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Article history: Stress Corrosion Cracking (SCC) is one of the most common failure phenomena in the wet hydrogen
Received 18 July 2016 sulfide environment. In this paper, the fracture failure of a fuel gas pipeline during operation has
Received in revised form 25 September 2016 been analyzed. Through service environmental investigation, crack morphology detection, and
Accepted 1 November 2016
stress analysis of fuel gas pipeline, the fracture has the morphology and characteristic of wet hydro-
Available online 3 November 2016
gen sulfide SCC in the welding joint between pipeline and flange. The analysis shows that the abnor-
mal martensitic microstructure in the pipeline has provided the advantage for SCC.
Keywords: © 2016 Elsevier Ltd. All rights reserved.
Wet hydrogen sulfide
Welding residual stress
Stress corrosion cracking
Fuel gas pipeline
1. Introduction
Pipelines have been widely used to increase continuity of production, transport efficiency and reduce costs in process indus-
try as well as in petrochemical industry [1–3]. But the petrochemical industry contains a variety of corrosive environment, and
the most common and serious failure of pipe is stress corrosion crack caused by hydrogen sulfide [4,5]. Especially, a welding
joint is susceptible to wet H2S environment [6,7]. The main characteristics of SCC are the multi-source and the bifurcation of
the intergranular or transgranular (or both) crack. In general, the crack orientation is perpendicular to the maximum principal
stress.
The main factors that affect the SCC of the material are the external operating environment and the internal metallurgy and
stress state of the components. The former is mainly affected by media, temperature, pressure and other factors, and the latter is
mainly affected by the material elements, microstructure, heat treatment and other factors [8–11]. The wet hydrogen sulfide
SCC has been paid more attention since 1950s. However, stress corrosion caused by wet hydrogen sulfide environment occurred
from time to time.
The investigation of the pipe operating condition shows that the medium in the pipeline contains wet hydrogen sulfide, and
the residual stress is high. In the present paper, the characteristics of SCC of wet hydrogen sulfide in pipeline weld are demon-
strated by analyzing medium environment, testing chemical composition, detecting fracture and simulating residual stress in
the welded joints. The results reveal that the synergistic effect of wet H 2 S and high residual stress is the main factor that
leads to the SCC.
⁎ Corresponding author.
E-mail address: xsg123@163.com (S. Xu).
http://dx.doi.org/10.1016/j.engfailanal.2016.11.001
1350-6307/© 2016 Elsevier Ltd. All rights reserved.
2 S. Xu et al. / Engineering Failure Analysis 71 (2017) 1–10
Table 1
Composition of dry gas (volume percentage).
2. Description
The leakage location of fuel gas pipeline in reforming unit is shown in Fig. 1. The leakage was caused by the cracking of the
pipe at the cross line between the fuel gas pipeline and the hot water gas pipeline.
The fuel gas pipe was made of 20 steel, and the flange was made of 1Cr5Mo. The internal pressure of the pipeline is fluctuated
between 0.5–0.77 MPa, and the operating temperature of the fuel gas is 18.64 °C. The main composition of dry gas in the pipeline
is methane, which also contains a small amount of H2S and condensed water. The specific composition is shown in Table 1.
3. Experimental analysis
The shear-lip is very narrow as shown in Fig. 2. When the crack is extended to the near surface, the shear stress is the leading
factor and causes shear tearing. The outer surface of the fracture has obvious shear-lip, and the shear-lip is very thin. Shear-lip
width reflects the material toughness, tear rate as well as the thickness of the component. Therefore, it can preliminary viewed
that toughness of the weld joint is poor, which may be caused by missing or improper stress relief annealing.
Table 2
Chemical composition of flange (wt.%).
Element C Si Mn P S Cr Mo Ni
GBT 1221-1992 1Cr5Mo ≤0.15 ≤0.50 ≤0.60 ≤0.035 ≤0.020 4.00–6.00 0.45–0.60 ≤0.60
NB/T 47008-2010 20# 0.17–0.23 0.15–0.40 0.60–1.00 ≤0.030 ≤0.020 ≤0.25 – ≤0.25
Measured 0.204 0.249 0.537 0.029 0.016 0.110 0.014 0.015
The fracture surface cracked along the pipeline and the flange weld joint, which is shown in Fig. 2. The fracture surface shows
low stress brittle fracture, and the macroscopic characteristics are as follows.
Spectral analysis for material composition of flange is shown in Table 2. According to the manufacture specification, the flange
might be made of 1Cr5Mo (GB/T 1221-1992 Heat-resisting steel bar) [12]. The results of chemical composition analysis show that
the content of Cr and Mo in chemical composition was too low, while the content of C was high. So the flange material is not
1Cr5Mo. According to the chemical composition control NB/T 47008-2010 Carbon and alloy steel forgings for pressure equipment
[13], the flange was made of 20 steel.
