You are on page 1of 6

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

IPC2012-90391
DEVELOPMENT OF GRADE X70 AND X80 FOR SOUR SERVICE LINE PIPE APPLICATIONS
Thorsten Staudt Aktien-Gesellschaft der Dillinger Httenwerke Dillingen/Saar, Germany Volker Schwinn Aktien-Gesellschaft der Dillinger Httenwerke Dillingen/Saar, Germany

Sven Raedersdorf GTS Industries Dunkirk, France

Martin Pant Europipe Mlheim an der Ruhr, Germany

Christoph Kalwa Europipe Mlheim an der Ruhr, Germany

Heiko Haverkamp Europipe Mlheim an der Ruhr, Germany

Christian Coppey Europipe Dunkerque Dunkirk, France

ABSTRACT The paper describes the results of elaborated development work and the application of the very latest technology on steel, plate and pipe making, the recent demand on grade API-5L X70 or even API-5L X80 for specific sour service applications can be met. Furthermore the paper will point out the overall production concept which provides the fundament for the production of such steels with consistent and reliable resistance to hydrogen induced cracking (HIC). The essential parameters will be explained. This includes the utilization of an appropriate quality assurance system. Recent achievements in terms of strength level, thickness and sour service conditions will be explained. Keywords: X70, X80, sour service, pH 3, thick wall

transport must remain economically efficient resulting in the use of carbon steel pipe. Considering higher strength steels may support a further cost reduction instead of enhancing wall thickness to cope with e.g. high external pressures in deep sea areas. Therefore manufacturers of heavy plates for sour service applications undertake major efforts in development of full sour API-5L X70 and X80 line pipe steels in the past [1-5]. STATE OF PRACTICE Steel design Steels for line pipes with demanding requirements like hydrogen induced cracking (HIC) resistance in combination with higher strength and/or higher wall thickness need a particular attention on the steel design. HIC mostly depends on the cleanliness of the steel and the given microstructure (Fig. 1). Potential microstructures prone to HIC should be avoided or minimized. Inclusions remaining in the steel should not form clusters but should be homogenously distributed. Additionally the microstructure should have the best possible homogeneity without banding and without any hardness spots. Imperfections as well as detrimental microstructures lead to H recombination and thus to stress increase. If the stress exceeds a critical material specific threshold crack initiation occurs and a detrimental microstructure alleviates the crack propagation. Therefore a certain microstructure is a key purpose of the steel design. The

INTRODUCTION API-5L X65 is meanwhile established and mostly used for sour service applications. However the worldwide demand on crude oil and natural gas is still growing. The increasing shortage of the resources make it necessary that the exploitation of the resources takes place under more difficult conditions, for example to exploit more and more sources with H2S containing media in inaccessible environments. The exploitation and

Copyright 2012 by ASME

application of the Thermo Mechanical Control Process (TMCP) provides a lot of metallurgical mechanisms to improve the microstructure which results in better HIC resistance [6,7].

adapted Ca treatment for inclusion shape control and to prevent MnS vertical type caster with special tight control and adapted casting process to minimize segregation and keep cleanness (soft reduction) TM multi stage rolling with accelerated cooling (ACC) after finish rolling with specific temperatures limit the contents of C, Mn and P to control the microstructure

Figure 1: Mechanisms considered for steel design [6]

Overall production system The production of high strength heavy wall sour service line pipe steels is a challenge. Therefore all production steps during steel making and plate rolling must be carefully optimized in terms of cleanliness and the homogeneity of their microstructure resulting in improved sour service properties. The latter is strongly affected by the casting of the slab and by the following rolling process. To guarantee a constant HIC resistance of the steel an overall production concept for the production of sour service steels is pursued (Fig. 2 and 3).

