WO2015033518A1 - 高強度ステンレス鋼管の製造方法および高強度ステンレス鋼管 - Google Patents
高強度ステンレス鋼管の製造方法および高強度ステンレス鋼管 Download PDFInfo
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- WO2015033518A1 WO2015033518A1 PCT/JP2014/004056 JP2014004056W WO2015033518A1 WO 2015033518 A1 WO2015033518 A1 WO 2015033518A1 JP 2014004056 W JP2014004056 W JP 2014004056W WO 2015033518 A1 WO2015033518 A1 WO 2015033518A1
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- steel pipe
- stainless steel
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 61
- 239000010935 stainless steel Substances 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 71
- 239000010959 steel Substances 0.000 claims abstract description 71
- 238000010791 quenching Methods 0.000 claims abstract description 63
- 230000000171 quenching effect Effects 0.000 claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 238000005496 tempering Methods 0.000 claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 238000011282 treatment Methods 0.000 claims abstract description 26
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- 238000005260 corrosion Methods 0.000 claims description 58
- 230000007797 corrosion Effects 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 50
- 229910000734 martensite Inorganic materials 0.000 claims description 40
- 238000005336 cracking Methods 0.000 claims description 31
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 2
- 238000003303 reheating Methods 0.000 abstract description 9
- 229910000859 α-Fe Inorganic materials 0.000 description 41
- 229910001566 austenite Inorganic materials 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 230000007423 decrease Effects 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 239000003129 oil well Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005098 hot rolling Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000005501 phase interface Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001887 electron backscatter diffraction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B19/00—Tube-rolling by rollers arranged outside the work and having their axes not perpendicular to the axis of the work
- B21B19/02—Tube-rolling by rollers arranged outside the work and having their axes not perpendicular to the axis of the work the axes of the rollers being arranged essentially diagonally to the axis of the work, e.g. "cross" tube-rolling ; Diescher mills, Stiefel disc piercers or Stiefel rotary piercers
- B21B19/04—Rolling basic material of solid, i.e. non-hollow, structure; Piercing, e.g. rotary piercing mills
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
- B21C23/002—Extruding materials of special alloys so far as the composition of the alloy requires or permits special extruding methods of sequences
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
- B22D11/002—Stainless steels
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- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- C—CHEMISTRY; METALLURGY
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- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
- C21D1/613—Gases; Liquefied or solidified normally gaseous material
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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C21D6/00—Heat treatment of ferrous alloys
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- 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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- 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
- C21D9/14—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes wear-resistant or pressure-resistant pipes
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C22C—ALLOYS
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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- 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
- C21D2211/001—Austenite
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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
- 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
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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
- C21D9/085—Cooling or quenching
Definitions
- the present invention is a 17% Cr high-strength stainless steel seamless tube or pipe for Oil Country Tubular, which is a steel mainly composed of two phases of martensite and ferrite. Goods) and a high-strength stainless steel pipe manufactured by the manufacturing method.
- high strength means yield strength: 758 MPa or more.
- Patent Document 1 states that “mass%, C: 0.01% or less, Si: 0.5% or less, Mn: 0.1 to 2.0%, P: 0.03% or less, S: 0. 0.005% or less, Cr: more than 15.5% and 17.5% or less, Ni: 2.5 to 5.5%, Mo: 1.8 to 3.5%, Cu: 0.3 to 3.5% V: 0.20% or less, Al: 0.05% or less, N: 0.06% or less, subjected to quenching and tempering treatment, yield strength: strength of 655 to 862 MPa and yield Ratio: High strength martensitic stainless steel seamless pipe for oil wells with excellent carbon dioxide corrosion resistance and sulfide stress corrosion cracking resistance having tensile properties of 0.90 or more, and its metal structure is 15% by volume. The above ferrite phase or a residual austenite phase of 25% or less is contained, and the balance is tempered martensite For oil wells a high strength martensitic stainless seamless steel tube "is disclosed that.
- 3Cu-9N ⁇ 11.5 is satisfied, and the balance is composed of Fe and inevitable impurities, and preferably a quenching-tempering treatment is performed, preferably the martensite phase is used as the base phase, and the ferrite phase is 10-60. Containing 30% by volume or less of an austenite phase.
- An inexpensive high-strength stainless steel pipe for oil wells having excellent SSC resistance and high toughness even in an environment where 2 S exists is disclosed.
- the metal structures of the stainless steel pipes described in Patent Documents 1 to 3 are all martensite phase + ferrite phase + residual austenite phase structure, and the volume fraction of the ferrite phase is 10 to 50%, or 60%. It is.
- a ferrite phase exists from a high temperature to a low temperature, and grain refining of the ferrite phase due to phase transformation cannot be expected.
- the conventional solution technique is to ensure toughness by reducing the structure of the material by hot rolling (plastic deformation).
- the present invention is made in order to solve the above-mentioned problems, and uses a 17% Cr steel having two phases of a martensite phase and a ferrite phase as a main phase as a starting material, and has high strength excellent in toughness. It aims at providing the manufacturing method of a stainless steel pipe.
- 17% Cr steel is a material with excellent strength and corrosion resistance.
- the structure is a delta-ferrite having a martensite phase and a ferrite phase as main phases, and the ferrite phase is generated at a high temperature. For this reason, it is difficult to refine the ferrite phase by heat treatment, and when the cumulative rolling reduction (cumulative rolling reduction ratio) in hot rolling is small, a coarse ferrite phase will be present in a network after rolling, and the The problem was that the toughness deteriorated.
- the inventors have intensively studied to solve this toughness problem, and heat treatment is performed a plurality of times even for 17% Cr steel, which is a steel having two phases of martensite phase and ferrite phase as main phases. It has been found that the structure can be modified and the toughness can be improved.
- the present invention has been made based on the above findings and further studies, and the gist of the present invention is as follows.
