US20190241989A1 - Martensitic stainless steel seamless pipe for oil country tubular goods, and method for producing same - Google Patents
Martensitic stainless steel seamless pipe for oil country tubular goods, and method for producing same Download PDFInfo
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- US20190241989A1 US20190241989A1 US16/343,829 US201716343829A US2019241989A1 US 20190241989 A1 US20190241989 A1 US 20190241989A1 US 201716343829 A US201716343829 A US 201716343829A US 2019241989 A1 US2019241989 A1 US 2019241989A1
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- 229910001105 martensitic stainless steel Inorganic materials 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 44
- 239000010959 steel Substances 0.000 claims description 44
- 238000001816 cooling Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 17
- 230000009466 transformation Effects 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 238000005496 tempering Methods 0.000 claims description 15
- 238000010791 quenching Methods 0.000 claims description 12
- 230000000171 quenching effect Effects 0.000 claims description 12
- 230000007797 corrosion Effects 0.000 abstract description 43
- 238000005260 corrosion Methods 0.000 abstract description 43
- 238000005336 cracking Methods 0.000 abstract description 24
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 22
- 230000035882 stress Effects 0.000 description 45
- 239000011651 chromium Substances 0.000 description 23
- 239000010936 titanium Substances 0.000 description 22
- 239000010955 niobium Substances 0.000 description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 239000003921 oil Substances 0.000 description 19
- 239000010949 copper Substances 0.000 description 17
- 239000011572 manganese Substances 0.000 description 15
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 229910000734 martensite Inorganic materials 0.000 description 6
- -1 chlorine ions Chemical class 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910001566 austenite Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002343 natural gas well Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
-
- 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 martensitic stainless steel seamless pipe for use in oil country tubular goods used in oil well and gas well applications such as in crude oil wells and natural gas wells, and to a method for producing such a martensitic stainless steel seamless pipe.
- the invention particularly relates to improvement of corrosion resistance in a severe corrosive environment containing carbon dioxide gas (CO 2 ), chlorine ions (Cl ⁇ ), and the like, and improvement of sulfide stress corrosion cracking resistance (SSC resistance) in a hydrogen sulfide (H 2 S)-containing environment.
- Oil country tubular goods used for mining of oil fields and gas fields of an environment containing CO 2 gas, Cl ⁇ , and the like often use 13% Cr martensitic stainless steel pipes.
- 13% Cr martensitic stainless steel pipes In order to meet the increasing demand for higher SSC resistance arising out of the world-wide development of oil fields of a severe corrosive environment containing hydrogen sulfide, there has been increasing use of modified 13% Cr martensitic stainless steel pipes containing a reduced carbon content, and increased Ni and Mo contents.
- PTL 1 discloses a 13% Cr steel basic composition containing Ni, Mo, and Cu, and a much smaller carbon content than in traditional compositions. These elements are contained to satisfy Cr+2Ni+1.1Mo+0.7Cu ⁇ 32.5, and Nb+V ⁇ 0.05% for at least one of Nb: 0.20% or less, and V: 0.20% or less.
- the composition is described as being capable of providing high strength with a yield strength of 965 MPa or more, and high toughness with a Charpy absorption energy at ⁇ 40° C. of 50 J or more, in addition to desirable corrosion resistance.
- PTL 2 describes a 13% Cr martensitic stainless steel pipe having an extremely low carbon content of 0.015% or less, and a Ti content of 0.03% or more. With such a composition, the 13% Cr martensitic stainless steel pipe can have high strength with a yield stress in the order of 95 ksi (655 to 758 MPa), low hardness with a Rockwell hardness HRC of less than 27, and excellent SSC resistance.
- PTL 3 describes a martensitic stainless steel that satisfies 6.0 ⁇ Ti/C ⁇ 10.1, where Ti/C has a correlation with a value obtained by subtracting the yield stress from the tensile stress. The technique described in this publication can produce a value of 20.7 MPa or more as the difference of the yield stress from the tensile stress, and can reduce the hardness variation, which deteriorates the SSC resistance.
- PTL 4 describes a martensitic stainless steel containing a specified amount of molybdenum satisfying Mo ⁇ 2.3 ⁇ 0.89Si+32.2C, and having a metal structure that is configured primarily from tempered martensite, carbides that have precipitated during tempering, and intermetallic compounds, such as the Laves phase and the ⁇ phase, that have finely precipitated during tempering.
- the technique described in this publication can achieve high strength with a 0.2% proof stress of 860 MPa or more, and excellent carbon dioxide corrosion resistance, and excellent sulfide stress corrosion cracking resistance.
- Recent oil fields and gas fields are developed in severe corrosive environments containing CO 2 , Cl ⁇ , and H 2 S. There are also rising concerns over increased H 2 S concentrations due to aging.
- the oil country tubular goods used in these environments are thus required to have excellent sulfide stress corrosion cracking resistance (SSC resistance), in addition to carbon dioxide corrosion resistance.
- SSC resistance sulfide stress corrosion cracking resistance
- the technique of PTL 1 is described as providing excellent carbon dioxide corrosion resistance.
- the technique cannot be said as providing the level of corrosion resistance that can withstand a severe corrosive environment.
- PTL 2 sulfide stress corrosion cracking resistance can be maintained under an applied stress of 655 MPa in an atmosphere of a 5% NaCl aqueous solution (H 2 S: 0.10 bar) with an adjusted pH of 3.5.
- PTL 3 describes providing sulfide stress corrosion cracking resistance in an atmosphere of a 20% NaCl aqueous solution (H 2 S: 0.03 atm, 002 balance.) with an adjusted pH of 4.5.
- PTL 4 describes providing sulfide stress corrosion cracking resistance in an atmosphere of a 25% NaCl aqueous solution (H 2 S: 0.003 MPa, 002 balance.) with an adjusted pH of 4.0.
- these techniques do not investigate sulfide stress corrosion cracking resistance in other atmospheres, and cannot be said as providing the level of sulfide stress corrosion cracking resistance that can withstand the today's more severe corrosive environments.
- high-strength means a yield stress of 758 MPa (110 ksi) or more. Preferably, the yield stress is 896 MPa or less.
- excellent sulfide stress corrosion cracking resistance means that a test piece dipped in a test solution (a 0.165 mass % NaCl aqueous solution; liquid temperature: 25° C., H 2 S: 1 bar, CO 2 balance) having an adjusted pH of 3.5 with addition of sodium acetate and hydrochloric acid does not crack even after 720 hours under an applied stress equal to 90% of the yield stress.
