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Proceedings of the 2012 9th International Pipeline Conference IPC2012 September 24-28, 2012, Calgary, Alberta, Canada


Tanja Schmidt Vallourec & Mannesmann Tubes Dsseldorf, Germany Thomas Haase Salzgitter Mannesmann Forschung Duisburg, Germany Christoph Bosch Salzgitter Mannesmann Forschung Duisburg, Germany

ABSTRACT The challenging environment appearing in recent and moreover future deep offshore explorations promoted the development of linepipe steel grades with reliable sour service resistance. Severe sour conditions such as the combination of elevated production temperature, increasing pipeline pressures and high stress loads initiated by modern laying methods or introduced during service are leading to increasing corrosion demands. Steel pipelines used for the transport of media containing wet Hydrogen Sulphide (H2S) are faced with the danger of the cracking phenomena HIC (Hydrogen Induced Cracking) and SSC (Sulphide Stress Cracking). To prove resistance to HIC and SSC, test specimens are typically tested according standardised test methods. The exposure of test specimens in a sour test solution to a H2S pressure of 1 bar for 96 h, as described in NACE TM0284 is used to prove HIC resistance. Commonly four-point bend testing as described in EFC publication no. 16 is performed for SSC resistance testing with the appliance of a specific load, typically 80 % of the actual yield strength. Within this work HIC testing at test conditions representing higher H2S partial pressures (up to 5 bar) and longer test durations (up to 6 months) have been performed on seamless quenched and tempered line pipe steel of grade X65 and X70 produced by VALLOUREC & MANNESMANN TUBES by plug and continuous mandrel mill process. Beside material in as delivered condition also pre-strained material was tested. SSC four-point bend testing has been performed on specimens which were strained up to 10 % of plastic strain in longitudinal direction.

INTRODUCTION Global increasing need of energy is driving the exploration of oil and gas resources towards highly complex discovery conditions. Future oil and gas reservoirs will show progressively extreme environment in terms of oil and gas composition, exploration depth, reservoir temperature and pressure. This demanding features will lead to challenging requirements profiles for pipe material in terms of grades, temperature and corrosion resistance. Sour media containing Hydrogen Sulphide (H2S) can be extremely hazardous to steel. In the presence of water corrosion reactions take place. The originating hydrogen atoms may diffuse into the steel resulting in Hydrogen Induced Cracking (HIC) and Sulphide Stress Cracking (SSC). SSC only occurs when the material is under residual or tensile stress. Because of the sudden occurrence of these cracking phenomena in service the usage of sour-service resistant steels is a very important aspect. Beyond the increasing demands due to more severe operation conditions linepipe material can be subject to plastic deformation during both laying and service operations. While the installation of linepipe by S- or J-lay methods leads to rather low plastic deformations, the material undergoes a minimum of two deformation steps of at least 2 % during reeling, when the pipe is spooled on and off the reel. In contrast to laying operations plastic deformations occurring during operations are neither controlled nor limited. In the event of buckling or in case of an external damage to the pipe, the plastic deformation can reach much higher values than during reeling.

