poIished and slowly loaded, the delayed plastic deformation caused by hydrogen
occurred only after the load-strain curve deviated from the straight line (Fig. 13.1). Once the
hydrogen induced delayed plasticity (HJDP) was observed, the specimen was immediately
unloaded, and then coloured by heat-tinting (350% 1.5 hr), no hydrogen induced delayed
cracking (HIDC) was observed on the fracture surface of the specimen (Fig. 13.2). However, if
the charged specimen had been loaded for a sufficiently long period of time at point B in Fig.
13.1, then HIDC appeared as a consequence of HIDP not only on the polished surface, but also
on the fracture surface (Fig. 13.3). This shows that the delayed plastic deformation is the
preceding steep of delayed cracking and the delayed cracking develops only after the delayed
plastic deformation has proceeded to a certain extent.

The fractographies of SCC of the ultra-high strength steel (No. 8) in water with different
polarization conditions are shown in Fig. 14. All are typical intergranular fractures. As the
strength of the steel was decreased, the mode of fracture was changed from intergranular to
quasi-cleavage (Fig. 14).
DISCUSSION
The experiments show that if the tensile strength of the steel is higher than a critical value
:. the delayed plasticity will
which is different in different polarziation conditions and K, > K ,\c,
occur in all the environments used. It was discovered that SCC was preceded by delayed

Stress corrosioncracking of low-alloy steel in water

Fig. 4. Nucleation and propagation of SCC of ultra-high strength in water with anodic polarization (No. 8, t
in hr) dark field x 25.

Fig. 5. Nucleation and propagation of SCC of ultra-high strength in water (open circuit, No. 8,), dark
field x 25.

119

WU-YANG CHU et al.

6. Nucleation and propagation of SCC of ultra-high strength in water with cathodic polarization (NO.
t in hr) x 25.

Fig. 7. Nucleation and propagation of XC of lower-strength steel in water (open circuit, No. 19, t in h0.
dark field X25.

Stress corrosion cracking of low-alloy steel ir. water

Fig. 8. Nucleation and propagation of SCC of lower strength steel in water with anodic polarization (No. 19,
1 in hr) x 25.

Fig. 9. Nucleation

and propagation of SCC of lower strength steel in water with cathodic polarization (No.
19, I in hr) x 25.

121

122

WU-YANG CHU et al.

Fig. II
Fig. 10. Nucleation and propagation of SCC of ultra-high strength in 0.1 N KZCr207solution (No. 18).dark
field x 25.
Fig. 11.The processes of HIDP and HIDC for ultra-high strength steel specimen after charging (No. 8) X25.

Fig. 12. The processes of HIDP and HIDC for lower strength steel specimen after charging (No. 19)x 25

Stress corrosion cracking of low-alloy steel in water

Fig. 13. Relation between HIDP and HIDC (No. 8, precharged specimen).

I...-~---

--

(b)

(a)

(4
Fig. 14. Fractographs of SCC of ultra-high strength steel in water (No. 8) (a) open circuit, (b) anodic
polarization, (c) cathodic polarization x 1000.

Fig. 15. Fractograph of SCC of lower strength steel in water (No. 12)x 1000.

123

Stress corrosion cracking of low-alloy steel in water

125

plasticity, as shown in Figs. 5-11. In other words, this delayed plasticity is the necessary and
sufficient condition for SCC.
Because the feature of the delayed plasticity and the relation between this delayed plasticity
and SCC in water are the same as the feature of HIDP and the relation between HIDP and
HIDC (comparing Figs. 4 and 7 with Figs. 11 and 12), the delayed plasticity observed in stress
corrosion in water is also caused by hydrogen. In aqueous solution, the occluded cell study of a
crack tip indicated that the PH value of the solution within the crack tip remains as 3.7-3.9,
even if the PH value of the bulk solution varies from 2 to 10[6]. This result provides the
necessary condition for the occurrence of the hydrogen-evolution
type of cathodic reaction
during corrosion, even for anodic polarization[6].
Our recent results to be published showed that if a stress gradient existed, e.g. in a bending
or pre-crack specimen and the tensile strength of the steel exceeded a critical value, hydrogen
could apparently reduce the local yield strength (see Figs. 16 and 17) though there were
arguments in whether hydrogen can reduce the yield strength of a smooth tensile specimen
(3.7). We believe that the mechanism of SCC in water is as follows: the hydrogen atom released
during cathodic reaction of corrosion tends to diffuse to and enrich in the front region of a
crack tip under a multiaxial stress gradient; when the effective concentration
of hydrogen
reaches a critical value, the effective yield strength in the local region of a crack tip can be
reduced considerably; consequently, hydrogen induced delayed plasticity and SCC can occur
under the action of a lower KZ value.
The delayed plastic deformation extended along 0 = + (~r/4) for ultra-high strength steels
(Fig. 5). and then rotating the coordinated axes 0 = (n/4), the shear stress T in the slip direction
in front of a crack tip can be calculated, i.e.

r = :(S, - 6,) sin 20 + T,, cos 20 = 0.328 &.