- a test solution a 0.165 mass % NaCl aqueous solution; liquid temperature: 25° C., H 2 S: 1 bar, CO 2 balance
- the present inventors conducted intensive studies of various alloy elements in a basic composition of a 13% Cr stainless steel pipe with regard to the effects of these elements on sulfide stress corrosion cracking resistance (SSC resistance) in a corrosive environment containing CO 2 , Cl ⁇ , and H 2 S.
- SSC resistance sulfide stress corrosion cracking resistance
- a martensitic stainless steel seamless pipe for oil country tubular goods having the desired strength, and excellent SSC resistance in a CO 2 —, Cl ⁇ —, and H 2 S-containing corrosive environment under an applied stress close to the yield stress can be produced when a composition containing C, Mn, Cr, Cu, Ni, Mo, W, Nb, N, and Ti in adjusted amounts that satisfy appropriate relations and ranges is subjected to appropriate quenching and tempering treatments.
- the martensitic stainless steel seamless pipe having a composition that comprises, in mass %, C: 0.035% or less, Si: 0.5% or less, Mn: 0.05 to 0.5%, P: 0.03% or less, S: 0.005% or less, Cu: 2.6% or less, Ni: 5.3 to 7.3%, Cr: 11.8 to 14.5%, Al: 0.1% or less, Mo: 1.8 to 3.0%, V: 0.2% or less, N: 0.1% or less, and the balance Fe and unavoidable impurities, and that satisfies the following formula (4) with the following formulae (1), (2), and (3),
- the martensitic stainless steel seamless pipe having a yield stress of 758 MPa or more.
- C, Mn, Cr, Cu, Ni, Mo, W, Nb, N, and Ti represent the content of each element in mass % (the content being 0 (zero) percent for elements that are not contained).
- composition further comprises, in mass %, at least one selected from Ti: 0.19% or less, Nb: 0.25% or less, W: 1.1% or less, and Co: 0.45% or less.
- aspects of the present invention can produce a martensitic stainless steel seamless pipe for oil country tubular goods having excellent sulfide stress corrosion cracking resistance (SSC resistance) in a CO 2 —, Cl ⁇ —, and H 2 S-containing corrosive environment, and high strength with a yield stress YS of 758 MPa (110 ksi) or more.
- SSC resistance sulfide stress corrosion cracking resistance
- a seamless stainless steel pipe is a martensitic stainless steel seamless pipe for oil country tubular goods.
- the martensitic stainless steel seamless pipe has a composition that contains, in mass %, C: 0.035% or less, Si: 0.5% or less, Mn: 0.05 to 0.5%, P: 0.03% or less, S: 0.005% or less, Cu: 2.6% or less, Ni: 5.3 to 7.3%, Cr: 11.8 to 14.5%, Al: 0.1% or less, Mo: 1.8 to 3.0%, V: 0.2% or less, N: 0.1% or less, and the balance Fe and unavoidable impurities, and that satisfies the following formula (4), (5), or (6) with the following formulae (1), (2), and (3).
- the martensitic stainless steel seamless pipe has a yield stress of 758 MPa or more.
- C, Mn, Cr, Cu, Ni, Mo, W, Nb, N, and Ti represent the content of each element in mass % (the content being 0 (zero) percent for elements that are not contained).
- composition of the steel pipe according to aspects of the present invention are as follows.
- “%” means percent by mass, unless otherwise specifically stated.
- Carbon is an important element involved in the strength of the martensitic stainless steel, and effectively improves the strength.
- a carbon content of more than 0.035% makes the hardness excessively high, and increases the sensitivity to sulfide stress corrosion cracking.
- the C content is limited to 0.035% or less in accordance with aspects of the present invention.
- the C content is 0.015% or less. More preferably, the C content is 0.0090% or less. Further preferably, the C content is 0.0075% or less. Desirably, carbon is contained in an amount of 0.005% or more to provide the desired strength.
- Silicon acts as a deoxidizing agent, and should be contained in an amount of 0.05% or more.
- a Si content of more than 0.5% deteriorates carbon dioxide corrosion resistance and hot workability. For this reason, the Si content is limited to 0.5% or less.
- the lower limit of Si content is preferably 0.10% or more, and the upper limit of Si content is preferably 0.30% or less.
- Manganese is an element that improves hot workability, and is contained in an amount of 0.05% or more. When contained in excess of 0.5%, the effect becomes saturated, and this leads to increased cost. For this reason, the Mn content is limited to 0.05 to 0.5%. Preferably, the Mn content is 0.40% or less.
- Phosphorus is an element that deteriorates carbon dioxide corrosion resistance, pitting corrosion resistance, and sulfide stress corrosion cracking resistance, and should be contained in as small an amount as possible in accordance with aspects of the present invention.
- an excessively small P content leads to increased manufacturing cost.
- the P content is therefore limited to 0.03% or less, a content that does not bring about an excessive loss of characteristics, and that is industrially feasible in terms of cost.
- the P content is 0.02% or less.
- Sulfur is an element that seriously deteriorates hot workability, and should desirably be contained in as small an amount as possible.
- a S content of 0.005% or less enables pipe production using common procedures, and accordingly the S content is limited to 0.005% or less in accordance with aspects of the present invention.
- the S content is 0.003% or less.
- Copper adds strength to the protective coating, and improves sulfide stress corrosion cracking resistance.
- a Cu content of more than 2.6% causes precipitation of CuS, and deteriorates hot workability.
- the Cu content is limited to 2.6% or less.
- the lower limit of Cu content is preferably 0.5% or more, and the upper limit of Cu content is preferably 2.0% or less.
- nickel When contained in an amount of 5.3% or more, nickel adds strength to the protective coating, and improves corrosion resistance. Nickel also forms a solid solution, and increases the steel strength in this content range. A Ni content of more than 7.3% makes the martensite phase unstable, and the strength deteriorates. For this reason, the Ni content is limited to 5.3 to 7.3%. Preferably, the Ni content is 5.7% or more, more preferably 6.0% or more.
- Chromium is an element that forms a protective coating, and improves the corrosion resistance. Chromium provides the corrosion resistance necessary for oil country tubular goods applications when contained in an amount of 11.8% or more. A Cr content or more than 14.5% facilitates ferrite generation, and the martensite phase cannot remain stable. For this reason, the Cr content is limited to 11.8 to 14.5%.
- the lower limit of Cr content is preferably 12.0% or more, and the upper limit of Cr content is preferably 13.5% or less.
- Aluminum acts as a deoxidizing agent.
