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The Effects of Sulfide Stress Cracking on the Mechanical Properties And 3HW6FL '2,V 7KHHIIHFWVRIVXO¿GHVWUHVVFUDFNLQJRQWKH mechanical properties and intergranular cracking of P110 casing steel in sour environments Hou Duo, Zeng Dezhi , Shi Taihe, Zhang Zhi and Deng Wenliang 6WDWH.H\/DERUDWRU\RI2LODQG*DV5HVHUYRLU*HRORJ\DQG([SORLWDWLRQ6RXWKZHVW3HWUROHXP8QLYHUVLW\&KHQJGX Sichuan 610500, China © China University of Petroleum (Beijing) and Springer-Verlag Berlin Heidelberg 2013 Abstract: 9DULDWLRQDQGGHJUDGDWLRQRI3FDVLQJVWHHOPHFKDQLFDOSURSHUWLHVGXHWRVXO¿GHVWUHVV cracking (SSC) in sour environments, was investigated using tensile and impact tests. These tests ZHUHFDUULHGRXWRQVSHFLPHQVZKLFKZHUHSUHWUHDWHGXQGHUWKHIROORZLQJFRQGLWLRQVIRUKRXUV WHPSHUDWXUH&SUHVVXUH03D+26SDUWLDOSUHVVXUH03DDQG&22SDUWLDOSUHVVXUH03D SUHORDGVWUHVVRIWKH\LHOGVWUHQJWK ıs PHGLXPVLPXODWHGIRUPDWLRQZDWHU7KHUHGXFWLRQLQ WHQVLOHDQGLPSDFWVWUHQJWKVIRU3FDVLQJVSHFLPHQVLQFRUURVLYHHQYLURQPHQWVZHUHDQG 54%, respectively. The surface morphology analysis indicated that surface damage and uniform plastic GHIRUPDWLRQRFFXUUHGDVDUHVXOWRIVWUDLQDJLQJ,PSDFWWRXJKQHVVRIWKHFDVLQJGHFUHDVHGVLJQL¿FDQWO\ DQGLQWHUJUDQXODUFUDFNLQJRFFXUUHGZKHQVSHFLPHQVZHUHPDLQWDLQHGDWDKLJKVWUHVVOHYHORIıs. Key words: Acidic solutions, high-temperature corrosion, hydrogen embrittlement, intergranular FRUURVLRQVXO¿GHVWUHVVFUDFNLQJ 1 Introduction corrosion cracking (SCC) which is an anodic cracking mechanism. 6WHHOVUHDFWZLWKK\GURJHQVXO¿GHIRUPLQJPHWDOVXO¿GHV Specifically, testing methods using the bend specimen and atomic hydrogen as corrosion byproducts. The atomic JHRPHWU\GHVFULEHGLQWKH$670VWDQGDUGV $670 hydrogen can diffuse into the metal matrix, creating hydrogen ,QWHUQDWLRQDO DQGWKHGRXEOHFDQWLOHYHUEHDP '&% HPEULWWOHPHQWDQGVXEVHTXHQWFUDFNLQJ7KLVLVWHUPHGVXO¿GH WHVWGHVFULEHGLQWKH1$&(VWDQGDUGV 1$&(,QWHUQDWLRQDO stress cracking (SSC) and is more severe at low pH values. 2005) are used in design/fitness for service evaluating and 6XO¿GHVWUHVVFUDFNLQJLVEHFRPLQJDNH\LVVXHGXHWRKLJK for determining material qualifications and specifications levels of H2S and CO2 in new natural gas reservoirs (Carneiro +D\&UDYHURHWDO *HOGHUHWDO HWDO.HUPDQLHWDO investigated the susceptibility of stainless steel to SSC in sour Furthermore, severe working conditions, to which environments containing H2S, CO2 and chloride using slow drilling equipment is exposed in reservoirs, require high VWUDLQUDWHWHVWLQJ 6657 $OEDUUDQHWDO VWXGLHGWKH grade steels capable of resisting SSC and withstanding high effects of heat-treatments on pipeline steel resistant to SSC, mechanical loads under conditions that encourage hydrogen XVLQJOLQHDUHODVWLFIUDFWXUHPHFKDQLFV /()0 RQVWDQGDUG HPEULWWOHPHQW +( =KDRDQG<DQJ=KDRHWDO LPSDFWVSHFLPHQV6HYHUDOUHVHDUFKHUV 5LWFKLHHWDO Crabtree and Gavin, 2005). 