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

IPC2012-90148

METALLURGICAL DESIGN AND DEVELOPMENT OF HIGH-GRADE LINE PIPE

HARA Takuya and FUJISHIRO Taishi Nippon Steel Corporation Kimitsu R&D Lab. 1 Kimitsu, Kimitsu City, Chiba, Japan SHINOHARA Yasuhiro and TSURU Eiji Nippon Steel Corporation Steel Research Labs. 20-1 Shinotomi, Futtsu City, Chiba, Japan

DOI Naoki, YAMASHITA Eiichi and MIYAZAKI Hideki Nippon Steel Corporation Kimitsu Works 1 Kimitsu, Kimitsu City, Chiba, Japan

ASAHI Hitoshi, TERADA Yoshio and MURATA Masahiko Nippon Steel Corporation Head Office 2-6-1 Marunouchi, Chiyoda, Tokyo, Japan subsidence and frost heave. In this case, a strain- as well as a stress-based design has been applied. Therefore, a highly deformable line pipe is required for the former to prevent the pipeline from fracturing.[1]-[7] Two critical strain limits apply for strain-based designs; namely tensile and compressive strain limits. In the case of the tensile strain limit, the critical strain to prevent the line pipe from fracturing at the girth weld is required when the pipeline is subjected to pressure resulting from bending. Generally, a tensile strain limit is required considering the defect size and any misalignment of the girth weld portion. Girth weld overmatching for the base metal in a longitudinal direction is an effective means of achieving a high tensile strain limit. Therefore, a narrow range of base metal strength before and after thermal aging is required. Conversely, the compressive strain limit requires a critical strain to prevent the line pipe from buckling when the pipeline is subject to bending. The compressive strain limit correlates to the work hardening ratio (n value), yield to tensile ratio (Y/T) or uniform elongation (U.El) of the base metal. With this in mind, a high n value, a low yield to tensile ratio and high uniform elongation for the base metal are required to obtain a high compressive limit. Therefore, to meet these requirements, highly deformable line pipe is required for strain-based design. Nippon Steel Corporation has also developed highly deformable highstrength line-pipe ranging from X60 to X100 suitable for strain-based designs.[8]-[15] Herein, the material design for highly deformable line pipes and the development of X60 and X100 highly deformable line pipes are described. Next, large diameter, heavy wall high-strength line pipe can be used for pipelines. Therefore, we have developed highstrength heavy wall line-pipe steels with the API 5L X70 or X80 grades. It is necessary to develop line pipes with the optimal balance of strength, low-temperature toughness, seam-

ABSTRACT The application of high-strength line pipes has enabled pipelines to operate at high pressure, generating cost savings for both gas transportation and construction. In general, highstrength line pipes require crack initiation resistance and crack arrestability at low temperatures, as well as field weldability. High strength and deformability for strain-based design and excellent sour resistance are also required. Moreover, composite properties are often required for high-strength line pipes. This paper describes our progress in this field with regard to metallurgical design and development. Metallurgical design aimed at achieving a good balance between strength, low temperature toughness and deformability for strain-based design is also described from the perspectives of grain refinement, microstructure and chemical composition. Metallurgical design focused on a good balance between strength and sour resistance in limited low chemical composition is described from the perspectives of microstructure and control to chemical composition and center segregation. These efforts have led to the development of highstrength heavy wall line pipes of API X60 to X100 grades offering excellent low temperature toughness and high deformability for stain-based design, while API grades X65 to X70 with good sour resistance have also been developed. INTRODUCTION Demand for natural gas transmission pipelines and LNG to supply global gas markets is increasing as a substitute to oil and coal. The use of high-strength line-pipe steels reduces transmission costs by enabling high-pressure transportation of natural gas. However, long-distance gas-transmission pipelines from remote areas sometimes traverse discontinuous permafrost, and are subject to ground movement caused by repeated thaw

