Corrosion Science, Vol. 32, No. 7, pp. 685-691, 1991 0010--938X/91 $3.00+0.

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Printed in Great Britain. 1991 Pergamon Press plc

THE EFFECT OF THE TEMPERING PROCESSES ON THE

SUSCEPTIBILITY TO STRESS CORROSION CRACKING OF
HIGH STRENGTH STEEL

B. PAWLOWSKi, A . MAZUR a n d S. GORCZVCA

The Academy of Mining and Metallurgy, 30-059 Krakow, A1.Mickiewicza 30, Poland

Abstract--The effect of tempering on susceptibility to stress corrosion cracking (SCC) of the high strength
steel was investigated using KI~ and Kls. tests. The dilatometric and electron microscopy techniques in
order to determine tempering processes were also used. Two tempering temperature ranges of high
susceptibility to SCC of tested steel were observed. It was concluded that the susceptibility of tested steel
to SCC is connected mainly with the effect of tempering on the solubility of hydrogen.

INTRODUCTION
IT IS WELL known that in aqueous environments stress corrosion cracking of high
strength low alloy steels occurs mainly by so-called hydrogen assisted cracking
(hydrogen embrittlement). 1
The physical mechanism by which hydrogen atoms are entering the steel and
cause embrittlement is still not clear. It is not known whether hydrogen atoms or
protons are the diffusing species in metals and there are at least five main different
theories explaining the role of hydrogen in the decreasing fracture toughness of
steel. 2-5

103

~E 10 4

10.5

O0

10~- I I I I I L I

As q 200 400 600

Tempering temperQture (C)
Flo. 1. Effect of tempering temperature on solubility of hydrogen for high strength alloy
steel. 6

Manuscript received 20 February 1990.

685
686 B. PAWLOWSKI,A. MAZURand S. GORCZYCA

600
MPa

2200 HV HV30

2000 TS
5OO

1800

1600

400
1400

1200

1000 I L i L L -- 300
0 100 200 300 400 500 600

Tempering temperature C
FIG. 2. Effect oftemperingtemperature on mechanical properties oftested steel.

The susceptibility of high strength steels to hydrogen assisted cracking in aqueous

solutions seems to depend mainly on the solubility of hydrogen in steel. The effect of
tempering temperature on solubility of hydrogen for several high strength alloy
steels has been established by Sakamoto and Takao. 6 Figure I shows some results of
their investigations.
The main objective of the present paper was to define more clearly the influence
of changes in microstructure (produced by quenching and tempering) on the
susceptibility to stress corrosion cracking of the high strength low alloy steel.

EXPERIMENTAL METHOD
The studies were performed on high strength low alloy steel. The chemical compositions of the steel
are as follows: C = 0 . 2 8 % , M n = l . 1 5 % , Si=1.01%, P = 0 . 0 2 2 % , S=0.006%, C r = 0 . 9 7 % ,
Ni = 1.40%.
The single edge notched specimens for Kit and Kis~. tests, round tensile specimens and dilatometric
specimens were cut from the steel bar of diameter 110 ram. Fracture toughness Kic was determined
according to the ASTM Standard EI 399-81. For the stress corrosion cracking measurements the
cantilever beam method described by Brown 7 was applied.
The open circuit SCC tests were performed in a 3.5% solution of sodium chloride (pH 7) at 20C.
The solution was changed every 48 h. After Kic. and Klscc tests the broken samples were analysed
using scanning electron microscope. For the phase transformation studies during continuous heating
(0.02C s - l ) of quenched and annealed specimens a Sadamel 18A dilatometer was used.
After dilatometric examinations the specimens for TEM observations were prepared.

EXPERIMENTAL RESULTS
The effect of tempering temperature on mechanical properties is shown in Fig. 2.
The graphs of K1c, K1sccand Kiscc/K~cvs tempering temperature are shown in Fig. 3.
 ....... L m

r.~

FIG. 4. Microfractographs of the specimens after Kit. (a,c) and Kj~(.(. (b,d) tests. The
specimens were quenched from 900C at oil then tempered at (a,b)--250C/3 h, (c,d)--
450C/3 h. Scanning electron microscopy.

687
 ;!; 1 ,~ m 0.5 ~ m

~, :. i~ ~ .... ~ .....
oo 0.5 /~m 0.5 F-m

{b) ~ (d)
FI6. 6. Transmission electron micrographs of specimens quenched (a) and tempered at 150C--(b),
35ooc--(c), 500U--(d).
 Tempering and stress corrosion cracking 6~q9

-3/2 Klscc
MNm Kic
80 ,0.8

70 Klsec ~ / 10.6

60 ~ . / ~ 0.4

50 ~ / 00.2

4O

30 Klscc ///~

10

0 I I I I
0 100 200 300 400 500 800
Tempering temperature C
FiG. 3. Fracturetoughness in terms of Ki<, K[~,< and KI~,.IK t, vs tempering temperature.