- An Al content of 0.01% or more effectively provides this effect. Because an Al content of more than 0.1% adversely affects toughness, the Al content is limited to 0.1% or less in accordance with aspects of the present invention. Preferably, the Al content is 0.01 to 0.03%.
- Molybdenum is an element that improves the pitting corrosion resistance caused by Cl ⁇ . Molybdenum needs to be contained in an amount of 1.8% or more to obtain the corrosion resistance necessary for a severe corrosive environment. The effect becomes saturated when the Mo content is more than 3.0%. Molybdenum is also an expensive element, and increases the manufacturing cost. For these reasons, the Mo content is limited to 1.8 to 3.0%.
- the lower limit of Mo content is preferably 2.4% or more, and the upper limit of Mo content is preferably 2.9% or less.
- Vanadium is contained in an amount of desirably 0.01% or more, in order to improve steel strength by precipitation strengthening, and to improve sulfide stress corrosion cracking resistance.
- a V content of more than 0.2% deteriorates toughness, and the V content is limited to 0.2% or less in accordance with aspects of the present invention.
- the lower limit of V content is preferably 0.01% or more, and the upper limit of V content is preferably 0.08% or less.
- Nitrogen is an element that greatly improves the pitting corrosion resistance.
- a N content of more than 0.1% causes formation of various nitrides, and deteriorates toughness.
- the N content is limited to 0.1% or less in accordance with aspects of the present invention.
- the N content is 0.003% or more.
- the lower limit of N content is more preferably 0.004% or more, further preferably 0.005% or more.
- the upper limit of N content is more preferably 0.08% or less, further preferably 0.05% or less.
- C, Mn, Cr, Cu, Ni, Mo, W, Nb, N, and Ti are contained in the foregoing ranges, and these are contained so as to satisfy the formula (4), (5), or (6) with the formulae (1), (2), and (3) below.
- Formula (1) is a formula that correlates with the residual ⁇ amount. By making the calculated value of formula (1) smaller, the residual austenite is reduced, and the hardness reduces, with the result that the sulfide stress corrosion cracking resistance improves.
- Formula (2) is a formula that correlates with the repassivation potential.
- Regeneration of the passivation coating occurs more easily, and repassivation improves by containing C, Mn, Cr, Cu, N Mo, W, Nb, N, and Ti in such amounts that formula (1) yields a value that satisfies the range of formula (4), (5), or (6), and by containing Mn, Cr, Cu, Ni, Mo, W, N, and Ti in such amounts that formula (2) yields a value that satisfies the range of formula (4), (5), or (6).
- Formula (3) is a formula that correlates with the pitting corrosion potential.
- the calculated value of formula (1) is preferably 5 to 45 in the following formula (4), and is preferably ⁇ 5 to 5 in the following formula (5).
- C, Mn, Cr, Cu, Ni, Mo, W, Nb, N, and Ti represent the content of each element in mass % (the content is 0 (zero) percent for elements that are not contained)
- the composition contains the balance Fe and unavoidable impurities.
- the foregoing basic composition may further contain one or more selectable elements selected from Ti: 0.19% or less, Nb: 0.25% or less, W: 1.1% or less, and Co: 0.45% or less, as needed.
- Titanium and niobium form carbides, and can reduce the solid-solution carbon. This makes it possible to reduce hardness. Excessively high Ti and Nb contents may deteriorate toughness, and the Ti and Nb contents are limited to 0.19% or less for Ti, and 0.25% or less for Nb when containing these elements.
- Tungsten and cobalt are elements that improve the pitting corrosion resistance.
- excessively high W and Co contents may deteriorate toughness, and increase the material cost.
- the W and Co contents are limited to 1.1% or less for W, and 0.45% or less for Co when containing these elements.
- aspects of the present invention use a steel pipe material of the composition described above.
- the method of production of the steel pipe material, or a seamless stainless steel pipe is not particularly limited, and any known seamless steel pipe production method may be used.
- a molten steel of the foregoing composition is made into steel using a steel making process such as by using a converter furnace, and formed into a steel pipe material, for example, a billet, using a method such as continuous casting, and ingot casting-slab rolling.
- the steel pipe material is heated, and hot worked using a known pipe manufacturing process, for example, such as the Mannesmann-plug mill process, and the Mannesmann-mandrel mill process to produce a seamless steel pipe of the foregoing composition.
- the process that follows the production of the steel pipe from the steel pipe material is not particularly limited.
- the steel pipe is subjected to quenching, in which the steel pipe is heated to a temperature equal to or greater than the Ac 3 transformation point, and air cooled to a cooling stop temperature of 100° C. or less at a cooling rate of 0.1° C./s or more, and this is followed by tempering at a temperature equal to or less than the Act transformation point.
- the steel pipe is subjected to quenching, in which the steel pipe is reheated to a temperature equal to or greater than the Ac 3 transformation point, maintained for preferably at least 5 min, and air cooled to a cooling stop temperature of 100° C. or less.
- the quenching heating temperature is less than the Ac 3 transformation point, heating cannot be made in the single austenite phase region, and a sufficient martensite structure cannot be obtained in the subsequent cooling. In this case, the desired high strength cannot be obtained. For this reason, the quenching heating temperature is limited to a temperature equal to or greater than the Ac 3 transformation point.
- air cooling means a cooling rate of 0.1° C./s or more.
- the tempering is a process by which the steel pipe is heated to a temperature equal to or less than the Ac 1 transformation point, maintained for preferably at least 10 min, and air cooled.
- the tempering temperature is higher than the Ac 1 transformation point, the martensite phase precipitates after the tempering, and it is not possible to obtain the desired high toughness and excellent corrosion resistance. For this reason, the tempering temperature is limited to a temperature equal to or less than the Ac 1 transformation point.
- the Ac 3 transformation point (° C.), and the Ac 1 transformation point (° C.) can be measured by a Formaster test, in which the test piece is given a heating and cooling temperature history, and the transformation point is detected from a small displacement due to expansion and contraction.
- Molten steels of the compositions shown in Table 1 were made into steel with a converter furnace, and cast into billets (steel pipe material) by continuous casting. The steel pipe material was then hot worked with a model seamless rolling machine, and air cooled (cooling rate of 0.5° C./s) to produce a seamless steel pipe measuring 83.8 mm in outer diameter and 12.7 mm in wall thickness.
- the seamless steel pipe was cut to obtain a test material, which was then subjected to quenching and tempering under the conditions shown in Table 2.
