WO2017138050A1 - 油井用高強度ステンレス継目無鋼管およびその製造方法 - Google Patents
油井用高強度ステンレス継目無鋼管およびその製造方法 Download PDFInfo
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- WO2017138050A1 WO2017138050A1 PCT/JP2016/004800 JP2016004800W WO2017138050A1 WO 2017138050 A1 WO2017138050 A1 WO 2017138050A1 JP 2016004800 W JP2016004800 W JP 2016004800W WO 2017138050 A1 WO2017138050 A1 WO 2017138050A1
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- steel pipe
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- 239000003129 oil well Substances 0.000 title claims abstract description 37
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 35
- 239000010935 stainless steel Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229910001566 austenite Inorganic materials 0.000 claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 27
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 27
- 230000000717 retained effect Effects 0.000 claims abstract description 20
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 18
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 99
- 239000010959 steel Substances 0.000 claims description 99
- 238000001816 cooling Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000005496 tempering Methods 0.000 claims description 18
- 238000010791 quenching Methods 0.000 claims description 14
- 230000000171 quenching effect Effects 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 abstract description 84
- 230000007797 corrosion Effects 0.000 abstract description 84
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 19
- 229910052799 carbon Inorganic materials 0.000 abstract description 16
- 229910052759 nickel Inorganic materials 0.000 abstract description 15
- 229910052748 manganese Inorganic materials 0.000 abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 45
- 238000012360 testing method Methods 0.000 description 44
- 238000005336 cracking Methods 0.000 description 42
- 238000000034 method Methods 0.000 description 38
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 28
- 230000000694 effects Effects 0.000 description 23
- 230000008569 process Effects 0.000 description 20
- 239000001569 carbon dioxide Substances 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- 239000003921 oil Substances 0.000 description 7
- 238000007654 immersion Methods 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000005728 strengthening Methods 0.000 description 6
- 239000012085 test solution Substances 0.000 description 6
- 238000009863 impact test Methods 0.000 description 5
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001035 Soft ferrite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 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
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
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
- C21D9/085—Cooling or quenching
-
- 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
- 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
- C21D1/19—Hardening; Quenching with or without subsequent tempering by interrupted quenching
- C21D1/22—Martempering
-
- 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
- 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
- C21D1/25—Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
-
- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
-
- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
-
- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/007—Heat treatment of ferrous alloys containing Co
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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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
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- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
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- C22C—ALLOYS
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- 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
- C22C38/40—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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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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
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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
Definitions
- the present invention relates to a 17Cr high strength stainless steel seamless steel pipe suitable for use in oil or gas wells (hereinafter simply referred to as oil wells) of crude oil or natural gas.
- the present invention improves the corrosion resistance especially in a severe corrosive environment containing carbon dioxide (CO 2 ) and chlorine ion (Cl ⁇ ) at high temperatures and in an environment containing hydrogen sulfide (H 2 S). Regarding improvement.
- CO 2 and Cl - also exhibits sufficient corrosion resistance in high temperature harsh corrosive environments to 230 ° C. containing, yield strength: 654MPa for oil wells stainless steel tube further has a high toughness and high strength of greater than (95 ksi) Can be manufactured stably.
- Patent Document 2 describes a high-strength stainless steel pipe for oil wells having high toughness and excellent corrosion resistance.
- C 0.04% or less
- Si 0.50% or less
- Mn 0.20 to 1.80%
- P 0.03% or less
- S 0.005% or less
- Cr 15.5 to 17.5 %
- Ni 2.5 to 5.5%
- V 0.20% or less
- Mo 1.5 to 3.5%
- W 0.50 to 3.0%
- Al 0.05% or less
- N 0.15% or less
- Cr, Mo, W, C satisfy a specific relationship
- Cr, Mo, W, Si, C, Mn, Cu, Ni, N satisfy a specific relationship
- Mo, W satisfy a specific relationship.
- a steel pipe having a composition containing the same and a structure containing a martensite phase as a base phase and a ferrite phase containing 10 to 50% by volume is obtained.
- Patent Document 3 describes a high-strength stainless steel pipe excellent in resistance to sulfide stress cracking and high-temperature carbon dioxide gas corrosion.
- C 0.05% or less
- Si 1.0% or less
- P 0.05% or less
- S less than 0.002%
- Cr more than 16% and 18% or less
- Mo 2 Over 3%
- Cu 1 to 3.5%
- Ni 3% or more and less than 5%
- Al 0.001 to 0.1%
- Mn 1% or less
- N 0.05% or less
- Mn and N Is contained so as to satisfy a specific relationship
- a martensite phase is mainly used, and a ferrite phase having a volume ratio of 10 to 40% and a residual austenite ( ⁇ ) phase having a volume ratio of 10% or less are included.
- the steel pipe has a structure including.
- the yield strength is 758 MPa (110 ksi) or higher, and it has sufficient corrosion resistance even in a high-temperature carbon dioxide environment of 200 ° C. Sufficient sulfide stress even when the environmental gas temperature is lowered. It is supposed to be a high-strength stainless steel pipe with cracking resistance and excellent corrosion resistance.
- Patent Document 4 describes a stainless steel pipe for oil wells.
- C 0.05% or less
- Si 0.5% or less
- Mn 0.01 to 0.5%
- P 0.04% or less
- S 0.01% or less
- Cr more than 16.0
- Mo 1.6 to 4.0%
- Cu 1.5 to 3.0%
- Al 0.001 to 0.10%
- N 0.050% or less
- Cr Cu, Ni and Mo specified
- the composition includes a composition in which (C + N), Mn, Ni, Cu and (Cr + Mo) satisfy a specific relationship, a martensite phase and a ferrite phase having a volume ratio of 10 to 40%, and a surface.
- the stainless steel pipe for oil wells has excellent corrosion resistance in a high temperature environment of 150 to 250 ° C. and excellent resistance to sulfide stress corrosion cracking at room temperature.
- Patent Document 5 describes a high-strength stainless steel pipe for oil wells having high toughness and excellent corrosion resistance.
- C 0.04% or less
- Si 0.50% or less
- Mn 0.20 to 1.80%
- P 0.03% or less
- S 0.005% or less
- Cr 15.5 to 17.5
- V 0.20% or less
- Mo 1.5 to 3.5%
- W 0.50 to 3.0%
- Al 0.05% or less
- N 0.15% or less
- Cr, Mo, W and C satisfy a specific relationship, Cr, Mo, W, Si, C, Mn, Cu, Ni and N, and Mo and W satisfy a specific relationship, respectively
- a steel pipe having a composition containing the largest crystal grain and having a structure in which the distance between any two points in the grain is 200 ⁇ m or less.
- the steel pipe has high strength exceeding yield strength: 654 MPa (95 ksi), excellent toughness, and sufficient corrosion resistance in a hot corrosive environment of 170 ° C. or higher containing CO 2 , Cl ⁇ , and H 2 S. Is going to show.