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weld properties and field weldability. In particular, when developing high-strength line pipes with heavy walls, it is essential to ensure excellent performance in terms of running ductile fractures. It is important to achieve high energy absorption and a high shear area for the pipe body in order to obtain a microstructure that ensures a running ductile fracture. Thus, we describe the metallurgical design used to obtain a pipe body with an excellent balance of strength and lowtemperature toughness and seam-weld technology for highstrength heavy wall line pipes. Finally, high-strength line pipes with excellent sour resistance can be used in pipelines. Therefore, we developed high-strength line-pipe steels with API 5L X65 or X70 grade. The development of line pipes with optimal balance of strength, low-temperature toughness and sour resistance is required. In particular, it is very difficult to meet both a drop weight tear test (DWTT) shear area of more than 85% and hydrogeninduced cracking (HIC) for high-strength line pipe. Finally, we detail the metallurgical design used to obtain a pipe body with excellent sour resistance for high-strength line pipes. METALLURGICAL DESIGN OF HIGHLY DEFORMABLE HIGH-STRENGTH LINE PIPES Highly deformable line pipes are required for strain-based designs. In other words, a high tensile strain limit and high compressive strain limit are required. In order to obtain the former, a narrow range of yield strength (YS) and tensile strength (TS) of the pipe body in a longitudinal direction is required in order to achieve girth weld overmatching to the base metal. In order to obtain a high compressive strain limit, a low Y/T ratio and high U.El of the pipe body in a longitudinal direction are necessary to prevent local buckling. The formation of a dual-phase microstructure reportedly improves pipe deformability as well as crack arrestability. Ferrite and bainite/martensite dual-phase microstructure or bainite and a martensite austenite constituent (M-A) dual-phase microstructure improve deformability. For example, the balance between the stress ratio, which is defined as the ratio of 1.5% flow stress to TS, and TS improved remarkably by switching from a bainite microstructure to one dual-phase microstructure as shown in Fig. 1. The Y/T ratio was also lowered by changing to a dual-phase microstructure.[11] In the case of a dual-phase microstructure, the formation of a banded structure or M-A is detrimental to low-temperature toughness. For a banded structure, the amount of energy absorbed is dramatically reduced due to the occurrence of separation. For steels with many M-As, the Ductile Brittle Transition Temperature (DBTT) deteriorates remarkably due to the formation of a brittle zone. Conversely, when secondary hard phases are uniformly distributed, the absorbed energy becomes equivalent to the level for a bainite microstructure. Therefore, the application of a fine dispersive dual-phase microstructure can effectively improve plastic deformation behavior as well as low-temperature toughness. The thermomechanical control process (TMCP) to obtain a fine dispersive

dual-phase microstructure is described.[11] There are some TMCP conditions for forming a dual-phase microstructure. The delayed quench process (DLQ), mild accelerated cooling process (MAC), and dual-phase process (DPP), which involves inter-critical rolling in the (+) region, are all TMCPs used to form a dual-phase microstructure as shown in Fig. 2. The MAC process was adopted in order to obtain a fine dispersed dualphase microstructure from the viewpoint of improving lowtemperature toughness, technological readiness, and cost effectiveness. The key technology is to disperse soft and hard phases through the wall thickness to improve work hardenability by using the optimized MAC process as shown in Fig. 3. This is the representative characteristic of dual-phase line pipe as shown in the upper part of Fig. 3. The characteristics of highly deformable line pipe are understood by comparing its dual-phase microstructure with the uniform structure.

16-mm thick plates

Fig. 1 Relationship between stress ratio and TS for bainite steel and dual-phase steel.
Temp. Finish rolling
DeLayed Quench(DLQ)

Ferrite
Dual phase process (DPP)

Bainite Martensite

Mild Accelerated Cooling (MAC)

Time

Fig. 2 Schematic of an accelerated cooling process to obtain a dual-phase microstructure.[11]

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S1 S4 S7 S10

300 -320 280 -300 260 -280 240 -260 220 -240 200 -220

S13 S16

180 -200 S19 160 -180

mm WT was achieved at 0.88 or lower. Figure 5 shows the distribution of the uniform elongation before thermal aging for the longitudinal direction. Uniform elongation for the longitudinal direction with 32.5- and 36-mm WT met the target value at 0.08 or higher. Figure 6 shows the distribution of the DWTT shear area at -20C before aging for the circumferential direction. The DWTT shear area at -20C for the circumferential direction with 32.5- and 36-mm WT met the target value at more than 85% or higher. Finally, Table 2 shows the representative mechanical properties after thermal aging at 250C for 5 min. for the longitudinal direction with 32.5- and 36-mm WT. The Y/T ratio after thermal aging for the longitudinal direction with 32.5- and 36-mm WT was achieved at 0.89 or lower. Meanwhile, uniform elongation after thermal aging for the longitudinal direction with 32.5- and 36-mm WT was achieved at less than 0.08 or higher. Thus, more than 17,000 metric tons of highly deformable high-strength X60 line pipe with heavy walls for ultra-low temperature usage were successfully and stably manufactured Table 1 Specification of X60 line pipe with 32.5- and 36-mm WT.[15]

