WO2015001759A1 - サワー環境で使用されるラインパイプ用継目無鋼管 - Google Patents
サワー環境で使用されるラインパイプ用継目無鋼管 Download PDFInfo
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- WO2015001759A1 WO2015001759A1 PCT/JP2014/003345 JP2014003345W WO2015001759A1 WO 2015001759 A1 WO2015001759 A1 WO 2015001759A1 JP 2014003345 W JP2014003345 W JP 2014003345W WO 2015001759 A1 WO2015001759 A1 WO 2015001759A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
- C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/02—Rigid pipes of metal
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/002—Bainite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/004—Dispersions; Precipitations
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/009—Pearlite
Definitions
- the present invention relates to a seamless steel pipe. More particularly, the present invention relates to a seamless steel pipe for a line pipe used in a sour environment containing hydrogen sulfide (H 2 S) which is a corrosive gas.
- H 2 S hydrogen sulfide
- Crude oil and natural gas contain wet hydrogen sulfide.
- Such an environment is called a sour environment.
- Line pipes carry crude oil and natural gas produced from oil and gas wells. Therefore, the line pipe is used in a sour environment.
- hydrogen embrittlement due to hydrogen sulfide becomes a problem.
- Hydrogen embrittlement includes hydrogen sulfide cracking and hydrogen-induced cracking (hereinafter referred to as HIC). Hydrogen sulfide cracking occurs in steel under static external stress. HIC occurs in steel in the absence of external stress. Line pipes are less subject to static external stress than oil well pipes. Therefore, the line pipe is particularly required to have HIC resistance.
- Patent Document 1 Japanese Patent Application Laid-Open No. 54-11119
- Patent Document 2 Japanese Patent Publication No. 58-18967
- Patent Document 3 Japanese Patent Application Laid-Open No. 52-111815
- Patent Document 4 Japanese Patent Application Laid-Open No. 61-60866
- Patent Document 5 Japanese Patent Application Laid-Open No. 2004-176172
- Patent Document 6 Japanese Patent Application Laid-Open No. 2004-143593
- Patent Document 1 contains Ca and Ce and spheroidizes MnS in the steel. As a result, Patent Document 1 describes that the HIC resistance of the steel for line pipes is increased.
- the steel for line pipes disclosed in Patent Document 2 contains Cu and Ni as essential elements, and further has a chemical composition satisfying Ca / S ⁇ 2.0. Thereby, it is described in Patent Document 2 that the HIC resistance of the steel for line pipes is increased.
- Patent Document 3 In the steel material for line pipes disclosed in Patent Document 3, the content of easily segregating elements such as Mn, P, and S is reduced, and alloy elements such as Cu, Ni, Cr, and Mo are further contained. Thus, Patent Document 3 describes that hydrogen intrusion into steel is suppressed and the HIC resistance of the steel for line pipes is increased.
- Patent Document 4 contains Ni and Cr and / or Mo. Thus, Patent Document 4 describes that the penetration of hydrogen into steel is suppressed and the HIC resistance of the steel for line pipes is increased.
- Patent Documents 5 and 6 contain Mo and V as essential elements, and precipitate ferrite at grain boundaries of the quenched structure of bainite and martensite, thereby suppressing embrittlement of the grain boundaries.
- Patent Documents 5 and 6 describe that excellent HIC resistance is obtained when the yield strength is 483 MPa or more.
- JP 54-11119 A Japanese Patent Publication No.58-18967 Japanese Patent Laid-Open No. 52-11118 JP 61-60866 A JP 2004-176172 A JP 2004-143593 A
- An object of the present invention is to provide a seamless steel pipe that is used for a line pipe used in a sour environment, has a yield strength of 400 MPa or less, and has excellent HIC resistance.
- the seamless steel pipe according to this embodiment is used for a line pipe used in a sour environment.
- the above seamless steel pipe is, by mass, C: 0.01 to 0.20%, Si: 0.05 to 0.50%, Mn: 0.3 to 2.0%, P: 0.02% or less S: 0.01% or less, Cr: 0.02 to 0.2%, sol.
- Al 0.001 to 0.100%, O: 0.0050% or less, N: 0.0100% or less, Ca: 0 to 0.0050%, Ti: 0 to 0.012%, and Nb: 0 Containing 0.012%, the balance containing Fe and impurities chemical composition, 10-50% area ratio ferrite and 0-5% pearlite, the balance tempered bainite and / or And a structure composed of tempered martensite, the number of inclusions having a particle size of 50 ⁇ m or more is 15/100 mm 2 or less, and has a yield strength of 400 MPa or less.
- the chemical composition of the seamless steel pipe according to this embodiment may include Ca: 0.0005 to 0.0050%.