- Patent Document 6 describes a high-strength martensitic stainless steel seamless steel pipe for oil wells.
- C 0.01% or less
- Si 0.5% or less
- Mn 0.1 to 2.0%
- P 0.03% or less
- S 0.005% or less
- Cr more than 15.5, 17.5% by mass %: Ni: 2.5-5.5%
- Mo 1.8-3.5%
- Cu 0.3-3.5%
- V 0.20% or less
- Al 0.05% or less
- N 0.06% or less
- the seamless steel pipe has a structure including a ferrite phase of 15% or more by volume or a residual austenite phase of 25% or less, and the balance being a tempered martensite phase.
- a composition containing W: 0.25 to 2.0% and / or Nb: 0.20% or less may be used.
- Patent Document 7 describes a stainless steel pipe for oil wells.
- C 0.05% or less
- Si 1.0% or less
- Mn 0.01 to 1.0%
- P 0.05% or less
- S less than 0.002%
- Cr 16 to 18 by mass% %
- Mo 1.8-3%
- Cu 1.0-3.5%
- Co 0.01-1.0%
- Al 0.001-0.1%
- O 0.05% or less
- N 0.05% or less Cr
- Ni, Mo, and Cu satisfy a specific relationship
- the ferrite phase is 10% or more and less than 60% by volume, 10% or less of retained austenite phase, and 40% or more of martensite.
- the stainless steel pipe has a structure containing a site phase. As a result, it is said that a stainless steel pipe for oil wells that can stably obtain high strength of yield strength: 758 MPa or more and excellent high temperature corrosion resistance can be obtained.
- the yield strength for oil well pipes is 862 MPa (125 ksi) or higher, and at a high temperature of 200 ° C or higher.
- it has excellent carbon dioxide corrosion resistance, excellent sulfide stress corrosion cracking resistance, and excellent sulfide stress cracking resistance even in severe corrosive environments including CO 2 and Cl ⁇ and H 2 S.
- it has been demanded to maintain excellent corrosion resistance.
- the present invention solves such a problem of the prior art, and yield strength: high strength of 862 MPa or more, excellent low temperature toughness and excellent corrosion resistance even when the wall thickness is large.
- An object of the present invention is to provide a steelless pipe and a method for producing the same.
- the wall thickness is large here refers to the case where the wall thickness is 25.4 mm or more.
- excellent low temperature toughness here refers to a case where the absorbed energy vE ⁇ 10 at a test temperature: ⁇ 10 ° C. in a Charpy impact test is 40 J or more.
- excellent corrosion resistance refers to a case where “excellent carbon dioxide corrosion resistance”, “excellent sulfide stress corrosion cracking resistance” and “excellent sulfide stress cracking resistance”. Shall.
- excellent carbon dioxide corrosion resistance here means that the test solution kept in the autoclave: 20 mass% NaCl aqueous solution (liquid temperature: 200 ° C., 30 atmospheres CO 2 gas atmosphere) When the piece is immersed and the immersion time is 336 hours, the corrosion rate is 0.125 mm / y or less.
- excellent sulfide stress corrosion cracking resistance refers to a test solution retained in an autoclave: 20% by mass NaCl aqueous solution (liquid temperature: 100 ° C., 30 atm CO 2 gas, 0.1 atm H 2 S atmosphere), the test piece was immersed in an aqueous solution adjusted to pH: 3.3 by adding acetic acid + sodium acetate, the immersion time was set to 720 hours, and 100% of the yield stress was applied as the applied stress. The case where cracks do not occur in the later test piece shall be said.
- excellent sulfide stress cracking resistance refers to a test solution retained in an autoclave: 20% by mass NaCl aqueous solution (liquid temperature: 25 ° C., 0.9 atm CO 2 gas, 0.1 atm H 2 2 S atmosphere), the test piece was immersed in an aqueous solution adjusted to pH 3.5 by adding acetic acid + sodium acetate, the immersion time was 720 hours, and 90% of the yield stress was applied as the load stress. The case where no cracks occur in the test piece.
- the present invention has been completed based on such knowledge and further investigation. That is, the gist of the present invention is as follows.
- Nb, Ta, C, N and Cu are the contents (mass%) of each element, and elements not contained are zero.
- a method for producing a high-strength stainless steel seamless steel pipe for oil wells according to any one of [1] to [4],
- the steel pipe material is heated at a temperature in the range of 1100 to 1350 ° C and subjected to hot working to form a seamless steel pipe with a predetermined shape.
- the seamless steel pipe is reheated to a temperature in the range of 850 to 1150 ° C, and subjected to a quenching treatment that cools the surface temperature to a cooling stop temperature of 50 ° C or less and over 0 ° C at a cooling rate higher than air cooling.
- a method for producing high-strength stainless steel seamless pipes for oil wells that is tempered by heating to a tempering temperature in the range of 500 to 650 ° C.
- a high-strength stainless steel seamless steel pipe having excellent resistance to sulfide stress corrosion cracking and excellent resistance to sulfide stress cracking and excellent corrosion resistance can be produced.
- the seamless steel pipe of the present invention is in mass%, C: 0.05% or less, Si: 1.0% or less, Mn: 0.1 to 0.5%, P: 0.05% or less, S: less than 0.005%, Cr: more than 15.0%, 19.0% Mo: 2.0% to 3.0%, Cu: 0.3 to 3.5%, Ni: 3.0% to less than 5.0%, W: 0.1 to 3.0%, Nb: 0.07 to 0.5%, V: 0.01 to 0.5%, Al: 0.001 to 0.1%, N: 0.010 to 0.100%, O: 0.01% or less, and Nb, Ta, C, N, and Cu satisfy the following formula (1), and the balance is Fe and inevitable impurities Stainless steel joint for oil wells having a composition and having a structure comprising a tempered martensite phase of 45% or more, a ferrite phase of 20 to 40%, and a residual austenite phase of more than 10% and 25% or less by volume. It is a steelless pipe.
- Nb, Ta, C, N and Cu are the contents (mass%) of each element, and are zero when not contained.
- C 0.05% or less C is an important element that increases the strength of martensitic stainless steel. In the present invention, it is desirable to contain 0.010% or more of C in order to ensure a desired high strength. On the other hand, if the C content exceeds 0.05%, the corrosion resistance decreases. Therefore, the C content is 0.05% or less. Preferably, the C content is 0.015% or more. Preferably, the C content is 0.04% or less.
- Si 1.0% or less
- Si is an element that acts as a deoxidizer, and in order to obtain such an effect, it is desirable to contain 0.005% or more of Si.
- Si content shall be 1.0% or less.
- the Si content is 0.1% or more.
- the Si content is 0.6% or less.
- Mn 0.1-0.5%
- Mn is an element that increases the strength of martensitic stainless steel, and needs to contain 0.1% or more of Mn in order to ensure a desired strength.
- the Mn content exceeds 0.5%, the toughness decreases. Therefore, the Mn content is 0.1 to 0.5%.
- the Mn content is 0.4% or less.
