Assessment of Stress Corrosion Cracking On Pipeline Steels Weldments Used in The Petroleum Industry by Slow Strain Rate Tests
Assessment of Stress Corrosion Cracking On Pipeline Steels Weldments Used in The Petroleum Industry by Slow Strain Rate Tests
Assessment of Stress Corrosion Cracking On Pipeline Steels Weldments Used in The Petroleum Industry by Slow Strain Rate Tests
1. Introduction
The Stress Corrosion Cracking (SCC) is a local corrosion process which is characterized by
the initiation and propagation of cracks. It takes place under the simultaneous action of
sustained tensile stresses and specific corrosive environment on a susceptible material.
The formation of SCC occurs below the yield strength of the material and typically below
the design stress and fatigue limit of an engineering structure. Since the first discovery of
SCC on the exterior surface of a buried high pressure natural gas transmission pipeline in
1965 (Leis & Eiber, 1997), SCC has continued to make a significant contribution to the
number of leaks and ruptures in pipelines.
Two forms of SCC can exist on buried steel pipelines (Beavers & Harle, 2001). The first
discovered form of SCC propagates intergranularly and is associated with a concentrated
alkaline electrolyte in contact with the steel surface, commonly called as high pH-SCC or
classical SCC. A second form of SCC was discovered in Canada in the early 1980. This form
of SCC propagates transgranularly and is associated with a dilute neutral pH electrolyte in
contact with the steel surface, commonly called as low pH-SCC, non-classical, or near
neutral pH-SCC. Currently, there are some mechanisms proposed to explain the SCC
occurrence including the following: (1) a role for hydrogen in enhancing crack tip
dissolution; (2) a possible synergistic growth by fatigue and corrosion.
For high pH-SCC it is observed that the mechanism involves anodic dissolution for crack
initiation and propagation. In contrast, for low pH-SCC is associated with the dissolution of
the crack tip and sides, accompanied by the ingress of hydrogen in the steel. Steels with high
tensile strength are more susceptible to SCC. Cracks propagate as a result of anodic
dissolution in front of their tip in SCC process, due to the embrittlement of their tip by
hydrogen based mechanism. It was revealed that cracking behavior of pipeline steel in the
soil environment depends of the cathodic protection applied. Applying different potentials
levels the dominance of SCC process changes. At relatively low potential, the steel cracking
is based primarily on the anodic dissolution mechanism. When the applied potential
increases negatively, hydrogen is involved in the cracking process, resulting in a
transgranular cracking mode (Liu et al, 2008).
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SCC can occur in both gas and liquid pipelines but is more common and catastrophic in gas
pipelines (Manfredi & Otegui, 2002). SCC is the most unexpected form of pipeline failure
that can involve no metal loss and must not be confused with wall thinning rupture. SCC on
pipelines begins with small cracks develop on the outside surface of the buried pipe. These
cracks are initially not visible to the eye and are most commonly found in colonies, with all
the cracks in the same direction, perpendicular to the stress applied.
This chapter describes the mechanical and environmental effects as well fracture
characteristics on SCC susceptibility of steels used in the oil industry using slow strain rate
tests (SSRT), which were carried out according to requirements of NACE TM-0198, ASTM
G-129 and NACE TM-0177 standards (NACE TM-0198, 2004; ASTM G-129, 2006; NACE TM
0177, 2005). Some tests were supplemented by potentiodynamic polarization and hydrogen
diffusion tests. SSRT were performed in samples which include the longitudinal and
circumferential weld bead of pipeline steels. The weld beads were produced using the
submerged arc welding (SAW) and shielded metal arc welding (SMAW) process.
The SCC susceptibility has been evaluated using the results of SSRT in air (as an inert
environment), sour solution according to NACE TM 0177 (solution A from method A) and
in some cases a simulated soil solution called NS4. The studies include the effect of pH,
temperature, microstructure, effect of multiple welding repairs and mechanical properties.
The steels studied are low carbon steels API X52, X60, X65 and X70.
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Susceptible
material
Tensile
stress
SCC
Corrosive
environment
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The CERT method commonly is used with smooth tensile specimens through the SSRT. In
these tests specimens are slowly strained in tension and simultaneously exposed to a
corrosive environment. SCC susceptibility is evaluated by comparison of failure times,
maximum stress, plastic elongation, strain or reduction in area to values obtained in tests
conducted in an inert environment (Air). From this comparison of the mechanical properties
mentioned above, a ratio is obtained. Additionally, scanning electron microscopy (SEM)
observations of samples with low ratios (<0.8) should be carried out. More details of the
evaluation of SCC susceptibility using SSRT is given on NACE TM-0198 and ASTM G-129.