1mm

1mm

1mm Fig. 3 Micro-hardness mapping of highly deformable line pipe (upper) and line pipe with uniform structure (lower). (load: 25 g) DEVELOPMENT OF HIGHLY DEFORMABLE HIGHSTRENGTH LINE PIPE Based on the material design of line pipes with an excellent balance of deformability and low-temperature toughness, mill production of X60 to X100 line-pipe steel was carried out. In particular, mass production of the X60 line pipe with 48 OD 36 mm and 48 OD 32.5 mm was carried out.[15] A total of 17,000 metric tons were manufactured at a mill. In this case, a continuous-cast slab of 300 t was melted in an LD converter, and then the slab was reheated and control-rolled into 32.5-mm and 36-mm thick plates, applying a mild accelerated cooling process. Then, a UOE pipe was manufactured. Here, the mechanical properties of the X60 line pipe with 48 OD 36-mm WT and 48 OD 32.5-mm WT were investigated in detail, especially, the mechanical properties before and after thermal aging, the DWTT properties, and the Charpy V-notch (CVN) properties. Tensile properties, CVN properties and DWTT properties were evaluated at a rate of one pipe per heat. Table 1 shows the specifications of the X60 line pipe with 32.5- and 36-mm WT. Mechanical properties before and after thermal aging at 250C for 5 min. were required for the longitudinal direction. CVN energy at -40C and a DWTT shear area at -20C were also required for the circumferential direction. Figure 4 shows the distribution of the yield/tensile ratio (Y/T) before thermal aging for the longitudinal direction. The Y/T ratio for the longitudinal direction with 32.5- and 36-

As pipe Thermal aging As pipe

Direction L L C

YS, MPa 415/515 415/535 415/515

TS, MPa Y/T U.El 495/630 0.88 0.08 495/650 0.89 0.08 520/630 0.85 -

CVN energy@-40 C, J 104(ave.)

DWTT SA@-20 C 0.85(ave.)

Table 2 Mechanical properties for longitudinal direction after thermal aging of X60 line pipe with 32.5- and 36-mm WT.[15]

32.5mm 36mm
30

YS, MPa TS, MPa 477 556 478 552

Y/T 0.86 0.87

U.El 0.11 0.11

longitudinal direction

32.5mmWT(n=62) 36mmWT(n=13)

25

Frequency

20 15 10 5 0
0.72- 0.74- 0.76- 0.78- 0.8- 0.82- 0.84- 0.86- 0.880.76 0.76 0.78 0.8 0.82 0.84 0.86 0.88 0.90

Yield to tensile ratio

Fig. 4 Y/T distribution of X60 line pipe with 36- and 32.5mm WT; white: 32.5 mm, black: 36 mm.[15]

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25
longitudinal direction 32.5mmWT(n=62) 36mmWT(n=13)

For X100 deformable line pipe, mass production of X100 line pipe with 42 OD 14.3-mm WT was carried out. A total of 2,000 metric tons were manufactured at a mill. Table 3 Mechanical properties of X80 and X100 deformable line pipes.[16]
thermal aging properties DWTT TSA85%* S-S curve Y/T Uel 0.5/2.0 1.0/5.0 24"OD15.3mmWT round house <0.90 >0.06 <0.93 <0.93 <-50oC X80 48"OD22mmWT round house <0.83 >0.07 <0.87 <0.89 <-40oC 40"OD16mmWT round house <0.85 >0.05 <0.89 <0.92 <-50oC X100 36"OD19.8mmWT round house <0.86 >0.05 <0.88 <0.93 <-40oC 42"OD14.3mmWT round house <0.90 >0.06 <0.94 <0.93 <-40oC *) Ductile brittle transition temperature with shear area of 85% or higher

20

Frequency

15 10 5 0 0.07- 0.08- 0.09- 0.1- 0.11- 0.12- 0.130.08 0.09 0.1 0.11 0.12 0.13 0.14

Uniform elongation
Fig. 5 Uniform elongation distribution of X60 line pipe with 36- and 32.5-mm WT; white: 32.5 mm, black: 36 mm.[15]
35 30
32.5mmWT(n=62) 36mmWT(n=13)