- P 0.05% or less
- P is an element that lowers corrosion resistance such as carbon dioxide corrosion resistance and sulfide stress cracking resistance, and is preferably reduced as much as possible in the present invention, but 0.05% or less is acceptable. Therefore, the P content is 0.05% or less. Preferably, the P content is 0.02% or less.
- S Less than 0.005% S is an element that significantly reduces hot workability and hinders stable operation of the hot pipe making process, and is preferably reduced as much as possible, but if less than 0.005%, Pipe production becomes possible. For this reason, the S content is less than 0.005%. Preferably, the S content is 0.001% or less.
- Cr 15.0% to 19.0% or less
- Cr is an element that contributes to the improvement of corrosion resistance by forming a protective film on the surface of the steel pipe. If the Cr content is 15.0% or less, the desired corrosion resistance cannot be ensured. For this reason, the content of Cr exceeding 15.0% is required. On the other hand, if the Cr content exceeds 19.0%, the ferrite fraction becomes too high and the desired strength cannot be ensured. For this reason, Cr content shall be made over 15.0% and 19.0% or less. Preferably, the Cr content is 16.0% or more. Preferably, the Cr content is 18.0% or less.
- Mo 2.0% greater than 3.0% or less
- Mo is a protective coating of the steel pipe surface is stabilized, Cl - and low pH increases the resistance to pitting, sulfide stress cracking resistance and sulfide stress corrosion cracking It is an element that enhances the properties. In order to acquire such an effect, it is necessary to contain Mo exceeding 2.0%.
- Mo is an expensive element, and the inclusion of Mo in excess of 3.0% leads to a rise in material cost and a decrease in toughness and resistance to sulfide stress corrosion cracking. For this reason, Mo content shall be 2.0% over and 3.0% or less.
- the Mo content is 2.2% or more.
- the Mo content is less than 2.8%. More preferably, the Mo content is 2.7% or less.
- Cu 0.3-3.5%
- Cu increases the retained austenite and contributes to the improvement of the yield strength YS by forming precipitates, so is a very important element that can obtain high strength without reducing the low temperature toughness. It also has the effect of strengthening the protective coating on the surface of the steel pipe to suppress hydrogen intrusion into the steel and enhancing the resistance to sulfide stress cracking and the resistance to sulfide stress corrosion cracking. In order to obtain such an effect, it is necessary to contain 0.3% or more of Cu. On the other hand, the inclusion of Cu exceeding 3.5% causes grain boundary precipitation of CuS and reduces hot workability. Therefore, the Cu content is set to 0.3 to 3.5%. Preferably, the Cu content is 0.5% or more. Preferably, the Cu content is 1.0% or more. Preferably, the Cu content is 3.0% or less.
- Ni 3.0% or more and less than 5.0%
- Ni is an element that contributes to improving the corrosion resistance by strengthening the protective film on the surface of the steel pipe. Ni also increases the strength of the steel by solid solution strengthening. Such an effect becomes remarkable when the Ni content is 3.0% or more.
- the Ni content of 5.0% or more decreases the stability of the martensite phase and decreases the strength. For this reason, Ni content shall be 3.0% or more and less than 5.0%.
- the Ni content is 3.5% or more.
- the Ni content is 4.5% or less.
- W 0.1-3.0% W is an important element that contributes to improving the strength of the steel and stabilizes the protective coating on the surface of the steel pipe, thereby improving the resistance to sulfide stress cracking and the resistance to sulfide stress corrosion cracking.
- W in combination with Mo, the resistance to sulfide stress cracking is particularly improved.
- it is necessary to contain 0.1% or more of W.
- the content of W exceeding 3.0% reduces toughness. Therefore, the W content is 0.1 to 3.0%.
- the W content is 0.5% or more.
- the W content is 0.8% or more.
- the W content is 2.0% or less.
- Nb 0.07 to 0.5%
- Nb combines with C and N and precipitates as Nb carbonitride (Nb precipitate), contributing to the improvement of yield strength YS, and is an important element in the present invention.
- Nb precipitate Nb carbonitride
- the Nb content is 0.07 to 0.5%.
- the Nb content is 0.07 to 0.2%.
- V 0.01 to 0.5%
- V is an element that contributes to improving the yield strength YS in addition to contributing to improvement in strength as a solid solution, and binding to C and N and precipitating as V carbonitride (V precipitate).
- V vanadium silicate
- the V content is set to 0.01 to 0.5%.
- the V content is 0.02% or more.
- the V content is 0.1% or less.
- Al 0.001 to 0.1%
- Al is an element that acts as a deoxidizer. In order to obtain such an effect, it is necessary to contain 0.001% or more of Al. On the other hand, if the Al content exceeds 0.1%, the amount of oxide increases, the cleanliness decreases, and the toughness decreases. Therefore, the Al content is set to 0.001 to 0.1%.
- Al is 0.01% or more.
- the Al content is 0.02% or more.
- the Al content is 0.07% or less.
- N 0.010 to 0.100%
- N is an element that improves pitting corrosion resistance. In order to acquire such an effect, N is contained 0.010% or more. On the other hand, when N is contained exceeding 0.100%, nitride is formed and toughness is reduced. Therefore, the N content is 0.010 to 0.100%. Preferably, the N content is 0.02% or more. Preferably, the N content is 0.06% or less.
- O 0.01% or less
- O oxygen
- the O content is 0.01% or less.
- Nb, Ta, C, N and Cu are contained in the above-described range, and the following (1) formula 5.1 ⁇ ⁇ (Nb + 0.5Ta) ⁇ 10 ⁇ 2.2 /(C+1.2N) ⁇ +Cu ⁇ 1.0 (1)
- Nb, Ta, C, N and Cu are the contents (mass%) of each element, and elements not contained are zero).
- the left side value of the formula (1) is less than 1.0, the amount of Cu precipitates, Nb precipitates and Ta precipitates is small, and the precipitation strengthening is insufficient, and the desired strength cannot be ensured as shown in FIG.
- the left side value of (1) Formula may be 1.0 or more.
- the value on the left side of the formula (1) is calculated with the element as zero.
- the left side value of the formula (1) is 2.0 or more.
- the balance other than the above components is composed of Fe and inevitable impurities.
- selective elements Ti: 0.3% or less, B: 0.0050% or less, Zr: 0.2% or less, Co: 1.0% or less and Ta: 0.1% or less, 1 type (s) or 2 or more types selected from among them can be contained.
- 1 type or 2 types chosen from Ca: 0.0050% or less and REM: 0.01% or less can also be contained.
- the selective element one or two selected from Mg: 0.01% or less and Sn: 0.2% or less can be selected and contained.
- Ti: 0.3% or less, B: 0.0050% or less, Zr: 0.2% or less, Co: 1.0% or less and Ta: 0.1% or less selected from Ti, B, Zr, Co and Ti Ta is an element that increases the strength, and can be selected as necessary and contained in one or more kinds.