It is our view that when the shearing stresses in a great distance in front of the crack tip are
all equal to the effective shear strength TT, first hydrogen induced delayed plasticity and then

PH
0

02
/,

20

50

80

mA/cmZ

Fig. 16. Variation of ratios of yield strength of the charged and uncharged bending specimens with charging
condition.

126

W&YANG

CHU et al

Steel
30CrMnSIN1,

T.S.iMPol
1760 I
1620
1440
1352
780 1
450 01

02

/r
Fig. 17. Variation

20

50

80

m&/cm

of T?'/T<of the charged and uncharged WOL specimens with charging ccmdition\

SCC will occur, i.e.

r: = 0.328 e;,

K,sc,c = DrT.

Our recent results to be published indicated that TTTis decreased with the increase in
hydrogen amount entering into a specimen and/or tensile strength. These new findings can be
used to explain the influence of the strength and environments on the Krsrt and dtr/di shown in
Figs. 3 and 4. The primary cause of the effect of environments on K rscc can be attributed to the
sufficiency of the supply of hydrogen. The cathodic polarization in water promotes the cathodic
evolution of hydrogen, the Krscc is thereby decreased. The anodic polarization retards the
evolution of hydrogen, therefore K ,sfC is increased. The inhibiting effect of Crz07 in
0.1 N KZCr207 solution is due to the fact that the concentration of H is decreased by the
following reaction:
Cr?O, = f 14Hi6e---+7H,O+2Cr.
It is interesting to point out that when the tensile strengths are the same, the KIscc: of
40CrNiMo and that of 30CrMnSi appear to be higher than those of 30CrMnSiNi: (Table 2). but
this effect cannot overshadow the effects of the strength and the amount of hydrogen.
CONCLUSIONS
(1) if the strength of the steel is higher than a critical value which is different for different
polarization conditions and Kr > Krscc, the delayed plasticity can certainly occur in all the
aqueous solutions used, and then the nucleation and propagation of SCC will follow. Thus
delayed plastic deformation induced by hydrogen is the necessary and sufficient condition for
SCC of low-alloy steels in aqueous solutions.
(2) For ultra-high strength steels, after the closure of the delayed plastic zones, SWs are
nucleated at their tips. These discontinuous cracks will grow and join each other with the
progress of the delayed plasticity.

Stress corrosion

cracking

of low-alloy

127

steel in water

(3) Neither anodic and cathodic polarization nor the inhibitor can change the feature of the
delayed plasticity and the relation between this delayed plasticity and XC in water and
aqueous solution.
(4) The Klscc are increased and the daldt decreased with the decrease in the strength of the
steel in all the environments used. The anodic polarization in water or the addition of K2Cr207
to water will increase the KIscc and decrease the da/dt. On the other hand, the cathodic
polarization in water will decrease Kfscc and increase the daldt.
4ckno,~,led,~ements-Thank~

are due to Mr. Tian-hua

Liu and Mr. Jyh-yih

Li for part of the experimental

work

REFERENCES
of the mechanism of stress corrosion cracking in high strength steels.
III Y. A. Marichev and I. L. Rosenfely, Investigation
Corrosion 32. 423-429 (1976).
PI J. C. Scully, The role of hydrogen in stress corrosion cracking. On effect of hydrogen on behaviour of materials (Edited
by A. W. Thompson
and 1. M. Bernstein) pp. 129-149. AIME, New York (1976).
cracking (Hydrogen
Embrittlement)
Met. Trans. 3, 427-451
[31 C. D. Beachem, A new mode1 for hydrogen-assisted
(1972).

[41 W. Y. Chu. C. M. Hsiao and S. Q. Li. Hydrogen

induced

delayed

plasticity

and cracking.

Scripfa

Mel.

13, 1063-1069

(1979).
and S. Q. Li. A new engineering
fracture toughness parameter
KMX (p). Scriprcl Met. 13.
1057-1062 (1979).
conditions at the tip of an advancing stress corroGon
161 J. .4. Smith, M. H. Peterson and B. F. Brown, Electrochemical
crack in AISI 4340 steel. Corrosion 26. 539-542 (1970).
of steels. Ann. Rec. Mot. Sri. 8, 539-542 (1978).
I71 R. A. Oriani. Hydrogen embrittlement

[51 W. Y. Chu. C. M. HGao

(Receioed

3 March

1981: receiced for puhlicc~tion I5 April 1981)