2.4.2 Slow strain rate tests (SSRT)
In recent years the SSRT has become widely used and accepted for SCC evaluations to
screen materials and to identify alloys that should not experience SCC in service. SSRT
involves the slow straining of a specimen of the steel of interest in a solution in which will
be in service. Typically a strain rate of the order of 1x10-6 in/sec is used, which is about four
orders of magnitude slower than strain rate used in a standard tensile test. A major
advantage of SSRT over CLT is that the test period is generally shorter. Thus, using SSRT we
can screening or evaluate materials in a fast way within a few days to determine SCC
susceptibility (Kane et al, 1997).
It is well known that the SSRT provides not only a useful information on SCC susceptibility
of the materials in any corrosive environments, but also a relatively short experimental time
to evaluate SCC susceptibility, where a maximum fracture time is that obtained at the lowest
strain rate in an inert environment. For that reason, SSRT has been widely used for SCC
assessment. However, to use SSRT for the SCC experiments, we need to compare the
parameters (time to failure, maximum stress, strain, reduction area, plastic elongation, etc.)
obtained in the corrosive environments with those in an inert environment. In addition, it
must be kept in mind that the specimens are always fractured in both environments, by
which in some cases it would be difficult to judge whether the fracture of the specimens
takes place by SCC or not (Nishimura & Maeda, 2004).
2.5 Stress corrosion cracking assessment
The susceptibility to SCC is evaluated according to NACE TM-0177 for CLT, and according
to NACE TM 0198 and ASTM G129 for SSR tests. To evaluate the SCC susceptibility through
SSRT is expressed in terms of the percentage reduction in area (%RA) calculated by the
following expression:
RA(%)
(Di 2 D f 2 )x 100
Di 2
(1)
where Df and Di are the final and the initial diameters of the tensile specimen respectively.
The reduction area ratio (RAR) after fracture for the specimen in the test environment (RAe)
to the corresponding value determined in the controlled environment (RAc) was calculated
according to the following expression:
RAR
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RAe
RAc
(2)
131
Additionally, the SCC susceptibility using the time to failure ratio (TFR) can be evaluated
according to the following equation:
TFR
TFe
TFc
(3)
where TFe is the time to failure determined for the material in the test environment and TFc
is the time to failure to the corresponding value determined in the controlled environment.
The similar way it can be assessed the SCC susceptibility using the plastic elongation
according to the following expressions:
E E
%EP F F PL x100
LI PL LI
EPR
EPe
EPc
(4)
(5)
where:
EP = Plastic strain to failure (%)
EF = Elongation at failure (mm/in)
EPL = Elongation at proportional limit (mm/in)
LI = Initial gauge length (mm/in) (usually 25.4 mm/1 in)
F = Stress at failure (MPa)
PL = Stress at proportional limit (MPa)
Ratios in the range of 0.8-1.0 normally denote high resistance to environment assisted
cracking (EAC), whereas low values (i.e.<0.5) show high susceptibility. Therefore, to
maximize the SCC resistance, it is desirable to obtain values of ratios as close to unity as
possible. Lower values of ratios generally indicate increasing susceptibility to SCC.
Complementary metallographic examination must be performed to establish whether or not
there is SCC on the samples. Overalls when there is some uncertainty in the assessment of
SCC susceptibility evaluating the mechanical properties (RAR, TFR, EPR). The presence of
cracks must be evaluated on the longitudinal section of the gage. The SEM observation it is
recommended when there is ratios lower than 0.8.
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3.1 Materials
In this work the susceptibility to SCC and corrosion of the main pipeline steels used in the
oil industry were investigated. API X52, X60, X65 and X70 pipeline steels were studied. The
chemical compositions and equivalent carbon (Ceq) are showed in Table 1. Dimensions of
the pipeline used in this study are showed in Table 2.
Steel
X52-A
X52-B
X60
X65
X70
C
0.080
0.090
0.020
0.070
0.027
Mn
1.05
0.89
1.57
1.46
1.51
Si
0.26
0.30
0.14
0.25
0.13
P
0.019
0.006
0.013
0.012
0.014
S
0.003
0.0015
0.002
0.002
0.002
Al
0.038
0.025
0.046
0.041
0.035
Nb
0.041
--0.095
0.047
0.093
Ni
0.019
0.05
0.17
0.050
0.16
V
0.054
0.036
0.004
0.069
0.004
Mo
--0.05
0.05
--0.004
Ti
0.002
0.016
0.014
0.017
0.011
Cr
0.02
0.07
0.26
0.02
0.27
Cu
0.019
0.12
0.30
0.09
0.28
Ceq
0.27
0.28
0.32
0.34
0.36
Diameter
(in)
36
8
42
24
36
Thickness
(in)
0.375
0.437
0.500
0.562
0.902
Fig. 2. Schematic representation where the specimens were obtained from the pipeline.