- Component composition is mass%, C: 0.005 to 0.05%, Si: 0.05 to 1.0%, Mn: 0.2 to 1.8%, P: 0.03% S: 0.005% or less, Cr: 14 to 20%, Ni: 1.5 to 10%, Mo: 1 to 5%, V: 0.5% or less, N: 0.15% or less, O : A steel material containing 0.01% or less, Al: 0.002 to 0.1%, the balance being Fe and unavoidable impurities is formed into a steel pipe of a predetermined dimension, and the steel pipe has a temperature of 750 ° C. or higher. After reheating to a temperature, a quenching process of cooling to 100 ° C.
- a method for producing a high-strength stainless steel pipe characterized by performing the tempering treatment at a temperature of 700 ° C. or lower after the above temperature.
- Component composition is mass%, C: 0.005-0.05%, Si: 0.05-1.0%, Mn: 0.2-1.8%, P: 0.03% S: 0.005% or less, Cr: 14 to 20%, Ni: 1.5 to 10%, Mo: 1 to 5%, V: 0.5% or less, N: 0.15% or less, O : A steel material containing 0.01% or less, Al: 0.002 to 0.1%, the balance being Fe and unavoidable impurities is formed into a steel pipe of a predetermined dimension, and the steel pipe has a temperature of 750 ° C. or higher. After reheating to a temperature, a quenching treatment for cooling to 100 ° C.
- production side of the high-strength stainless steel pipe quenching treatment of the final which comprises carrying out at deposition temperatures above the temperature of the ⁇ -phase and M 23 C 6 in quenching treatment .
- the quenching heating temperature is set to two or more levels, and the high-strength stainless steel according to (1) or (2) Steel pipe manufacturing method.
- the steel material further contains at least one kind selected from Cu: 3.5% or less and W: 3% or less by mass%.
- the manufacturing method of the high strength stainless steel pipe in any one.
- the steel material further contains at least one selected from the group consisting of Nb: 0.5% or less, Ti: 0.3% or less, and B: 0.01% or less in mass%.
- the steel material further contains one or more kinds selected from Ca: 0.01% or less, REM: 0.01% or less, and Zr: 0.2% or less by mass%.
- Component composition is mass%, C: 0.005-0.05%, Si: 0.05-1.0%, Mn: 0.2-1.8%, P: 0.03% S: 0.005% or less, Cr: 14 to 20%, Ni: 1.5 to 10%, Mo: 1 to 5%, V: 0.5% or less, N: 0.15% or less, O : 0.01% or less, Al: 0.002 to 0.1%, the balance is made of Fe and inevitable impurities, the thickness is 19.1 mm or more, and the Charpy absorbed energy at ⁇ 10 ° C.
- Sulfide stress cracking test A test piece compliant with ACE-TM0177 Method A, cut out from a high-strength stainless steel tube, was added to a 20% by mass NaCl aqueous solution (liquid temperature: 20 ° C., H 2 S: 0.1 atm, CO 2 : 0.9 atm. Sulfide stress cracking test conducted under the condition that the atmospheric stress is immersed in an aqueous solution adjusted to pH: 3.5 by adding acetic acid + Na acetate and the load stress is 90% of the yield stress.
- the component composition contains W
- the structure has a ferrite-martensite interface
- the Mo content at the ferrite-martensite interface is three times or more the Mo content
- the component composition further includes at least one selected from the group consisting of Cu: 3.5% or less and W: 3% or less in terms of mass%.
- the high strength stainless steel pipe according to any one of the above.
- the component composition further includes one or more selected from the group consisting of Nb: 0.5% or less, Ti: 0.3% or less, and B: 0.01% or less in mass%.
- the high-strength stainless steel pipe according to any one of (8) to (11).
- the component composition further includes one or more kinds selected from Ca: 0.01% or less, REM: 0.01% or less, and Zr: 0.2% or less in mass%.
- the high-strength stainless steel pipe according to any one of (8) to (12).
- ingredient composition the reason for defining the ingredient composition of the high-strength stainless steel pipe will be explained.
- the component% means mass% unless otherwise specified.
- Both the steel pipe before reheating and the like and the high-strength stainless steel pipe of the present invention have the same component composition, and the technical significance is the same.
- C 0.005 to 0.05%
- C is an important element related to corrosion resistance and strength. From the viewpoint of corrosion resistance, it is preferable that C is as small as possible. However, from the viewpoint of securing the strength, 0.005% or more of C is required. On the other hand, when the amount of C exceeds 0.05%, Cr carbide increases, and solid solution Cr that effectively acts on corrosion resistance decreases. Therefore, the C content is in the range of 0.005 to 0.05%. Preferably it is 0.005 to 0.030% of range.
- Si 0.05 to 1.0% Si is added for deoxidation. If the amount of Si is less than 0.05%, the deoxidation effect is not sufficient, and if it exceeds 1.0%, the CO 2 corrosion resistance and hot workability are reduced. For this reason, the amount of Si is made 0.05 to 1.0% in range. Preferably it is 0.1 to 0.6% of range. More preferably, it is in the range of 0.1 to 0.4%.
- Mn 0.2 to 1.8% Mn is added from the viewpoint of securing the strength of the base material. If the amount of Mn is less than 0.2%, the effect is not sufficient, and if the amount of Mn exceeds 1.8%, the toughness decreases. Therefore, the Mn content is in the range of 0.2 to 1.8%. Preferably it is 0.2 to 1.0% of range. More preferably, it is in the range of 0.2 to 0.7%.
- the P content is 0.03% or less. Preferably it is 0.02% or less.
- the S amount is set to 0.005% or less. Preferably it is 0.003% or less.
