Professional Documents
Culture Documents
1183-1196, 1987
Printed in Great Britain
0010-938X/87$3.00+ 0.00
PergamonJournalsLtd.
T E S T I N G T H E R E S I S T A N C E O F W E L D S IN L O W - A L L O Y
STEELS TO H Y D R O G E N - I N D U C E D STRESS C O R R O S I O N
CRACKING
H. PIRCHERand G. SUSSEK
Thyssen Stahl AG, Duisburg, F.R.G.
Abstract--Laboratory experiments are described in which various tests were conducted to examine the
influence of welding on the resistance to hydrogen-induced stress corrosion cracking (HSCC) of low-alloy
steels. The structure of the heat-affected zone, the hardness resulting from it, and the influence of the
welding conditions are given special consideration in the evaluation of the corrosion tests. Multi-pass
welded joints, single-pass bead-on-plate welds and on weld thermal simulated specimens executed with
varying cooling times t8/5are discussed. Constant load tests are conducted according to NACE TM-01-77,
and constant deflection tests according to Stahl Eisen Priifblatt 1861, with H2S-saturated NACE Test
solution of pH 3. Steels with a low hardening tendency, in combination with suitable welding conditions,
have proven to be advantageous. A hardness reduction through tempering can have positive or negative
effects on the corrosion resistance, depending on the steel grade involved. It is not recommended to derive
generally applicable hardness criteria from the test results since different information has been obtained
in this regard by the respective test techniques. Conclusive answers are attained only from tests involving
large or full-scale specimens under realistic corrosive and mechanical loading conditions.
INTRODUCTION
CASES IN which d a m a g e has b e e n c a u s e d by h y d r o g e n - i n d u c e d stress c o r r o s i o n
c r a c k i n g to p r e s s u r e vessels a n d p i p e l i n e s fed with HES-bearing c o n d e n s a t e s constit u t e a f a m i l i a r p h e n o m e n o n . P r i m a r i l y a f f e c t e d a r e p l a n t a n d e q u i p m e n t u s e d in gas
a n d c r u d e oil p r o d u c t i o n as well as the d o w n s t r e a m p r o c e s s i n g installations.l-3 T h e
q u e s t i o n as to w h a t m i n i m u m c o n t e n t s o f H2S are sufficient to b r i n g a b o u t h y d r o g e n i n d u c e d d a m a g e ( s o u r gas c o n d i t i o n s ) is given d i f f e r e n t a n s w e r s in the v a r i o u s
existing t e c h n i c a l g u i d e l i n e s , specifications, a n d s t a n d a r d s . 3'4 If t h e d a n g e r exists o f
t h e s e limit v a l u e s b e i n g e x c e e d e d , the s i m u l t a n e o u s p r e s e n c e o f an a q u e o u s p h a s e
can l e a d to c o r r o s i o n . T h e risk o f d a m a g e can b e r e d u c e d b y using m a t e r i a l s t h a t h a v e
an e l e v a t e d r e s i s t a n c e to h y d r o g e n - i n d u c e d stress c o r r o s i o n c r a c k i n g ( H S C C ) . T h e s e
a r e p r e d o m i n a n t l y l o w - a l l o y steels t h a t a r e s e l e c t e d a n d p r o c e s s e d a c c o r d i n g to
c e r t a i n criteria. D i f f e r e n t c r i t e r i a can be u s e d to assess w h e t h e r a m a t e r i a l is at risk
t h r o u g h H S C C . 5 I d e a l l y , t h e s e are critical stresses b e l o w w h i c h no stress c o r r o s i o n
c r a c k i n g occurs, o r critical stress levels b e l o w which c r a c k g r o w t h can b e p r e c l u d e d ,
b e it static o r a l t e r n a t i n g stress that is i n v o l v e d .
T h e n o r m a l p r o c e d u r e for d e t e r m i n i n g t h e H S C C resistance o f a steel consists of
e x p o s i n g tensile s p e c i m e n s to c o n s t a n t l o a d s in a suitable e l e c t r o l y t e s o l u t i o n at r o o m
t e m p e r a t u r e . 3 A n e x a m p l e w o r t h y o f m e n t i o n is the test specified in N A C E S t a n d a r d
TM-01-77.
This paper was presented at the Conference on 'Hydrogen Sulphide-Induced Environment Sensitive
Fracture of Steels' which was held in Amsterdam on 10-12 September 1986 and which was organized by
the Working Party of the European Federation of Corrosion on Stress Corrosion Test Methods.