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Cylindrical tensile specimens with a gauge length of 25.4 mm (1 inch) and 3.81 mm (0.150
inches) gauge diameter were machined from the pipeline perpendicular to weld bead as is
shown in Figure 2.
3.2 Experimental set-up
To perform the SSR tests in the NACE solution saturated with H2S and NS4 solution, a 500
mL glass autoclave as is shown in Figure 3(a) was used. The autoclave containing the
specimen was externally heated by means of a heating element to the temperature required.
A Solartron potentiostat controlled by a desktop computer was used for potentiodynamic
polarization. The SSRT were performed in an Inter-Corr machine type M-CERT with load
capacity of 44 kN and total extension of 50 mm as is shown in Figure 3(b).
Fig. 3. (a) Autoclave and (b) M-CERT machine used to perform the SSRT.
3.3 SCC susceptibility of API X52 and X70 pipeline steels
The susceptibility to SCC in a sour solution saturated with H2S (commonly called as
sulphide stress corrosion cracking, SSCC), of API X52 and X70 steels was studied using
SSRT. SCC tests were performed in samples which include the longitudinal weld bead of the
pipeline steels. The SSRT tests were performed at room temperature in air and with the
NACE solution saturated with H2S at 50C and at room temperature, using a strain rate of
1x10-6 in/sec. Cylindrical tensile specimens were machined from the tube according to the
NACE TM-0198 standard as was shown in Figure 2.
The test solution according to the standard NACE TM-0177 consists of 50 g of NaCl and 5 g
of glacial acetic acid dissolved in 945 g of distilled water. The solution was subsequently
saturated with H2S at a flux rate of 100 to 200 mL/min for 20 minutes.
Table 3 shows the ultimate tensile strength (UTS), elongation (EL), percentage of reduction
in area (RA), reduction in area ratio (RAR) obtained from the SSRT curves. From Table 3 can
be observed that specimens tested in air showed the maximum %RA, which indicate a high
ductility compared with those tested in aggressive environment. The X52 specimens tested
in the NACE solution saturated with H2S at room temperature presented the maximum
susceptibility to SCC. This is in agreement with results reported in the literature (Lopez et al,
1996; NACE TM 0177, 2005; Perdomo et al, 2002). Meanwhile, the maximal susceptibility to
SCC in X70 specimens tested in NACE solution saturated with H2S was at 50 C.
SSRT tests are widely used to evaluate the susceptibility to stress corrosion cracking of
various materials (Wang et al, 2001; Casales et al, 2000, 2004; Parking & Beavers, 2003; Chen
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et al, 2002; Wang et al, 2002; Zhang et al, 1999; Brongers et al, 2000; Park et al, 2002; Beavers &
Koch, 1992; Liou et al, 2002). The failure time for samples tested in air, NACE solution at
20C and NACE solution at 50C was around 45, 20, 27 and 41, 23 and 39 hours for the X52
and X70 steels respectively. It is clear that specimens tested in the sour solution saturated
with H2S presented high susceptibility to SCC. Corrosion was found to be an important
factor in the initiation of some of the cracks. The susceptibility to SCC was manifested as a
decrease in the mechanical properties, e.g., strain values before failure, ultimate tensile
strength, reduction in area, time to failure and in some cases the presence of secondary
cracking along the gauge length of the specimen.
Steel
X52
X70
Air
UTS
(MPa)
391
EL
(mm)
2.03
NACE+H2S at 25C
249
NACE+H2S at 50C
%RA
RAR
Failure zone
55.6
N/A
1.42
13.8
0.248
233
1.88
7.25
0.130
Air
NACE+H2S at 25C
462
213
2.64
1.21
50.98
6.91
N/A
0.135
NACE+H2S at 50C
355
2.03
4.38
0.085
Base Metal
Weld
bead/HAZ
Weld
bead/HAZ
Weld bead
Weld bead
Weld
bead/HAZ
Environment
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formation of a neck in the failure zone was absent for the tests performed in the NACE
solution, which it is related to the brittle fracture. The SCC of low strength steels is
characterized by transgranular fracture, in contrast to intergranular fracture of high strength
steels (Shim & Byrne, 1990; Asahi et al, 1988; Tsay et al, 2000).