- a test piece for structure observation was collected from the quenched and tempered test material, and was polished, and measured for residual austenite ( ⁇ ) amount by an X-ray diffraction method.
- I ⁇ represents the integral intensity of ⁇
- R ⁇ represents a crystallographic theoretical value for ⁇
- I ⁇ represents the integral intensity of ⁇
- R ⁇ represents a crystallographic theoretical value for ⁇
- a strip specimen specified by API standard 5CT was collected from the quenched and tempered test material, and subjected to a tensile test according to the API specifications to determine its tensile characteristics (yield stress YS, tensile stress TS).
- the Ac 3 point (° C.) and the Ac 1 point (° C.) shown in Table 2 were measured by conducting a Formaster test for a test piece (measuring 4 mm in diameter ⁇ 10 mm) collected from the quenched test material. Specifically, the test piece was heated to 500° C. at 5° C./s, maintained for 10 minutes after raising the temperature to 920° C. at 0.25° C./s, and cooled to room temperature at 2° C./s. The Ac 3 point (° C.) and the Ac 1 point (° C.) were found by detecting the expansion and contraction of the test piece with the temperature history.
- the SC test was conducted according to NACE TM0177, Method A.
- the test environment was created by using a 0.165 mass % NaCl test solution after adjusting the solution pH to 3.5 by addition of 0.41 g/L of CH 3 COONa and HCl, and the test was conducted under a hydrogen sulfide partial pressure of 0.1 MPa, and an applied stress equal to 90% of the yield stress.
- the martensitic stainless steel seamless pipes of the present examples all had high strength with a yield stress of 758 MPa or more, and excellent SSC resistance that did not involve cracking even under the applied stress in the H 2 S environment. Comparative Examples outside the range of the present invention did not show excellent SSC resistance, though the desired levels of high strength were obtained.
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Abstract
Description
- This is the U.S. National Phase application of PCT/JP2017/033008, filed Sep. 13, 2017, which claims priority to Japanese Patent Application No. 2016-208420, filed Oct. 25, 2016, the disclosures of these applications being incorporated herein by reference in their entireties for all purposes.
- The present invention relates to a martensitic stainless steel seamless pipe for use in oil country tubular goods used in oil well and gas well applications such as in crude oil wells and natural gas wells, and to a method for producing such a martensitic stainless steel seamless pipe. The invention particularly relates to improvement of corrosion resistance in a severe corrosive environment containing carbon dioxide gas (CO2), chlorine ions (Cl−), and the like, and improvement of sulfide stress corrosion cracking resistance (SSC resistance) in a hydrogen sulfide (H2S)-containing environment.
- Rising crude oil prices, and the increasing shortage of petroleum resources have prompted active development of deep oil fields that were unthinkable in the past, and oil fields and gas fields of a severe corrosive environment containing carbon dioxide gas, chlorine ions, and hydrogen sulfide. Steel pipes for oil country tubular goods (OCTG) intended for such an environment need to be made of materials having high strength, and excellent corrosion resistance.
- Oil country tubular goods used for mining of oil fields and gas fields of an environment containing CO2 gas, Cl−, and the like often use 13% Cr martensitic stainless steel pipes. In order to meet the increasing demand for higher SSC resistance arising out of the world-wide development of oil fields of a severe corrosive environment containing hydrogen sulfide, there has been increasing use of modified 13% Cr martensitic stainless steel pipes containing a reduced carbon content, and increased Ni and Mo contents.
- PTL 1 discloses a 13% Cr steel basic composition containing Ni, Mo, and Cu, and a much smaller carbon content than in traditional compositions. These elements are contained to satisfy Cr+2Ni+1.1Mo+0.7Cu≤32.5, and Nb+V≥0.05% for at least one of Nb: 0.20% or less, and V: 0.20% or less. The composition is described as being capable of providing high strength with a yield strength of 965 MPa or more, and high toughness with a Charpy absorption energy at −40° C. of 50 J or more, in addition to desirable corrosion resistance.
- PTL 2 describes a 13% Cr martensitic stainless steel pipe having an extremely low carbon content of 0.015% or less, and a Ti content of 0.03% or more. With such a composition, the 13% Cr martensitic stainless steel pipe can have high strength with a yield stress in the order of 95 ksi (655 to 758 MPa), low hardness with a Rockwell hardness HRC of less than 27, and excellent SSC resistance. PTL 3 describes a martensitic stainless steel that satisfies 6.0≤Ti/C≤10.1, where Ti/C has a correlation with a value obtained by subtracting the yield stress from the tensile stress. The technique described in this publication can produce a value of 20.7 MPa or more as the difference of the yield stress from the tensile stress, and can reduce the hardness variation, which deteriorates the SSC resistance.
- PTL 4 describes a martensitic stainless steel containing a specified amount of molybdenum satisfying Mo≥2.3−0.89Si+32.2C, and having a metal structure that is configured primarily from tempered martensite, carbides that have precipitated during tempering, and intermetallic compounds, such as the Laves phase and the δ phase, that have finely precipitated during tempering. The technique described in this publication can achieve high strength with a 0.2% proof stress of 860 MPa or more, and excellent carbon dioxide corrosion resistance, and excellent sulfide stress corrosion cracking resistance.
- Recent oil fields and gas fields are developed in severe corrosive environments containing CO2, Cl−, and H2S. There are also rising concerns over increased H2S concentrations due to aging. The oil country tubular goods used in these environments are thus required to have excellent sulfide stress corrosion cracking resistance (SSC resistance), in addition to carbon dioxide corrosion resistance. The technique of PTL 1 is described as providing excellent carbon dioxide corrosion resistance. However, there is no investigation of sulfide stress corrosion cracking resistance, and the technique cannot be said as providing the level of corrosion resistance that can withstand a severe corrosive environment.
- It is stated in PTL 2 that sulfide stress corrosion cracking resistance can be maintained under an applied stress of 655 MPa in an atmosphere of a 5% NaCl aqueous solution (H2S: 0.10 bar) with an adjusted pH of 3.5. PTL 3 describes providing sulfide stress corrosion cracking resistance in an atmosphere of a 20% NaCl aqueous solution (H2S: 0.03 atm, 002 balance.) with an adjusted pH of 4.5. PTL 4 describes providing sulfide stress corrosion cracking resistance in an atmosphere of a 25% NaCl aqueous solution (H2S: 0.003 MPa, 002 balance.) with an adjusted pH of 4.0. However, these techniques do not investigate sulfide stress corrosion cracking resistance in other atmospheres, and cannot be said as providing the level of sulfide stress corrosion cracking resistance that can withstand the today's more severe corrosive environments.