- Ti, B, Zr, Co, and Ta have the effect of improving the resistance to sulfide stress cracking in addition to the effects described above.
- Ta is an element that brings about the same effect as Nb, and a part of Nb can be replaced with Ta. In order to obtain such an effect, it is desirable to contain Ti: 0.01%, B: 0.0001% or more, Zr: 0.01% or more, Co: 0.01% or more, and Ta: 0.01% or more.
- Ca 0.0050% or less
- REM 0.01% or less
- Both Ca and REM contribute to the improvement of resistance to sulfide stress corrosion cracking through the control of sulfide morphology. It can contain 1 type or 2 types as needed. In order to acquire such an effect, it is desirable to contain Ca: 0.0001% or more and REM: 0.001% or more. On the other hand, even if Ca: 0.0050% and REM: 0.01% are contained in excess, the effect is saturated and an effect commensurate with the content cannot be expected. For this reason, when it contains, it is preferable to limit to Ca: 0.0050% or less and REM: 0.01% or less, respectively.
- Mg and Sn are elements that improve corrosion resistance, and select one or two as required. Can be contained. In order to acquire such an effect, it is desirable to contain Mg: 0.002% or more and Sn: 0.01% or more. On the other hand, even if the Mg content exceeds 0.01% and Sn content exceeds 0.2%, the effect is saturated and an effect commensurate with the content cannot be expected. For this reason, when it contains, it is preferable to limit to Mg: 0.01% or less and Sn: 0.2% or less, respectively.
- the seamless steel pipe of the present invention has the above-described composition and has a volume ratio of 45% or more tempered martensite phase as the main phase, 20 to 40% ferrite phase, and 10% to 25% residual. It has a structure composed of an austenite phase.
- the tempered martensite phase is the main phase in order to ensure the desired strength.
- at least 20% or more of the ferrite phase is precipitated as the second phase by volume ratio.
- the ferrite phase is precipitated by 20% or more by volume ratio.
- the progress of sulfide stress corrosion cracking and sulfide stress cracking can be suppressed, and desired corrosion resistance can be ensured.
- the ferrite phase is 20 to 40% by volume.
- an austenite phase (residual austenite phase) is precipitated in addition to the ferrite phase as the second phase. Due to the presence of residual austenite phase, ductility and toughness are improved. In order to obtain the effect of improving the ductility and toughness while ensuring the desired strength, the residual austenite phase is precipitated at a volume ratio exceeding 10%. On the other hand, the precipitation of a large amount of austenite phase exceeding 25% by volume cannot secure the desired strength. For this reason, a residual austenite phase shall be 25% or less by volume ratio. Preferably, the retained austenite is more than 10% and 20% or less by volume.
- a tissue observation test piece was measured with a Villera reagent (a reagent in which picric acid, hydrochloric acid and ethanol were mixed at a ratio of 2 g, 10 ml and 100 ml, respectively).
- the structure is corroded and the structure is imaged with a scanning electron microscope (magnification: 1000 times), and the structure fraction (volume%) of the ferrite phase is calculated using an image analyzer.
- the X-ray diffraction test piece is ground and polished so that the cross section (C cross section) perpendicular to the tube axis direction becomes the measurement surface, and the amount of retained austenite ( ⁇ ) is measured using the X-ray diffraction method. .
- the fraction of the tempered martensite phase is the remainder other than the ferrite phase and the residual ⁇ phase.
- the structure of the seamless steel pipe of the present invention can be adjusted by heat treatment (quenching treatment and tempering treatment) under specific conditions described later.
- the structure is a tempered martensite phase having a volume ratio of 45% or more, 20 to 40
- the desired strength can be obtained by adjusting so as to be composed of 10% ferrite phase and 10% to 25% residual austenite phase.
- the starting material (steel pipe material) is heated at a temperature in the range of 1100 to 1350 ° C. and subjected to hot working to form a seamless steel pipe having a predetermined shape.
- a tempering process is performed to produce seamless steel pipes for oil wells.
- the starting material is a steel pipe material having the above composition.
- the production method of the starting material is not particularly limited, and any of the generally known methods for producing a steel pipe material can be applied, but the molten steel having the above composition is melted by a conventional melting method such as a converter, It is preferable to use a slab (steel material) such as a billet by a normal casting method such as a continuous casting method. Needless to say, the present invention is not limited to this. There is no problem even if the slab is further subjected to hot rolling to use a steel slab having a desired dimensional shape as a steel pipe material.
- the heating temperature is in the range of 1100-1350 ° C.
- the heating temperature is less than 1100 ° C, the hot workability is lowered and soot is frequently generated during pipe making.
- the heating temperature exceeds 1350 ° C. and becomes a high temperature, the crystal grains become coarse and the low temperature toughness decreases. For this reason, the heating temperature in the heating step is set to a temperature in the range of 1100 to 1350 ° C.
- the heated steel pipe material is subjected to hot working in a hot pipe making process to be a seamless steel pipe having a predetermined shape.
- the hot pipe forming process is preferably a normal Mannesmann-plug mill type or Mannesmann-mandrel mill type hot pipe forming process, but there is no problem even if it is a seamless steel pipe by hot extrusion by a press method. .
- cooling treatment may be performed.
- the cooling process need not be particularly limited. If it is the composition range of this invention, the structure
- a heat treatment including a quenching process and a tempering process is further performed.
- the quenching process is a process of reheating to a temperature in the range of heating temperature: 850 to 1150 ° C and then cooling to a cooling stop temperature at a surface temperature of 50 ° C or less and exceeding 0 ° C at a cooling rate higher than air cooling. If the heating temperature is less than 850 ° C., the reverse transformation from martensite to austenite does not occur, and the transformation from austenite to martensite does not occur during cooling, and the desired strength cannot be ensured. On the other hand, when the heating temperature is higher than 1150 ° C., the crystal grains become coarse. For this reason, the heating temperature in the quenching process is set to a temperature in the range of 850 to 1150 ° C. Preferably, the heating temperature of the quenching process is 900 ° C. or higher. Preferably, the heating temperature of the quenching process is 1000 ° C. or less.
- the cooling stop temperature for cooling in the quenching process is set to 50 ° C. or less and over 0 ° C.
- cooling rate over air cooling is 0.01 ° C./s or more.
- the soaking time is preferably 5 to 30 minutes in order to make the temperature uniform in the thickness direction and prevent the material from changing.
- the tempering process is a process of heating a tempering temperature of 500 to 650 ° C. to the seamless steel pipe subjected to the quenching process. Moreover, it can cool naturally after this heating. If the tempering temperature is less than 500 ° C., the desired tempering effect cannot be expected because the temperature is too low. On the other hand, when the tempering temperature is higher than 650 ° C., an as-quenched martensite phase is generated, and desired high strength, high toughness, and excellent corrosion resistance cannot be achieved. Therefore, the tempering temperature is in the range of 500 to 650 ° C. Preferably, the tempering temperature is 520 ° C. or higher. Preferably, the tempering temperature is 630 ° C. or lower.