Fig. 4. Optical macrographs of the longitudinal sections (X70 steel) of the specimens after
cracked, showing the zone where they failed: (a) tested in air, (b) tested in NACE solution at
25C and (c) tested in NACE solution at 50C
Mechanical fracture techniques have been used to quantify the stress effects and the sour
environment effects in the cracking. Figure 5 shows SEM micrographs of the near surface
cross-section micrographs in the failed SSRT specimens tested in the NACE solution
saturated with H2S. The path of the crack was very irregular with brittle appearance (Figure
5a). In addition, it is observed that X70 steel is more susceptible to the corrosion attack as
shown in Figure 5(b), showing secondary cracks after being fractured in a NACE solution
saturated with H2S at 50C. It was observed that at 25C, the attack was in the pitting form
and it was less severe than at 50C. Meanwhile, at 50C the attack was in the form of microcracks (Fig. 5b) and it was more homogeneous along the gauge section of the specimen.
a)
X-52
b)
X-70
Primary crack
Secondary crack
Fig. 5. SEM micrographs of tensile fractured samples (a) X52 steel showing the appearance
of the fracture surface (primary crack) tested at 25C, and (b) X70 steel showing the
secondary cracks in the longitudinal gauge section, tested at 50C.
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3.4 Effect of multiple repairs in girth welds of API X52 pipeline on SCC
3.4.1 Slow strain rate tests carried out in NACE solution
Sulphide stress corrosion cracking (SSCC) susceptibility of four conditions of shielded
metal arc welding repairs and one as welded specimen of the girth weld in seamless API
X52 PSL2 steel pipe was evaluated using SSRT. The SSR tests were performed in air and in
a sour solution saturated with H2S both at room temperature to a constant elongation rate
of 1x10-6 in/sec. The SSCC susceptibility was evaluated in function of the reduction in
area ratio and elongation plastic ratio and also was manifested as a decrease in the
mechanical properties. The dimensions of the line pipe were 8 inches (203.2mm) in
diameter and 0.437 inches (11.1mm) in nominal wall thickness, with V-bevel at 30 in the
welding. The chemical composition was showed in Table 1 (X52-B). The girth welds were
obtained from the quality control department of the company Construcciones Maritimas
Mexicanas (CMM-PROTEXA), carried out by qualified welders under a qualified welding
procedure according to API 1104 standard (API 1104, 2005), using the SMAW process,
with a 0.125 inch in diameter consumable filler rod E-6010 for the root and hot pass and
with a 0.185 inches electrode E-7010G for the subsequent passes. The original weld (0R)
was repaired by arc air and hand disc grinder to a depth between the root and hot pass
and rewelding using the same welding procedure (1R). To simulate multiple welding
repairs, the repaired weld was similarly removed and welded again, to obtain a second
(2R), third (3R) and fourth (4R) welding repair. X-ray inspection was used to verify the
quality of the welded unions after each welding repair according to the requirements of
API-1104.
Several tests (SSRT) were carried out for each one of the welding repair conditions, for both,
in air and NACE solution. Profiles obtained from the SSRT are shown in Figure 6.
Fig. 6. Stress versus strain profiles obtained from SSRT for all repair conditions (a) Tested in
air; (b) tested in NACE solution saturate with H2S at room temperature.
SCC susceptibility was evaluated of the results obtained from SSRT according to NACE TM
0198 and ASTM G129. The results are showed in Table 4. The strength, elongation and
reduction in area decreases significantly when the samples are exposed to the NACE
solution saturate with H2S. This behavior could be attributed to combined action between
tensile stress and the specific corrosive environment. In fact, the synergic effect between the
stress, chloride and sulphide (obtained of hydrogen sulphide) increased significantly the
susceptibility to SSCC.
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According to the results of RAR and EPR is clear that the specimens tested in the NACE
solution saturated with H2S exhibited high susceptibility to SSCC. It is suggested that
decrease in mechanical properties is due to a hydrogen embrittlement mechanism, because
the fractured samples showed little deformation in the gauged section and there is not
formation of neck in the failure zone. From the different welding repair conditions, the
second repair showed the best performance and behavior in the tests, for both, in air and in
the NACE solution.
Condition
Environment
RA, %
EP, %
RAR
EPR
Failure zone
Base metal
Air
87.62
23.26
As welded
Air
83.16
15.00
BM
First repair
Air
86.86
16.18
BM
Second repair
Air
86.88
16.69
BM
Third repair
Air
82.30
14.37
BM
Fourth repair
Air
86.34
15.51
Base metal
NACE Solution
10.40
4.92
0.118
0.211
BM
As welded
NACE Solution
6.17
1.34
0.074
0.089
ICHAZ
First repair
NACE Solution
7.84
1.22
0.090
0.075
ICHAZ
Second repair
NACE Solution
9.30
1.65
0.107
0.098
ICHAZ
Third repair
NACE Solution
4.87
0.689
0.059
0.047
ICHAZ
Fourth repair
NACE Solution
5.26
0.984
0.060
0.063
ICHAZ
Table 4. Summary of the SSRT results to evaluate the SCC susceptibility of multiple repairs
in girth welds of API X52
According to Lant et al. (Lant et al, 2001) the temper bead technique generates overlap beads
producing grain refinement in the coarse grained heat affected zone (CGHAZ) of the
previous bead and decreases the residual stresses due to the input of additional thermal
energy. Considering this assumption, this it is the reason for which the second welding
repair presents the best mechanical behavior, for both, in air and in NACE solution.
