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Journal of Chinese Society for Corrosion and protection  2015, Vol. 35 Issue (2): 129-136    DOI: 10.11902/1005.4537.2014.058
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Effect of Martensite/Austenite (M/A) Constituent on H2S Resistance of High Strength Pipeline Steels
SHI Xianbo1,2, WANG Wei1, YAN Wei1, SHAN Yiyin1, YANG Ke1()
1. Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2. University of Chinese Academy of Sciences, Beijing 100049, China
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Abstract  

Resistance to hydrogen sulfide (H2S) corrosion was studied for two X90 grade high strength pipeline steels with the same microstructure of acicular ferrite (AF). The results showed that the AF microstructure with fine martensite/austenite (M/A) constituent had better resistances to both hydrogen-induced cracking (HIC) and sulfide stress corrosion cracking (SSC). The larger size M/A constituent in AF microstructure deteriorated the H2S-resistance of the steels such as that with the decreasing pH value and increasing immersion time, the density of hydrogen-induced blisters on the steel surface increased and the HIC parameters increased, while its time-to-failure of SSC was shorter compared to the steel with finer M/A constituent. The different susceptibilities to H2S cracking of the two high strength pipeline steels were interpreted from the view points of size and quantity of M/A constituent, which was observed from the HIC propagation path by SEM. It is suggested that X90 pipeline steels for sour gas/oil service should have a lower amount of M/A constituent (<8%) and an effective M/A constituent size control (<2 μm) by TMCP as well as a proper chemical composition optimization, thereby to ensure their resistance to H2S.
Key words:  high strength pipeline steel      acicular ferrite      martensite/austenite constituent      hydrogen-induced cracking      sulfide stress corrosion cracking     
Received:  24 April 2014     
ZTFLH:  TG142.1  
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Xianbo SHI
Wei WANG
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SHI Xianbo, WANG Wei, YAN Wei, SHAN Yiyin, YANG Ke. Effect of Martensite/Austenite (M/A) Constituent on H2S Resistance of High Strength Pipeline Steels. Journal of Chinese Society for Corrosion and protection, 2015, 35(2): 129-136.

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https://www.jcscp.org/EN/10.11902/1005.4537.2014.058     OR     https://www.jcscp.org/EN/Y2015/V35/I2/129

Steel C Si Mn S P Mo Cu Cr Ni Al Nb+V+Ti Fe
A 0.046 0.14 1.53 0.0014 0.0050 0.20 0.31 0.30 0.10 0.061 0.132 Bal.
B 0.046 0.10 1.68 0.0013 0.0050 0.19 0.30 0.29 0.20 0.031 0.117 Bal.
Table 1  Chemical compositions of the experimental steels
Steel Rolling temperature / ℃ Accelerated cooling
Cooling rate ℃/s Final cooling temperature / ℃
A 1100 1056 1000 892 854 800 772 15 300
B 1079 1046 987 890 835 800 750 20 ---
Interpass reduction distribution / mm 80~60 60~45 45~30 30~24 24~16 16~11 11~8 --- ---
Table 2  Measured processing parameters in TMCP of the experimental steels
Fig.1  Schematic diagram of specimen for HIC test and the faces to be examined (unit: mm)
Fig.2  Schematic diagram of specimen for SSC test at constant load (unit: mm)
Fig.3  OM (a, c) and SEM (b, d) images of A steel (a, b) and B steel (c, d)
Steel ?Yield strength(YS / MPa) Ultimate tensile
strength (UTS / MPa) 		YS/UTS
ratio 		Elongation
% 		Uniform
elongation / % 		Impact
tough / J
A 620 720 0.86 23.5 8.6 116
B 657 729 0.90 23.5 9.4 116
Table 3  Mechanical properties of the experimental steels
Fig.4  Surface photographs of two experimental steels immersed in NACE TM0284 solution: (a) Steel A, pH=2.7 (oh), 3.2 (96 h); (b) Steel B, pH=2.7 (oh), 3.2 (96 h); (c) Steel A, pH=1.9 (oh), 3.0 (288 h); (d) Steel B, pH=1.9 (oh), 3.0 (288 h)
Fig.5  Morphology of hydrogen induced blistering cracking and hydrogen induced cracking in Steel B
Steel Sample The initial pH=2.7 and the ending pH=3.2, 96 hours Steel Sample The initial pH=1.9 and the ending
pH=3.0, 288 hours
CSR / % CLR / % CTR / % CSR / % CLR / % CTR / %
A 1 0 0 0 A 7 0.03 11.4 0.3
2 0 0 0 8 0 0 0
3 0 0 0 9 0 0 0
Average 0 0 0 Average 0.01 3.8 0.1
B 4 0.3 60.9 1.9 B 10 1.2 67.0 3.1
5 0.1 35.8 0.7 11 1.1 39.1 3.4
6 0.2 22.3 0.7 12 0.1 13.1 0.9
Average 0.2 39.7 1.1 Average 0.8 39.7 2.5
Table 4  Results of cracking parameters on two experimental steels
Fig.6  Hydrogen induced crack propagation paths in Steel A corroded for 288 h (a) and Steel B corroded for 96 h (b) and 288 h (c)
Fig.7  Optical microstructures of Steel A (a) and Steel B (b) etched by Lapara reagent
Fig.8  Distributions of average size of M/A islands in Steel A (a) and Steel B (b)
Steel Microstructure Yield strength / MPa Loading strength Time / h
A AF+M/A 620 80%, 496 MPa ＞720
90%, 558 MPa ＞720
B AF+M/A 657 80%, 526 MPa 479
90%, 591 MPa 203
Table 5  Results of SSC experiments for two tested steels
Fig.9  Fractographs of SSC fracture at 90%σs loading for Steel B: (a) macrograph of the fracture surface, (b) a higher magnification of area I in Fig.9a, (c) a higher magnification of area II in Fig.9b
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