- Cr 14-20% Cr is an element that improves the corrosion resistance by forming a protective surface film. Cr contributes particularly to the improvement of resistance to CO 2 corrosion and resistance to sulfide stress corrosion cracking. Such an effect is recognized by making the Cr content 14% or more. On the other hand, if the Cr content exceeds 20%, the austenite phase and the ferrite phase increase, the desired high strength cannot be maintained, and the toughness and hot workability deteriorate. Therefore, the Cr content is in the range of 14 to 20%. Preferably it is in the range of 15-19%. More preferably, it is in the range of 16 to 18%.
- Ni 1.5-10% Ni is to strengthen the protective film, resistance to CO 2 corrosion (carbon dioxide-corrosion resistance), has an effect of improving the pitting corrosion resistance (pitting corrosion resistance) and sulfide stress corrosion cracking resistance, further, a solid solution Increases the strength of the steel by solute strengthening. Such an effect is recognized when the Ni content is 1.5% or more. On the other hand, if the Ni content exceeds 10%, the desired high strength cannot be obtained, and the hot workability deteriorates. Therefore, the Ni content is in the range of 1.5 to 10%. Preferably it is 2 to 8% of range. More preferably, it is in the range of 3 to 6%.
- Mo 1-5% Mo is an element that increases resistance to pitting corrosion caused by Cl - ions. The effect is recognized by making Mo amount 1% or more. If the amount of Mo exceeds 5%, the austenite phase and the ferrite phase increase, the desired high strength cannot be maintained, and the toughness and hot workability deteriorate. On the other hand, if the Mo content exceeds 5%, intermetallics precipitate, and the toughness and resistance to sulfide stress corrosion cracking deteriorate. Therefore, the Mo amount is set in the range of 1 to 5%. Preferably it is 1.5 to 4.5% of range. More preferably, it is in the range of 2 to 4%.
- V 0.5% or less V improves the strength of steel by precipitation strengthening and further improves the resistance to sulfide stress corrosion cracking. Therefore, the V amount is desirably 0.02% or more. However, when the V content exceeds 0.5%, the toughness is lowered. Therefore, the V amount is 0.5% or less. Preferably it is 0.03 to 0.3% of range.
- N 0.15% or less
- N is an element that improves pitting corrosion resistance. The effect becomes remarkable when the N content is 0.01% or more. On the other hand, if the N content exceeds 0.15%, various nitrides are formed and the toughness deteriorates. Therefore, the N amount is 0.15% or less. Preferably it is 0.13% or less. More preferably, it is 0.1% or less.
- O 0.01% or less O is present as an oxide in steel and adversely affects various properties. Therefore, it is preferable to reduce as much as possible in order to improve the properties.
- the O amount is set to 0.01% or less. Preferably it is 0.008% or less. More preferably, it is 0.006% or less.
- Al 0.002 to 0.1% Al is added to sufficiently deoxidize the molten steel. If the amount of Al is less than 0.002, the deoxidation effect is not sufficient, and if the amount of Al exceeds 0.1%, the amount of Al dissolved in the base material increases and the base material toughness decreases. Therefore, the Al content is set in the range of 0.002 to 0.1%. Preferably it is 0.01 to 0.07% of range. More preferably, it is in the range of 0.02 to 0.06%.
- the above are the basic chemical components of the present invention, and the balance consists of Fe and inevitable impurities.
- the high-strength stainless steel pipe may further contain one or more selected from Cu and W as selective elements for the purpose of enhancing stress corrosion cracking resistance.
- Cu 3.5% or less
- Cu is an element that strengthens the protective coating and suppresses the penetration of hydrogen into the steel, and improves the resistance to sulfide stress corrosion cracking.
- it is desirable to contain 0.3% or more of Cu.
- the amount of Cu exceeds 3.5%, grain boundary precipitation of CuS is caused and hot workability is deteriorated. Therefore, when Cu is contained, the amount is preferably 3.5% or less. More preferably, it is in the range of 0.5 to 2.5%.
- W 3% or less W contributes to improving the strength of steel and further improves the resistance to sulfide stress corrosion cracking. For this reason, it is desirable to contain 0.5% or more of W. However, if the amount of W exceeds 3%, the ⁇ phase precipitates, and the toughness and corrosion resistance deteriorate. Therefore, when W is contained, the amount is preferably 3% or less. More preferably, it is in the range of 0.5 to 2%.
- the high-strength stainless steel pipe of the present invention may further contain one or more selected from Nb, Ti, and B as a selective element for the purpose of increasing the strength.
- Nb 0.5% or less Nb contributes to increasing the strength and toughness of the steel, so it is desirable to contain 0.02% or more. However, when the Nb amount exceeds 0.5%, the toughness is lowered. Therefore, when Nb is contained, the amount is preferably 0.5% or less. More preferably, it is in the range of 0.03 to 0.3%.
- Ti 0.3% or less Ti contributes to improving the strength of steel and further improves the resistance to sulfide stress corrosion cracking, so it is desirable to contain 0.02% or more. However, if the Ti content exceeds 0.3%, coarse precipitates are generated, and the toughness and sulfide stress corrosion cracking resistance are reduced. Therefore, when Ti is contained, the amount is preferably 0.3% or less. More preferably, it is in the range of 0.03 to 0.1%.
- B 0.01% or less B contributes to improving the strength of the steel and further improves the resistance to sulfide stress corrosion cracking and hot workability. However, when the amount of B exceeds 0.01%, toughness and hot workability are deteriorated. Therefore, when B is contained, the amount is preferably 0.01% or less. More preferably, it is in the range of 0.001 to 0.004%.
- the high-strength stainless steel pipe of the present invention may further contain one or more selected from Ca, REM, and Zr as selective elements for the purpose of improving the material.
- Ca, REM, and Zr are elements that contribute to the improvement of resistance to sulfide stress corrosion cracking.
- the high-strength stainless steel pipe can contain these elements as necessary.
- the amount is preferably Ca: 0.01% or less, REM: 0.01% or less, and Zr: 0.2% or less.
- a stainless steel pipe having the above-described component composition is cooled to room temperature at a cooling rate equal to or higher than that of air cooling after pipe formation to obtain a starting material.