Frequency

25 20 15 10 5 0 80-85 85-90 90-95 95-100

o

Circumferential direction

100

DWTT SA at -20 C, % Fig. 6 Distribution of DWTT shear area for X60 line pipe with 36- and 32.5-mm WT; white: 32.5 mm, black: 36 mm.[15]
Next, the mechanical properties of API X80- and X100grade highly deformable high-strength line pipe are described.[16] The mechanical properties of X80 and X100 line pipe suitable for strain- as well as stress-based designs are summarized in Table 3. The stress-strain curves of X80 and X100 line pipes indicated a round-house type before and after thermal aging of up to 240C, while the yield to tensile ratio after thermal aging of up to 240C was less than 0.90 for X80 and X100 line pipes. Uniform elongation of 6% or higher for X80 line pipes and of 5% or higher for X100 line pipes was obtained. A stress ratio of 0.5/2.0 with 0.94 or lower and 1.0/5.0 with 0.93 or lower was also achieved for X80 and X100 line pipes respectively. For low-temperature toughness, a DWTT shear area of 85% or higher was obtained down to -40C for X80 and X100 line pipes. Thus, excellent deformability after thermal aging as well as low temperature toughness was achieved for X80 and X100 line pipes.

METALLURGICAL DESIGN OF HIGH-TOUGHNESS AND HIGH-STRENGTH LINE PIPE A high shear area is necessary to ensure sufficient crack arrestability at the design temperature. A low ductile-to-brittle transition temperature (DBTT) is also necessary in the case of lower design temperatures. Generally, grain refining is very effective for lowering DBTT. As mentioned above, having a high DWTT shear area of 85% or higher at the design temperature is one of the key objectives when developing highstrength line-pipe steels with thick walls. In order to resolve these problems, lowering DBTT is very effective, for which grain refining of the pipe body is vital.[17] Figure 7 shows the relationship between DWTT 85% transition temperature and average effective grain size for 32-mm thick heavy plate. The effective grain size is defined as the domains where the difference in crystal orientation between the adjacent domains is greater than 15 from Electron Back-Scattered Pattern (EBSP) measurement.
0

32mm thick plates

-20

SA85%, /oC

-40

-60 1/2t Ave. pancake thickness -80 17 19 21

-0.5

1/d, mm

Fig. 7 Relationship between the transition temperature of DWTT 85% and average grain size. (32-mm-thick plates) For example, an average effective grain size of less than 3.0 m is needed to achieve DWTT 85% transition temperature at -20C. Figure 8 shows the Scanning Electron Microscope (SEM) image and the effective grain boundary mapping with an average grain size of 2.4 m. Uniform and fine grains were observed in this microstructure.

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Mid-thickness

Fig. 8 SEM image and effective grain mapping with average grain size of 2.4 m. (Mid-thickness, 32-mm-thick plate) The transformation texture after heavy plate rolling was developed with increasing strength.[18] When developing the transformation texture, it is very difficult to achieve DWTT 85% shear area because a brittle crack runs through the developed {100} after initiating just under the notch. The formation of this brittle fracture, namely a so-called slant fracture, must be suppressed. Figure 9 shows the relationship between DWTT 85% transition temperature and texture with 32-mm-thick plates. The horizontal axis was defined as {100} integration to the plane rotated from 40 in the axis of the rolling direction. The DWTT shear area deteriorated with the formation of a slant fracture due to {100} integration to the plane rotated at 40 in the axis of the rolling direction. Therefore, grain refining and controlling texture are vital for improving DWTT 85% transition temperature.
0 32mmWT -10

Mid-thickness

-20

-30

-40

-50 0 1 2 3

{100} intensity rotated 40o from RD

Fig. 9 Relationship between DWTT 85% transition temperature and texture (32-mm thick plate) RD: rolling direction