- the chemical composition of the seamless steel pipe according to the present embodiment may include at least one selected from the group consisting of Ti: 0.002 to 0.012% and Nb: 0.002 to 0.012%. Good.
- the seamless steel pipe of this embodiment is excellent in HIC resistance even at a low strength of 400 MPa or less.
- FIG. 1 is a schematic diagram for explaining cluster-like inclusions.
- the present inventors investigated and examined the occurrence of HIC in a low-strength seamless steel pipe, and obtained the following knowledge.
- HIC occurs by the following mechanism. Hydrogen accumulates around coarse inclusions in the steel, forming the origin of HIC. A crack is created when the material yields due to an increase in the starting hydrogen pressure. Dislocations and hydrogen further accumulate at the crack tip. As a result, HIC occurs.
- Blisters a type of HIC, are particularly likely to occur in low-strength seamless steel pipes.
- Blisters are blisters (cracks) that occur near the surface of the steel material and extend in the axial direction of the steel material. Even if the crack area ratio CAR obtained by the CAR test described later is 0%, blisters may be present. In conventional seamless steel pipes with high strength (strength higher than 400 MPa), even if blisters are generated, the strength is high, so that it does not lead to leakage of transported fluid. Therefore, blisters are not particularly problematic.
- a plurality of blisters arranged in the thickness direction may be connected to generate a large crack (HIC). Therefore, it is preferable that the generation of blisters is suppressed in a low-strength seamless steel pipe.
- a low-strength seamless steel pipe is manufactured by allowing it to cool as it is after pipe production.
- the seamless steel pipe has a two-phase structure of ferrite and pearlite. And since there is much ratio of the ferrite with low yield strength, a ferrite yields and HIC tends to generate
- produce since there is much ratio of the ferrite with low yield strength, a ferrite yields and HIC tends to generate
- the seamless steel pipe of the present embodiment performs quenching and tempering despite its low strength.
- the area ratio of ferrite in steel (hereinafter referred to as ferrite ratio) becomes 50% or less.
- tempered bainite and / or tempered martensite are formed instead of ferrite. Since the strength of bainite and martensite is higher than that of ferrite, yield due to hydrogen pressure is suppressed. Therefore, generation
- the area ratio of pearlite in the tissue (hereinafter referred to as pearlite ratio) is set to less than 5%.
- HIC tends to occur.
- the following can be considered as the reason.
- Hydrogen ions from the corrosion reaction are adsorbed on the steel surface and enter the steel as atomic hydrogen. Hydrogen that has entered the steel diffuses and accumulates around the carbides that make up the pearlite phase. Internal cracking is caused by the internal pressure of hydrogen accumulated around the carbide. Therefore, the HIC resistance of steel having a locally pearlite phase is low. If the pearlite ratio is lowered, the hydrogen embrittlement resistance is improved. In particular, if the pearlite ratio is less than 5%, excellent HIC resistance can be obtained even at low strength.
- the number of coarse inclusions in the steel is small.
- the number of inclusions (the number of coarse inclusions) having a particle size of 50 ⁇ m or more (hereinafter referred to as coarse inclusions) N is 15/100 mm 2 or less, HIC (including blisters) ) Is suppressed.
- the seamless steel pipe according to this embodiment has the following chemical composition.
- C 0.01 to 0.20% Carbon (C) increases the hardenability and increases the strength of the steel. If the C content is too low, the above effect cannot be obtained.
- the seamless steel pipe of this embodiment is connected to other seamless steel pipes as a line pipe by circumferential welding. Therefore, if the C content is too high, the heat-affected zone (HAZ) of circumferential welding is cured and the SSC resistance is lowered. Furthermore, if the C content is too high, the toughness of the welded portion in the steel for line pipes is lowered. Therefore, the C content is 0.01 to 0.20%.
- the minimum with preferable C content is higher than 0.01%, More preferably, it is 0.03%, More preferably, it is 0.05%.
- the upper limit with preferable C content is less than 0.20%, More preferably, it is 0.15%.
- Si 0.05 to 0.50% Silicon (Si) deoxidizes steel. If the Si content is too low, this effect cannot be obtained. On the other hand, if the Si content is too high, the toughness of the weld heat affected zone decreases. If the Si content is too high, more ferrite is generated. Therefore, the HIC resistance decreases. Therefore, the Si content is 0.05 to 0.50%.
- the minimum with preferable Si content is higher than 0.05%, More preferably, it is 0.10%, More preferably, it is 0.16%.
- the upper limit with preferable Si content is less than 0.50%, More preferably, it is 0.30%.
- Mn 0.3 to 2.0%
- Manganese (Mn) increases the hardenability of the steel and increases the strength of the steel. Mn further increases the toughness of the steel. If the Mn content is too low, this effect cannot be obtained. On the other hand, if the Mn content is too high, HIC tends to occur due to hardening of the steel by Mn segregation and formation of MnS. Therefore, the Mn content is 0.3 to 2.0%.