- the manufacturing method of the stainless steel pipe which is the starting material is not particularly limited, and generally known methods for manufacturing seamless steel pipes and ERW steel pipes can be applied.
- these steel pipe materials are heated to form a pipe manufacturing process (Mannesmann plug mill process) or Mannesmann mandrel mill process. Is used to make a stainless steel pipe having the above-described composition of the desired dimensions. In addition, it is good also as a seamless steel pipe by the hot extrusion by a press system.
- a steel pipe material manufactured by a generally known method may be formed by a generally known method to form an electric resistance steel pipe.
- the above stainless steel pipe as a starting material is reheated to 750 ° C. or higher (holding time (soaking time) is 20 minutes) and then cooled to 100 ° C. or lower at a cooling rate of air cooling or higher.
- the reheating temperature is 750 ° C. or higher because it is necessary to reversely transform martensite to austenite. Further, the reheating temperature is preferably 1100 ° C. or less because it prevents the coarsening of the structure. Further, the reheating and holding time is preferably 5 minutes or more from the viewpoint of soaking, and preferably 120 minutes or less for the purpose of preventing coarsening of the structure.
- the reason why the cooling rate after reheating and holding is set to air cooling or more is to prevent the precipitation of carbonitrides and intermetallic compounds during the cooling process and cause martensitic transformation.
- the reason for setting the cooling stop temperature to 100 ° C. or less is to obtain a martensite structure in an amount necessary to achieve a desired strength.
- the metal structure in the fully quenched state exhibits a martensite phase-ferrite phase in which a chi phase that inhibits toughness is present as a precipitate, and residual austenite ( ⁇ ) of 30% by volume or less may be present.
- the quenching process is repeated. That is, in the present invention, the quenching process is performed a plurality of times. It is preferable that the quenching treatment performed a plurality of times has a quenching heating temperature (quenching temperature) of two or more levels, rather than the same conditions. This is because, since the equilibrium ferrite fraction differs depending on the respective quenching levels, the formation of ferrite or austenite occurs and the generated structure becomes finer even if the equilibrium state is approached at each level.
- a preferable quenching temperature after the second time is 960 to 1060 ° C.
- cooling is performed to 100 ° C. or less at a cooling rate of air cooling or higher.
- Residual ⁇ may be present based on a two-phase structure of martensite-ferrite by the second quenching. Since this process corresponds to “a process performed at a temperature equal to or higher than the temperature at which the ⁇ phase and M 23 C 6 are dissolved”, the present process may be a final quenching process.
- the toughness is further improved by repeating the quenching twice or more.
- the final quenching process is performed at a temperature equal to or higher than the temperature at which the ⁇ phase and M 23 C 6 are dissolved because the presence of the ⁇ phase and M23C6 adversely affects toughness and SSC resistance.
- Tempering is performed to obtain toughness.
- the structure becomes a structure composed of a tempered martensite phase, a ferrite phase and a small amount (30% or less) of retained austenite phase.
- a high strength stainless steel pipe having desired high strength, higher toughness, and excellent corrosion resistance is obtained.
- the tempering temperature is set to 700 ° C. or lower. Further, the tempering temperature is preferably 500 ° C. or higher from the viewpoint of toughness and SSC resistance.
- the timing which performs a tempering process is twice after the quenching process which repeats twice or more (namely, after the last quenching process), or after each quenching process (namely, quenching process and tempering process) Repeat above).
- High-strength stainless steel pipe A high-strength stainless steel pipe has the same component composition as the raw steel material. Therefore, the component composition of the high-strength stainless steel pipe can be adjusted by the component composition of the steel material.
- the main structure is a martensite and ferrite phase.
- the structure is mainly composed of two phases of martensite and a ferrite phase, and a structure containing 10 to 60% by volume of the ferrite phase. If the ferrite phase is less than 10% by volume, the hot workability is lowered, and if it exceeds 60% by volume, the strength decreases.
- the volume percentage of the ferrite phase is preferably 15 to 50 volume%.
- a residual austenite phase of 30% by volume or less may be included.
- the ⁇ phase (chi phase) adversely affects toughness and SSC resistance (sulfide stress corrosion cracking resistance).
- the amount of ⁇ phase is acceptable if it is 1% by volume or less.
- the average particle size of martensite is preferably 6.0 ⁇ m or less for the purpose of improving toughness.
- the measuring method of the average particle diameter of a martensite is the method of recognizing what has an orientation difference of 15 degree
- the structure preferably has a ferrite-martensite interface, and the Mo content at the interface is preferably at least three times the Mo content of the component composition for the purpose of improving toughness.
- the W content at the interface is at least three times the W content of the component composition because of improved toughness.
- the high strength stainless steel pipe having the above component composition and structure has the following characteristics.
- the Charpy absorbed energy at ⁇ 10 ° C. can be increased to 30 J or more.
- the Charpy absorbed energy is a value measured by a method conforming to ISO 148-1.
- sulfide stress corrosion cracking resistance which a test piece does not fracture for 720 hours or more by the following sulfide stress cracking test.
- Sulfide stress cracking test A test piece having a parallel part of 25.4 mm ⁇ diameter of 6.4 mm cut out from a high-strength stainless steel pipe was placed in a 20 mass% NaCl aqueous solution (liquid temperature: 20 ° C., H 2 S: 0.1 atm, CO 2 : 0.9 atm. In the atmosphere) and immersed in an aqueous solution adjusted to pH: 3.5 by adding acetic acid + Na acetate, and a stress stress resistance test for sulfide is conducted under a condition that the load stress is 90% of the yield stress.
- thickness can be made 19.1 mm or more.