The microstructure as well as the mechanical properties obtained for the different weld
repair conditions were shown elsewhere (Vega et al, 2008). Micrographs of the fracture
surface specimens were shown elsewhere (Vega et al, 2009). In air, all the specimens
exhibited a ductile type of failure (the presence of quasi-cleavage fracture mixed with
microvoid coalescence was observed). Meanwhile, in NACE solution saturated with H2S
showed a brittle fracture with a transgranular appearance. The brittle fracture is related to
the higher stress concentration by the lost metal regions due to anodic dissolution (pits and
general corrosion) and the diffusion of atomic hydrogen into the entrapping sites during the
welding process. Additionally, the diffusion of hydrogen and the stresses close to the crack
initiations sites develop the initiation and the growing of cracks.
The specimens tested in air for the different conditions of repair, the failure occurred in the
BM very close to the interface with the HAZ. For the samples tested in the NACE solution
for all the repair conditions, the failure occurred mainly along the intercritical heat affected
zone (ICHAZ) as is shown in Figure 7.
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Fig. 7. Optical micrographs of longitudinal section of fracture samples from SSRT showing
failure zone of specimens tested in NACE solution at room temperature, a) first repair; b)
second repair; c) third repair; d) fourth repair
SSCC in steels and in welded line pipes of low and medium strength has also been
denominated as stress oriented hydrogen induced cracking (SOHIC) (Takahashi, 1995,
1996a, 1996b; Carneiro, 2003). The SOHIC is divided in two stages: in the first stage, cracks
parallel to applied stress are formed by the hydrogen induced cracking (HIC) mechanism; in
the latter stage, the cracks link perpendicularly to applied stress like SSCC. All the found
cracks in the different welding repair conditions agree with the theory proposed by the
SOHIC mechanism; cracks formed parallel to the applied stress after link with cracks
formed perpendicular to the direction of the applied stress, preferentially induced along the
ICHAZ as is shown in Figure 8.
Most of the failures reported by SSCC or SOHIC in welded line pipes of low and medium
strength have occurred in the ICHAZ (Kimura, 1989; Takahashi, 1996; Endo, 1994).
According to Takahashi et al. (Takahashi, 1996) the applied stress acts to enhance shear
stress around the first parallel formed cracks to the stress and the shear stress can cause local
yielding which facilitates the vertical linking of the parallel cracks to break the specimen
eventually.
McGaughy et al. (McGaughy, 1992; McGaughy & Boyles, 1990) evaluated the effects of
SMAW repairs on the residual stress distribution of girth welds in API 5L X65 line pipe. The
girth welds contained repairs which included a single, double and a full wall repair. The
results showed that increasing number of welding repairs increased the level of axial and
hoop residual stresses, inside and outside surface of the line pipe. This suggested that the
contribution of the residual stresses together with the presence of discontinuities near to the
fracture interface makes the WB/HAZ interface more susceptible zone to SCC.
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Fig. 8. Scanning electron microscopy images showing parallel and perpendicular cracks
found along ICHAZ (sample with third repair).
3.4.2 Slow strain rate tests carried out in NS4 solution
The susceptibility to SCC in girth welds of seamless API X52 steel pipe containing multiple
shielded metal arc welding (SMAW) repairs and one as-welded condition were evaluated
using SSRT according to NACE TM-0198 standard. The SSRT were performed in air and
NS4 solution at pH 10 (basic) and pH 3 (acid) at room temperature and at constant
elongation rate of 1x10-6 in/sec. Cylindrical tensile specimens were transversal machined to
the direction of the application to the girth weld. The specimens according to the number of
repairs were identified as 0R (as-welded), 1R, 2R, 3R and 4R respectively.
The experimental research about SCC in pipelines considering the external environment
have been studied using NS4 solutions (Elboujdaini et al, 2000; Pan et al, 2006; Bulger &
Luo, 2000; Fang et al, 2007; Lu & Luo, 2006), this as results of investigations about the
chemical composition of the solution on the surface of the pipeline failed by SCC. The main
goal using NS4 solution is to simulate the chemical composition of the soil. The great
majority of these studies were made in the base metal of pipeline steels; there are few
studies on the longitudinal and circumferential welding but none reported in function of the
number of repairs. The chemical composition of the soil solution use to carry out the SSRT is
shown in Table 5.