It is necessary to achieve a pipe body with high upper shelf energy from the viewpoint of running ductile fracture arrest capability. Microstructure control to increase this absorbed energy is described. Reducing the fraction of inclusions and precipitates and refining inclusions and precipitates are very effective for improving the absorbed energy. Upper self-energy increases with reduced carbon content, which is attributable to the reduction of carbide and M-A (Martensite-Austenite constituent). Upper self-energy also increases with a reduction in the sulfur and oxygen content as well as the carbon content.[19] Therefore, reducing the size and fraction of sulfide and oxide as well as carbide and M-A are effective for the running ductile arrest capability. As mentioned before, lowering DBTT is effective for crack arrestability, while grain refining and controlling texture are important in order to obtain low DBTT. On the other hand, having high energy absorption is effective for high crack initiation resistance. Reducing the volume fraction of inclusions and precipitates and refining these particles are important for having high energy absorption. Optimizing the bainite and martensite fractions is important to achieve high strength with excellent crack arrestability and crack initiation resistance. The transformation texture develops with increasing bainite and martensite fractions. When the transformation texture develops, the material is prone to slant fracture as brittle fracture because {100} develops on the plane rotated 40 from the rolling plane in the axis of the rolling direction. Therefore, optimizing bainite and martensite fractions is vital to achieve an optimal balance of strength and low-temperature toughness. Finally, optimizing the chemical composition and TMCP condition for heavy plate rolling is effective for optimizing bainite and martensite fractions. The seam weld is the primary region for crack initiation in UOE line pipes. Adequate toughness of the seam-weld metal and Heat Affected Zone (HAZ) is required at the minimum service temperature. First, the metallurgical design used to improve the seam-weld HAZ toughness is described. It is important to improve the toughness in the coarse grain HAZ (CGHAZ). Generally, suppressing coarse austenite grains by applying the pinning particle and microstructure refining by applying intra-granular ferrite or intra-granular bainite are all methods of improving CGHAZ toughness.[20]-[22] Suppression of coarse austenite grains by applying titanium nitride or oxides, or refining grains by utilizing titanium oxides to apply intra-granular transformation, or the combined suppression of the coarse austenite grains and grain refining by applying intra-granular transformation, are very effective for improving seam-weld HAZ toughness. Next, the metallurgical concept of seam-weld metal is described. Acicular ferrite has been applied to improve weld metal toughness up to the X100 line pipe. Optimization of the weld metal chemical composition and the welding condition was important for the frequent formation of acicular ferrite nucleated from oxides.

TSA85%, /oC

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A y-groove cracking test was conducted using X80 to X120 line-pipe plates, while Gas Metal Arc Welding (GMAW) wires were also used. No cracking occurred, even without preheating, which is attributable to the suppressed excess increase in hardness due to the application of low carbon content. DEVELOPMENT OF HIGH-STRENGTH THICKWALLED LINE PIPE Based on the metallurgical concept of API grade X80 highstrength line pipe with thick walls, several tens of pipes were manufactured for full-scale burst tests with a 56-inch outer diameter and 27.7-mm wall thickness.[23] The tensile properties of the sample pipe were shown in Table 4. The YS, TS, total elongation (EL) and yield/tensile ratio (Y/T) in the circumferential direction meet the target values, while the DWTT transition curves are as indicated in Fig. 10. The DWTT 85% transition temperature was -60C or lower. The CVN absorbed energy was 300 J or higher at -60C. Seam-weld toughness was as shown in Fig. 11. The CVN energy with the notch position of the weld metal and HAZ meet the target values. These pipes, with excellent pipe properties, were used for the full-scale burst test. A full-scale burst test was conducted, with the subsequent pipe fracture appearing as indicated in Fig. 12. The applied air pressure was 15 MPa. This is a very high pressure based on SNIP specifications, being 25% above the pipeline operating pressure of 11.8 MPa. The test temperature was 5C. As shown in Fig. 12, the crack in the sample pipe on the left side next to the initiation pipe was arrested. These pipes were confirmed to offer superior running ductile fracture resistance. Table 4 Tensile properties of the sample pipe.[23]
Flat specimen GOST W=30mm,GL=165mm YS YS TS EL uEL Y/T 0.2 0.5 0.5 555 640 18 min 665 760 92 max 584 574 700 23 9.8 82 4722-01-0003 Bot C 567 564 701 23 10.0 80 4722-01-0009 Bot C No Pipe No Round bar specimen GOST d=10mm,GL=50mm YS YS TS EL uEL Y/T 0.2 0.5 0.5 555 640 18 665 760 92 561 573 684 24 12.9 84 560 556 672 24 11.8 83

Based on the trial production, mass production of X70 high-toughness high-strength line pipe with 40 OD 29.8-mm WT was carried out. The required temperature is -42C. That is, CVN energy for base metal and seam welds of more than 50 J and DWTT shear area of more than 85% at -42C must be satisfied. A total of 3,000 metric tons were manufactured at a mill.
350 CVN energy at -40 C, /J 300 250 200 150 100 50 0
WM
2mm from outside surface root

FL Notch position

FL+2mm

Fig.11 Seam welds toughness with different notches.[23]