- (C) Strengthening of Martensite Phase-Ferrite Phase Interface If the quenching temperature prior to the final quenching is the ⁇ phase and M 23 C 6 precipitation temperature range, the martensite phase-ferrite phase interface A precipitate is deposited. By making the final quenching temperature equal to or higher than the temperature at which the ⁇ phase disappears, the precipitate is dissolved, but the ⁇ phase and M 23 C 6 contain a large amount of Mo and W. For this reason, the Mo and W concentrations increase at the interface between the martensite phase and the ferrite phase after dissolution of the precipitate. This is thought to strengthen the martensite phase-ferrite phase interface and improve toughness.
- the ⁇ phase and M 23 C 6 precipitation temperature were determined by performing equilibrium diagram calculation or quenching at various temperatures, and confirming the presence of ⁇ phase and M 23 C 6 by observing the sample. Can be obtained.
- Molten steel having the composition shown in Table 1 is melted in a converter, cast into a billet (steel pipe material) by a continuous casting method, hot-rolled by a Mannesmann-plug mill method, and a joint having an outer diameter of 273 mm and a wall thickness of 26.25 mm. Steel-free pipes were used. A specimen material was cut out from the obtained seamless steel pipe and subjected to quenching and tempering treatment under the conditions shown in Table 2-1.
- the structural fraction of the ferrite phase was determined by the following method.
- the above-mentioned specimen for tissue observation is corroded with Villera reagent, and the tissue is photographed at 1000 times with a scanning electron microscope (SEM). %) was defined as the volume fraction (%) of the ferrite phase.
- the fraction of retained austenite structure was measured using an X-ray diffraction method. Measured specimens are taken from the quenched and tempered specimens, and the X-ray diffraction shows the diffracted X-ray integrated intensity (diffracted) of the (220) plane of ⁇ (gamma) and the (211) plane of ⁇ (alpha). X-ray (integral intensity) was measured and converted using the following formula (1).
- an API arc specimen (by strip specimen specified by API standard) 5CT is taken from the specimen material that has been quenched and tempered, and tensile test (tensile test specified in accordance with API regulations (American Petroleum Institute rule)). ) To determine the tensile characteristics (yield strength YS, tensile strength TS).
- a V-notched test bar (10 mm thick) is collected from the specimen material subjected to quenching and tempering treatment in accordance with the provisions of JIS Z 2242, and the Charpy impact test (Charpy impact test) is performed. test), and the absorbed energy vE ⁇ 10 (J) at ⁇ 10 ° C. was determined and evaluated.
- a corrosion test piece (corrosion specimen) having a thickness of 3 mm, a width of 30 mm, and a length of 40 mm is fabricated by machining from a specimen material subjected to quenching and tempering treatment, and a corrosion test (corrosion test) is performed. Carried out.
- the corrosion test is performed by immersing a test piece in a 20% by mass NaCl aqueous solution (liquid temperature: 230 ° C., CO 2 gas atmosphere at 100 atm) held in an autoclave. (soaking period) was carried out for 14 days. The weight of the test piece after the test was measured, and the corrosion rate calculated from the weight loss before and after the corrosion test was obtained.
- a 6.4 mm round bar test piece was produced by machining from a test piece material subjected to quenching and tempering treatment, and a stress corrosion cracking test (stress corrosion cracking resistance test) Carried out.
- the stress corrosion cracking resistance test was performed using a test solution: 20% by mass NaCl aqueous solution (liquid temperature: 20 ° C., H 2 S: 0.1 atm, CO 2 : 0.9 atm) in acetic acid + acetic acid + Na acetate.
- the test piece was immersed in an aqueous solution adjusted to pH: 3.5 by adding (sodium acetate), and the immersion period was 720 hours, and 90% of the yield stress was applied as applied stress.
- the test piece after the test was observed for cracks.
- Tables 2-1 and 2-2 are continuous tables.
- steel J is a comparative steel in which Mo is outside the scope of the invention and steel K is outside the scope of the invention.
- Table 2-1 shows the results of heat treatment.
- the first quenching process or quenching and tempering process is shown in the heat treatment column 1
- the final quenching and tempering process is shown in the heat treatment column 2.
- Steel pipe No. 1 to 4, 6 to 9, and 11 to 12 are QTQT type heat treatments in which quenching and tempering treatment is performed twice.
- 5 and 10 are QQT type heat treatments in which the first heat treatment is only quenching and the second (final) heat treatment is quenching and tempering treatment.
- Steel pipe No. 13 is a comparative example in which the quenching and tempering process is performed only once.
- Both the examples of the invention yield strength: 758 MPa or more, tensile strength: and more high strength 827 MPa, absorbed energy vE at -10 ° C. -10: and more high toughness 30 J, CO 2, Cl - hints of hot Excellent corrosion resistance (corrosion resistance to carbon dioxide gas) under corrosive environment, corrosion rate: 0.127 mm / y (year) or less, no cracking even in an atmosphere containing H 2 S, and resistance to sulfide stress corrosion It is a seamless steel pipe with excellent crackability.
- the desired high strength is not obtained, the corrosion resistance is lowered, the low temperature toughness is inferior, or the sulfide stress corrosion cracking resistance is lowered. .