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As an increasing strength of carbon and low alloy steels impairs the corrosion and especially SSC behaviour, also plastic deformations have this potential as indicated by ISO 15156 and EFC 16 standards [1, 2]. Even though corresponding results were published recently [3], the experience on the effect of plastic deformation on the corrosion behaviour of linepipe material is still rare so far and predominantly limited to smaller deformation values. Both HIC and SSC result from the hydrogen uptake of steel during corrosion in the presence of H2S. While HIC is related to the internal accumulation of molecular hydrogen at suitable locations, SSC is caused by hydrogen embrittlement [4]. Strain hardening leads to an increased dislocation density in the steel and thus to an accelerated hydrogen uptake as well as an increase of the overall hydrogen concentration in the steel [5]. Nevertheless, a direct relationship between hydrogen content and embrittlement of steel has not been finally proved yet [6]. The use of seamless quenched and tempered pipe in grades up to X65 for flowlines and risers in offshore exploration is common. Beside steady good mechanical properties, this type of material is known for excellent sour service resistance. With increasing water depth the shift to high strength steel grades up to X80 become more and more likely in order to serve the deep water demands. These steels base on low carbon concepts and contain higher alloying content compared to standard grades. Hence they demand a more complex heat treatment during pipe fabrication, especially when sour service resistance is required. In order to fulfil sophisticated customer requirements regarding sour service performance, modern alloying concept for seamless pipe changed to low carbon analysis. Although high yield strength up to 80ksi is securely achieved, the concepts are leading to low Carbon Equivalent (CEIIW/ CEPCM). The related low hardness level is known to be beneficial for welding and sour service performance. But even though hardness values are a widely used criterion for defining steel as to be susceptible to SSC [1], plastic strain does not necessarily increase the hardness above the recommended values of 250 HV10. Recent results indicate that the SSC resistivity can also be impacted after plastic deformation without hardness values above the given limit value [3]. PIPE MATERIAL Continuous pre-material quality is one of the key influencing factors for steady sour service resistance of line pipe steels. In order to guarantee stable material properties and fine homogeneous microstructure throughout entire production, it is of particular importance to limit influencing factors on steel quality like cleanliness, residual element level and segregation distribution. In order to assure constant pre-material quality, unique steel source is used by V & M TUBES for all sour service line pipe projects. The chemical composition of investigated steels is given in Table 1.

Table 1 Chemical composition of investigated steels Grade C Mn Si Cu Mo X65 0.10 1.40 0.35 0.20 0.18 X70 0.08 1.50 0.35 0.20 0.30 X80 0.08 1.60 0.35 0.20 0.30
Grade X65 X70 X80 Cr 0.10 0.10 0.10 Ni 0.20 0.25 0.30 V 0.07 0.07 0.07 CEIIW 0.38 0.38 0.41 CEPCM 0.21 0.19 0.19

Another major influencing factor is the heat treatment of pipe. Special emphasis has to be laid on appropriate temperate control and selection of soaking times during heat treatment. Full body water quenching is vital fine grained and homogeneous Bainite structure. Special emphasis has been laid on controlling precipitation formation in terms of size and distribution. An overview of mechanical properties is given in Table 2. Table 2 Mechanical property of investigated steels YS TS Max. Grade [MPa] [MPa] YS/UTS X65 450-570 535-665 0.88 X70 485-605 570-760 0.90 X80 555 - 675 625 - 760 0,92 Grade X65 X70 X80 Min. CVN at -30C [J] > 300 > 250 > 250 Max. Hardness [HV10] 230 248 270

Pipes used for this investigation were produced using continuous cast steel billets, hot rolled using plug mill or continuous mandrel mill process followed by full body inside and outside water quenching and tempering. Table 3 gives an overview over pipe material included in this publication.

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Table 3 Overview on tested line pipe material Pipe # Grade Size Rolling method 1 323 x 53.0 Pilger X65 2 X65 168 x 11.1 Continuous 3 X65 315 x 11.1 Plug 4 X65 315 x 11.1 Plug 5 X65 356 x 25.4 Plug 6 X65 406 x 21.4 Plug 7 X65 377 x 18.8 Plug 8 X65 168 x 17.3 Continuous 9 X65 219 x 20.0 Plug 10 X65 273 x 18.3 Plug 11 X65 356 x 15.9 Plug 12 X70 323 x 18.0 Plug 13 X80 323 x 12.7 Plug 14 X65 219 x 22.3 Plug