Figure 3: Overall production concept

Pipe manufacturing For sour gas resistant steel pipes above a certain size longitudinally submerged arc welded pipes are most economical. Plates are crimped subsequently formed to a U-shape and then to an O-shape, welded with the high efficient submerged arc welding process in a back-to-back layer technology using up to five wires and finally expanded for good geometry. Because the deformation ratio from plate to pipe implies a further sensitivity to HIC the forming parameters have to be chosen carefully. The application of high quality welding consumables guarantees proper weld seams that meet all sour gas requirements especially in terms of hardness. Comprehensive quality control steps during production ensure that all pipes are in good condition and are in accordance with costumers specification. Traceability from steel making via plate rolling to pipe manufacturing with recording all parameters make sure that for each pipe in a pipeline the manufacturing process can be reconstructed. Quality assurance system To produce high quality HIC grades the target window for production is very small to meet the mechanical and HIC properties because of complexity of the requirements and resultant steel design. Nevertheless the most important factor is to get stable and mainly reproducible material properties throughout the whole delivered tonnage, especially HIC resistance [6]. Anyway, different deviations or incidents can happen during production, with significant influences on HIC properties but no or small influences on the mechanical properties. This is schematically shown by Fig. 4. For such circumstances a special adapted quality control system

Figure 2: Production philosophy of sour service steels [6]

The concept includes the steel-, plate- and pipe-making as well as a specific quality assurance system. The key to successful production of sour service steels is the mill equipment with the following general production strategy [811]: - vacuum treatment by tank degassing - very low sulfur process: typically S 0.0010 % - cleanness treatment: typically O 0.0020 %

Copyright 2012 by ASME

for HIC resistant steels exists. This quality control system rejects slabs for rolling with the risk for not meeting the HIC testing requirements. In addition slabs from the beginning and the end of the rejected part are HIC tested. This additional testing is necessary to prove the conformity with specification. Besides this well controlled processes with high process stability all processing stages are evident for a reliable homogeneous material behavior.

The statistic of 376 measurements presents a very good result in production related view. More than 80 % of the specimens didnt show any cracks. HIC testing was also performed on a number of pipes with pH 3 with solution A according to NACE Standard TM 0284-03 [12]. Due to the high quality of plate material, no HICindications were detected after evaluation according to NACE. Furthermore after a loading of 80% actual yield strength (AYS) for 720 h in solution A (pH 2.7 before saturation pH 3.3 at test start pH 3.8 at test end) according NACE Standard TM 0177 [13] with 1 bar H2S concentration no SSC cracks were found neither in base metal nor weld seam. Table 1 shows results of tensile and Battelle drop weight tear (BDWT) tests from the production. X65 tensile properties are surely achieved as well as BDWTT results at -10C, tested with full wall specimen.
YS transverse, MPa Av Min Max 507 457 545 TS transverse, MPa 576 536 606 BDWTT, full, -10C, % SA 94 85 100

X65 29.6 mm pH 3

Figure 4: Aspects of quality assurance using the example of casting incidents

Table 1: Pipe results of API-5L X65 with a thickness of 29.6 mm

Production example A production example for the state of practice is a project with grade API-5L X65 with a diameter of 24 and a wall thickness of 29.6 mm for full sour service, pH 3 and 1 bar H2S, was specified on plate. The HIC test results on plate according to NACE Standard TM 0284-03 in test solution A (pH before saturation is 2.7, at the start of the test after H2S saturation pH is less than 3.3 and at test end pH is less than 4.0 [12,13]) are illustrated in Fig. 5.
100 90 80

relative frequency, %

70 60 50 40 30 20 10 0 0 2 4 6 8 10

DEVELOPMENT OF FULL SOUR API-5L X70 AND X80 The status of heavy wall X65 material encouraged the development of higher strength sour gas resistant material. The step from API-5L X65 to X70 or even X80 for sour service involves a modification of the chemical composition. A necessary measure is the increase of the carbon equivalent (CEIIW, PCM). In order to avoid a negative effect of the HIC resistance the minimization of the segregation behavior through the optimization of the casting process, e.g. the type of caster and the use of the soft reduction technique is a key issue [8,10]. Table 2 describes the chemical composition of full sour API-5L X65 to X80. Main differences are an increasing Mn content as well as an increase in carbon equivalent from API-5L X65 to X80. Additionally, Mo is alloyed to X80 to meet mechanical requirements.
C X65 X70 X80 0.04 0.30 Si Mn 1.40 alloying Cu, Ni Cu, Ni Cu, Ni, Mo Nb, Ti microalloying CEIIW 0.32 0.36 0.39 PCM 0.14 0.16 0.17