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Abstract
Description
(耐硫化物応力割れ試験)
高強度ステンレス鋼管から切り出したACE-TM0177 Method Aの規定に準拠する験片を、20質量%NaCl水溶液(液温:20℃、H2S:0.1気圧、CO2:0.9気圧の雰囲気)に酢酸+酢酸Naを加えてpH:3.5に調整した水溶液浸漬し、負荷応力が降伏応力の90%の条件で行う耐硫化物応力割れ試験。
はじめに、高強度ステンレス鋼管の成分組成を規定した理由を説明する。なお、成分%は、特に限定しない限りすべて質量%を意味する。再加熱等の処理を行う前の鋼管、本発明の高強度ステンレス鋼管はいずれも同様の成分組成であり、技術的意義は同様である。
Cは、耐食性および、強度に関係する重要な元素である。耐食性の観点からは、Cはできるだけ少ないほうが好ましい。しかし、強度を確保する観点からは、0.005%以上のCの含有を必要とする。また、C量が0.05%を超えると、Cr炭化物が多くなり、耐食性に有効に作用する固溶Crが減少する。そこで、C量は0.005~0.05%の範囲とする。好ましくは0.005~0.030%の範囲である。
Siは、脱酸のために添加する。Si量が0.05%未満では脱酸効果が十分でなく、1.0%を超えると、耐CO2腐食性や熱間加工性(hot workability)が低下する。このため、Si量は0.05~1.0%の範囲とする。好ましくは0.1~0.6%の範囲である。より好ましくは0.1~0.4%の範囲である。
Mnは母材強度を確保する観点から添加する。Mn量が0.2%未満ではその効果が十分でなく、Mn量が1.8%を超えると、靭性が低下する。そこで、Mn量は0.2~1.8%の範囲とする。好ましくは0.2~1.0%の範囲である。より好ましくは0.2~0.7%の範囲である。
P量が0.03%を超えると、靭性および耐硫化物応力腐食割れ性(sulfide stress corrosion cracking resistance)が共に劣化する。そこで、P量は0.03%以下とする。好ましくは0.02%以下である。
S量が0.005%を超えると、母材靭性が低下し、熱間加工性が低下する。そこで、S量は0.005%以下とする。好ましくは0.003%以下である。
Crは保護被膜(protective surface film)を形成して耐食性を向上させる元素である。Crは、とくに耐CO2腐食性、耐硫化物応力腐食割れ性の向上に寄与する。このような効果はCr量を14%以上にすることで認められる。また、Cr量が20%を超えると、オーステナイト相やフェライト相が増大し、所望の高強度が保てないうえ、靭性および、熱間加工性も劣化する。そこで、Cr量は14~20%の範囲とする。好ましくは15~19%の範囲である。より好ましくは16~18%の範囲である。
Niは、保護被膜を強固にして、耐CO2腐食性(carbon dioxide-corrosion resistance)、耐孔食性(pitting corrosion resistance)および耐硫化物応力腐食割れ性を高める作用を有し、さらに、固溶強化(solute strengthening)により鋼の強度を増加させる。このような効果はNi量を1.5%以上にすることで認められる。また、Ni量が10%を超えると所望の高強度が得られなくなり、熱間加工性も劣化する。そこで、Ni量は1.5~10%の範囲とする。好ましくは2~8%の範囲である。より好ましくは3~6%の範囲である。
MoはCl-イオンによる孔食(pitting corrosion)に対する抵抗性を増加させる元素である。その効果はMo量を1%以上にすることで認められる。Mo量が5%を超えるとオーステナイト相(austenite phase)やフェライト相が増大し、所望の高強度が保てないうえ、靭性および、熱間加工性も劣化する。また、Mo量が5%を超えると、金属間化合物(intermetallics)が析出し、靭性および、耐硫化物応力腐食割れ性が劣化する。そこで、Mo量は1~5%の範囲とする。好ましくは1.5~4.5%の範囲である。より好ましくは2~4%の範囲である。
Vは、析出強化(precipitation strengthening)により鋼の強度を向上させ、さらに耐硫化物応力腐食割れ性を向上させる。そこで、V量は0.02%以上にすることが望ましい。しかし、V量が0.5%を超えると、靭性が低下する。そこで、V量は0.5%以下とする。好ましくは0.03~0.3%の範囲である。
Nは、耐孔食性を向上させる元素である。その効果はN量を0.01%以上にすることで顕著となる。一方、N量が0.15%を超えると、種々の窒化物を形成して、靭性が劣化する。そこで、N量は0.15%以下とする。好ましくは0.13%以下である。より好ましくは0.1%以下である。
Oは、鋼中で酸化物として存在し、各種特性に悪影響を及ぼすため、特性向上のためにはできるだけ低減することが好ましい。特に、O量が0.01%を超えると、熱間加工性、耐食性、耐硫化物応力割れ性および靭性が著しく低下する。そこで、O量は0.01%以下とする。好ましくは0.008%以下である。より好ましくは0.006%以下である。
Alは溶鋼を十分に脱酸するために添加される。Al量が0.002未満では脱酸効果が十分でなく、Al量が0.1%を超えると、母材中に固溶するAl量が多くなり、母材靭性が低下する。そこで、Al量は0.002~0.1%の範囲とする。好ましくは0.01~0.07%の範囲である。より好ましくは0.02~0.06%の範囲である。
Cuは、保護被膜を強固にして鋼中への水素の侵入を抑制し、耐硫化物応力腐食割れ性を高める元素である。本発明においてはCuを0.3%以上含有することが望ましい。しかし、Cu量が3.5%を超えると、CuSの粒界析出(grain boundary precipitation)を招き、熱間加工性が低下する。そこで、Cuを含有する場合は、その量は3.5%以下とすることが好ましい。より好ましくは0.5~2.5%の範囲である。
Wは、鋼の強度向上に寄与するとともに、さらに耐硫化物応力腐食割れ性を向上させる。このため、Wを0.5%以上含有することが望ましい。しかし、W量が3%を超えると、χ相が析出し、靭性、耐食性が低下する。そこで、Wを含有する場合は、その量は3%以下とすることが好ましい。より好ましくは0.5~2%の範囲である。
Nbは、鋼の強度増加や靭性向上に寄与するので、0.02%以上含有することが望ましい。しかし、Nb量が0.5%を超えると、靭性が低下する。そこで、Nbを含有する場合は、その量は0.5%以下とすることが好ましい。より好ましくは0.03~0.3%の範囲である。