The weld seam and flange were cut and prepared for the metallurgical examination. Metallurgical structure of flange is
ferrite + widmanstatten (Fig. 3), weld seam is acicular ferrite (Fig. 4). The Chemical composition analysis results show that the
flange material is 20 steel, and the normalized microstructure of 20 steel is ferrite + pearlite. Therefore, the microstructure of
the flange is abnormal.
There is a bright layer (Fig. 5(a)) on the weld pipe side after metallographic structure of weld seam etched by 4% HNO3 alcohol
solution. It is found that the microstructure of the bright layer, etched by aqua regia, is lath martensite (Fig. 5(b)). The lath mar-
tensite is a low carbon martensite. As the width of the lath is narrow, the martensite group is presented under the optical micro-
scope, shown in Fig. 5(b). As low carbon steel, the 20 steel pipe should be used under normalizing heat treatment, and the
microstructure should be ferrite + pearlite. The Martensite is formed by the transformation of the supercooled austenite, after
rapid cooling under Mf. Therefore, the presence of martensite reflects that the heat treatment of the pipe is abnormal.
In the martensitic microstructure of the white bright layer, the dendrite intergranular cracks (Fig. 6) and the transgranular
cracks were found (Fig. 7). The microstructure of retained austenite that was not completely transformed into martensite can
be observed in Fig. 6(b). The intergranular cracks (Fig. 6) morphology show wide branch and a shape of rock candies cracking
under the optical microscope. The transgranular cracks (Fig. 7) show a shape of river pattern. The crack morphology is character-
ized by typical SCC.
Sampling positions are shown in Fig. 8. The mud-like pattern (Fig. 9) was observed in the SEM photo before cleaning. After
ultrasonic cleaning, the secondary cracks morphology on fracture surface is shown in Fig. 10. SEM photos of fracture show sub-
stantially no plastic deformation, and secondary cracks can be observed everywhere.
Corrosion product Energy Dispersive Spectrometer (EDS) found Cl, S, Na, K, Ca, and other elements (Fig. 11 and Table 3). S
element is widely distributed and its content is high in the corrosion products, the weight between 1% and 8%. Cl element is
also high content in the corrosion products.
SEM and EDS analysis revealed that the fracture has obvious characteristics of SCC. The fracture surface is rich in sulfur con-
tent, and the operation environment contains hydrogen sulfide and compensated water. From fracture characteristics of SEM and
EDS analysis, it can be concluded that the fracture is the SCC in wet hydrogen sulfide environment.
(a) SEM fractograph of corrosion products (b) EDS result of corrosion products (wt.%)
The welding residual stress simulation results show that welding residual stress value is very high, but the tensile stress is re-
duced under operating state. The stress value (axial stress and hoop stress) on the weld joint is reduced by about 100 MPa. The
residual stress is the stress caused by cooling shrinkage of the welding joint, and the inner pressure leads to tensile stress. There-
fore, the direction of the two stresses is roughly opposite, superposition effects will appear.
Table 3
Chemical composition of corrosion products using EDS (wt.%).
Element C O Si S Cl Na Al
(a) Radial stress (S11) (b) Axial stress (S22) (c) Hoop stress (S33)
The component works in the wet hydrogen sulfide environment, and the H2S concentration is 1000 μL/L (Table 1). Therefore,
there is a SCC environment in the operating environment of the component [14].
The stress analysis shows that the fracture crack position of the component is not the position of the maximum tensile stress,
but the tensile stress is relatively large. This is because the resistance ability of different microstructure to hydrogen sulfide stress
corrosion is inconsistent. Literatures [15,16] showed that the microstructure of the acicular ferrite was superior to the stress cor-
rosion resistance, while the martensite microstructure was very limited. SCC is decided by two aspects: internal metallurgy, stress
state, and external operating environment. The microstructure of weld fusion zone is acicular ferrite, the flange microstructure is
ferrite + widmanstatten, and the microstructure of pipe is lath martensite. The SCC occurs at HAZ near the pipe where the stress
is large and the microstructure is weak to hydrogen sulfide corrosion.
Combined with the operating environment, the crack appearance, and the stress state of the component, the fracture failure is
judged to be the SCC caused by wet hydrogen sulfide. The existence of chloride may promote the process of SCC. When the crack
in the weld is expanded to a certain critical value, a low stress brittle overload fracture accident occurred.
Radial stress
300 Axial stress
Hoop stress
200
100
Stress(MPa)
-100
-200
6. Conclusions
Acknowledgment
The authors wish to express their gratitude for the financial support by National Natural Science Foundation of China
(51404284), Fundamental Research Funds for the Central Universities (15CX05011A), and Applied Fundamental Research Funds
of Qingdao City (15-9-1-95-jch).
10 S. Xu et al. / Engineering Failure Analysis 71 (2017) 1–10
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