7RULELRHWDO7KRPSVRQHWDO LQYHVWLJDWHGWKH Therefore, it is essential to evaluate different methods main variables that affect SSC of steel in sour environments. for the determination of the ability of a material to resist Although the DCB test is standardized, it is widely known cracking in sour environments (Grabtree and Gavin, 2005). WKDWXVLQJWKH1$&(70PHWKRG' '&%WHVW WHVWLQJ 7KH1DWLRQDO$VVRFLDWLRQRI&RUURVLRQ(QJLQHHUV1$&( procedure can affect the value obtained for the fracture International, adopts different methods for evaluating a K toughness ( IC). In this procedure, variables such as the material’s susceptibility to stress corrosion cracking (SCC) K height of the wedge (the initially applied I) and the pH of in a wet H26HQYLURQPHQW6XO¿GHVWUHVVFUDFNLQJ 66& LVD WKHVROXWLRQFDQDOVRDIIHFWWKH¿QDOUHVXOWV 0DFNHWDO form of hydrogen embrittlement which is a cathodic cracking Cravero et al, 2010). mechanism. It should not be confused with the term stress There is an urgent need to develop better methods for evaluating the mechanical properties of metals after exposure *Corresponding author. email: [email protected] to aqueous H2S/CO2 environments with high H2S partial Received December 17, 2012 3HW6FL SUHVVXUHV6HYHUDOUHVHDUFKHUV 6ULQLYDVDQDQG.DQH reported that the susceptibility of pipeline steels to HIC in 6ULQLYDVDQDQG7HEEDO1HVLFHWDO6PLWKDQG NaCl solutions saturated with high pressure of H2S depended Joosten, 2006) discussed that there are currently no generally RQWKHK\GURJHQSHUPHDELOLW\RIVWHHO0DQ\VWXGLHV 6KLPDGD accepted prediction algorithms for any form of H2S corrosion. HWDO2WHJXLHWDO6WROODQG:LONLQVRQ There are still many uncertainties about the corrosive have also investigated the conditions that make metals reactions that lead to pitting, which is the most common mode more prone to intergranular cracking and have assessed of sour service equipment failure. Zhang et al (2011) found the deformation mechanisms of hydrogen embrittlement that the hydrogen sulfide content in some wells exceeded induced by temperature susceptibility. In addition, other 10vol.% in the Sichuan sour gas fields in China. In these VFLHQWLVWV 9HQHJDVHWDO3DOHWDO KDYHUHSRUWHG wells, the partial pressure of H26UHDFKHGDERXW03DDQG the mechanisms associated with intergranular corrosion and WKHWHPSHUDWXUHZDV&6LQFHQRSUDFWLFDOH[SHULHQFH VXO¿GHFUDFNLQJEXWWKHUHLVQRWPXFKLQIRUPDWLRQDERXW66& had been available for the corrosion of carbon steels under susceptibility in V-notched specimens and loss in mechanical these extreme conditions, it is difficult to design effective properties caused by hydrogen damage in sour environments. evaluation methods for the corrosion-resistance of materials. In this study, we used P-110 casing steel specimens to Zhang et al (2011) studied the ability of sulfur to accelerate examine loss in tensile and impact strengths under sour the corrosion of carbon steel in wet H2S environments, conditions. Using a high temperature high pressure (HTHP) showing that sulfur severely accelerated SSC. However, DXWRFODYH KRPHPDGH03D& DORDGLQJ¿[WXUHIRU the methods discussed above cannot be used to evaluate the WHQVLOHVSHFLPHQVDQGDORDGLQJ¿[WXUHIRUEHQGVSHFLPHQV variations and degradations of mechanical properties of steel we measured the tensile and impact properties of P-110 equipment and casings in sour wells, and cannot suggest casing specimens before and after they were exposed to the the strength criteria as a standard. For these reasons, it is VRXUHQYLURQPHQWVWHPSHUDWXUHDW&WRWDOSUHVVXUH important to learn about hydrogen embrittlement, study the 03D+26SDUWLDOSUHVVXUH03DDQG&22 partial pressure 2 hydrogen concentration