Tiは、鋼の強度向上に寄与するとともに、さらに耐硫化物応力腐食割れ性の改善に寄与するので、0.02%以上含有することが望ましい。しかし、Ti量が0.3%を超えると粗大な析出物が生成し、靭性や耐硫化物応力腐食割れ性が低下する。そこで、Tiを含有する場合は、その量は0.3%以下とすることが好ましい。より好ましくは0.03~0.1%の範囲である。
Bは、鋼の強度向上に寄与するとともに、さらに耐硫化物応力腐食割れ性や熱間加工性の改善に寄与するので、0.0005%以上含有することが望ましい。しかし、B量が0.01%を超えると、靭性および、熱間加工性が低下する。そこで、Bを含有する場合は、その量は0.01%以下とすることが好ましい。より好ましくは0.001~0.004%の範囲である。
Ca、REMおよび、Zrはいずれも、耐硫化物応力腐食割れ性の改善に寄与する元素である。高強度ステンレス鋼管は、これらの元素を、必要に応じて選択して含有できる。このような効果を得るためには、Ca:0.001%以上、REM:0.001%以上、Zr:0.001%以上含有することが望ましい。しかし、Ca:0.01%、REM:0.01%、Zr:0.2%をそれぞれ超えて含有しても、効果が飽和し、鋼中の清浄度が著しく低下し、靭性が低下するようになる。そこで、これらの元素を含有する場合は、その量はCa:0.01%以下、REM:0.01%以下、Zr:0.2%以下とすることが好ましい。
以下に本発明の製造方法について説明する。
出発素材である上記ステンレス鋼管を、750℃以上に再加熱保持(保持時間(均熱時間)は20分)後、空冷以上の冷却速度で100℃以下まで冷却する。
高強度ステンレス鋼管は、原料である鋼素材と同じ成分組成を有する。したがって、高強度ステンレス鋼管の成分組成は、鋼素材の成分組成により調整可能である。
(耐硫化物応力割れ試験)
高強度ステンレス鋼管から切り出した平行部25.4mm×直径6.4mmの試験片を、20質量%NaCl水溶液(液温:20℃、H2S:0.1気圧、CO2:0.9気圧の雰囲気)に酢酸+酢酸Naを加えてpH:3.5に調整した水溶液に浸漬し、負荷応力が降伏応力の90%の条件で行う耐硫化物応力割れ試験。
焼入処理を繰り返すことにより、マルテンサイト組織は、オーステナイト組織への変態、再度マルテンサイト組織への変態を繰り返すので、マルテンサイト組織が微細化し、靭性が向上する。
最終焼入れ以外の焼入れ温度が、最終焼入れ温度よりも低く、焼入れ保持時間(均熱時間)が長時間である場合には、フェライト分率が低下する。最終焼入れ温度の焼入れ保持時間(均熱時間)が短時間である場合には、フェライト分率は低下した状態で保持されるので、さらに靭性が向上する。
最終焼入れより前の焼入処理温度が、χ相および、M23C6の析出温度域であれば、マルテンサイト相-フェライト相の界面に前記析出物が析出する。最終焼入れ温度をχ相が消滅する温度以上とすることで、上記析出物は溶解するが、χ相および、M23C6はMoやWを多く含む。このため、上記析出物の溶解後のマルテンサイト相-フェライト相の界面ではMoおよび、W濃度が高くなる。これによりマルテンサイト相-フェライト相の界面が強化され、靭性が向上すると考えられる。なお、χ相および、M23C6の析出温度は、平衡状態図計算の実施又は、さまざまな温度で焼入れ処理を実施し、サンプルの観察にてχ相、M23C6の有無を確認することで求めることができる。
ここで、Iα:αの積分強度、Rα:αの結晶学的理論計算値(crystallographical theoretic calculation)、Iγ:γの積分強度
Rγ:γの結晶学的理論計算値である。
なお、マルテンサイト相の分率はこれらの相以外の残部として算出した。
Claims (13)
- 成分組成が、質量%で、C:0.005~0.05%、Si:0.05~1.0%、Mn:0.2~1.8%、P:0.03%以下、S:0.005%以下、Cr:14~20%、Ni:1.5~10%、Mo:1~5%、V:0.5%以下、N:0.15%以下、O:0.01%以下、Al:0.002~0.1%を含有し、残部がFeおよび不可避的不純物からなる鋼素材を所定寸法の鋼管に造管し、該鋼管に、750℃以上の温度に再加熱後、空冷以上の冷却速度で100℃以下まで冷却する焼入処理を二回以上繰り返し、かつ、前記焼入処理で最終の焼入処理はχ相とM23C6の析出温度以上の温度で行い、ついで700℃以下の温度で焼戻処理を施すことを特徴とする高強度ステンレス鋼管の製造方法。
- 成分組成が、質量%で、C:0.005~0.05%、Si:0.05~1.0%、Mn:0.2~1.8%、P:0.03%以下、S:0.005%以下、Cr:14~20%、Ni:1.5~10%、Mo:1~5%、V:0.5%以下、N:0.15%以下、O:0.01%以下、Al:0.002~0.1%を含有し、残部がFeおよび不可避的不純物からなる鋼素材を所定寸法の鋼管に造管し、該鋼管に、750℃以上の温度に再加熱後、空冷以上の冷却速度で100℃以下まで冷却する焼入処理と、ついで700℃以下の温度で焼戻しを行う焼戻処理とを、二回以上繰り返して施し、かつ、前記焼入処理で最終の焼入処理はχ相とM23C6の析出温度以上の温度で行うことを特徴とする高強度ステンレス鋼管の製造方法。
- 前記焼入処理において、焼入処理を二回以上繰り返して行う場合において、焼入加熱温度を2水準以上とすることを特徴とする請求項1または2に記載の高強度ステンレス鋼管の製造方法。
- 前記鋼素材に、更に、質量%で、Cu:3.5%以下、W:3%以下の中から選ばれる一種以上を含有することを特徴とする請求項1乃至3の何れかに記載の高強度ステンレス鋼管の製造方法。
- 前記鋼素材に、更に、質量%で、Nb:0.5%以下、Ti:0.3%以下、B:0.01%以下の中から選ばれる一種以上を含有することを特徴とする請求項1乃至4の何れかに記載の高強度ステンレス鋼管の製造方法。
- 前記鋼素材に、更に、質量%で、Ca:0.01%以下、REM:0.01%以下、Zr:0.2%以下の中から選ばれる一種以上を含有することを特徴とする請求項1乃至5の何れかに記載の高強度ステンレス鋼管の製造方法。
- 請求項1乃至6の何れかに記載の製造方法で製造してなることを特徴とする高強度ステンレス鋼管。
- 成分組成が、質量%で、C:0.005~0.05%、Si:0.05~1.0%、Mn:0.2~1.8%、P:0.03%以下、S:0.005%以下、Cr:14~20%、Ni:1.5~10%、Mo:1~5%、V:0.5%以下、N:0.15%以下、O:0.01%以下、Al:0.002~0.1%を含有し、残部がFeおよび不可避的不純物からなり、
厚みが19.1mm以上であり、
-10℃でのシャルピー吸収エネルギーが30J以上であり、