- It is accordingly an object according to aspects of the present invention to provide a martensitic stainless steel seamless pipe having high strength, and excellent sulfide stress corrosion cracking resistance, intended for oil country tubular goods. Aspects of the present invention are also intended to provide a method for producing such a martensitic stainless steel seamless pipe for oil country tubular goods.
- As used herein, “high-strength” means a yield stress of 758 MPa (110 ksi) or more. Preferably, the yield stress is 896 MPa or less.
- As used herein, “excellent sulfide stress corrosion cracking resistance” means that a test piece dipped in a test solution (a 0.165 mass % NaCl aqueous solution; liquid temperature: 25° C., H2S: 1 bar, CO2 balance) having an adjusted pH of 3.5 with addition of sodium acetate and hydrochloric acid does not crack even after 720 hours under an applied stress equal to 90% of the yield stress.
- In order to achieve the foregoing objects, the present inventors conducted intensive studies of various alloy elements in a basic composition of a 13% Cr stainless steel pipe with regard to the effects of these elements on sulfide stress corrosion cracking resistance (SSC resistance) in a corrosive environment containing CO2, Cl−, and H2S. As a result of the investigation, the present inventors have found that a martensitic stainless steel seamless pipe for oil country tubular goods having the desired strength, and excellent SSC resistance in a CO2—, Cl−—, and H2S-containing corrosive environment under an applied stress close to the yield stress can be produced when a composition containing C, Mn, Cr, Cu, Ni, Mo, W, Nb, N, and Ti in adjusted amounts that satisfy appropriate relations and ranges is subjected to appropriate quenching and tempering treatments.
- Aspects of the present invention were completed on the basis of these findings after further studies, and are as follows.
- [1] A martensitic stainless steel seamless pipe for oil country tubular goods,
- the martensitic stainless steel seamless pipe having a composition that comprises, in mass %, C: 0.035% or less, Si: 0.5% or less, Mn: 0.05 to 0.5%, P: 0.03% or less, S: 0.005% or less, Cu: 2.6% or less, Ni: 5.3 to 7.3%, Cr: 11.8 to 14.5%, Al: 0.1% or less, Mo: 1.8 to 3.0%, V: 0.2% or less, N: 0.1% or less, and the balance Fe and unavoidable impurities, and that satisfies the following formula (4) with the following formulae (1), (2), and (3),
- the martensitic stainless steel seamless pipe having a yield stress of 758 MPa or more.
-
−109.37C+7.307Mn+6.399Cr+6.329Cu+11.343Ni−13.529Mo+1.276W+2.925Nb+196.775N−2.621Ti−120.307 Formula (1) -
−0.0278Mn+0.0892Cr+0.00567Ni+0.153Mo−0.0219W−1.984N+0.208Ti−1.83 Formula (2) -
−1.324C+0.0533Mn+0.0268Cr+0.0893Cu+0.00526Ni+0.0222Mo−0.0132W−0.473N−0.5Ti−0.514, Formula (3) - In the formulae (1) to (3), C, Mn, Cr, Cu, Ni, Mo, W, Nb, N, and Ti represent the content of each element in mass % (the content being 0 (zero) percent for elements that are not contained).
-
−10≤formula (1)≤45, −0.25≤formula (2)≤−0.20, and 0.10≤formula (3)≤0.20 Formula (4) - [2] The martensitic stainless steel seamless pipe for oil country tubular goods according to item [1], wherein the composition further comprises, in mass %, at least one selected from Ti: 0.19% or less, Nb: 0.25% or less, W: 1.1% or less, and Co: 0.45% or less.
- [3] A′ method for producing the martensitic stainless steel seamless pipe for oil country tubular goods of item [1] or [2], the method comprising:
- making a steel pipe out of a steel pipe material;
- subjecting the steel pipe to quenching in which the steel pipe is heated to a temperature equal to or greater than the Ac3 transformation point, and air cooled to a cooling stop temperature of 100° C. or less at a cooling rate of 0.1° C./s or more; and tempering the steel pipe at a temperature equal to or less than the Ac1 transformation point.
- Aspects of the present invention can produce a martensitic stainless steel seamless pipe for oil country tubular goods having excellent sulfide stress corrosion cracking resistance (SSC resistance) in a CO2—, Cl−—, and H2S-containing corrosive environment, and high strength with a yield stress YS of 758 MPa (110 ksi) or more.
- A seamless stainless steel pipe according to aspects of the present invention is a martensitic stainless steel seamless pipe for oil country tubular goods. The martensitic stainless steel seamless pipe has a composition that contains, in mass %, C: 0.035% or less, Si: 0.5% or less, Mn: 0.05 to 0.5%, P: 0.03% or less, S: 0.005% or less, Cu: 2.6% or less, Ni: 5.3 to 7.3%, Cr: 11.8 to 14.5%, Al: 0.1% or less, Mo: 1.8 to 3.0%, V: 0.2% or less, N: 0.1% or less, and the balance Fe and unavoidable impurities, and that satisfies the following formula (4), (5), or (6) with the following formulae (1), (2), and (3). The martensitic stainless steel seamless pipe has a yield stress of 758 MPa or more.
-
−109.37C+7.307Mn+6.399Cr+6.329Cu+11.343Ni−13.529Mo+1.276W+2.925Nb+196.775N−2.621Ti−120.307 Formula (1) -
−0.0278Mn+0.0892Cr+0.00567Ni+0.153Mo−0.0219W−1.984N+0.208Ti−1.83 Formula (2) -
−1.324C+0.0533Mn+0.0268Cr+0.0893Cu+0.00526Ni+0.0222Mo−0.0132W−0.473N−0.5Ti−0.514, Formula (3) - In the formulae (1) to (3), C, Mn, Cr, Cu, Ni, Mo, W, Nb, N, and Ti represent the content of each element in mass % (the content being 0 (zero) percent for elements that are not contained).
-
−10≤formula (1)≤45, −0.25≤formula (2)≤−0.20, and 0.10≤formula (3)≤0.20 Formula (4) -
−10≤formula (1)≤5, −0.355≤formula (2)≤−0.25, and 0.0255≤formula (3)≤0.10 Formula (5) -
−10≤formula (1)≤−5, −0.39≤formula (2)≤−0.35, and −0.15≤formula (3)≤0.025 Formula (6) - The reasons for specifying the composition of the steel pipe according to aspects of the present invention are as follows. In the following, “%” means percent by mass, unless otherwise specifically stated.