- the holding time is preferably 5 to 90 minutes in order to make the temperature uniform in the thickness direction and prevent the material from changing.
- the structure of the seamless steel pipe becomes a structure composed of a tempered martensite phase as a main phase and a ferrite phase and a retained austenite phase.
- it can be set as the high strength stainless steel seamless steel pipe for oil wells which has desired intensity
- the yield strength YS of the high-strength stainless steel seamless pipe for oil wells obtained by the present invention is 862 MPa or more, and it has excellent low temperature toughness and excellent corrosion resistance.
- the yield strength YS is 1034 MPa or less.
- Molten steel having the composition shown in Table 1 was melted in a converter and cast into billets (slab: steel pipe material) by a continuous casting method.
- the obtained steel pipe material (slab) was subjected to heat treatment to be heated to 1250 ° C.
- the heated steel pipe material was then hot-worked using a seamless rolling mill to obtain a seamless steel pipe (outer diameter 297 mm ⁇ ⁇ thickness 34 mm) and air-cooled to room temperature (25 ° C.).
- test material was cut out from the obtained seamless steel pipe, and after reheating to the quenching heating temperature shown in Table 2, the test material was cooled to water and heated to the tempering temperature shown in Table 2, A tempering treatment for air cooling (cooling) was performed.
- the cooling rate with water cooling during the quenching treatment was 11 ° C./s
- the cooling rate with air cooling (cooling) during the tempering treatment was 0.04 ° C./s.
- test material shock-treated steel pipe
- structure observation tensile test
- impact test impact test
- corrosion resistance test The test method was as follows.
- a test piece for structure observation was collected from the obtained heat-treated test material so that the cross section in the tube axis direction was an observation surface.
- the obtained specimen for tissue observation was corroded with Virella reagent (a reagent in which picric acid, hydrochloric acid and ethanol were mixed at a ratio of 2 g, 10 ml and 100 ml, respectively), and the tissue was imaged with a scanning electron microscope (magnification: 1000 times). And the structure fraction (volume%) of the ferrite phase was computed using the image-analysis apparatus.
- Virella reagent a reagent in which picric acid, hydrochloric acid and ethanol were mixed at a ratio of 2 g, 10 ml and 100 ml, respectively
- an X-ray diffraction test piece is taken from the heat-treated test material obtained, ground and polished so that a cross section (C cross section) orthogonal to the tube axis direction becomes a measurement surface, and an X-ray diffraction method is performed. The amount of retained austenite ( ⁇ ) was measured.
- the fraction of the tempered martensite phase is the remainder other than the ferrite phase and the residual ⁇ phase.
- Tensile test API American Petroleum Institute
- arc-shaped tensile test specimens are collected from the obtained heat-treated test material so that the tube axis direction is the tensile direction, and a tensile test is performed in accordance with the API regulations.
- the tensile properties (yield strength YS, tensile strength TS) were determined. Those with a yield strength YS of 862 MPa or more were accepted as high strength, and those with yield strength less than 862 MPa were rejected.
- Corrosion resistance test A corrosion test piece having a thickness of 3 mm, a width of 30 mm and a length of 40 mm was produced from the obtained heat-treated test material by machining, a corrosion test was performed, and the carbon dioxide gas corrosion resistance was evaluated.
- the corrosion test is performed by immersing the above-mentioned corrosion test piece in a test solution held in an autoclave: 20 mass% NaCl aqueous solution (liquid temperature: 200 ° C., CO 2 gas atmosphere of 30 atm) for an immersion period of 14 days ( 336 hours). About the test piece after a test, the weight was measured and the corrosion rate calculated from the weight loss before and behind a corrosion test was calculated
- the presence or absence of pitting corrosion on the surface of the test piece was observed using a magnifying glass with a magnification of 10 times for the test piece after the corrosion test.
- the presence of pitting means the case where the diameter is 0.2 mm or more. Those without pitting corrosion were accepted, and those with pitting corrosion were rejected.
- a round bar-shaped test piece (diameter: 6.4 mm ⁇ ) was produced from the obtained specimen material according to NACE (National Association of Corrosion and Engineering) (TM0177) Method A, and then subjected to sulfide stress cracking resistance. The test (SSC (Sulfide Stress Cracking) test) was conducted.
- acetic acid + Na acetate was added to a test solution held in an autoclave: 20 mass% NaCl aqueous solution (liquid temperature: 100 ° C., H 2 S: 0.1 atm, CO 2 : 30 atm atmosphere)
- the test piece was immersed in an aqueous solution adjusted to pH: 3.3, the immersion period was set to 720 hours, and 100% of the yield stress was applied as the applied stress.
- the presence or absence of a crack was observed. Those without cracks were accepted and those with cracks were rejected.
- the SSC resistance test was carried out by adding acetic acid + Na acetate to the test solution retained in the autoclave: 20 mass% NaCl aqueous solution (liquid temperature: 25 ° C., H 2 S: 0.1 atm, CO 2 : 0.9 atm).
- the test piece was immersed in an aqueous solution adjusted to pH: 3.5, the immersion period was set to 720 hours, and 90% of the yield stress was applied as the applied stress.
- the test piece after the test was observed for cracks. Those without cracks were accepted and those with cracks were rejected.
- FIG. 1 shows the results of Table 3 in relation to the formula (1) and the yield strength YS.
- the structure is not in the range of tempered martensite phase: 45% or more, ferrite phase: 20-40%, and residual austenite phase: more than 10% and 25% or less, the figure shows Excluded.
- the yield strength YS 862 MPa or more can be achieved while maintaining the low temperature toughness with the residual ⁇ amount exceeding 10%.
- Formula (1) is expressed by the following formula.
- Nb, Ta, C, N and Cu are the contents (mass%) of each element, and elements not contained are zero.
- the yield strength YS high strength of 862 MPa or more
- the absorbed energy at ⁇ 10 ° C . high toughness of 40 J or more
- the corrosion resistance in a high temperature corrosive environment of 200 ° C. containing CO 2 and Cl 2 For oil wells that have excellent (carbon dioxide corrosion resistance), no cracking (SSC, SCC) in an environment containing H 2 S, and excellent sulfide stress cracking resistance and sulfide stress corrosion cracking resistance It is a high-strength stainless steel seamless steel pipe.
- steel pipe No. 24 (steel No. X) does not contain W, sulfide stress corrosion cracking resistance (SSC resistance) and sulfide resistance. Corrosion cracking resistance (SCC resistance) was rejected. Furthermore, the volume ratio of the retained austenite phase was 10% or less, and the toughness was unacceptable.
- Steel pipe No. 25 (steel No. Y) did not contain W and Nb, the left side value of formula (1) was less than 1.0, and the strength was not acceptable. Moreover, it did not contain W, and sulfide stress corrosion cracking resistance (SSC resistance) and sulfide corrosion cracking resistance (SCC resistance) were rejected. Furthermore, the volume ratio of the retained austenite phase was 10% or less, and the toughness was unacceptable.