was elongated and compressed two times, each time with a strain of +/- 3 %. In the second step ageing was performed at 250 C in air for 60 min. Corrosion tests in the shape of HIC, NACE tensile and four point bend SSC tests were performed on specimens prepared from all test rings. The SSC tests were conducted in two corrosive environments with different loads. For both test types three specimens were tested per condition and pipe. Additionally, on pipe 10 a full scale reeling simulation by four-point bending was performed. From the exposed part of the pipe only specimens for the more demanding NACE A tensile test were machined in 600 and 1200 position of the pipe. Operational Plastic Deformation The effect on the SSC resistance of plastic deformations beyond values occurring during reeling was tested by bend beam tests. The various plastic deformations were applied on reeling coupons machined from pipes 11 to 13. Coupons were strained up to values shortly below the maximum elongation without necking. The maximum plastic deformation being applied was 10 % for the X65 and the X70 and 8 % for the X80. From these coupons tensile specimens were machined in order to determine the actual yield strength (AYS) after plastic deformation i. e. strain hardening. Four point bend test specimens were machined from the same coupons and subsequently loaded to 80 or 90 % of AYS. After the loading process the specimens underwent a standard four point bend SSC test. Additionally to the SSC tests on pre-strained material the direct influence of plastic strain in a corrosive environment was investigated. For that purpose, round bar tensile specimens were machined from pipes 12 and 14. These specimens were tested in slow strain rate tests with strain rates varying between 1.0*106 s-1 and 5.5*10-6 s-1. Corrosion Testing Standard HIC testing was performed according to NACE standard TM0284 with additional ultrasonic inspection (UT) of the tested specimens [7]. After test termination the specimens were cleaned, visually inspected and investigated by UT and equidistant metallographic sectioning as per NACE TM0284. Crack evaluation was undertaken with an optical microscope using a magnification of 100x. The crack area ratio (CAR) was determined from UT and crack length ratio (CLR), crack thickness ratio (CTR) and crack sensitivity ratio (CSR) were calculated for each metallographic section. For HIC testing under more severe conditions either the test duration was extended or the partial pressure of H2S was increased. Tests were performed with test durations of 4 days (which is the standard test duration as per NACE TM0284), 720 h (30 days, which is typically used for SSC resistance testing), 3 and 6 months at a partial pressure of 1 bar H2S. Additional tests were performed in an autoclave at H2S partial pressures of 2 and 5 bar for 96 h.

TEST PROCEDURE HIC testing under severe conditions HIC resistance testing for line pipe steel is generally performed in a test according to NACE standard TM0284 [7]. The test conditions given there are not intended to reproduce service conditions but to represent an extremely severe sour environment. Material that passes HIC testing is normally deemed suitable for all sour-service conditions. The concept of fit-for-purpose testing, where the test environment is less severe in terms of pH and H2S partial pressure and based on later service conditions has recently gained increasing importance [8]. Objective of this study however was to investigate the performance of seamless quenched and tempered pipes under test conditions more severe than given in NACE TM0284. HIC resistance testing has been performed in accordance with the aforementioned NACE standard. For these investigations from each of pipes 1 to 4 a set of rectangular test specimens of size 100 mm x 20 mm at full wall thickness for each investigated test conditions has been tested. PLASTIC DEFORMATION To simulate potential plastic deformations three different investigations were carried out: A reeling simulation with subsequent corrosion testing to cover the effect of laying operations and Slow Strain Rate tests as well as systematic high plastic deformation with subsequent corrosion testing to cover damage occurring during operations. Simulated Reeling The reeling simulation was performed on coupons cut from six different pipe rings (pipes 5 to 10) with plastic deformation and ageing being applied on these coupons. First the material

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Two different types of SSC tests were performed. The material tested in the reeling simulation underwent both tensile and 4-point bend tests, while tests with higher plastic strains were carried out by means of four point bend tests. Both tests were conducted according to NACE standard TM0177-2005 [9], whereat specimens for the 4-point bend tests were stressed according to the ASTM standard G39-99 [10]. Crack evaluation was performed under an optical microscope using a magnification of 10x. Two different conditions were applied during the tensile and 4-point bend tests on specimens originating from simulated reeling. Condition 1 (standard) was an elastic load of 80 % AYS in NACE test solution A (pH 3, 1 bar H2S) and fit-for-purpose condition 2 a load of 90 % AYS in a modified solution with pH 3.5 and 0.1 bar H2S. For the higher plastic deformations, specimens were additionally loaded to 80 or 100 % AYS after deformation and tested under standard conditions. Slow strain rate testing was conducted on the basis of NACE standard TM0198-2004 developed for corrosion resistant alloys.[11] Tests were performed in NACE TM0177 test solution A with 1 bar H2S. For evaluation of the test results also tests in air were conducted. The interpretation of results is carried out by comparing results obtained in the corrosive environment with results from a test in air. Strain rates of 1.0*10-6 s-1, 1.4*10-6 s-1 and 5.5*10-6 s-1 were chosen for the investigation. RESULTS & DISCUSSION