- Carbon is an important element involved in the strength of the martensitic stainless steel, and effectively improves the strength. However, a carbon content of more than 0.035% makes the hardness excessively high, and increases the sensitivity to sulfide stress corrosion cracking. For this reason, the C content is limited to 0.035% or less in accordance with aspects of the present invention. Preferably, the C content is 0.015% or less. More preferably, the C content is 0.0090% or less. Further preferably, the C content is 0.0075% or less. Desirably, carbon is contained in an amount of 0.005% or more to provide the desired strength.
- Silicon acts as a deoxidizing agent, and should be contained in an amount of 0.05% or more. A Si content of more than 0.5% deteriorates carbon dioxide corrosion resistance and hot workability. For this reason, the Si content is limited to 0.5% or less. The lower limit of Si content is preferably 0.10% or more, and the upper limit of Si content is preferably 0.30% or less.
- Manganese is an element that improves hot workability, and is contained in an amount of 0.05% or more. When contained in excess of 0.5%, the effect becomes saturated, and this leads to increased cost. For this reason, the Mn content is limited to 0.05 to 0.5%. Preferably, the Mn content is 0.40% or less.
- Phosphorus is an element that deteriorates carbon dioxide corrosion resistance, pitting corrosion resistance, and sulfide stress corrosion cracking resistance, and should be contained in as small an amount as possible in accordance with aspects of the present invention. However, an excessively small P content leads to increased manufacturing cost. The P content is therefore limited to 0.03% or less, a content that does not bring about an excessive loss of characteristics, and that is industrially feasible in terms of cost. Preferably, the P content is 0.02% or less.
- Sulfur is an element that seriously deteriorates hot workability, and should desirably be contained in as small an amount as possible. A S content of 0.005% or less enables pipe production using common procedures, and accordingly the S content is limited to 0.005% or less in accordance with aspects of the present invention. Preferably, the S content is 0.003% or less.
- Copper adds strength to the protective coating, and improves sulfide stress corrosion cracking resistance. However, a Cu content of more than 2.6% causes precipitation of CuS, and deteriorates hot workability. For this reason, the Cu content is limited to 2.6% or less. The lower limit of Cu content is preferably 0.5% or more, and the upper limit of Cu content is preferably 2.0% or less.
- When contained in an amount of 5.3% or more, nickel adds strength to the protective coating, and improves corrosion resistance. Nickel also forms a solid solution, and increases the steel strength in this content range. A Ni content of more than 7.3% makes the martensite phase unstable, and the strength deteriorates. For this reason, the Ni content is limited to 5.3 to 7.3%. Preferably, the Ni content is 5.7% or more, more preferably 6.0% or more.
- Chromium is an element that forms a protective coating, and improves the corrosion resistance. Chromium provides the corrosion resistance necessary for oil country tubular goods applications when contained in an amount of 11.8% or more. A Cr content or more than 14.5% facilitates ferrite generation, and the martensite phase cannot remain stable. For this reason, the Cr content is limited to 11.8 to 14.5%. The lower limit of Cr content is preferably 12.0% or more, and the upper limit of Cr content is preferably 13.5% or less.
- Aluminum acts as a deoxidizing agent. An Al content of 0.01% or more effectively provides this effect. Because an Al content of more than 0.1% adversely affects toughness, the Al content is limited to 0.1% or less in accordance with aspects of the present invention. Preferably, the Al content is 0.01 to 0.03%.
- Molybdenum is an element that improves the pitting corrosion resistance caused by Cl−. Molybdenum needs to be contained in an amount of 1.8% or more to obtain the corrosion resistance necessary for a severe corrosive environment. The effect becomes saturated when the Mo content is more than 3.0%. Molybdenum is also an expensive element, and increases the manufacturing cost. For these reasons, the Mo content is limited to 1.8 to 3.0%. The lower limit of Mo content is preferably 2.4% or more, and the upper limit of Mo content is preferably 2.9% or less.
- Vanadium is contained in an amount of desirably 0.01% or more, in order to improve steel strength by precipitation strengthening, and to improve sulfide stress corrosion cracking resistance. A V content of more than 0.2% deteriorates toughness, and the V content is limited to 0.2% or less in accordance with aspects of the present invention. The lower limit of V content is preferably 0.01% or more, and the upper limit of V content is preferably 0.08% or less.
- Nitrogen is an element that greatly improves the pitting corrosion resistance. However, a N content of more than 0.1% causes formation of various nitrides, and deteriorates toughness. For this reason, the N content is limited to 0.1% or less in accordance with aspects of the present invention. Preferably, the N content is 0.003% or more. The lower limit of N content is more preferably 0.004% or more, further preferably 0.005% or more. The upper limit of N content is more preferably 0.08% or less, further preferably 0.05% or less.
- In accordance with aspects of the present invention, C, Mn, Cr, Cu, Ni, Mo, W, Nb, N, and Ti are contained in the foregoing ranges, and these are contained so as to satisfy the formula (4), (5), or (6) with the formulae (1), (2), and (3) below. Formula (1) is a formula that correlates with the residual γ amount. By making the calculated value of formula (1) smaller, the residual austenite is reduced, and the hardness reduces, with the result that the sulfide stress corrosion cracking resistance improves. Formula (2) is a formula that correlates with the repassivation potential. Regeneration of the passivation coating occurs more easily, and repassivation improves by containing C, Mn, Cr, Cu, N Mo, W, Nb, N, and Ti in such amounts that formula (1) yields a value that satisfies the range of formula (4), (5), or (6), and by containing Mn, Cr, Cu, Ni, Mo, W, N, and Ti in such amounts that formula (2) yields a value that satisfies the range of formula (4), (5), or (6). Formula (3) is a formula that correlates with the pitting corrosion potential. Pitting corrosion, which becomes an origin of sulfide stress corrosion cracking, can be suppressed, and the sulfide stress corrosion cracking resistance greatly improves by containing C, Mn, Cr, Cu, Ni, Mo, W, N, and Ti in such amounts that formula (3) yields a value that satisfies the range of formula (4), (5), or (6). With the calculated value of formula (1) satisfying the range of formula (4), the hardness increases when the calculated value of formula (1) is 10 or more. However, regeneration of a passivation coating occurs more prominently, and the pitting corrosion can be suppressed more effectively when the calculated values of formulae (2) and (3) satisfy the range of formula (4). This improves the sulfide stress corrosion cracking resistance.
- The calculated value of formula (1) is preferably 5 to 45 in the following formula (4), and is preferably −5 to 5 in the following formula (5).