CEIIW = C+Mn/6+(Cr+Mo+V)/5+(Ni+Cu)/15 PCM = C+Si/30+(Mn+Cr+Cu)/20+Mo/15+V/10+Ni/60+5*B

CLR, % (average of 3 sections)

Table 2: Chemical composition in weight percent (wt.-%)

Figure 5: Relative frequency of the CLR values on plate of API-5L X65 with a thickness of 29.6 mm for testing in NACE Standard TM 0284-03 solution A

Also important is the TM rolling strategy with an adjusted cooling process with focus on the finish cooling temperature [7]. Figure 6 illustrates the dependency of the HIC resistance by the CLR value on the ACC final cooling temperature.

Copyright 2012 by ASME

plates the evaluation of CAR provides a more reliable assessment criterion. The material of the formed and welded pipe was tested to prove fulfillment of specified strength and toughness properties. As shown in Table 3 yield and tensile strength exceeds the specified level of API X70 well. As expected CVN toughness is
100 90 80

relative frequency, %

70 60 50 40 30 20

Figure 6: Influence of the ACC final cooling temperature on CLR values (schematically)

At medium final cooling temperatures an optimal range in terms of HIC resistance exists. Higher final cooling temperatures as well as no ACC result in pronounced banded structures whereas too low final cooling temperatures lead to increased fraction of hard second phase. Both microstructures are very detrimental for HIC resistance. At the range of optimum ACC the microstructure consists of homogeneous fine grain ferrite and bainite [6,14]. The optimum ACC range is amongst other influences depending on the carbon equivalent, the casting process and the rolling parameters [14]. The microstructure concept of the both, API-5L X70 and X80, is granular bainite [15]. This microstructure consists of fine grain irregular ferrite with small amounts of bainite and MA constituents. Qualification program To provide a pipe made of advanced material ready for use a comprehensive test program was elaborated. Besides corrosion tests a full mechanical technological characterisation including Tensile, Charpy-V notch- (CVN-) and BDWT-testing was performed on pipes. Besides testing the pipe material girth welds were prepared and tested with respect to SSC and on mechanical-technological properties. Two heat inputs were considered to reflect the range of different welding processes for laying. Some of the samples were pre-strained with a plastic strain up to 2.4 % which were tested according to the non strained weld samples. API-5L X70, 19.1 mm Figure 7 shows the results of HIC testing on plate according to NACE Standard TM 0284-03 in test solution A [12,13]. The diagram presents the relative frequency of the CAR (crack area ratio) values and shows an excellent HIC resistance of the material. Over 90 % of the tested plates are devoid of any cracks. CAR is defined as an area of ultrasonic indications related to the total top view area of the specimen as percentage. Per definition CAR represents the total specimen and can deliver more definite information about the HIC behavior of the specimen than the crack length ratio (CLR) as average of three sections. Therefore for the development of

10 0 0 2 4 6 8 10

CAR, %

Figure 7: Relative frequency of the CAR values on plate of API-5L X70 with a thickness of 19.1 mm for testing in NACE Standard TM 0284-03 solution A

very high and also the BDWT test gives almost full shear fracture surface results. The HIC testing on pipe in solution A of NACE Standard TM 0284-03 showed no to minor indications.
YS transverse, MPa Av Min Max 509 495 527 TS transverse, MPa 598 589 617 CVN transverse, -20C J 442 435 451 BDWTT, -20C, % SA 99 98 100

X70 19.1 mm pH 3

Table 3: Pipe results of API-5L X70 with a thickness of 19.1 mm

API-5L X70, 30.0 mm For the further development API-5L X70 plates and pipes with a thickness of 30.0 mm were produced. Despite the higher wall thickness HIC test results were similar as illustrated for the lower wall thickness of 19 mm in Fig. 7. The plates were formed to pipes with an outer diameter of 813.0 mm (32) and a t/D ratio of 3.7 %. The production and the testing of the material were accomplished according to DNV OS-F101 [16]. The required mechanical properties on pipe were met. Also the tested pipes showed an outstanding HIC performance. As demonstrated in Fig. 8, there are more than 90 % of the specimens without any cracks. Figure 9 shows photographs of optical microscope and scanning electron microscope from the center of the plate. As a consequence of optimized production parameters even the microstructure in the center of the plate is very homogeneously