NSC

NSC

NSC

Fig. 12 Pipe fracture appearance after full-scale burst test.[23] METALLURGICAL DESIGN OF HIGH-STRENGTH SOUR LINE PIPE Most investigations on HIC have been performed in specific environments, such as NACE TM0284 solution A (H2S partial pressure (PH2S) is 0.1 MPa and pH is from 2.7 to 4.0) and TM0284 solution B (PH2S is 0.1 MPa and pH is from 4.8 to 5.3)[24]. In order to meet HIC resistance, it is required that the Crack Length Ratio (CLR), which is defined as the total crack length in the wide direction divided by total width (20 mm) is less than 10%, or 15% in NACE TM0284 solutions A and B.[25] In order to meet the target values of CLR of being less than 10% or 15%, the following technologies are adopted; (1) Reduction in sulfur content and calcium treatment to reduce elongated manganese sulfide (MnS) inclusions; when sulfur content is less than 10 ppm and the calcium to sulfur ratio (Ca/S) is more than two or the effective sulfide shape control parameter (ESSP) defined as [Ca]x(1-124 [O])/(1.25x [S]) exceeds 1.3, the shape of the sulfide is completely controlled and HIC does not occur;[26]-[27] (2) Reduction in inclusions

Initiation pipe

100 90 80 70 60 4722-01-0009 50 -80 -60 -40 -20 0 20 40 Temperature, /oC

Fig. 10 DWTT transition curve of the sample pipe.[23]

DWTT SA, /%

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other than MnS and impurities in steel; recently, it has become possible to produce highly pure steel with a sulfur content of less than 10 ppm, phosphorus content of less than 100 ppm and oxygen content of less than 25 ppm (S 10 ppm, P 100 ppm and O 25 ppm); (3) Low carbon and low manganese type chemical compositions and reduction in the center segregation by soft reduction; application of optimum reduction with divided rolls improves the center segregation level of the slab. This is attributed to a significant decrease in manganese and phosphorus segregation; (4) Usage of accelerated cooling after controlled rolling to obtain a uniform microstructure; an accelerated cooling process causes uniform carbon distribution in the center-segregated region as well as in the nonsegregation area and fine dispersion of the second phase, resulting in reduction of the maximum hardness in the centersegregated zone.[28] Generally, the maximum hardness in the center-segregated zone is limited to within 250 Hv as shown in Fig. 13.[25],[29] Speaking precisely about HIC occurrence, these arose at inclusions such as elongated MnS or integrated Ti, Nb carbon-nitride by increasing hydrogen pressure at the interface between inclusions and the matrix. HIC occurred due to the hydrogen concentration entering from a sour environment exceeding the critical hydrogen concentration. HIC is determined by the critical hydrogen, inclusions length and fracture toughness of the matrix, which is represented as micro-hardness. The relationship among the critical hydrogen concentration, inclusion length and maximum hardness at the center segregation in terms of HIC occurrence is clarified.[30][31] Therefore, the maximum hardness and maximum inclusion size is predicted to prevent HIC in NACE TM0284 solutions A and B. Moreover, Nippon Steel Corporation introduced a new continuous casting machine in 2007 in order to control the center-segregated zone. Representative hardness mapping at the center-segregated zone after introducing the new continuous casting machine for X65 sour-resistant line pipe is shown in Fig. 14. Maximum hardness at the center-segregated zone can be controlled at less than 250 Hv (25 g) even if manganese content of 0.1% or higher increases compared to before introducing the new continuous casting machine. Thus, API X70 grade high-strength sour-resistant line pipe has been developed at Nippon Steel Corporation.

Number indicates hardness under 25 g load

Fig. 13 Relationship between hardness, phosphorus and manganese content.

S 250-270 230-250 S 210-230 S 190-210 S 170-190 S S S S S S S

Fig. 14 Relationship between hardness mapping and manganese concentration. (load: 25 g) CONCLUSIONS This paper describes the metallurgical design of highly deformable, high-strength line pipe; high-toughness, highstrength line pipe with heavy wall; and high-strength sourresistant line pipe. Based on these designs, Nippon Steel Corporation has developed highly deformable high-strength line pipes from API X60 to X100 grade, high-toughness highstrength line pipe with heavy wall up to X80, and high-strength sour-resistant line pipe up to X70. The main conclusions are as follows: (1) Dual-phase microstructure is effective for improving deformability. A fine dispersed soft and hard structure is very effective for improving plastic deformation behavior as well as low-temperature toughness. Therefore, a fine dispersive dual-phase microstructure was applied for highly deformable line pipes with excellent low temperature toughness. (2) Excellent deformability after thermal aging as well as lowtemperature toughness was achieved for a mill production of 17,000 metric tons of X60 line pipes and 2,000 metric

DEVELOPMENT OF HIGH-STRENGTH SOUR LINE PIPE As mentioned above, good sour-resistant line pipe up to API X70 grade has been developed by introducing a new continuous casting machine. The sour-resistant heavy wall X65 line pipe for low temperature usage has also been developed. Mass production of the X65 and X70 sour-resistant line pipe was carried out using the new continuous casting machine. A total of 100,000 metric tons or more of sour-resistant line pipe up to API X70 grade has been manufactured at the mill.