Stress vs. Strain profiles obtained from the SSRT performed performed in air and in the NS4
solution both at room temperature for the different welding repair conditions are shown in
Figure 9. Base metal (BM) presented the maximum strain for SSRT carried out in air (26%)
and in NS4 solution (20% with pH 3 and 23% with pH 10) in comparison with the four
weldments. Specimens tested in air showed a strain about 16-19% meanwhile the specimens
tested in NS4 showed a strain between 14-19% with pH 3 and pH 10 respectively.
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Compound
Sodium bicarbonate
(NaHCO3)
Calcium chloride (CaCl2)
Magnesium sulfate
(MgSO4)
Potassium chloride (KCl)
Composition
(gr/L)
0.483
0.137
0.131
0.122
Fig. 9. Stress versus strain profiles obtained from the SSRT in function of pH and number of
repairs, a) in air, b) in NS4 solution with pH 3 and c) in NS4 solution with pH 10.
From the analysis of these curves we obtain results of reduction in area (RA), plastic
elongation (EP), reduction in area ratio (RAR) and elongation plastic ratio (EPR) which are
shown in Table 6. RAR and EPR were calculated according to NACE TM 0198. Ratios in the
range of 0.8-1.0 indicate that steel has high resistance to SCC, whereas low values (i.e. <0.5)
show high susceptibility.
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Condition
BM
0 rep
1 rep
2 rep
3 rep
4 rep
BM
0 rep
1 rep
2 rep
3 rep
4 rep
BM
0 rep
1 rep
2 rep
3 rep
4 rep
141
YS
(MPa)
386.1
356.0
379.9
384.1
359.7
379.2
UTS
(MPa)
475.2
437.5
464.2
456.2
427.4
455.9
RA
(%)
89.10
85.74
88.10
88.53
84.60
86.34
Ep
(%)
23.26
15.00
16.18
16.69
14.37
15.51
NS4, pH=3
396.8
325.9
322.5
351.8
318.1
329.7
464.8
423.0
427.5
438.2
354.9
428.8
88.13
84.10
86.84
86.90
83.91
85.01
19.72
14.17
15.47
16.69
13.78
15.00
0.98
0.98
0.98
0.98
0.99
0.98
0.84
0.94
0.95
1.00
0.95
0.96
NS4, pH=10
357.0
316.0
324.9
340.6
344.6
318.0
467.7
428.4
446.3
415.2
436.8
412.1
87.62
83.16
86.86
86.88
82.30
86.10
18.34
14.98
15.51
16.22
12.99
14.60
0.98
0.96
0.98
0.98
0.97
0.99
0.78
0.99
0.95
0.97
0.90
0.94
Environment
Air
RAR
EPR
Table 6. Assessment of the susceptibility to SCC obtained from the SSR tests
According to these results, it is clear that the specimens tested in the NS4 solution not
exhibited susceptibility to SCC. In addition, secondary cracks or corrosion were not
observed in the specimens after made the SSR tests. The strength, elongation and reduction
in area decreases slightly when the samples are exposed to the NS4 solution.
Passive film rupture, anodic dissolution and repassivation are the generally accepted
mechanism on SCC, but this is dependent on the strain rate. If the strain rate is too high, the
material fails predominantly under mechanical loading, and the environment did not have
time to damage the material. By other hand, at too slow strain rate the passive film formed
over a longer period of time will be too dense to be ruptured by the slow strain rate.
SEM observations of the fracture surfaces of specimens tested in air and NS4 solution with
pH of 3 and 10 showed microvoids coalescence for all the conditions studied which is
characteristic of a ductile type of fracture. Figure 10 shows SEM images of the fracture
surface after SSRT were performed.
As the strain increases the neck formation in the gauge section before the samples failed was
observed. This was reflected in the assessment of reduction area on the fracture surface. On
the edge of the fracture surface an intergranular type of fracture was observed, towards the
centre of the fracture change to a ductile type.
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Fig. 10. Fracture surfaces after made the SSRT, a) in air, b) NS4 solution with pH 3 and c)
NS4 solution with pH-10.
Optical micrographs of the longitudinal sections for specimens tested in NS4 solution with
pH-10 showing the failure zone are shown in Figure 11. The specimens tested in NS4
solution with pH of 3 and 10 for the different conditions of repair, the failure occurred in the
BM/HAZ interface without presence of secondary cracks in the gauge section.
Fig. 11. Optical micrographs of longitudinal section of fractured samples from SSRT
performed in NS4 solution with pH-10 showing failure zone, a) as welded; b) first repair; c)
second repair; d) third repair; e) fourth repair.
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The results showed that increasing number of welding repairs increased the level of axial
and hoop residual stresses, inside and outside surface of the line pipe. The SCC
susceptibility was expressed in function of the reduction in area ratio and elongation ratio.