Manuscript received 5 November 1986.
1183
1184
Steel
A
B
C
D
E
Alloying components
C,
C,
C,
C,
C,
Mn,
Mn
Mn,
Mn,
Mn,
Ni
Nb, V
Cr, Mo
Cr, Mo, Ni, V
TEST MATERIALS
Mechanical properties
(N mm -2)
Yield strength
Tensile strength
375
385
440
510
730
535
520
575
605
850
C-equivalent
%
(IIW)
0.46
0.40
0.39
0.38
0.79
HSCC testing of steels and welded joints in many cases involves also constant
deflection test specimens because of the comparatively small amount of apparatus
that is required. Examples of three-point bending test specimens are described for
homogeneous materials in DIN 509156 and for welded joints in Stahl-Eisen Specification 1861.7
Laboratory experiments are reported below in which, with the aid of various
testing techniques, the extent to which low-alloy steels are influenced either by their
microstructure or by welding with respect of their resistance to HSCC. The structure
of the heat-affected zone and the hardness resulting in connection with the welding
conditions are given special consideration in the evaluation of the corrosion experiments.
EXPERIMENTAL METHOD
The experiments were carried out on five differently alloyed structural steels (Table 1) that had been
modified with reference to their carbon equivalent and whose yield strengths ranged between 375 and
730 N mm -2. Two of the steels (A, B) had been normalized, one (C) thermomechanically rolled, and two
(D, E) water-quenched and tempered. All of these steels had undergone a calcium treatment by the
TN-process s and as a result had shape-controlled inclusions and sulphur contents <20 ppm.
Two kinds of corrosion experiments were performed (Table 2), using constant load and constant
deflection rate tests. Tested under constant load in deadweight testers using smooth tensile specimens
were (a) the base metal; (b) welded joints with different welding conditions characterized by the
corresponding cooling times ts/s. This is the time required during the cooling of a weld bead and its
heat-affected zone (HAZ) to pass through the temperature range of 800-500C. 9 The weldments were
performed using filler metals matched to the different steel grades. The tensile specimens were made
perpendicular to the weld, thereby encompassing the base metal, the HAZ, and the weld metal; and (c)
weld-simulated specimens with two austenitized states corresponding to the coarse grain H A Z and the fine
grain HAZ, and with different cooling times t8/5.
Tested in constant deflection tests using three-point bending specimens were: (a) the base metal; (b)
welded joints; and (c) bead-on-plate welds with different cooling times t815. For the making of bending
TABLE 2.
1185
specimens perpendicular to the weld, the plate was ground so that the layer with the zone of maximum
hardness was encompassed. All tests were carried out in the as-welded condition and following a
stress-relief anneal at 580C.
The experiments were performed exclusively under conditions of free corrosion in pH 3 solutions as
specified in NACE TM-01-77.1 After the corrosion tests, all the specimens were subjected to a
metallographic inspection of the fracture location. Apart from hardness measurements, the transformation behavior of the individual steels was determined by recording ~
diagrams of the coarse-grained
and of the fine-grained heat-affected zone.
EXPERIMENTAL
RESULTS
Base metals
Figure 1 gives the results of the constant load tests involving the normalized
structural steel A. The tests were performed at room temperature in accordance with
the guidelines specified in NACE TM-01-771 for the testing of the HSCC resistance
of metallic materials. The findings are characteristic of a well-defined HSCC system.
A threshold stress of Rcrit/720 = 190 N mm -2 was established after an exposure time of
720 h. This is roughly equivalent to a value of 50% of the yield strength of Re] = 375 N
mm -2.
Contained in Fig. 2 are the results of all five steels showing the critical stress
relating to the actual yield strength of the steels. The threshold stresses that were
determined lie between 15 and 90% of the respective yield strengths.
The results of HSCC tests involving Mn-alloyed structural and pipe steels and the
five investigated steels are given in Fig. 3, showing the yield strength values against
the threshold stresses for HSCC determined after 720 h of exposure. The steels can
be divided in accordance with former results u into two strength categories which
display different behaviour with regard to HSCC resistance. For steels having yield
strengths up to 650 N mm -2, the threshold stress for HSCC increases with increasing
yield strength. For high strength steels with yield strengths >650 N mm -2, a contrary
tendency was established; the critical stress for HSCC decreases with increasing yield
strength, i.e. the materials become more susceptible to HSCC. Presupposing a
yield/tensile strength ratio of 0.8, for a yield strength of 650 N mm -2, a tensile
700
600
SO0
E
E 400
3oo
200
100
0
I
10
100
1000
FIG. 1.