Copyright 2012 by ASME

without any segregation lines. The key feature of the structure is a fine irregular ferrite grain with small amounts of homogeneously distributed bainite and martensite/austenite (M/A) constituents. This structure provides the basis for the excellent HIC resistance.
100 90 80

relative frequency, %

70 60 50 40 30 20 10 0 0 2 4 6 8 10

The microstructure of the API-5L X80 is represented by photographs of optical microscope and scanning electron microscope from the center of the plate in Fig. 11. Despite of the higher alloying content, through the optimization of the production parameters the microstructure remains homogeneously and shows no segregation line in the center of the plate. The matrix consists of irregular ferrite and some lath ferrite. Compared with API-5L X70 it reveals higher amounts of second phase constituents, which are M/A and bainite. This higher amount is attributed to the higher content of alloying elements such as Mo.
100 90 80

relative frequency, %

70 60 50 40 30 20 10 0 0 2 4 6 8 10

CLR, % (average of 3 sections)

Figure 8: Relative frequency of the CLR values on pipe of API-5L X70 with a thickness of 30.0 mm for testing in NACE Standard TM 0284-03 solution A

CAR, %

Figure 10: Relative frequency of the CAR values on plate of API5L X80 with a thickness of 19.1 mm for testing in NACE Standard TM 0284-03 solution A

Figure 9: Microstructure of the center of the plate of API-5L X70 with a thickness of 30.0 mm

All results obtained on the X70 girth welds fulfilled all requirements in the as welded as well as in the 2.4 % prestrained condition. SSC specimen non strained and pre-strained from welds welded with low and high heat input exhibited no cracks in pH 3, 1 bar H2S solution. API -5L X80, 19.1 mm The results of the API-5L X80 for sour service were also successful. The official test requirements for HIC were defined at pH 5 according to NACE Standard TM 0284-03 (test solution B) [12,13]. The HIC specimens didnt show any cracks. Because of this result an additional internal testing was done on plate again with CAR as assessment criterion at pH 3 according to NACE Standard TM 0284-03 in test solution A [12,13]. The results of this testing are illustrated in Fig. 10. The diagram presents the relative frequency of the CAR values and with more than 90 % of the specimens without any cracks again an excellent HIC performance on plate could be reached.

Figure 11: Microstructure of the center of the plate of API-5L X80 with a thickness of 19.1 mm

The mechanical technological test results of the pipe are presented in table 4. The strength properties, yield and tensile strength, are well in accordance with the specified level of API X80. As expected CVN toughness is very high and also the BDWT test gives almost full shear fracture surface results. In a first step the corrosion resistance was tested in test solution B of NACE Standard TM 0284-03 [12]. Showing no indications in this environment the tests were performed in the more severe solution A of NACE Standard TM 0284-03 [12]. The results showed no to minor indications.

Copyright 2012 by ASME

X80 19.1 mm pH 3

YS transverse, MPa Av Min Max 585 569 598

TS transverse, MPa 682 669 703

CVN transverse, -20C J 396 375 417

BDWTT, -20C, % SA 96 93 100

Table 4: Pipe results of API-5L X80 with a thickness of 19.1 mm

All results obtained on the X80 girth welds fulfilled all requirements in the as welded as well as in the 1.2 % prestrained condition. SSC specimen non strained and pre-strained welds welded with low and high heat input exhibited no cracks in pH 5, 1 bar H2S solution also with 2.4 % pre-strain.

CONCLUSION API-5L X70 and X80 UOE linepipe steels for full sour service applications has been developed successfully by the optimization of the basic production processes. The improvements of the continuous casting technology and the TM rolling strategy including the important ACC process lead to an excellent HIC and SSC resistance on plate as well as on pipe even in test solution A (pH 3) according to NACE Standard TM 0284-03. It was demonstrated that an enhancement of Manganese level above 1.40 wt.-% has no detrimental effect on the corrosion resistance of pipes as long as metallurgical measures in the steel plant and the rolling mill are used to control cleanness of the steels microstructure.