- the minimum with preferable Mn content is higher than 0.3%, More preferably, it is 0.5%.
- the upper limit with preferable Mn content is less than 2.0%, More preferably, it is 1.6%.
- P 0.02% or less Phosphorus (P) is an impurity. P segregates to form a hardened structure in the steel. In the case of a seamless steel pipe, a hardened structure is easily formed in the vicinity of the inner surface of the steel pipe, and HIC is easily generated. For this reason, the P content is preferably as low as possible. Therefore, the P content is 0.02% or less. The preferred P content is less than 0.02%.
- S 0.01% or less Sulfur (S) is an impurity. S forms MnS. MnS is the starting point of HIC. Accordingly, a lower S content is preferable. However, reducing the S content is costly. In the seamless steel pipe of this embodiment, the S content may be 0.01% or less in order to reduce the manufacturing cost. In the seamless steel pipe of this embodiment, even if it contains S content higher than 0.003%, if it has the structure mentioned later, excellent HIC resistance is exhibited.
- Chromium (Cr) strengthens the steel by increasing the hardenability of the steel. If the Cr content is too low, this effect cannot be obtained. On the other hand, if the Cr content is too high, ferrite is excessively generated and the HIC resistance is lowered. If the Cr content is too high, a hardened structure is generated locally in the steel, or uneven corrosion of the steel surface is caused. Therefore, the Cr content is 0.02 to 0.2%.
- the minimum with preferable Cr content is higher than 0.02%, More preferably, it is 0.05%.
- the upper limit with preferable Cr content is less than 0.2%.
- Al 0.001 to 0.100%
- Aluminum (Al) deoxidizes steel. If the Al content is too low, deoxidation will be insufficient, and surface flaws will occur on the steel slab, leading to hard deterioration. On the other hand, if the Al content is too high, cracks and the like occur in the slab. Therefore, the Al content is 0.001 to 0.100%.
- a preferable lower limit of the Al content is higher than 0.001%.
- the upper limit with preferable Al content is less than 0.100%, More preferably, it is 0.07%.
- Al content means content of acid-soluble Al (sol.Al).
- Oxygen (O) is an impurity. O forms coarse oxides or oxide clusters to lower the toughness and HIC resistance of the steel. Therefore, it is preferable that the O content is as low as possible. Therefore, the O content is 0.0050% or less. A preferable O content is 0.0030% or less.
- N 0.0100% or less Nitrogen (N) is an impurity. N forms coarse nitrides and lowers the toughness and SSC resistance of the steel. Therefore, a lower N content is preferable. Therefore, the N content is 0.0100% or less. A preferable N content is 0.006% or less.
- the balance of the chemical composition of the seamless steel pipe of this embodiment is composed of Fe and impurities.
- Impurities here refer to ores and scraps used as raw materials for steel, or elements mixed from the environment of the manufacturing process.
- Mo, V, Cu, and Ni are impurities. Even if these alloy elements are not used, the seamless steel pipe of the present embodiment exhibits excellent HIC resistance.
- the seamless steel pipe of this embodiment may further contain Ca.
- Ca 0 to 0.0050%
- Calcium (Ca) is a selective element. Ca suppresses clogging of the tundish nozzle during casting. Ca further controls the form of MnS to enhance the corrosion resistance of the steel. If the Ca content is too low, this effect cannot be obtained. On the other hand, if the Ca content is too high, inclusions form clusters, and the toughness and HIC resistance of the steel decrease. Therefore, the Ca content is 0 to 0.0050%. A preferable lower limit of the Ca content is 0.0005%. The upper limit with preferable Ca content is less than 0.0050%.
- the seamless steel pipe of the present embodiment may further contain one or more selected from the group consisting of Ti and Nb. All of these elements refine steel.
- Titanium (Ti) is a selective element. Ti, like Nb, combines with C and N to form carbonitrides and refines the steel by the pinning effect. Since grain boundaries increase due to finer graining, the progress of cracks in HIC such as blisters is prevented by the grain boundaries. Therefore, the HIC resistance is increased. However, if the Ti content is too high, TiN becomes coarse. In this case, coarse TiN becomes the starting point of HIC, and the HIC resistance decreases. Therefore, the Ti content is 0 to 0.012%. The minimum with preferable Ti content is 0.002%, More preferably, it is 0.005%. The upper limit with preferable Ti content is 0.010% or less.
- Niobium (Nb) is dissolved in ferrite to increase the strength of the steel. Nb further combines with C and N to form carbonitrides and refines the steel by the pinning effect. On the other hand, if the Nb content is too high, coarse Nb carbonitride is formed. Coarse Nb carbonitride is the starting point for HIC. Therefore, the Nb content is 0 to 0.012%. The minimum with preferable Nb content is 0.002%. The upper limit with preferable Nb content is 0.010% or less.