1186
'
tilt
10
F-1-T
100
I
1000
Failure time [ h ]
FIG. 2.
700
600
E
E 500
Z
400 ~
300
oo
200
~3
100 - 0
100
200 300
400
500
600 700
800
Fro. 3.
Cross sechon
Specimen KB 5
Steel A
20mm
FI{;. 4.
5mm
Constant deflection tests on base metal (NaCI solution pH 3, H2S saturated, 720 h).
1187
ts/5 = 15 s
ts/5 = 5 s
'lO
500
{'\
~00
>
I
/ t $ / 5 =5 s
300
t B/s = 15 s
I .,';"z,
I
./
200
Bose motor
100
Weld
I
FIG. 5.
10
Dqstclnce [ m m
1188
12
1189
Transverse micro-sections taken from multipass butt welds performed on structural steel A are shown in Fig. 5. As is evident from the short cooling time ts/5 = 5 s,
the manual arc weld was fabricated with a very small heat input. The submerged arc
weld was executed with the cooling time t8/5 = 15 s. In both cases the last weld bead
of the cover pass was deposited intentionally at the interface to the base metal. The
hardness curves shown in the diagram were in both cases measured at a distance of
0.5 mm from the plate surface in such a way as to encompass only those structural
zones that in the as-welded condition had not undergone any tempering treatment as
a result of subsequent weld beads.
As can be seen from the displayed hardness curves, the maximum hardness values
characterizing the transformation structures can be influenced by the welding
conditions. The relation between the maximum hardness values and the cooling time
ts/5 for the different welding conditions is illustrated for the investigated example in
Fig. 6. The maximum hardnesses are measured in the portion designated as the
coarse-grain zone, that is, in the region of the heat-affected zone subjected to the
highest temperature. Of course, the maximum values can change as a result of
tempering or due to the influence of heat during subsequent welding passes.
In Fig. 7, the time-temperature-transformation (TI-T) diagram ~2determined for
the coarse-grain zone characterizes the H A Z structures attributable to the respective
cooling times. The samples were heated so as to achieve a mean austenite grain
diameter of d m = 0.176 mm, which corresponds to the grain size number G2 in
Euronorm 103-71. The thermal cycles during cooling also concurred with those of
real welds with different cooling times t8/5. Also depicted is the accompanying T T T
diagram for the fine-grain zone (grain size G 9, dm= 0.016 ram) of the heat-affected
zone. The martensite hardness is almost identical in both cases, it being governed
mainly by the carbon content. The higher hardness of the coarse-grain zone mostly
resulting for the same cooling time is due to the retarded transformation reactions in
this zone.
Constant load tests in which smooth tensile specimens and three different welding
conditions were used, yielded the result shown in Fig. 8. When testing steel A, the
specimens removed at right angles to the weld fractured invariably in the region of
CoorsegroinedHAZ
Fine g. . . . d HAZ
]00
~,
0
I
10
I00
F0~i. 6.
Steel A: hardness, of the heat affected zone for different wcl,.ling [)aramctcrs.
1190
H. PIRCHERand G. SUSSEr
Chemical composition ( % )
c i s,
"1"
'lc
l"ol"'
I v I
~ soo
2
~"
E
M
Aust
300
I00
HVlO
....
Jj
'
[
1o
1(3(3
the non-heat-affected base metal, irrespective of the welding conditions and the
post-weld heat treatment.
Different results are obtained if, instead of specimens removed from the weld,
use is made of specimens in which individual structures of the heat-affected zone have
been produced by means of a weld simulation. Figure 9 gives the results of tests
involving the previously mentioned structural steel A. The coarse-grain zones
heat-treated to simulate different welding cycles accounted for roughly 10 mm of the
test length. In these tests both the cooling time t8/5 and the postheat treatment
influenced the HSCC resistance. The comparatively hard structures in the case of
IOOO
100
.C
oJ
,,o
1o
10
loo
1191
100
.wO
OQ
I
__t-Z_--q------.l.-~
.....
t -.,-'~'-~- ~ -
IO
ea
Io
IOO
F](;. 9.