REFERENCES [1] Takeuchi, I., Kushida, T., Okaguchi, S., Yamamoto, A. and Miura, M., 2004, Development of High Strength Line Pipe for Sour Service and Full Ring Evaluation in Sour Environment, Proc. of OMAE 2004: 23rd International Conference on Offshore Mechanics and Artic Engineering, OMAE2004-51028; Vancouver [2] Kobayashi, K., Omura, T., Takahashi, N., Minato, I. and Yamamoto, A., 2009, High Strength Sour Grade Line Pipe X70, Pipeline Technology Conference, Ostend2009-022, Ostend [3] Kobayashi, K., Omura, T., Takahashi, N., Minato, I. and Yamamoto, A., 2010, Advanced Technologies for Manufacturing High Strength Sour Grade UOE Line Pipe, 2010, Proc. of the 8th International Pipeline Conference, IPC2010-31106, Calgary

[4] Ishikawa, N., Shinmiya, T., Shikanai, N., Muraoka, R. and Kakihara, S., 2009, Recent Advance in High Strength Linepipes for Heavy Sour Service, Pipeline Technology Conference, Ostend2009-059, Ostend [5] Terada, Y., Tamehiro, H., Kojima, A., Ogata, Y. and Katayama, K., 1995, Development of X80 UOE Line Pipe for Sour Service, Pipeline Technology, II, R. Denys (Editor), Elsevier Science B. V., pp. 421-434 [6] Schwinn, V. and Thieme, A., 2006, TMCP Steel Plates for Sour Service Linepipe Application, Int. Seminar of Modern Steels for Gas and Transmission Pipelines, Problems and Prospects, Moscow [7] Schwinn, V., Bauer, J., Flss, P., Kirsch, H.-J. and Amoris, E., 2011, Recent Developments and Applications of TMCP Steel Plates, Revue de Mtallurgie, 108, pp. 283-294 [8] Lachmund, H. and Bruckhaus, R., 2006, Steelmaking Process Basic Requirements for Sophisticated Linepipe Applications, Int. Seminar of Modern Steels for Gas and Transmission Pipelines, Problems and Prospects, Moscow [9] Bannenberg, N., Streielberger, A. and Schwinn, V., 2007, New Steel Plates for the Oil and Gas Industry, steel research int., 78(3), pp. 185-188 [10] Harste, K., Klingbeil, J., Schwinn, V., Bannenberg, N. and Bergmann, B., 2000, The New Continuous Caster at Dillinger Htte to Produce Semi Products for High Quality Heavy Plates, Stahl und Eisen, 129(2), pp. 53-59 [11] Stalheim, D. G. and Hoh, B., 2010, Guidelines for Production of API Pipelines Steels Suitable for Hydrogen Induced Cracking (HIC) service applications, Proc. of the 8th International Pipeline Conference, IPC2010-31299, Calgary [12] NACE Standard TM0284-2003, Evaluation of pipeline and pressure vessel steels for resistance to hydrogeninduced cracking, Houston [13] NACE Standard TM0177-2005, Laboratory testing of metal for resistance to specific forms of environment cracking in H2S environments, Houston [14] Tamehiro, H., Takeda, T., Matsuda, S., Yamamoto, K. and Okumura, N., 1985, Effect of Accelerated Cooling after Controlled Rolling on the Hydrogen Induced Cracking Resistance of Line Pipe Steel, Transactions ISIJ, 25, pp. 982988 [15] Zajac, S., Schwinn, V. and Tacke, K.-H., 2005, Characterisation and Qualification of Complex Bainitic Microstructures in High and Ultra-high Strength Linepipe Steels, Material Science Forum, 500-501, pp. 387-394 [16] Offshore Standard DNV-OS-F101, 2007, Submarines Pipeline Systems, Section 7: Construction-Linepipe

Copyright 2012 by ASME