- Steel pipe No. 26 (steel No. Z) had a left side value of formula (1) of less than 1.0, and a desired strength could not be obtained.
- Steel pipe No. 27 (steel No. AA) had an Nb content of less than 0.07% by mass and a left-side value of formula (1) of less than 1.0, and the desired strength could not be obtained.
- Steel pipe No. 28 (steel No. AB) had an Nb content of less than 0.07% by mass, and the left side value of formula (1) was less than 1.0, and the desired strength could not be obtained. Furthermore, the volume fraction of the ferrite phase was less than 20%, and the sulfide stress cracking resistance (SSC resistance) and sulfide stress corrosion cracking resistance (SCC resistance) were rejected.
- SSC resistance sulfide stress cracking resistance
- SCC resistance sulfide stress corrosion cracking resistance
- Steel pipe No. 29 (steel No. AC) has a Cr content of over 19.0 mass%, a tempered martensite phase volume ratio of less than 45%, and a ferrite phase volume ratio of over 40%.
- the desired strength could not be obtained.
- the Mo content was 2.0% by mass or less, and the carbon dioxide gas corrosion resistance, sulfide stress crack resistance (SSC resistance) and sulfide stress corrosion crack resistance (SCC resistance) were rejected.
- Steel pipe No. 30 (steel No. AD) has a Cr content of 15.0% by mass or less, a Cu content of over 3.5% by mass, a volume ratio of residual austenite phase of 10% or less, toughness and resistance Carbon dioxide corrosivity was unacceptable.
- Steel pipe No. 31 (steel No. AE) has a Ni content of 5.0% by mass or more, a volume ratio of the tempered martensite phase of less than 45%, and a volume ratio of the retained austenite phase of more than 25%. The desired strength could not be obtained.
- Steel pipe No. 32 (steel No. AF) has a Mo content of 2.0% by mass or less, a Cu content of less than 0.3% by mass, a Ni content of less than 3.0% by mass, and a volume of residual austenite phase. The rate was 10% or less, and toughness, carbon dioxide corrosion resistance, sulfide stress cracking resistance (SSC resistance) and sulfide stress corrosion cracking resistance (SCC resistance) were rejected.
- SSC resistance sulfide stress cracking resistance
- SCC resistance sulfide stress corrosion cracking resistance
- Steel pipe No. 33 (steel No. M) had a volume ratio of residual austenite phase of 10% or less and failed toughness.
- Steel pipe No. 34 (steel No. AG) has a Cu content of less than 0.3% by mass, and does not obtain the desired strength. Sulfide stress crack resistance (SSC resistance) and sulfide stress corrosion crack resistance (SCC resistance) was rejected.
- SSC resistance Sulfide stress crack resistance
- SCC resistance sulfide stress corrosion crack resistance
- Steel pipe No. 35 (steel No. AH) had an Nb content of less than 0.07% by mass, and a desired strength could not be obtained.
- Steel pipe No. 36 (steel No. AI) had a value on the left side of formula (1) of less than 1.0, and the desired strength could not be obtained.
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Abstract
Description
5.1×{(Nb+0.5Ta)-10-2.2/(C+1.2N)}+Cu≧1.0 ‥‥(1)
(ここで、Nb、Ta、C、NおよびCu:各元素の含有量(質量%)であり、含有しない場合はゼロとする。)
を満足するように、調整する必要があることを知見した。より具体的には、本発明者らは、特定の成分組成とし、特定の組織とし、さらに上記の式(1)を満たすようにすることで、所望の強度と靭性が得られることを知見した。
C :0.05%以下、 Si:1.0%以下、
Mn:0.1~0.5%、 P :0.05%以下、
S :0.005%未満、 Cr:15.0%超え19.0%以下、
Mo:2.0%超え3.0%以下、 Cu:0.3~3.5%、
Ni:3.0%以上5.0%未満、 W :0.1~3.0%、
Nb:0.07~0.5%、 V :0.01~0.5%、
Al:0.001~0.1%、 N :0.010~0.100%、
O :0.01%以下
を含有し、かつ、Nb、Ta、C、NおよびCuが下記(1)式を満足し、残部Feおよび不可避的不純物からなる組成を有し、
体積率で、45%以上の焼戻マルテンサイト相と、20~40%のフェライト相と、10%超え25%以下の残留オーステナイト相と、からなる組織を有し、降伏強さYS:862MPa以上を有する油井用高強度ステンレス継目無鋼管。