下記耐硫化物応力割れ試験にて試験片が720時間以上破断しない耐硫化物応力腐食割れ性を有することを特徴とする高強度ステンレス鋼管。
(耐硫化物応力割れ試験)
高強度ステンレス鋼管から切り出したNACE-TM0177 Method Aの規定に準拠する丸棒試験片を、20質量%NaCl水溶液(液温:20℃、H2S:0.1気圧、CO2:0.9気圧の雰囲気)に酢酸+酢酸Naを加えてpH:3.5に調整した水溶液に浸漬し、負荷応力が降伏応力の90%の条件で行う耐硫化物応力割れ試験。 - さらにマルテンサイトの平均粒径が6.0μm以下であることを特徴とする請求項8に記載の高強度ステンレス鋼管。
- さらに、前記成分組成はWを含有し、
組織はフェライト-マルテンサイト界面を有し、
前記フェライト-マルテンサイト界面におけるMo含有量が、Mo含有量の3倍以上であり、
前記フェライト-マルテンサイト界面におけるW含有量が、W含有量の3倍以上であることを特徴とする請求項8又は9に記載の高強度ステンレス鋼管。 - 前記成分組成は、さらに、質量%で、Cu:3.5%以下、W:3%以下の中から選ばれる一種以上を含有することを特徴とする請求項8乃至10の何れかに記載の高強度ステンレス鋼管。
- 前記成分組成は、さらに、質量%で、Nb:0.5%以下、Ti:0.3%以下、B:0.01%以下の中から選ばれる一種以上を含有することを特徴とする請求項8乃至11の何れかに記載の高強度ステンレス鋼管。
- 前記成分組成は、さらに、質量%で、Ca:0.01%以下、REM:0.01%以下、Zr:0.2%以下の中から選ばれる一種以上を含有することを特徴とする請求項8乃至12の何れかに記載の高強度ステンレス鋼管。
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- 2014-08-04 US US14/916,265 patent/US10151012B2/en active Active
- 2014-08-04 BR BR112016004849-0A patent/BR112016004849B1/pt active IP Right Grant
- 2014-08-04 MX MX2016002824A patent/MX2016002824A/es unknown
- 2014-08-04 CN CN201480048919.6A patent/CN105579597A/zh active Pending
- 2014-08-04 EP EP14842892.3A patent/EP3042968B1/en active Active
- 2014-08-04 WO PCT/JP2014/004056 patent/WO2015033518A1/ja active Application Filing
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WO2016132403A1 (ja) * | 2015-02-20 | 2016-08-25 | Jfeスチール株式会社 | 高強度継目無厚肉鋼管およびその製造方法 |
JP6037031B1 (ja) * | 2015-02-20 | 2016-11-30 | Jfeスチール株式会社 | 高強度継目無厚肉鋼管およびその製造方法 |
US10837073B2 (en) | 2015-02-20 | 2020-11-17 | Jfe Steel Corporation | High-strength heavy-walled stainless steel seamless tube or pipe and method of manufacturing the same |
WO2017010036A1 (ja) * | 2015-07-10 | 2017-01-19 | Jfeスチール株式会社 | 高強度ステンレス継目無鋼管およびその製造方法 |
JPWO2017010036A1 (ja) * | 2015-07-10 | 2017-07-13 | Jfeスチール株式会社 | 高強度ステンレス継目無鋼管およびその製造方法 |
US10876183B2 (en) | 2015-07-10 | 2020-12-29 | Jfe Steel Corporation | High-strength seamless stainless steel pipe and method of manufacturing high-strength seamless stainless steel pipe |
EP3333276A4 (en) * | 2015-08-04 | 2019-01-09 | Nippon Steel & Sumitomo Metal Corporation | STAINLESS STEEL AND STAINLESS STEEL MATERIAL FOR OIL WELLS |
US10378079B2 (en) | 2015-08-04 | 2019-08-13 | Nippon Steel Corporation | Stainless steel and stainless steel product for oil well |
EP3460087A4 (en) * | 2016-05-20 | 2019-11-06 | Nippon Steel Corporation | STEEL BAR FOR DOWNHOLE ELEMENT AND DOWNHOLE ELEMENT |
Also Published As
Publication number | Publication date |
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CN105579597A (zh) | 2016-05-11 |
MX2016002824A (es) | 2016-06-22 |
EP3042968A1 (en) | 2016-07-13 |
US10151012B2 (en) | 2018-12-11 |
JP6139479B2 (ja) | 2017-05-31 |
AR097538A1 (es) | 2016-03-23 |
US20160215359A1 (en) | 2016-07-28 |
EP3042968B1 (en) | 2020-12-09 |
BR112016004849B1 (pt) | 2022-03-22 |
EP3042968A4 (en) | 2016-08-31 |
BR112016004849A2 (ja) | 2017-08-01 |
JP2015071822A (ja) | 2015-04-16 |
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