-
−109.37C+7.307Mn+6.399Cr+6.329Cu+11.343Ni−13.529Mo+1.276W+2.925Nb+196.775N−2.621Ti−120.307 Formula (1) -
−0.0278Mn+0.0892Cr+0.00567Ni+0.153Mo−0.0219W−1.984N+0.208Ti−1.83 Formula (2) -
−1.324C+0.0533Mn+0.0268Cr+0.0893Cu+0.00526Ni+0.0222Mo−0.0132W−0.473N−0.5Ti−0.514, Formula (3) - In the formulae (1) to (3), C, Mn, Cr, Cu, Ni, Mo, W, Nb, N, and Ti represent the content of each element in mass % (the content is 0 (zero) percent for elements that are not contained)
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−10≤formula (1)≤45, −0.25≤formula (2)≤−0.20, and 0.10≤formula (3)≤0.20 Formula (4) -
−10≤formula (1)≤5, −0.355≤formula (2)≤−0.25, and 0.0255≤formula (3)≤0.10 Formula (5) -
−10≤formula (1)≤−5, −0.39≤formula (2)≤−0.35, and −0.15≤formula (3)≤0.025 Formula (6) - In addition to the foregoing components, the composition contains the balance Fe and unavoidable impurities. The foregoing basic composition may further contain one or more selectable elements selected from Ti: 0.19% or less, Nb: 0.25% or less, W: 1.1% or less, and Co: 0.45% or less, as needed.
- Titanium and niobium form carbides, and can reduce the solid-solution carbon. This makes it possible to reduce hardness. Excessively high Ti and Nb contents may deteriorate toughness, and the Ti and Nb contents are limited to 0.19% or less for Ti, and 0.25% or less for Nb when containing these elements.
- Tungsten and cobalt are elements that improve the pitting corrosion resistance. However, excessively high W and Co contents may deteriorate toughness, and increase the material cost. For this reason, the W and Co contents are limited to 1.1% or less for W, and 0.45% or less for Co when containing these elements.
- A preferred method for producing the martensitic stainless steel seamless pipe for oil country tubular goods according to aspects of the present invention is described below.
- Aspects of the present invention use a steel pipe material of the composition described above. The method of production of the steel pipe material, or a seamless stainless steel pipe, is not particularly limited, and any known seamless steel pipe production method may be used.
- Preferably, a molten steel of the foregoing composition is made into steel using a steel making process such as by using a converter furnace, and formed into a steel pipe material, for example, a billet, using a method such as continuous casting, and ingot casting-slab rolling. The steel pipe material is heated, and hot worked using a known pipe manufacturing process, for example, such as the Mannesmann-plug mill process, and the Mannesmann-mandrel mill process to produce a seamless steel pipe of the foregoing composition.
- The process that follows the production of the steel pipe from the steel pipe material is not particularly limited. Preferably, the steel pipe is subjected to quenching, in which the steel pipe is heated to a temperature equal to or greater than the Ac3 transformation point, and air cooled to a cooling stop temperature of 100° C. or less at a cooling rate of 0.1° C./s or more, and this is followed by tempering at a temperature equal to or less than the Act transformation point.
- In accordance with aspects of the present invention, the steel pipe is subjected to quenching, in which the steel pipe is reheated to a temperature equal to or greater than the Ac3 transformation point, maintained for preferably at least 5 min, and air cooled to a cooling stop temperature of 100° C. or less. This produces a fine martensite phase, and high toughness. When the quenching heating temperature is less than the Ac3 transformation point, heating cannot be made in the single austenite phase region, and a sufficient martensite structure cannot be obtained in the subsequent cooling. In this case, the desired high strength cannot be obtained. For this reason, the quenching heating temperature is limited to a temperature equal to or greater than the Ac3 transformation point. Here, “air cooling” means a cooling rate of 0.1° C./s or more.
- Quenching of the steel pipe is followed by tempering. The tempering is a process by which the steel pipe is heated to a temperature equal to or less than the Ac1 transformation point, maintained for preferably at least 10 min, and air cooled. When the tempering temperature is higher than the Ac1 transformation point, the martensite phase precipitates after the tempering, and it is not possible to obtain the desired high toughness and excellent corrosion resistance. For this reason, the tempering temperature is limited to a temperature equal to or less than the Ac1 transformation point. The Ac3 transformation point (° C.), and the Ac1 transformation point (° C.) can be measured by a Formaster test, in which the test piece is given a heating and cooling temperature history, and the transformation point is detected from a small displacement due to expansion and contraction.
- Aspects of the present invention are further described below through Examples.
- Molten steels of the compositions shown in Table 1 were made into steel with a converter furnace, and cast into billets (steel pipe material) by continuous casting. The steel pipe material was then hot worked with a model seamless rolling machine, and air cooled (cooling rate of 0.5° C./s) to produce a seamless steel pipe measuring 83.8 mm in outer diameter and 12.7 mm in wall thickness.
- The seamless steel pipe was cut to obtain a test material, which was then subjected to quenching and tempering under the conditions shown in Table 2. A test piece for structure observation was collected from the quenched and tempered test material, and was polished, and measured for residual austenite (γ) amount by an X-ray diffraction method.
- Specifically, the diffraction X-ray integral intensities of the γ (220) plane and the α (211) plane were measured. The results were then converted using the following equation.
-
γ(Volume fraction)=100/(1+(IαRγ/IγRα)) - In the equation, Iα represents the integral intensity of α, Rα represents a crystallographic theoretical value for α, Iγ represents the integral intensity of γ, and Rγ represents a crystallographic theoretical value for γ.
- A strip specimen specified by API standard 5CT was collected from the quenched and tempered test material, and subjected to a tensile test according to the API specifications to determine its tensile characteristics (yield stress YS, tensile stress TS). The Ac3 point (° C.) and the Ac1 point (° C.) shown in Table 2 were measured by conducting a Formaster test for a test piece (measuring 4 mm in diameter ϕ×10 mm) collected from the quenched test material. Specifically, the test piece was heated to 500° C. at 5° C./s, maintained for 10 minutes after raising the temperature to 920° C. at 0.25° C./s, and cooled to room temperature at 2° C./s. The Ac3 point (° C.) and the Ac1 point (° C.) were found by detecting the expansion and contraction of the test piece with the temperature history.