IOO
,~--- I
2
IO
lO
I00
F[(;. t0+
1192
H. PIRCHERand G. SUSSEK
I00
.c
~_ lO
10
Cooling time
FiG. 11.
I00
ts/5 [ s ]
Steel C: constant load tests in NACE TM-01-77-type solution using weld simulated tensile specimens.
Post-weld heat treatment primarily serves the purpose of reducing the residual
stresses in the weld region. Generally, the maximum hardness in the heat-affected
zone is also reduced at the same time. A decline in hardness, however, does not
always lead to an improvement in HSCC resistance. This is illustrated by Fig. 11
which gives the results of tests on Nb-V-micro-alloyed structural steel C. The cracks
occurred in the coarse-grained zone, which is the region of maximum hardness and
simultaneously, where these three point bending specimens are concerned, also the
region of the highest mechanical stress. The changes in hardness achieved through
tempering led to increased susceptibility to HSCC in the practical range of welding
conditions.
Regarding the non-welded tensile specimens under NACE test conditions, steel
Iooo
"
"
os welded
.w-O
I
"
@@
t
I0
lO0
FIG. 12.
1193
100
10
o
"
10
100
Steel E:
constant
D attained a very high threshold level of 90% of the yield strength. Welding led to a
deterioration of the HSCC resistance, as is shown by the example of weld-simulated
specimens in Fig. 12. At the selected stress level of 400 N mm -2, the coarse-grained
zone of the specimens with cooling times <30 s proved to be rather susceptible.
Tempering had no influence on the corrosion behaviour. The welded joints including
the bead-on-plate weldments behaved similarly, with it also having to be said that
here the weld metal proved to be susceptible to HSCC in many cases.
Comparison with the results yielded by high strength steel E reveal the extent to
which susceptibility to HSCC can still rise. Figure 13 shows the results yielded by the
welded tensile specimens at a stress level of 200 N mm-:, which corresponds to
roughly 25% of the actual yield strength. The fractures occurring solely in the
coarse-grain zone led to failure after a few hours. The cracks were partly intercrystalline. Although stress-relief annealing partly improved the resistance, improvements
of this order of magnitude are, however, technically irrelevant.
From the transformation characteristics (Fig. 14) of this steel it is possible to
derive the structures of the coarse-grained zone (grain size G 4, d m -- 0.088 mm) in
the practical range of welding conditions. When the cooling time @5 is <30 s, this
steel displays a fully martensitic structure. As expected, hardness values of more than
400 HV 10 are measured in this connection.
Overall evaluation
Figure 15 contains the HSCC test results, marked by large symbols, determined
for the five steels from welded round tensile specimens. Results from previous series
of tests have also been added, t3
It can be seen from the diagram that, in the as-welded condition, up to a hardness
of around 350 HV 10 the cracks did not occur in the hardest zone of the HAZ, but in
softer structure zones. Only where the hardnesses are greater than 350 HV 10 can the
H. PIRCHERand G. SUSSEK
1194
Chemicolcomposition('I.)
l
C
Si
Mn AI
Cr
Cu Mo L N
Ni
V I
0.16 0.23 1.07 0,051 1.19 0.26 0.S0p.00Sl 1.25 0.06]
800
700
6OO
s00
~00
300
10o
0
100
10
CooLingtime te/s I s ]
FIG, 1 4 .
location of the cracking and of the maximum hardness be identical, i.e. only then
does the maximum hardness value take on the significance attributed to it. Tempering
can cause the limit stated for the as-welded condition to shift to lower values. An
example is Mn-V-alloyed steel C which fractured even when having a hardness of
260 HV in the coarse-grain region of the HAZ. It should also be pointed out that in
many cases the weld metal represents the weakest part of the joint.
All results of the tests on steels A - E involving smooth tensile specimens heat
treated to simulate welding are shown in Fig. 16. The fracture locations are separated
according to base material and coarse-grained zone. In the constant load tests, the
large homogeneous H A Z structures produced by weld simulation react much more
critically to corrosion than the narrow H A Z of real welds. As long as the hardness did
not fall below a value of 300 HV, all of the steels displayed fractures solely in the
100
.0
Fracture : Bose m e t a l
Weld deposit
80
o H A Z - P a r t i a t t y ustenitic
HAZ-Coorse-groined
60
11
eee
40
20
o
A
JV~
FIG. 15.
150
200
tOO
~50
250
300
350
Maximum hardness HV 10 in HAZ
500
to
-Bose
1195
n~tat
O
e-i
Q)
g,
- HAZ - -
Lt.