and evaluate the effects of material 03DSUHORDGVWUHVVRIWKH\LHOGVWUHQJWK ıs IRU properties in order to develop new testing methods and hours. identify proper strength criteria for well casings in sour environments. ([SHULPHQWDO To date, most research on hydrogen embrittlement has investigated absorption of hydrogen into line pipe steels and 2.1 Materials and corrosive medium susceptibility of these steels to hydrogen induced cracking Standard tensile test specimens with an outside diameter (HIC) in solutions saturated with high pressure H2S and CO2. (OLD]HWDO UHSRUWHGWKDWVWHHO¶VVXVFHSWLELOLW\WR+,& of 6.35 mm were machined from P-110 casing (an outside and its absorbed hydrogen content increased as the partial GLDPHWHURIPPDZDOOWKLFNQHVVRIPPDQG D\LHOGVWUHQJWK ı RINVL 03D DFFRUGLQJWRWKH pressures of H2S and CO2 increased. Several researchers s 0LFKOHUDQG1DXPDQQ:RRGWOLDQG.LHVHOEDFK 1$&(70PHWKRGDVVKRZQLQ)LJ L(101±1) 38.1±0.1 38.1±0.1 G 1×45° 15.8±0.1 15.8±0.1 1×45° 1.6 1.6 0.8 A R R F D F 0.03A Dimension Standard specimen 0.03 A D (mm) ij6.35±0.13 G (mm) 25.4 R (mm) L (mm) 101±1 F -0.02 (mm) ij10 -0.07 Fig. 1 Dimensions of standard tensile test specimens Sub-size specimens for the Charpy impact test were size specimens were 10 mm × 5 mm × 55 mm, containing a 2 PDFKLQHGIURP3FDVLQJDFFRUGLQJWRWKH$670( mm-deep V notch. The chemical composition of P-110 casing DQG$670$VWDQGDUGV7KHGLPHQVLRQVRIWKHVHVXE is listed in Table 1. 3HW6FL Simulated water was prepared to match as closely as 700 possible the analysis of formation water obtained from ı=ıs×80%=606 MPa 600 the Puguang gas-field in Sichuan Province, China and its ȟ=0.28% properties are listed in Table 2. The corrosive medium was 500 saturated with H26 SXUH DQG&22 SXUH DQG N and CH is 2 SXUH ZDVXVHGIRUSUHVVXUL]DWLRQ+2 4 400 not used in this test. 300 Table 1 Chemical composition of P-110 casing Stress, MPa 200 Chemical composition, wt% Steel grade 100 CSi0Q PSCr0R Others 0 P110 0.32 0.34 0.013 0.006 2.42 Ni 0.00 0.08 0.16 0.24 0.32 Strain, % Table 2 Properties of simulated formation water Fig. 3 Stress-strain curve of the tensile specimen during preloading Composition, g/L Density pH Salinity 3 + + 2+ 2+ ņ ņ ņ g/cm value g/L Na K Ca 0J Cl SO4 HCO3 10.0 11.4 2.43 126.5 0.71 0.71 UHPRYHGIURPWKHORDGLQJ¿[WXUHDQGWKHQWKHWHQVLOHWHVWLQJ was conducted on these specimens. All evaluations were repeated three times and averaged. 2.2 Tensile testing This autoclave was designed and constructed to allow the The tensile specimen was mounted onto a specialized introduction of multiphase flow. The maximum operating ORDGLQJ¿[WXUHIRUWHQVLOHVSHFLPHQVƗ, shown in Fig. 2. With SUHVVXUHDQGWHPSHUDWXUHZHUH03DDQG&7KH DQ076WHQVLOHWHVWLQJPDFKLQH 076&RUSRUDWLRQ loading fixture and the autoclave were made of Hastelloy 0LQQHDSROLV86$ DSUHORDGZDVDSSOLHGRQWKHWHQVLOH C-276. The difference in the thermal expansion coefficient specimen until the stress and strain of the specimen reached EHWZHHQ+DVWHOOR\&DQGFDUERQVWHHOZDVRQO\ . 03D ıs DQGUHVSHFWLYHO\7KHVWUHVVVWUDLQ ȝP P & DW& DQGWKHVWUDLQRIWKH3FDVLQJ curve of a tensile specimen is shown in Fig. 3. Then, the VSHFLPHQZDV PP 7KHUHIRUHWKHIL[WXUHZDV nut number was screwed down to maintain
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