Table 4 Results of HIC testing under severe conditions Pipe 1, 2, 3, 4 metallography UT test conditions CAR CLR CTR CAR 1 bar H2S, 96 h 0.0% 0.0% 0.0% 0.0%
1 bar H2S, 1 mo 1 bar H2S, 3 mo 1 bar H2S, 6 mo 3 bar H2S, 96 h 5 bar H2S, 96 h 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%

Figure 1 HIC specimens after exposure of 6 month HIC testing under severe conditions The results for ultrasonic inspection and metallographic examination are summarized in Table 4. None of the test specimens from all four investigated pipes showed any indication of HIC, even after the worst test condition with six months exposure time. The CAR determined by UT was in general 0.0%, whereat for pipe A with 53 mm wall thickness the UT investigation was performed from both sides. No HIC cracks have been determined by metallographic examination of three equidistant sections per specimen. Therefore CLR, CTR and CSR are 0.0 % for all specimens. Visual appearance of the specimen surface after 720 h and at 3 and 5 bar H2S was not different compared to 96 h standard test duration, however the specimens tested for 3 and 6 months showed remarkable general corrosion attack on the surfaces as expected for the severe exposure conditions (see Figure 1). Some localised corrosion attack was also observed, resulting in shallow pits not deeper than 450 m (Figure 2). The results confirm the excellent HIC resistance of the pipe material. If in a standard HIC test after 96 h no HIC cracking occurred, also longer exposure did not lead to any cracking. For the investigated pipes covering the three different rolling processes of V&M TUBES it has been highlighted that the material is also HIC resistant under more severe conditions than the already conservative test according to NACE TM0284. However, to avoid general and localised corrosion in the field, appropriate concepts of corrosion inhibition need to be considered.

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The application of plastic deformations leads to the expected increase of the AYS. Values finally reaching the UTS starting at a plastic strain of 7 % for the X65 and X70 or 6 % for the X80 (s. Table 6). As a consequence the Y/T-ratio draws near and reaches a value of one with increasing plastic deformation. Furthermore, the elongation at failure decreased with increasing plastic strain. All these effects express the cold hardening caused by the mechanical treatment of the material. Figure 2 Micrographs of surface attack on HIC specimens after exposure of 6 months

Table 6 Tensile test results

Plastic deformation /% 0 10 0 10 0 8 Rt0.5 / MPa 489 653 533 652 617 734 Rm / MPa 607 660 607 654 682 739 Rt0.5 / Rm /% 81 99 88 100 90 99

Simulated Reeling In case of NACE tensile tests under standard conditions only one out of 24 tested specimens from the six different tested pipes failed with a time to failure of 586 h. All other specimens passed the test with a time to failure of more than 720 h. An influence of the two different applied reeling simulations coupons or full scale was not detected. Under the less severe fit for purpose test conditions (EFC 16, pH 3.5, 0.1 bar H2S) all 18 specimens passed the test (see Table 5). Also the second SSC test displayed no failures on the four point bend specimens. After test duration of 720 h cracks were detected in none of the specimens from the six reeling simulation conditions. Table 5 Time to failure in NACE tensile tests after reeling simulation
Pipe No. 1 2 3 4 5 6 6 (full scale) 600 6 (full scale) 120 0 standard condition 100 % H2S Load: 80 % AYS >720 / >720 / 586 >720 / >720 / >720 >720 / >720 / >720 >720 / >720 / >720 >720 / >720 / >720 >720 / >720 / >720 >720 / >720 / >720 >720 / >720 / >720 FFP condition 10 % H2 S Load: 90 % AYS >720 / >720 / >720 >720 / >720 / >720 >720 / >720 / >720 >720 / >720 / >720 >720 / >720 / >720 >720 / >720 / >720 not tested not tested