1
o
20

oo i0
o

- I0 i , , i l

i00 200 300 400 500

800
TemperatureC
FIG. 5. Thermalexpansioncoefficientat different tempering temperature for quenched (curve A) and
annealed (curve B) specimens.
690 B. PAWLOWSKI,A. MAZURand S. GORCZYCA

Typical microfractographs taken for specimens after Kic and K1sc~ tests are
presented in Fig. 4.
The changes on thermal expansion coefficient vs temperature for quenched
(curve A) and annealed (curve B) specimens are shown in Fig. 5.
Microstructures of quenched and tempered specimens are presented in Fig. 6.

DISCUSSION
The first tempering temperature range (200-400C) of high susceptibility (in
terms of Klscc/Klc) of tested steel to SCC (Fig. 3) is almost the same as the
temperature range of the maximum solubility of hydrogen in steel (Fig. 1) estab-
lished by Sakamoto and Takao. The dilatometric and electron microscopy examin-
ations (Figs 5 and 6), have indicated that at this range of tempering temperatures
intensive nucleation of e carbides occurs (see Fig. 6b).
This high susceptilibity to hydrogen-induced cracking observed at this tempera-
ture range seems to be caused by intensive precipitation of e carbides that increases
the solubility of hydrogen in steel. Most probably the interfaces between the e
carbides and martensitic matrix act as the hydrogen traps and increase the solubility
of hydrogen in steel.
The residual microstresses developed by nucleation of e carbides are also an
additional factor increasing the susceptibility of tempering steel to SCC.
The second tempering temperature range of susceptibility starts at 350C. As is
shown in Fig. 5, starting from 350C, a significant change of thermal expansion
coefficient occurs. This is due to the transformation of e carbides to cementite. This
was confirmed by electron microscopy observations (Fig. 6c).
At the same temperature, the transformation of retained austenite into tempered
martensite has started (X-ray analysis results, not cited here). The solubility of
hydrogen atoms in austenite is higher then in martensite and therefore, during SCC
testing the retained austenite concentrates more hydrogen than surrounding mar-
tensitic structure. Consequently, such martensite is more brittle than martensitic
matrix formed during quenching. The fracture toughness of steel thereby decreases.
Most probably, this mechanism takes place for the tested steel tempered at
temperatures above the 350-400C range, with the maximum at about 450C. X-Ray
analysis has shown that for tempering at 450C there is no retained austenite.
The decrement of the K~sc,,/K~ ratio at the tempering temperature 450C could
also be explained by a change of SCC mechanism from one hydrogen induced
cracking to another. After tempering at this temperature the recrystallised regions
were observed in the microstructure (Fig. 6d) resulting in a lowering of mechanical
properties (Fig. 2). A change of SCC mechanism needs further investigation.

CONCLUSION
The effect of tempering temperature on the susceptibility of tested steel to stress
corrosion cracking is connected with the effect on solubility of hydrogen in steel.
The two tempering temperature ranges of high susceptibility to SCC were
observed.
The first one (200-400C), caused by intensive nucleation of e carbides, is thought
to increase the solubility of hydrogen in steel.
The second, starting from 350C, seems to be connected with the transformation
of retained austenite into hydrogen supersaturated martensite. Above 450C the
 Tempering and stress corrosion cracking 691

susceptibility of tested steel to SCC could also be explained by a change in stress

corrosion cracking mechanism.

REFERENCES
1. B. F. BROWN, The Theory of Stress Corrosion Craackingin Alloys (Ed. J. C. SCULLY). p. 186. NATO
Scientific Affairs Division, Brussels (1971 ).
2. C. ZAPPFE and C, SIMS, Trans. A1ME 145, 437 (1941).
3. E. PETCH and P. STABLES,Nature 169,842 (1952).
4. A. R. TROIANO, Trans. A S M 52, p. 54 (196(I).
5. C. D. BEACHEM, Metall. Trans. 3,437 (1972).
6. Y. SAKaMOTOand K. TAKAO, Proc. 2nd Int. Congress Hydrogen in Metals, Paris, Vol. 1, paper 1A8
(1977).
7. B. F. BROWN and C. D. Beachem, Corros. Sci. 5,745 (1965).