Fro. 16.
100
200
300
Hardness HVl0mox HAZ
400
500
HAZ. In the range between 300 HV and 230 HV, the hardest structure zone proved
only in individual cases to be particularly susceptible to HSCC. Steels C and D did
not behave much better in this intermediate range in spite of their low carbon
equivalent of CE ~< 0.40%, as compared, for example, with steel A which had a CE
= 0.45%. Only below 230 HV did the weld simulation heat treatment remain without
effect. Once again, the fractures occurred in the unaffected base metal or in
individual cases at the partly austenitized or overtempered interface.
The results of the constant deflection tests involving welded bend specimens are
shown in Fig. 17. A differentiation is made between specimens that displayed cracks
in the HAZ and specimens which survived the corrosion test without HSCC or had
incipient cracks in the weld metal. A picture emerges similar to that for the
weld-simulated specimens. In the intermediate range between 300 HV and 230 HV,
cracking can occur in the HAZ. Below 230 HV in the HAZ no susceptibility to HSCC
could be observed in the welded bend specimens in spite of stressing that was
ascertainably beyond the elastic limit.
CONCLUDING REMARKS
The question arises as to how the obtained results can be put to use for practical
corrosion protection. Informative insights have been obtained for the individual
NOfl~cture
dq)osit
__:Jm--AAA~:
~ ~
Q.
tl.
Fro. 17.
100
200
300
Hordness HV 10mox HAZ
t.00
500
1196
H. PIRCHERand G. SUSSEK
steels regarding the relation between corrosion resistance and the structure of the
H A Z which stimulate thoughts on how contributions can be made towards enhancing
the safety of plant and equipment through the choice of suitable materials and
welding conditions. Steels having a low hardening tendency in connection with
certain welding conditions have been proved to be advantageous. A hardness
reduction through tempering can have positive or negative effects on the corrosion
resistance, depending on the steel grade involved.
It does not appear possible to derive generally applicable hardness criteria from
the test results obtained in the laboratory experiments since different information is
yielded in this regard by the respective test techniques. Conclusive answers are
obtained only from tests involving large or full scale specimens under realistic
corrosive and mechanical conditions. In this connection, it needs to be clarified
whether round tensile specimens, whose threshold stress in the NACE test is always
less than the yield strength, characterize the material behaviour under service
conditions, or whether bend specimens are more suitable which in some cases, when
stressed beyond the elastic limit, indicate extensive HSCC resistance for low-alloy
steels and their welds.
Acknowledgement--This project was partly financed by the Ministry of Research and Technology of the
Federal Republic of Germany, whom the authors would like to thank.
REFERENCES
1. M. REUTER,Techn. Uberwachung15, 10, 65,101 (1974).
2. W. C. VOLLMER,Corrosion 8,326 (1952).
3. NACE-Standard MR-01-75, Materials requirement sulphide stress cracking resistant metallic
material for oil field equipment.
4. DVGW-Regelwerk, Arbeitshlatt G 260, Technische Regeln fi~r die Gasbeschaffenheit, January
(1973).
5. H. PIRCHER,in Wasserstoffund Korrosion, pp. 75-124. Verlag I. Kuron (1986).
6. DIN 50915. Priifungvonunlegierten und niedriglegierten Stfihlen aufBestfindigkeit gegeninterkristalline Spannungsrikorrosion.
7. Stahl-Eisen-Prfifblatt 1861-82, Prfifung von SchweiBverbindungen an unlegierten und niedriglegierten Stfihlen auf ihre Best~indigkeit gegen SpannungsriBkorrosion.
8. E. F()RSTER,W. KLAPDAR,H. RICHTER,H.-W. ROMMERSWINKEL,E. SPETZLERand J. WENDORFF,Stahl
u. Eisen 94,479 (1974).
9. J. DEGENKOLBE,D. UWERand H. WEGMANN,IIW Doc. IX--1336-84.
10. NACE-Standard TM-01-77, Testing of metals for resistance to sulfide stress cracking at ambient
temperatures.
11. H. PIRCHERand R. P()PPERLING,gwfgas/erdgas 127, 80 (1986).
12. U. LOITER,B. MOSGENand H. PIRCHER,Thyssen Techn. Bet. 16, 13 (1984).
13. H. PIRCHERand G. SUSSEK,Stahlu. Eisen 182,503 (1982).