X65 X70 X80

Although material was subject to massive strain hardening, none of the specimens tested in the subsequent four point bend SSC-tests failed independent of the applied plastic deformation and the additional elastic load. Even though all specimens show a large number of stress grooves, especially in the area of the highest tensile stress, no specimen evolved SSC cracks. Slow Strain Rate Testing The results of the SSR tests with different strain rates and the resultant ductility parameters according to NACE TM01982004 are given in Table 7 (X65, pipes 14 and 15) and 8 (X70, pipe 12); the exemplary stress/strain diagrams for the specimens from pipe 14 in Figure 3. Compared to the SSR-tests conducted in air, all specimens tested in the corrosive environment showed a decrease of the ductility parameters. The time-to-failure, reduction of area and plastic elongation at failure are reduced, while the final fracture load was increased. The applied strain rate seems to have only a minor influence on the ductility parameters. Solely the plastic elongation at failure, also obvious in the corresponding stress/strain diagrams, displays a somewhat significant difference for the two tested strain rates applied to the X65 (pipe 14). Table 7 Ductility parameters from SSR tests with differing strain rates on X65 (pipe 14)
Specimen 1 2 3 4 5 6 Strain rate / s -1 1.4E-06 Time-to-failure / min 1570 515 555 1500 534 240 ratio / % 32.8 35.6 35.6 16.0 Reduction Plastic elongation of area at failure / % ratio / % / % ratio / % 87.4 22.7 17.3 19.8 4.7 20.7 19.0 21.7 5.2 22.9 85.6 25.4 18.0 21.0 6.9 27.2 13.7 16.0 6.9 27.2

The HIC resistance of the material was tested with three specimens per deformation condition. HIC indications were neither found in the ultrasonic investigation nor in the metallographic sectioning of the tested specimens. In all three different corrosion tests the performance of the materials did not differ from corresponding results obtained on non-reeled and non-aged material. High Plastic Deformation The stress-strain curves of the undeformed materials show the typical appearance with distinct elastic limit, high elongation at fracture and a Y/T-ratio of at least 0.9 (X80) or clearly below (X70 and especially X65). The determined yield and ultimate tensile strength values are in full accordance with the corresponding specifications.


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600 500 400 300 200 100 0 0 5 10 15 20 25 30

Strain / %
1 2 3 4 5 6

Figure 3 Stress/strain diagrams of the SSR tests with differing strain rates on X65, pipe 14 Pictures of the gauge sections of SSR test specimens 1 and 2 in pickled condition are given in Figure 4. The effect of the corrosive environment on the ductility of the material becomes pretty apparent when comparing the specimens: While the specimen tested in air shows the typical strong necking of a ductile material, the specimen in the corrosive environment displays reduced constriction resulting from the hydrogen embrittlement. Furthermore, the specimen tested in the corrosive environment shows additional secondary cracks in the necked region.

CONCLUSION The investigated pipe material shows excellent HIC resistance at test conditions, which were far more severe than the standard test conditions, giving additional safety for use in sour service applications. Even though the eligibility of simulating reeling by deforming small coupons instead of the full pipe is still under discussion [3, 12], these tests provide a cheap and feasible method for evaluation of the effect of reeling on the corrosion resistance of quenched and tempered seamless line pipe material in grades up to X80. In contrast to results found in the course of other investigations [3] this study demonstrates that the resistance of the tested line pipe material towards SSC and HIC is not impaired by the combination of a double strain of +/3 % and the subsequent simulated aging. This assumption is additionally supported by the identical results of the full-scale reeling test carried out in the course of this investigation. High plastic strains up to the maximum elongation without necking lead to a clear strain hardening but do not seem to increase the susceptibility towards SSC independent of the tested material. Even under additional elastic loads of up to 90 % of the AYS after plastic deformation no SSC was observed. Even though SSR testing according to NACE standard TM0198 was originally developed for corrosion resistant alloys, all carbon steel materials tested in this investigation displayed only certain susceptibility towards hydrogen embrittlement and other hydrogen related cracking mechanisms. This was indicated by the reduced elastic properties of the specimens in the corrosive environment. Compared to the, for a carbon steel, excellent results observed on the X65 the material of grade X70 displayed a slightly higher susceptibility to the aforementioned corrosion mechanisms. The different tested strain rates seem to have only minor influence on the ductility parameters. Altogether, the broad range of testing under partially extreme severe conditions proved a remarkable high corrosion resistance of all tested quenched and tempered seamless line pipe materials. ACKNOWLEDGMENTS The authors would like to thank Vallourec & Mannesmann Tubes, Germany for financial support of this work. Furthermore, we are indebted to Vallourec & Mannesmann Tubes, Germany and Salzgitter Mannesmann Forschung GmbH, Germany for the permission to publish this work. REFERENCES [1] ISO15156-2:2003 (plus corrigenda) / NACE MR0175 Petroleum and natural gas industries Materials for use in H2S-containing environments in oil and gas production NACE/ANSI/ISO. (International Organization for Standardization, ISO Central Secretariat, 1, ch. de la VoieCreuse, CP 56, CH-1211 Geneva 20, Switzerland or NACE International, 1440 South Creek Drive, Houston, TX, USA 77084-4906).