- the structure of the seamless steel pipe of this embodiment contains 10 to 50% ferrite and 0 to less than 5% pearlite in area ratio, and the balance is tempered bainite and / or tempered martensite.
- the area ratio of ferrite (ferrite ratio) and the area ratio of pearlite (pearlite ratio) are obtained by the following method.
- an observation area of 160 ⁇ m ⁇ 120 ⁇ m is selected for each of the outer surface, the center of the wall, and the inner surface.
- Samples containing each observation area are taken.
- the surface including the observation region of each sample (referred to as an observation surface) is polished.
- the polished observation surface is etched using a night etching solution.
- an optical microscope observation field: 160 ⁇ m ⁇ 120 ⁇ m, observation magnification: 500 times
- the area ratio (%) of the specified ferrite and the area ratio (%) of pearlite are measured by a point calculation method.
- the average of the measured ferrite area ratio and pearlite area ratio is defined as the ferrite ratio (%) and pearlite ratio (%) of the seamless steel pipe, respectively.
- the ferrite ratio is 50% or less, and tempered bainite and / or tempered martensite are formed as phases other than ferrite. Therefore, it is possible to suppress the occurrence of HIC due to the yield of ferrite having low strength.
- pearlite may not be contained. That is, the pearlite rate may be 0%.
- the area ratio of pearlite that is prone to cracking is 0 to less than 5%, HIC hardly occurs and excellent HIC resistance can be obtained. Furthermore, since the ferrite ratio is 10% or more, embrittlement of the crystal grain boundary is suppressed. Therefore, even if a minute fracture occurs in the steel, the extension of the crack is suppressed, and excellent HIC resistance can be obtained.
- the number of inclusions (coarse inclusions) having a particle size of 50 ⁇ m or more is 15/100 mm 2 or less.
- the particle size and number of inclusions are measured by the following method. Samples are taken at any cross section parallel to the axial direction of the seamless steel pipe. The sample includes an observation region having a center of thickness and an area of 100 mm 2 . The surface including the observation region (observation surface) is mirror-polished. Inclusions (sulfide inclusions (MnS, etc.), oxide inclusions (Al 2 O 3 etc.) and carbonitride inclusions) in the observation area of the polished surface of each polished sample are observed with an optical microscope. Identify. Specifically, in the observation region, oxide inclusions, sulfide inclusions, and carbonitride inclusions are specified based on the contrast and shape of the optical microscope.
- the particle size of each specified inclusion means the maximum ( ⁇ m) of straight lines connecting two different points on the interface between the inclusion and the parent phase.
- the particle size is determined by regarding the cluster-like particle group as one inclusion. More specifically, the center axis of each particle is defined in three or more particle groups as shown in FIG. The shortest distance in the direction of the central axis between adjacent particles is defined as a distance d ( ⁇ m). Further, the distance between the central axes of adjacent particles is defined as a center distance s ( ⁇ m).
- these particle groups are regarded as one inclusion.
- the determination method for regarding the cluster-like particle group as one inclusion is the same as JIS G0555 (2003) 5.2.3. Inclusions having a particle size of 50 ⁇ m or more are specified as coarse inclusions.
- ⁇ Steel with the above chemical composition is melted and refined by a well-known method. Subsequently, the molten steel is made into a continuous cast material (slab, bloom or billet) by a continuous casting method.
- Continuous casting process In continuous casting, it is preferable that the cooling rate is high. Further, it is preferable to promote the floating separation of large inclusions by controlling the casting temperature by adopting a tundish heater or the like. By these, the number N of coarse inclusions can be controlled to 15/100 m 2 or less.
- the molten steel holding temperature in the tundish is set to 1540 ° C. or higher.
- coarse inclusions aggregate and float in the tundish and are removed from the steel.
- the cooling rate in the temperature range of 1500 ° C. to 1200 ° C. is set to 50 ° C./min or more to prevent the inclusions from coarsening and to uniformly disperse them.
- billet making process When the continuous cast material is slab or bloom, the continuous cast material is hot-worked to produce a billet.
- billets are produced by rolling a slab or a bloom.
- the billet is hot-formed to produce a seamless steel pipe.
- the billet is heated in a heating furnace.
- the billet extracted from the heating furnace is hot-worked to produce a seamless steel pipe.
- piercing and rolling based on the Mannesmann method is performed to manufacture a raw pipe.
- the produced raw pipe is further subjected to stretching rolling and constant diameter rolling by a mandrel mill, a reducer, a sizing mill or the like to produce a seamless steel pipe.
- the ferrite ratio and the pearlite ratio in the structure are reduced by quenching to generate bainite and / or martensite.
- the quenching temperature is A 1 point or more, and the cooling rate is 5 ° C./sec or more.