5.1×{(Nb+0.5Ta)-10-2.2/(C+1.2N)}+Cu≧1.0 ‥‥(1)
ここで、Nb、Ta、C、NおよびCu:各元素の含有量(質量%)であり、含有しない元素はゼロとする。
鋼管素材を、加熱温度:1100~1350℃の範囲の温度で加熱し、熱間加工を施して所定形状の継目無鋼管とし、
前記熱間加工後に、前記継目無鋼管を850~1150℃の範囲の温度に再加熱し、空冷以上の冷却速度で表面温度が50℃以下0℃超えの冷却停止温度まで冷却する焼入れ処理を施し、500~650℃の範囲の焼戻温度に加熱する焼戻処理を施す油井用高強度ステンレス継目無鋼管の製造方法。
5.1×{(Nb+0.5Ta)-10-2.2/(C+1.2N)}+Cu≧1.0 ‥‥(1)
ここで、Nb、Ta、C、NおよびCu:各元素の含有量(質量%)であり、含有しない場合はゼロとする。
Cは、マルテンサイト系ステンレス鋼の強度を増加させる重要な元素である。本発明では、所望の高強度を確保するために、0.010%以上のCを含有することが望ましい。一方、0.05%を超えてCを含有すると、耐食性が低下する。このため、C含有量は0.05%以下とする。好ましくは、C含有量は0.015%以上である。好ましくは、C含有量は0.04%以下である。
Siは、脱酸剤として作用する元素であり、このような効果を得るためには、0.005%以上のSiを含有することが望ましい。一方、1.0%を超えてSiを含有すると、熱間加工性が低下する。このため、Si含有量は1.0%以下とする。好ましくは、Si含有量は0.1%以上である。好ましくは、Si含有量は0.6%以下である。
Mnは、マルテンサイト系ステンレス鋼の強度を増加させる元素であり、所望の強度を確保するために、0.1%以上のMnの含有を必要とする。一方、0.5%を超えてMnを含有すると、靭性が低下する。このため、Mn含有量は0.1~0.5%とする。好ましくは、Mn含有量は0.4%以下である。
Pは、耐炭酸ガス腐食性、耐硫化物応力割れ性等の耐食性を低下させる元素であり、本発明ではできるだけ低減することが好ましいが、0.05%以下であれば許容できる。このため、P含有量は0.05%以下とする。好ましくは、P含有量は0.02%以下である。
Sは、熱間加工性を著しく低下させ、熱間造管工程の安定操業を阻害する元素であり、できるだけ低減することが好ましいが、0.005%未満であれば、通常工程のパイプ製造が可能となる。このようなことから、S含有量は0.005%未満とする。好ましくは、S含有量は0.001%以下である。
Crは、鋼管表面の保護皮膜を形成して耐食性向上に寄与する元素であり、Cr含有量が15.0%以下では、所望の耐食性を確保することができない。このため、15.0%超のCrの含有を必要とする。一方、19.0%を超えるCrの含有は、フェライト分率が高くなりすぎて、所望の強度を確保できなくなる。このため、Cr含有量は15.0%超え19.0%以下とする。好ましくは、Cr含有量は16.0%以上である。好ましくは、Cr含有量は18.0%以下である。
Moは、鋼管表面の保護皮膜を安定化させて、Cl-や低pHによる孔食に対する抵抗性を増加させ、耐硫化物応力割れ性および耐硫化物応力腐食割れ性を高める元素である。このような効果を得るためには、2.0%超えのMoを含有する必要がある。一方、Moは高価な元素であり、3.0%を超えるMoの含有は、材料コストの高騰を招くとともに、靭性、耐硫化物応力腐食割れ性の低下を招く。このため、Mo含有量は2.0%超え3.0%以下とする。好ましくは、Mo含有量は2.2%以上である。好ましくは、Mo含有量は2.8%未満である。さらに好ましくは、Mo含有量は2.7%以下である。
Cuは、残留オーステナイトを増加させ、かつ析出物を形成して降伏強さYSの向上に寄与するため、低温靭性を低下させることなく高強度を得ることができる非常に重要な元素である。また、鋼管表面の保護皮膜を強固にして鋼中への水素侵入を抑制し、耐硫化物応力割れ性および耐硫化物応力腐食割れ性を高める効果も有する。このような効果を得るためには、0.3%以上のCuの含有を必要とする。一方、3.5%を超えるCuの含有は、CuSの粒界析出を招き、熱間加工性を低下させる。このため、Cu含有量は0.3~3.5%とする。好ましくは、Cu含有量は0.5%以上である。好ましくは、Cu含有量は1.0%以上である。好ましくは、Cu含有量は3.0%以下である。
Niは、鋼管表面の保護皮膜を強固にして耐食性向上に寄与する元素である。また、Niは、固溶強化により鋼の強度を増加させる。このような効果は3.0%以上のNiの含有で顕著になる。一方、5.0%以上のNiの含有は、マルテンサイト相の安定性が低下し、強度が低下する。このため、Ni含有量は3.0%以上5.0%未満とする。好ましくは、Ni含有量は3.5%以上である。好ましくは、Ni含有量は4.5%以下である。
Wは、鋼の強度向上に寄与するとともに、鋼管表面の保護皮膜を安定化させて、耐硫化物応力割れ性および耐硫化物応力腐食割れ性を高めることができる重要な元素である。Wは、Moと複合して含有することにより、とくに耐硫化物応力割れ性を顕著に向上させる。このような効果を得るためには、0.1%以上のWの含有を必要とする。一方、3.0%を超えるWの含有は、靭性を低下させる。このため、W含有量は0.1~3.0%とする。好ましくは、W含有量は0.5%以上である。好ましくは、W含有量は0.8%以上である。好ましくは、W含有量は2.0%以下である。
Nbは、CおよびNと結合しNb炭窒化物(Nb析出物)として析出し、降伏強さYSの向上に寄与し、本発明では重要な元素である。このような効果を得るためには0.07%以上のNbの含有を必要とする。一方、0.5%を超えるNbの含有は、靭性および耐硫化物応力割れ性の低下を招く。このため、Nb含有量は0.07~0.5%とする。好ましくは、Nb含有量は0.07~0.2%である。
Vは、固溶として強度の向上に寄与するほか、C、Nと結合しV炭窒化物(V析出物)として析出し、降伏強さYSの向上に寄与する元素である。このような効果を得るためには、0.01%以上のVの含有を必要とする。一方、0.5%を超えるVの含有は、靭性および耐硫化物応力割れ性の低下を招く。このため、V含有量は0.01~0.5%とする。好ましくは、V含有量は0.02%以上である。好ましくは、V含有量は0.1%以下である。
Alは、脱酸剤として作用する元素である。このような効果を得るためには、0.001%以上のAlの含有を必要とする。一方、0.1%を超えてAlを含有すると、酸化物量が増加し清浄度が低下し、靭性が低下する。このため、Al含有量は0.001~0.1%とする。好ましくは、Alは0.01%以上である。好ましくは、Al有量は0.02%以上である。好ましくは、Al含有量は0.07%以下である。
Nは、耐孔食性を向上させる元素である。このような効果を得るためには、Nを0.010%以上含有する。一方、0.100%を超えてNを含有すると、窒化物を形成して靭性を低下させる。このため、N含有量は0.010~0.100%とする。好ましくは、N含有量は0.02%以上である。好ましくは、N含有量は0.06%以下である。
O(酸素)は、鋼中では酸化物として存在するため、各種特性に悪影響を及ぼす。このため、本発明では、できるだけ低減することが望ましい。とくに、Oが0.01%を超えると、熱間加工性、耐食性、靭性が低下する。このため、O含有量は0.01%以下とする。
5.1×{(Nb+0.5Ta)-10-2.2/(C+1.2N)}+Cu≧1.0 ‥‥(1)
(ここで、Nb、Ta、C、NおよびCu:各元素の含有量(質量%)であり、含有しない元素はゼロとする。)を満足するように調整して含有する。(1)式の左辺値が1.0未満では、Cu析出物、Nb析出物およびTa析出物の析出量が少なく、析出強化が不十分で、図1に示すように、所望の強度を確保できない。このため、本発明では、(1)式の左辺値が1.0以上となるように、Nb、Ta、C、NおよびCuの含有量を調整する。なお、上述したように(1)式に記載の元素を含有しない場合には、(1)式の左辺値は当該元素を零(ゼロ)として算出するものとする。好ましくは、(1)式の左辺値は2.0以上である。