The yield strength, tensile strength and ductility of the welded joints shown a decrease
when they are exposed to the NS4 solution. The metallographic observations of the
fractured specimens show that the most susceptibility area to SCC was the BM/HAZ
interface.
3.5 SCC susceptibility of API X60 and X65 pipeline steels
The SCC susceptibility of API X60 and X65 longitudinal weld beads was evaluated using
SSRT in a brine solution saturated with H2S at room temperature (25C), 37C and 50C. The
tests were supplemented by potentiodynamic polarization curves and hydrogen permeation
measurements. Longitudinal weld beads produced by SMAW process were analyzed. The
chemical composition of these steels was shown in Table 1. These types of pipes are
typically used in the Mexican pipeline systems for transporting hydrocarbons.
Figure 12 shows micrographs of the X60 and X65 steels weldments. These figures clearly
show the different microstructures found in a weldment, which consists mainly of
polygonal and coarse acicular ferrite. This microstructure optimizes the strength and the
toughness of the weld beads (Bhatti, 1984; Dolby, 1976; Kirkwood, 1978; Asahi, 1994).
Fig. 12 Microstructures obtained by optical microscopy of the weld bead: (a-c) API X60 steel,
(d-f) API X65 steel.
The welding industry has recognized that weld induced stresses play an important role in
SCC phenomena. Each year, tens of millions of dollars are expended to replace or repair
pipes and vessels that suffer SCC or hydrogen embrittlement (HE). When H2S is present in
the pipelines transporting hydrocarbons, this type of brittle failure is known as sulfide stress
corrosion cracking, and it has been established as a particular case of hydrogen
embrittlement (Tsay et al, 2000). The transport of these types of products always induces
failures in the pipeline systems, and is very frequently in the weld beads.
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(6)
where %RAAIR and %RANACE are the percentage reduction in area values in air and in the
NACE solution saturated with H2S. The results are plotted in Figure 13(a). Values close to
the unit mean that the steel is highly susceptible to SCC, whereas values close to zero mean
that the steel is immune to SSCC. Thus, Figure 13(a) clearly shows that, in all cases,
regardless of the temperature, both steels are highly susceptible to SCC, and the effect of the
temperature is negligible, although the tendency is that this susceptibility increases with
increasing temperature. X60 pipeline steel was more susceptible to SCC than the X65 steel,
although this difference seems to be negligible.
Hydrogen permeation tests were carried out using the two-component DevanathanStachurski cell (Devanathan & Stachurski, 1962). Figure 13(b) shows the effect of the
temperature on the hydrogen uptake (C0) for both steels. It is clear that the amount of
hydrogen uptake increases with temperature for both steels, being always higher in the X60
than in the X65 steel. All these results are consistent with those found in the literature (Asahi
et al., 1994). The corrosion rate, taken as the corrosion current density, Icorr, the amount of
hydrogen uptake for the weldments, C0, and the SSCC susceptibility increased with an
increase in the temperature from 25C to 50C. Although anodic dissolution seems to play
an important role in the cracking mechanism, the most likely mechanism for the cracking
susceptibility of X60 and X65 weldments in H2S solutions seems to be hydrogen
embrittlement (Natividad et al., 2006).
1.0
4.00E-012
(a)
3.50E-012
X-60
0.9
(b)
X-60
3.00E-012
-1 -1
C0 (mol H m s )
X-65
ISCC
0.8
0.7
2.50E-012
2.00E-012
X-65
1.50E-012
1.00E-012
0.6
25
30
35
T( C)
40
45
50
5.00E-013
25
30
35
T ( C)
40
45
50
Fig. 13. (a) Effect of temperature on the ISSCC values for both steels and (b) on the hydrogen
uptake for both steels.
Potentiodynamic polarization curves were performed at a sweep rate of 1.0 mV/s using a
fully automated potentiostat controlled with a desktop computer. The scanning started at
500 mV, with respect to Ecorr, and finished at 300 mV more positive than Ecorr, at a scanning
rate of 1 mV/s. Corrosion current values (Icorr) were calculated using Tafel extrapolation.
Figure 14 show the effect of temperature on the polarization curves for X60 and X65 pipeline
steels. As expected in these solutions, there is no passive region in any of the cases, only
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active dissolution. For both steels, the Ecorr decreases as the temperature is increased, with
the most noble value at 25C and 600 mV, and the most active at 50C and around 800
mV. The Ecorr value for the X60 steel at 37C was 650 mV whereas for the X65 steel, it was
700 mV.
-200
-200
a)
37C
b)
50C
-400
25C
Potential (mV)
Potential (mV)
-400
-600
-800
-600
-800
-1000
-1000
25C
-1200
-1200
X-60
37C
X-65
-1400
50C
-1400
-5
-4
-3
-2
2
Log (i)[mA/cm ]
-1
-6
-5
-4
-3
-2
-1
]
Log(i) [mA/cm
Fig. 14. Polarization curves obtained from weld bead at different temperatures in the NACE
solution saturated with H2S, (a) X60; (b) X65 steel.