- the steel structure at the quenching temperature consists of two phases of ferrite and austenite.
- the lower limit of the quenching temperature is the Ar1 point.
- the lower limit of the quenching temperature is the Ac1 point.
- the lower limit of the quenching temperature is 3 points A.
- a preferable lower limit of the quenching temperature is the Ar3 point.
- the minimum of the preferable quenching temperature is Ac3 point. In this case, since the structure of the steel at the quenching temperature is an austenite single phase, the formation of ferrite and pearlite can be further suppressed, and the yield strength can be increased.
- the upper limit of the preferable quenching temperature is 980 ° C, more preferably 950 ° C. In this case, it can suppress that a crystal grain coarsens and toughness deteriorates remarkably. Therefore, the toughness of steel is increased.
- the tempering temperature in the tempering process is set to A c1 point or less. Furthermore, in order to suppress the generation of pearlite during the tempering process, the tempering parameter PL defined by the following equation (1) is set to less than 19500.
- PL (T + 273) ⁇ (21.3 ⁇ 5.8 ⁇ C + log (t)) (1)
- the tempering temperature (° C.) is substituted for T in the formula (1), and the carbon content (%) of the seamless steel pipe is substituted for C.
- the holding time (soaking time, unit is hr) at the tempering temperature T (° C.) is substituted for t.
- the tempering parameter PL is 19500 or more
- a part of bainite and martensite in the steel becomes austenite. Therefore, pearlite is produced from austenite during cooling after soaking. As a result, the area ratio of pearlite in the steel becomes 5% or more.
- the tempering parameter PL is less than 19500, it is possible to suppress the generation of pearlite during the tempering process. Therefore, in the structure of the seamless steel pipe of the present embodiment, the pearlite ratio can be less than 5%.
- the seamless steel pipe of this embodiment manufactured under the above manufacturing conditions has excellent HIC resistance even at low strength.
- the temperature of the molten steel in the tundish during continuous casting was as shown in Table 2 (see “Tundish Temperature” column).
- the cooling rate in the temperature range of 1500 ° C. to 1200 ° C. was 50 ° C./min or more for all numbers.
- a seamless steel pipe was manufactured using the manufactured billet. Specifically, the billet was heated to 1100 ° C., and then a blank pipe was manufactured using a punching machine (piercer). Thereafter, stretch rolling was performed with a mandrel mill, and constant diameter rolling was performed with a reducer, to produce seamless steel pipes with numbers 1 to 40 having outer diameters and wall thicknesses shown in Table 2.
- the heat treatment (normalization treatment, quenching and tempering treatment) shown in Table 2 was performed on the manufactured seamless steel pipes as necessary.
- temperature (° C.) is described in the “norm” column corresponding to the number in Table 2
- normalization is performed at the normalization temperature described in “N temperature” in Table 2 for the seamless steel pipe of that number.
- the numerical values are described in the “Quenching” column and “Tempering” column in Table 2, the corresponding numbered seamless steel pipes are quenched at the quenching temperature (° C.) described in “Q temperature” in the quenching column.
- tempering was carried out while maintaining the soaking time (min) described in “T time” at the tempering temperature (° C.) described in “T temperature” of the tempering column.
- the cooling rate when quenching was 5 ° C./sec or more.
- PL tempering parameter PL with a corresponding number is described. When quenching was performed, the cooling rate during quenching was 5 ° C./sec or more.
- yield strength test A round bar tensile test piece having a parallel portion with an outer diameter of 6.35 mm and a length of 25.4 mm was taken from each of the seamless steel pipes of each number. The parallel part was parallel to the axial direction of the seamless steel pipe. Using the collected round bar tensile test pieces, a tensile test was performed at room temperature (25 ° C.) to obtain a yield strength YS (total elongation 0.5%) (MPa).
- Test pieces (thickness 12 to 30 mm, width 20 mm, length 100 mm) were collected from each thickness of the seamless steel pipes from all thickness positions except 1 mm or less from the outermost surface and 1 mm or less from the innermost surface.
- the test piece had a pair of surfaces corresponding to the outer and inner surfaces of the seamless steel pipe.
- the area of HIC generated in each test piece after the test was measured by an ultrasonic flaw detection method, and the crack area ratio CAR (%) was obtained from the formula (B).
- the area of the test piece in Formula (B) was 20 mm x 100 mm.
- the standard measurement conditions were HIC when the sound pressure was such that 80% or more of the B1 echo was obtained with the A scope, and the reflection echo was 20% or more.
- Crack area ratio CAR area of HIC generated on specimen / area of specimen (B)
- the number of blisters (pieces / 20 cm 2 ) generated on the test piece after the test was counted by the following method.
- the surface of the test piece after the test (20 mm width ⁇ 100 mm length corresponding to the inner surface and the outer surface of the seamless steel pipe) was visually observed.