Ti、B、Zr、CoおよびTaはいずれも、強度を増加させる元素であり、必要に応じて選択して1種以上、含有することができる。Ti、B、Zr、CoおよびTaは、上記した効果に加えて、耐硫化物応力割れ性を改善する効果も有する。特に、TaはNbと同様の効果をもたらす元素であり、Nbの一部をTaに置き換えることができる。このような効果を得るためには、Ti:0.01%、B:0.0001%以上、Zr:0.01%以上、Co:0.01%以上およびTa:0.01%以上、それぞれ含有することが望ましい。一方、Ti:0.3%、B:0.0050%、Zr:0.2%、Co:1.0%およびTa:0.1%を、それぞれ超えて含有すると、靭性が低下する。このため、含有する場合には、Ti:0.3%以下、B:0.0050%以下、Zr:0.2%以下、Co:1.0%以下およびTa:0.1%以下に限定することが好ましい。
CaおよびREMはいずれも、硫化物の形態制御を介して耐硫化物応力腐食割れ性の改善に寄与する元素であり、必要に応じて1種または2種含有できる。このような効果を得るためには、Ca:0.0001%以上およびREM:0.001%以上含有することが望ましい。一方、Ca:0.0050%およびREM:0.01%を、それぞれ超えて含有しても、効果が飽和し、含有量に見合う効果が期待できなくなる。このため、含有する場合には、Ca:0.0050%以下およびREM:0.01%以下にそれぞれ、限定することが好ましい。
MgおよびSnはいずれも、耐食性を向上させる元素であり、必要に応じて1種または2種を選択して含有できる。このような効果を得るためには、Mg:0.002%以上およびSn:0.01%以上、それぞれ含有することが望ましい。一方、Mg:0.01%およびSn:0.2%をそれぞれ超えて含有しても、効果が飽和し、含有量に見合う効果が期待できなくなる。このため、含有する場合には、Mg:0.01%以下およびSn:0.2%以下に、それぞれ限定することが好ましい。
γ(体積率)=100/(1+(IαRγ/IγRα))
(ここで、Iα:αの積分強度、Rα:αの結晶学的理論計算値、Iγ:γの積分強度、Rγ:γの結晶学的理論計算値)
を用いて換算する。
得られた熱処理済み試験材から、管軸方向断面が観察面となるように組織観察用試験片を採取した。得られた組織観察用試験片をビレラ試薬(ピクリン酸、塩酸およびエタノールをそれぞれ2g、10mlおよび100mlの割合で混合した試薬)で腐食して走査型電子顕微鏡(倍率:1000倍)で組織を撮像し、画像解析装置を用いて、フェライト相の組織分率(体積%)を算出した。
γ(体積率)=100/(1+(IαRγ/IγRα))
(ここで、Iα:αの積分強度、Rα:αの結晶学的理論計算値、Iγ:γの積分強度、Rγ:γの結晶学的理論計算値)
を用いて換算した。なお、焼戻しマルテンサイト相の分率は、フェライト相および残留γ相以外の残部である。
得られた熱処理済み試験材から、管軸方向が引張方向となるように、API(American Petroleum Institute)弧状引張試験片を採取し、APIの規定に準拠して、引張試験を実施し引張特性(降伏強さYS、引張強さTS)を求めた。降伏強さYSが862MPa以上のものを高強度であるとして合格とし、862MPa未満のものは不合格とした。
得られた熱処理済み試験材から、JIS Z 2242の規定に準拠して、試験片長手方向が管軸方向となるように、Vノッチ試験片(10mm厚)を採取し、シャルピー衝撃試験を実施した。試験温度は、-10℃とし、-10℃における吸収エネルギーvE-10を求め、靭性を評価した。なお、試験片は各3本とし、得られた値の算術平均を当該鋼管の吸収エネルギー(J)とした。-10℃における吸収エネルギーvE-10が40J以上のものを高靭性であるとして合格とし、40J未満のものは不合格とした。
得られた熱処理済み試験材から、厚さ3mm×幅30mm×長さ40mmの腐食試験片を機械加工によって作製し、腐食試験を実施し、耐炭酸ガス腐食性を評価した。
5.1×{(Nb+0.5Ta)-10-2.2/(C+1.2N)}+Cu≧1.0 ‥‥(1)
ここで、Nb、Ta、C、NおよびCu:各元素の含有量(質量%)であり、含有しない元素はゼロとする。
Claims (5)
- 質量%で、
C :0.05%以下、 Si:1.0%以下、
Mn:0.1~0.5%、 P :0.05%以下、
S :0.005%未満、 Cr:15.0%超え19.0%以下、
Mo:2.0%超え3.0%以下、 Cu:0.3~3.5%、
Ni:3.0%以上5.0%未満、 W :0.1~3.0%、
Nb:0.07~0.5%、 V :0.01~0.5%、
Al:0.001~0.1%、 N :0.010~0.100%、
O :0.01%以下
を含有し、かつ、Nb、Ta、C、NおよびCuが下記(1)式を満足し、残部Feおよび不可避的不純物からなる組成を有し、
体積率で、45%以上の焼戻マルテンサイト相と、20~40%のフェライト相と、10%超え25%以下の残留オーステナイト相と、からなる組織を有し、降伏強さYS:862MPa以上を有する油井用高強度ステンレス継目無鋼管。
記
5.1×{(Nb+0.5Ta)-10-2.2/(C+1.2N)}+Cu≧1.0 ‥‥(1)
ここで、Nb、Ta、C、NおよびCu:各元素の含有量(質量%)であり、含有しない元素はゼロとする。 - 前記組成に加えてさらに、質量%で、Ti:0.3%以下、B:0.0050%以下、Zr:0.2%以下、Co:1.0%以下、Ta:0.1%以下のうちから選ばれた1種または2種以上を含有する請求項1に記載の油井用高強度ステンレス継目無鋼管。
- 前記組成に加えてさらに、質量%で、Ca:0.0050%以下、REM:0.01%以下のうちから選ばれた1種または2種を含有する請求項1または2に記載の油井用高強度ステンレス継目無鋼管。
- 前記組成に加えてさらに、質量%で、Mg:0.01%以下、Sn:0.2%以下のうちから選ばれた1種または2種を含有する請求項1~3のいずれかに記載の油井用高強度ステンレス継目無鋼管。
- 請求項1~4のいずれかに記載の油井用高強度ステンレス継目無鋼管の製造方法であり、
鋼管素材を、加熱温度:1100~1350℃の範囲の温度で加熱し、熱間加工を施して所定形状の継目無鋼管とし、
前記熱間加工後に、前記継目無鋼管を850~1150℃の範囲の温度に再加熱し、空冷以上の冷却速度で表面温度が50℃以下0℃超えの冷却停止温度まで冷却する焼入れ処理を施し、500~650℃の範囲の焼戻温度に加熱する焼戻処理を施す油井用高強度ステンレス継目無鋼管の製造方法。
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JP2017508580A JP6156609B1 (ja) | 2016-02-08 | 2016-11-02 | 油井用高強度ステンレス継目無鋼管およびその製造方法 |
EP16889754.4A EP3385403B1 (en) | 2016-02-08 | 2016-11-02 | High-strength seamless stainless steel pipe for oil country tubular goods and method of manufacturing high-strength seamless stainless steel pipe |
US16/076,138 US11085095B2 (en) | 2016-02-08 | 2016-11-02 | High-strength seamless stainless steel pipe for oil country tubular goods and method of manufacturing high-strength seamless stainless steel pipe |
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US20200157646A1 (en) | 2020-05-21 |
BR112018015713B1 (pt) | 2021-11-16 |
MX2018009591A (es) | 2018-09-11 |
AR107544A1 (es) | 2018-05-09 |
US11085095B2 (en) | 2021-08-10 |
EP3385403A4 (en) | 2018-12-05 |
EP3385403A1 (en) | 2018-10-10 |
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