Table 8 Ductility parameters from SSR tests on X70 (pipe 12)

Specimen Air (mean) 1 2 3 Strain rate / s -1 1.0E-06 1.0E-06 1.0E-06 1.0E-06 Time-to-failure / min 4106 833 852 958 ratio / % 20.3 20.8 23.4 Reduction Plastic elongation of area at failure /% ratio / % / % ratio / % 82.9 24.3 10.7 13.0 1.8 7.2 10.1 12.1 1.8 7.4 6.5 7.8 2.2 8.9

The X70 features a stronger decrease of the ductility parameters than the X65. In comparison, the determined ratios between test in air and in the corrosive medium are some 10 % lower indicating a slightly increased susceptibility towards hydrogen embrittlement.

Stress / MPa

Figure 4 Gauge sections of the SSR-test specimens 1 and 2, X65, pipe 14

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[2] European Federation of Corrosion (EFC) Publication No.16, First and Second Editions. Guideline on materials requirements for carbon and low alloy steels for H2Scontaining environments in oil and gas production. (1995, 2002). (Published for European Federation of Corrosion by Maney Publishing on behalf of The Institute of Materials, 1 Carlton House Terrace, London, SW1Y 5DB UK). [3] Hammond, R. I., Holmes, B. K. , Pargeter, R. J. and Bond, S.: Investigation of Effect of Plastic Straining on C-Mn Steel Pipelines Prior to Sour Service. Corrosion 2011, Paper No. 11110 (Houston, Tx, USA; NACE International 2011). [4] Berkowitz, B. J. and Heubaum F. H.: The role of hydrogen in sulphide stress cracking in low alloy steels. Corrosion 40:240-245, 1984. [5] Hudson, R. M. and Stragand G. L.: Effect of cold drawing on hydrogen behaviour in steel. Corrosion, 16:253t-257t, 1960. [6] Takai, K. and Watanuki, R.: Hydrogen in trapping states innocuous to environmental degradation of high-strength steels. ISIJ 43:520-526, 2003. ISIJ (Iron and Steel Institute of Japan), Niikura Building (2F), 2 KandaTsukasacho 2-chome, Chiyoda-ku, Tokyo, 101-0048 Japan. [7] NACE TM0284-2003: Evaluation of Pipeline and Pressure Vessels Steels for Resistance to HydrogenInduced Cracking, NACE, Houston, Texas, 2003.

[8] Bosch, C.; Haase, T., Liessem, A. and Schroeder, J. HIC Performance of Heavy Wall Large Diameter Pipes for Sour Service Applications under Fit-For-Service Conditions Corrosion 2010, Paper No. 10280 (Houston, Tx, USA; NACE International 2010). [9] NACE TM0177-2005: Laboratory Testing of Metals for Resistance to Sulfide Stress Cracking and Stress Corrosion Cracking in H2S Environments, NACE, Houston, Texas, 2005. [10] ASTM-G-39-99: Standard Practice for Preparation and Use of Bent-Beam Stress-Corrosion Test Specimens, ASTM International, West Conshohocken, Pennsylvania, 2005. [11] NACE TM0198-2004: Slow Strain Rate Test Method for Screening Corrosion-Resistant Alloys (CRAs) for Stress Corrosion Cracking in Sour Oilfield Service, NACE, Houston, Texas, 2004. [12] Noecker II, F. F., Pickens, G., Wilken, G., Dunn, G., Lillig, D., Jin, HW. and Ayer, R., 2009, Test Method to Evaluate the Effect of Reeling on Sour Service performance of CMn Steel Linepipe and Girth Welds, 2009, Proceedings of the Nineteenth (2009) International OFFSHORE AND POLAR ENGINEERING CONFERENCE, Osaka, Japan, Volume IV, pp. 290-297.

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