- the total number of blisters generated on the surface was counted to determine the number of blisters (pieces / 20 cm 2 ).
- the quenching temperature was in a two-phase region, but the ferrite ratio and pearlite ratio in the structure were appropriate. Therefore, the crack area ratio CAR was 0%, and the number of blisters was 0/20 cm 2 .
- the tundish temperature was too low at less than 1540 ° C. Therefore, the number N of coarse inclusions exceeded 15/100 mm 2 .
- the tundish temperature was too low at less than 1540 ° C. Therefore, the number N of coarse inclusions exceeded 15/100 mm 2 .
- test numbers 24 to 26 and 31 to 33 the chemical composition was appropriate and the quenching and tempering treatment was performed, but the tempering parameter PL was 19500 or more. Therefore, although the structure contains ferrite and bainite and / or martensite, the pearlite ratio is 5% or more. As a result, the crack area ratio was 0.2% or more, and the number of blisters was 5/20 cm 2 or more.
- the chemical composition was appropriate, the quenching and tempering treatment was performed, and the tempering parameter PL was less than 19500, but the tundish temperature was too low at less than 1540 ° C. Therefore, the number N of coarse inclusions exceeded 15/100 mm 2 . Therefore, although the crack area ratio CAR was 0%, the number of blisters was 5/20 cm 2 or more, and the HIC resistance was low.
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Abstract
Description
本実施形態による継目無鋼管は、以下の化学組成を有する。
炭素(C)は、焼入れ性を高めて鋼の強度を高める。C含有量が低すぎれば、上記効果が得られない。一方、本実施形態の継目無鋼管はラインパイプとして、円周溶接により、他の継目無鋼管と接続される。したがって、C含有量が高すぎれば、円周溶接の熱影響部(HAZ)が硬化して耐SSC性が低下する。さらに、C含有量が高すぎれば、ラインパイプ用鋼材における溶接部の靱性が低下する。したがって、C含有量は0.01~0.20%である。C含有量の好ましい下限は0.01%よりも高く、さらに好ましくは0.03%であり、さらに好ましくは0.05%である。C含有量の好ましい上限は0.20%未満であり、さらに好ましくは0.15%である。
シリコン(Si)は、鋼を脱酸する。Si含有量が低すぎれば、この効果が得られない。一方、Si含有量が高すぎれば、溶接熱影響部の靱性が低下する。Si含有量が高すぎればさらに、フェライトが過剰に生成される。そのため、耐HIC性が低下する。したがって、Si含有量は0.05~0.50%である。Si含有量の好ましい下限は0.05%よりも高く、さらに好ましくは0.10%であり、さらに好ましくは0.16%である。Si含有量の好ましい上限は0.50%未満であり、さらに好ましくは0.30%である。
マンガン(Mn)は鋼の焼入れ性を高めて鋼の強度を高める。Mnはさらに、鋼の靱性を高める。Mn含有量が低すぎれば、この効果は得られない。一方、Mn含有量が高すぎれば、Mn偏析による鋼の硬化、及び、MnSの形成により、HICが発生しやすくなる。したがって、Mn含有量は0.3~2.0%である。Mn含有量の好ましい下限は0.3%よりも高く、さらに好ましくは、0.5%である。Mn含有量の好ましい上限は2.0%未満であり、さらに好ましくは1.6%である。
燐(P)は不純物である。Pは、偏析して鋼中に硬化組織を形成する。継目無鋼管の場合、硬化組織が鋼管内面近傍に形成されやすく、HICが発生しやすくなる。そのため、P含有量はなるべく低い方が好ましい。したがって、P含有量は0.02%以下である。好ましいP含有量は0.02%未満である。