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tons of X100 line pipes. (3) Lowering the ductile brittle transition temperature (DBTT) is effective for crack arrestability. Grain refining and controlling texture are important for lowering DBTT. (4) Having high energy absorption is effective for improving crack initiation resistance. Reducing the volume fractions of inclusions and precipitates and refining these particles is important for improving energy absorption. (5) Optimizing the bainite fraction is a key technology to achieve optimal balance among strength, low DBTT and high energy absorption. (6) Suppression of the coarse grain and/or microstructure refining by applying intra-granular ferrite or intra-granular bainite are methods to improve CGHAZ toughness. Optimization of the microstructure is key to improving seam-weld toughness at the design temperature. (7) Based on these metallurgical designs, X80 high-strength line pipe steel with 56" OD 27.7-mm WT with high energy absorption of more than 300 J at -60C and low DWTT 85% DBTT of -60C or lower was manufactured. These pipes could be successfully arrested in the full-scale burst test. Mass production of 3,000 metric tons of X70 line pipe with 40 OD 29.8-mm WT with -42C requirement was carried out. (8) Reduction in sulfur content and calcium treatment to reduce elongated manganese sulfide (MnS) inclusions is required for sour-resistant line pipe. Highly pure steel with sulfur content of less than 10 ppm, phosphorus content of less than 100 ppm and oxygen content of less than 25 ppm was required. Low carbon and low manganese type chemical compositions and reduction in the center segregation by soft reduction are also required for sourresistant line pipe. (9) Uniform microstructure with micro-hardness of less than 250 Hv (25 g) is applied by using new a continuous casting machine and accelerated cooling after controlled rolling. (10) Mass production of the X65 and X70 sour-resistant line pipe was carried out using the new continuous casting machine. A total of 100,000 metric tons or more of sourresistant line pipe up to API X70 grade were manufactured at the mill. REFERENCES [1] Glover, A (2002). Application of Grade 550 (X80) and Grade 690 (X100) in Arctic climates, Proc. of the International Pipe Dreamers Conference, Yokohama, Japan, pp. 33-52. [2] Denys, R, and Glover, A (1994). Conf. Mismatching of welds, ESIS 17, 1994, London. [3] Denys, R, Waele, W, Lefevre, A, and Baets, P (2004). Weld strength mismatch effects on plastic straining capacity of axially-loaded pipelines, Proc. of the International Pipeline Technology Conference, Ostend, Belgium, pp. 209233.