Metallographic cross sections of X60 and X65 steels are shown in Figure 15. The cracks were
transgranular in nature predominantly, and, just as indicated by the polarization curve that
the corrosion rate increased as the temperature increased, the amount of corrosion products
inside the cracks is more pronounced at 50 than at 25C. Cross sections of the gage section of
X60 steel showed secondary cracks as is shown in Figure 15(a). For X65 steel, no cracks
were observed, only pits, as is shown in Figure 15(b).
Fig. 15. Cross-sections of weldments tested in the NACE solution saturated with H2S. (a)X60
steel at 50C, (b)X65 steel at 50C.
4. Conclusions
This chapter presents the mechanical and environmental effects as well as fracture
characteristics on SCC susceptibility of steels used in the oil industry using SSRT. The tests
were performed in samples which include the longitudinal and circumferential weld bead of
pipeline steels. The steels studied are low carbon steels API X52, X60, X65 and X70. These
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steels were evaluated in a brine solution saturated with H2S according to NACE TM 0177 (to
evaluate sulphide stress corrosion cracking susceptibility). Additionally, some
circumferential weldments of API X52 were evaluated in NS4 solution.
The results of the SSRT carried out in API X52 and X70 steels to evaluate the SCC
susceptibility revealed that specimens tested in the NACE solution saturated with H2S at
room temperature and 50C, presented high susceptibility to SCC, reflected in the
degradation of mechanical properties. The specimens tested in air exhibited a ductile type of
fracture. Whereas, in the corrosive solution, the specimens shown a brittle fracture. Both
steels presented a corrosive attack in the form of anodic dissolution of the material. The X52
steel showed best resistance to SCC. All the cracks, primary and secondary were
perpendicular to the applied tension axis, being indicative of SCC. These cracks were related
to the diffusion of atomic hydrogen promoting the embrittlement damage. The failure of
samples tested in air occurred in some cases in the weld joint, but in presence of the NACE
solution the failure always occurred in the HAZ.
SCC susceptibility of API X52 with multiple welding repairs in girth welds of pipelines was
evaluated by means of SSRT in NACE solution saturated with H2S. According to the results
of RAR and EPR, it is clear that welding joints are susceptible to SCC. The specimens tested
in air for the different conditions of repair, the failure occurred in the BM very close to the
interface with the HAZ. In presence of NACE solution saturated with H2S at room
temperature, the most susceptible zone to SCC was the ICHAZ following the SOHIC.
Although in presence of imperfections like pores and non-metallic inclusions near to the
interface with the HAZ, fusion line becomes the most susceptible zone to SCC. Using
temper bead technique contributes to the reinforcement of the mechanical behavior,
improving resistance to SCC as was observed in the second welding repair. The temper
bead technique generates overlap beads producing grain refinement in the coarse grained
heat affected zone of the previous bead and decreases the residual stresses due to the input
of additional thermal energy.
The susceptibility to SCC in girth welds of seamless API X52 steel pipe containing multiple
welding repairs was evaluated using SSRT in soil solution. The SSRT were performed in air
and NS4 solution at pH 10 (basic) and pH 3 (acid) at room temperature. The main goal using
NS4 solution is to simulate the chemical composition of the soil. According to the RAR and
EPR results, it is clear that the specimens tested in the NS4 solution not exhibited
susceptibility to SCC. In addition, secondary cracks or corrosion were not observed in the
specimens after perform the SSRT. The strength, elongation and reduction in area decreases
slightly when the samples are exposed to the NS4 solution. SEM observations of the fracture
surfaces of specimens tested in air and NS4 solution with pH of 3 and 10 showed
microvoids coalescence for all the conditions studied which is characteristic of a ductile type
of fracture. The metallographic observations of the fractured specimens show that the most
susceptible area to SCC was the BM/HAZ interface.
The SCC susceptibility considering the effects of the temperature on the corrosion rate, and
hydrogen uptake of API X60 and X65 weldments through SSRT was carried out. The SCC
susceptibility and corrosion rate, taken as Icorr, for both weldments, increased with an
increase in the temperature from 25 to 50C, as well as the amount of hydrogen uptake for
the weldments. The most likely mechanism for the cracking susceptibility of X60 and X65
weldments in sour solutions seems to be hydrogen embrittlement, but anodic dissolution
seems to play an important role in the cracking mechanism. Specimens tested in NACE
solution showed brittle type of fracture, with a very small percentage reduction in area
values, and the gage section shown a large number of secondary cracks.
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