硫黄(S)は不純物である。Sは、MnSを形成する。MnSはHICの起点となる。したがって、S含有量は低い方が好ましい。しかしながら、S含有量の低減はコストが掛かる。本実施形態の継目無鋼管では製造コストを抑えるため、S含有量を0.01%以下にすればよい。本実施形態の継目無鋼管では、S含有量が0.003%よりも高く含有されていても、後述の組織を有していれば、優れた耐HIC性を示す。
クロム(Cr)は鋼の焼入れ性を高めて鋼を強化する。Cr含有量が低すぎれば、この効果が得られない。一方、Cr含有量が高すぎれば、フェライトが過剰に生成して耐HIC性が低下する。Cr含有量が高すぎればさらに、鋼中において局部に硬化組織が発生したり、鋼の表面の不均一な腐食の原因となったりする。したがって、Cr含有量は0.02~0.2%である。Cr含有量の好ましい下限は0.02%よりも高く、さらに好ましくは0.05%である。Cr含有量の好ましい上限は0.2%未満である。
アルミニウム(Al)は鋼を脱酸する。Al含有量が低すぎれば、脱酸不足となり、鋼片に表面疵等が発生して硬質の劣化を招く。一方、Al含有量が高すぎれば、鋳片に割れ等が発生する。したがって、Al含有量は0.001~0.100%である。Al含有量の好ましい下限は0.001%よりも高い。Al含有量の好ましい上限は0.100%未満であり、さらに好ましくは0.07%である。本明細書において、Al含有量は、酸可溶Al(sol.Al)の含有量を意味する。
酸素(O)は不純物である。Oは粗大な酸化物、又は酸化物のクラスタを形成して鋼の靱性及び耐HIC性を低下する。そのため、O含有量はなるべく低い方が好ましい。したがって、O含有量は0.0050%以下である。好ましいO含有量は0.0030%以下である。
窒素(N)は不純物である。Nは粗大な窒化物を形成して鋼の靱性及び耐SSC性を低下する。そのため、N含有量は低い方が好ましい。したがって、N含有量は0.0100%以下である。好ましいN含有量は0.006%以下である。
本実施形態の継目無鋼管はさらに、Caを含有してもよい。
カルシウム(Ca)は選択元素である。Caは、鋳込み時のタンディッシュノズルの詰まりを抑制する。Caはさらに、MnSの形態を制御して鋼の耐食性を高める。Ca含有量が低すぎれば、この効果が得られない。一方、Ca含有量が高すぎれば、介在物がクラスタを形成し、鋼の靱性及び耐HIC性が低下する。したがって、Ca含有量は0~0.0050%である。Ca含有量の好ましい下限は0.0005%である。Ca含有量の好ましい上限は0.0050%未満である。
チタン(Ti)は選択元素である。TiはNbと同様に、C及びNと結合して炭窒化物を形成し、ピンニング効果により鋼を細粒化する。細粒化により粒界が増加するため、ブリスタ等のHICの割れの進展が粒界により阻止される。そのため、耐HIC性が高まる。しかしながら、Ti含有量が高すぎれば、TiNが粗大化する。この場合、粗大なTiNがHICの起点となり、耐HIC性が低下する。したがって、Ti含有量は0~0.012%である。Ti含有量の好ましい下限は0.002%であり、さらに好ましくは0.005%である。Ti含有量の好ましい上限は0.010%以下である。
ニオブ(Nb)は、フェライトに固溶して鋼の強度を高める。Nbはさらに、C及びNと結合して炭窒化物を形成し、ピンニング効果により鋼を細粒化する。一方、Nb含有量が高すぎれば、粗大なNb炭窒化物が形成される。粗大なNb炭窒化物はHICの起点となる。したがって、Nb含有量は0~0.012%である。Nb含有量の好ましい下限は0.002%である。Nb含有量の好ましい上限は0.010%以下である。
本実施形態の継目無鋼管の組織は、面積率で、10~50%のフェライトと、0~5%未満のパーライトとを含有し、残部は焼戻しベイナイト及び/又は焼戻しマルテンサイトからなる。
本実施形態の継目無鋼管ではさらに、鋼中の介在物のうち、50μm以上の粒径を有する介在物(粗大介在物)の個数が15個/100mm2以下である。
N=TN/観察領域の総面積 (A)
本実施形態によるサワー環境で使用されるラインパイプ用継目無鋼管の製造方法の一例を説明する。
連続鋳造時において、冷却速度は速い方が好ましい。また、タンディッシュヒータを採用する等して、鋳込み温度を制御して大型介在物の浮上分離の促進を図ることが好ましい。これらによって、粗大介在物数Nを15個/100m2以下に制御できる。
連続鋳造材がスラブ又はブルームの場合、連続鋳造材を熱間加工してビレットを製造する。たとえば、スラブやブルームを分塊圧延して、ビレットを製造する。
本実施形態では、焼入れ処理により、組織中のフェライト率及びパーライト率を低減し、ベイナイト及び/又はマルテンサイトを生成する。焼入れ温度は、A1点以上とし、冷却速度は5℃/sec以上とする。
本実施形態では、焼戻し処理における焼戻し温度をAc1点以下とする。さらに、焼戻し処理時においてパーライトが生成されるのを抑制するために、次の式(1)で定義される焼戻しパラメータPLを19500未満とする。
PL=(T+273)×(21.3-5.8×C+log(t)) (1)
式(1)中のTには、焼戻し温度(℃)が代入され、Cには、継目無鋼管の炭素含有量(%)が代入される。tには、焼戻し温度T(℃)での保持時間(均熱時間、単位はhr)が代入される。
上述の試験方法により、光学顕微鏡にて各番号の継目無鋼管の組織(フェライト、パーライト、ベイナイト及び/又はマルテンサイト)を特定した。さらに、点算法により、フェライト率(%)、パーライト率(%)を求めた。
上述の測定方法により、各番号の継目無鋼管の粗大介在物数Nを求めた。
各番号の継目無鋼管の各々から、外径6.35mm、長さ25.4mmの平行部を有する丸棒引張試験片を採取した。平行部は継目無鋼管の軸方向に平行であった。採取された丸棒引張試験片を用いて、常温(25℃)で引張試験を行い、降伏強度YS(全伸び0.5%)(MPa)を求めた。