[4] Glover, A, and Rothwell, B (2004). Yield strength and plasticity of high strength pipelines, Proc. of the International Pipeline Technology Conference, Ostend, Belgium, pp. 65-79. [5] Hillenbrand, HG, Graef, MK, Grob-Weegr, J, Knauf, G, and Marewski, U (2002). Development of line pipe for deepwater applications, Proc. of the 12th International Offshore and Polar Engineering Conference and Exhibition, Kitakyushu, Japan. [6] Liessem, A., Graef, KM, Knauf, G, and Marewski, U. (2004). Influence of thermal treatment on mechanical properties of UOE line pipe, Proc. of the International Pipeline Technology Conference, Ostend, Belgium, pp. 1263-1281. [7] Al-Sharif, AM, Preston, R (1996). Improvement in UOE pipe collapse resistance by thermal aging, Proc. of the 28th Annual Offshore Technology Conference, Houston, USA, pp. 549-588. [8] Terada, Y, Tamehiro, H, Morimoto, H, Hara, T, Tsuru, E and Asahi, H, Sugiyama, M, Doi, N, Murata, M, and Ayukawa, N (2003). X100 line pipe with excellent HAZ toughness and deformability, Proc. of OMAE2003-37392, 22nd International Conference on Offshore Mechanics and Arctic Engineering, Cancun, Mexico. [9] Terada, Y, Tamehiro, H, Yamashita, M, Ayukawa, N and Hara, T (1997). Development of API X100 UOE Line Pipe, NIPPON STEEL TECHNICAL REPORT No. 72, January pp. 47-52. [10] Terada, Y, Kojima, A, Hara, T, Morimoto, H, Tsuru, E, Asahi, H, Kiyose, A, Sugiyama, M, Nakashima, T, Doi, N, Murata, M, and Ayukawa, N (2004) Recent development of high-strength line pipes in hostile environments, Proc. of the International Pipeline Technology Conference, Ostend, Belgium, pp. 1603-1617. [11] Shinohara, Y, Tsuru, E, Hara, T, Asahi, H, Terada, Y, and Doi, N (2005). OMAE2005-67055, Proc. of OMAE05, 24th International Conference on Offshore Mechanics and Arctic Engineering, Halkidiki, Greece. [12] Shinohara, Y, Tsuru, E, Hara, T, Asahi, H, Terada, Y and Doi, N. (2006). OMAE2006-92302, Proceedings of OMAE2006 25th International Conference on Offshore Mechanics and Arctic Engineering, Hamburg, Germany. [13] Shinohara, Y, Tsuru, Asahi, H, E, Hara, T, Terada, Y, Doi, N and Ayukawa, N (2008). Int. Journal of Offshore and Polar Engineering, ISOPE, Vol. 18, No. 3, pp. 220-225. [14] Hara, T, Shinohara, Y, Terada, Y, and Asahi, H, Doi, N (2008). Metallurgical design and development of highly deformable high-strength line pipe steels suitable for strainbased design, Proc. of IPC2008, 7th International Pipeline Conference, Calgary, Alberta, Canada. [15] Hara. T, E, Shinohara, Y, Hattori. Y, Muraki. T, and Doi. N, (2011). Development and Mass Production of X60 Highly Deformable Line Pipe Suitable for Strain-based Design, Proc of the Seventeenth (2011) International

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Offshore and Polar Engineering Conference, ISOPE, Hawaii, USA. [16] Hara T, Shinohara Y, Terada Y, Asahi H, and Doi N, Development of highly deformable high-strength line pipe suitable for strain-based design, Pipeline Technology Conference of 2009, Ostend, Belgium, 2009. [17] Pickering et al, Physical metallurgy and the design of steels (1978). [18] Inagaki H, Kurihara K, and Kozasu I, Influence of Crystallographic Texture on the Strength and Toughness of the Controlled Rolled High Tensile Strength Steel, Tetsu-toHagane, 61, 7, pp. 991-1011 (1973). [19] Hara T, Asahi H, Morimoto H, Terada Y, Sugiyama M, Metallurgical design and development of X120 highstrength line pipe steel, Proc. of the 1st Int. Symposium on Steel Science, Kyoto, Japan (2007). [20] Terada Y. et al., 22nd Int. Conf. on Offshore Mechanics and Arctic Engineering, 2003-37391 (2003). [21] Chijiiwa R. et al, Int. Conf. on Offshore Mechanics and Arctic Engineering 5(1988), p.165. [22] Shinohara Y., Hara T and Asahi H, Shigesato G, CAMPISIJ, 16, 3, p.1531 (2003) [23] Hara T, Fujishiro T, Terada Y, Inoue T, Asahi H, and N. Doi, Development of high-strength heavy-wall line pipe, Pipeline Technology Conference 2009, Ostend, Belgium, 2009. [24] NACE Standard TM0284-2011, Evaluation of Pipeline and Pressure Vessel Steels for Resistance to HydrogenInduced Cracking (Houston TX: NACE), 2011. [25] NACE Standard MR0284-2003, "Petroleum and natural gas industriesMaterials for use in H2S-containing environments in oil and gas production," (Houston TX: NACE), 2003. [26] Ushijima. K., et al, Int. Conf. on HSLA Steels Technology and Application, 1984, 403. [27] Tamehiro. H., et al, Trans. ISIJ, 25, 1985, 982. [28] Ogibayashi. S, et al, 7th Japan-Germany Seminar, (Dusseldorf, Germany), 1987, 309. [29] Tamehiro. H., Yoshino T, Abe. M, Yurioka. N, 8th Int. Conf. on Offshore Mechanics and Arctic Engineering (OMAE89) Hague Netherland, 1989, 5, 982. [30] Hara. T, Asahi H., and Ogawa H., Corrosion, 60, 12, 2004, 1113. [31] Hara T. and Asahi H., Quantitative study on conditions of HIC occurrence for X65 line-pipe steels the proceedings of 13th International Corrosion Congress, Beijing China (2005).

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