各番号の継目無鋼管から試験片(厚さ12~30mm、幅20mm、長さ100mm)を最外面から1mm以下、最内面から1mm以下を除く全肉厚位置から採取した。試験片は、継目無鋼管の外面及び内面に相当する一対の表面を有した。
割れ面積率CAR=試験片に発生したHICの面積/試験片の面積 (B)
表2を参照して、番号1~10、22、23、29、30、38及び39では、化学組成が適切であり、焼入れ及び焼戻しが実施された。さらに、鋳込み時のタンディッシュ温度、焼入れ温度、焼戻し温度も適切であり、焼戻しパラメータPLも適切であった。そのため、降伏強度は400MPa未満であり、組織中のフェライト率及びパーライト率は適切であった。さらに、粗大介在物数Nも15個/100mm2以下であった。その結果、割れ面積率CARはいずれも0%であり、ブリスタ個数も0個/20cm2であった。したがって、これらの番号では、優れた耐HIC性が得られた。
Claims (3)
- 質量%で、
C:0.01~0.20%、
Si:0.05~0.50%、
Mn:0.3~2.0%、
P:0.02%以下、
S:0.01%以下、
Cr:0.02~0.2%、
sol.Al:0.001~0.100%、
O:0.0050%以下、
N:0.0100%以下、
Ca:0~0.0050%、
Ti:0~0.012%、及び
Nb:0~0.012%、
を含有し、残部はFe及び不純物である化学組成と、
面積率で10~50%のフェライトと、0~5%未満のパーライトとを含有し、残部は焼戻しベイナイト及び/又は焼戻しマルテンサイトからなる組織とを備え、
粒径が50μm以上の介在物個数が15個/100mm2以下であり、
400MPa以下の降伏強度を有する、サワー環境で使用されるラインパイプ用継目無鋼管。 - 請求項1に記載のラインパイプ用継目無鋼管であって、
前記化学組成は、Ca:0.0005~0.0050%を含有する、ラインパイプ用継目無鋼管。 - 請求項1又は請求項2に記載のラインパイプ用継目無鋼管であって、
前記化学組成は、
Ti:0.002~0.012%、及び、
Nb:0.002~0.012%からなる群から選択される1種以上を含有する、ラインパイプ用継目無鋼管。
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- 2014-06-23 MX MX2015017740A patent/MX2015017740A/es active IP Right Grant
- 2014-06-23 CN CN201480038139.3A patent/CN105358725B/zh active Active
- 2014-06-23 US US14/901,746 patent/US10094008B2/en active Active
- 2014-06-23 JP JP2015525040A patent/JP6028863B2/ja active Active
- 2014-06-23 BR BR112015031596-8A patent/BR112015031596B1/pt active IP Right Grant
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CN107614722A (zh) * | 2015-05-07 | 2018-01-19 | 新日铁住金株式会社 | 高强度钢板及其制造方法 |
CN107614722B (zh) * | 2015-05-07 | 2019-08-27 | 日本制铁株式会社 | 高强度钢板及其制造方法 |
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KR20220017485A (ko) * | 2019-07-09 | 2022-02-11 | 제이에프이 스틸 가부시키가이샤 | 내황산 노점 부식성이 우수한 이음매 없는 강관 및 그의 제조 방법 |
KR102587687B1 (ko) | 2019-07-09 | 2023-10-10 | 제이에프이 스틸 가부시키가이샤 | 내황산 노점 부식성이 우수한 이음매 없는 강관 및 그의 제조 방법 |
Also Published As
Publication number | Publication date |
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CN105358725B (zh) | 2019-02-15 |
EP3018229A1 (en) | 2016-05-11 |
US20160369381A1 (en) | 2016-12-22 |
JP6028863B2 (ja) | 2016-11-24 |
EP3018229A4 (en) | 2017-03-29 |
BR112015031596B1 (pt) | 2020-03-03 |
US10094008B2 (en) | 2018-10-09 |
AR096726A1 (es) | 2016-01-27 |
EP3018229B1 (en) | 2018-09-05 |
MX2015017740A (es) | 2016-06-21 |
JPWO2015001759A1 (ja) | 2017-02-23 |
SA515370317B1 (ar) | 2016-06-01 |
CN105358725A (zh) | 2016-02-24 |
BR112015031596A2 (pt) | 2017-07-25 |
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