- The SC test was conducted according to NACE TM0177, Method A. The test environment was created by using a 0.165 mass % NaCl test solution after adjusting the solution pH to 3.5 by addition of 0.41 g/L of CH3COONa and HCl, and the test was conducted under a hydrogen sulfide partial pressure of 0.1 MPa, and an applied stress equal to 90% of the yield stress.
- The results are presented in Table 2.
-
TABLE 1 Composition (mass %) Steel Ti, Nb, W, No. C Si Mn P S Cu Ni Cr Al Mo V N Co A 0.0088 0.205 0.11 0.013 0.0009 2.04 7.25 14.16 0.052 2.513 0.010 0.0471 Nb: 0.091 B 0.0075 0.200 0.45 0.015 0.0010 2.50 6.40 13.30 0.020 2.600 0.015 0.0085 Ti: 0.025, Nb: 0.08 C 0.0075 0.200 0.40 0.015 0.0010 2.40 6.25 13.20 0.020 2.550 0.015 0.0085 Ti: 0.05, Nb: 0.01 D 0.0075 0.200 0.40 0.015 0.0010 1.80 6.00 12.30 0.040 2.850 0.015 0.0075 Ti: 0.05, Nb: 0.005 E 0.0075 0.200 0.40 0.015 0.0010 0.40 5.70 12.00 0.040 2.550 0.015 0.0075 Ti: 0.05, Nb: 0.005 F 0.0075 0.200 0.40 0.015 0.0010 1.60 5.70 12.20 0.040 2.600 0.015 0.0075 Ti: 0.05, Nb: 0.005 G 0.0075 0.204 0.41 0.015 0.0009 2.40 6.24 13.22 0.020 2.553 0.015 0.0043 — H 0.0059 0.198 0.41 0.014 0.0010 1.81 5.99 12.32 0.042 2.850 0.014 0.0065 — I 0.0063 0.200 0.40 0.015 0.0009 0.41 5.71 12.02 0.043 2.552 0.014 0.0066 — J 0.0076 0.210 0.45 0.014 0.0011 2.51 6.40 13.30 0.020 2.605 0.015 0.0032 W: 0.16 K 0.0072 0.195 0.40 0.013 0.0010 0.39 5.71 12.00 0.042 2.550 0.016 0.0074 Co: 0.2 L 0.0069 0.189 0.42 0.014 0.0009 1.95 6.34 12.57 0.046 2.555 0.018 0.0070 — M 0.0080 0.192 0.11 0.013 0.0009 2.03 7.21 12.32 0.052 2.529 0.013 0.0067 — N 0.0060 0.195 0.10 0.012 0.0008 2.00 7.16 12.38 0.043 2.519 0.014 0.0064 — O 0.0064 0.216 0.21 0.018 0.0011 0.01 5.85 12.62 0.044 2.179 0.018 0.0056 — P 0.0072 0.223 0.20 0.014 0.0011 0.01 5.98 12.04 0.037 2.168 0.018 0.0076 — Composition (mass %) Steel Value of Value of Value of Applied No. formula (1) (*1) formula (2) (*2) formula (3) (*3) formula (*4) Remarks A 40.8 −0.238 0.114 (4) Compliant Example B 22.4 −0.234 0.155 (4) Compliant Example C 19.4 −0.245 0.126 (4) Compliant Example D 2.8 −0.278 0.054 (5) Compliant Example E −7.4 −0.353 −0.087 (6) Compliant Example F 0.8 −0.327 0.026 (5) Compliant Example G 18.7 −0.245 0.154 (4) Compliant Example H 3.0 −0.285 0.084 (5) Compliant Example I −7.0 −0.359 −0.059 (6) Compliant Example J 21.3 −0.231 0.168 (4) Compliant Example K −7.2 −0.363 −0.063 (6) Compliant Example L 13.5 −0.307 0.097 (4) Comparative Example M 20.2 −0.320 0.084 (4) Comparative Example N 20.0 −0.315 0.084 (4) Comparative Example O −0.7 −0.355 −0.096 (5) Comparative Example P −2.5 −0.411 −0.113 (6) Comparative Example The balance is Fe and unavoidable impurities (*1) Formula (1): −109.37C + 7.307Mn + 6.399Cr + 6.329Cu + 11.343Ni − 13.529Mo + 1.276W + 2.925Nb + 196.775N − 2.621Ti − 120.307 (*2) Formula (2): −0.0278Mn + 0.0892Cr + 0.00567Ni + 0.153Mo − 0.0219W − 1.984N + 0.208Ti − 1.83 (*3) Formula (3): −1.324C + 0.0533Mn + 0.0268Cr + 0.0893Cu + 0.00526Ni + 0.0222Mo − 0.0132W − 0.473N − 0.5Ti − 0.514 (*4) The formula used for determination Formula (4): −10 ≤ formula (1) ≤ 45, −0.25 ≤ formula (2) ≤ −0.20, and 0.10 ≤ formula (3) ≤ 0.20 Formula (5): −10 ≤ formula (1) ≤ 5, −0.35 ≤ formula (2) ≤ −0.25, and 0.025 ≤ formula (3) ≤ 0.10 Formula (6): −10 ≤ formula (1) ≤ −5, −0.39 ≤ formula (2) ≤ −0.35, and −0.15 ≤ formula (3) ≤ 0.025 -
TABLE 2 Tensile Quenching Tempering characteristics Heating Cooling Heating Structure Yield Tensile SSC Steel Ac3 temper- Holding stop Ac1 temper- Holding Residual stress stress resistance pipe Steel point ature time temperature point ature time γ (*1) YS TS test No. No. (° C.) (° C.) (min) Cooling (° C.) (° C.) (° C.) (min) (volume %) (MPa) (MPa) Cracking Remarks 1 A 750 920 20 Air 25 640 615 60 43.5 835 986 Absent Present cooling Example 2 B 750 920 20 Air 25 645 625 60 25.6 828 952 Absent Present cooling Example 3 C 755 920 20 Air 25 635 630 60 21.7 851 967 Absent Present cooling Example 4 D 750 920 20 Air 25 630 615 60 5.3 846 929 Absent Present cooling Example 5 E 755 920 20 Air 25 660 565 60 0.0 829 864 Absent Present cooling Example 6 F 745 920 20 Air 25 635 625 60 2.4 863 892 Absent Present cooling Example 7 G 755 920 20 Air 25 635 625 60 22.1 830 964 Absent Present cooling Example 8 H 750 920 20 Air 25 625 615 60 6.3 851 903 Absent Present cooling Example 9 I 755 920 20 Air 25 655 600 60 0.0 832 871 Absent Present cooling Example 10 J 750 920 20 Air 25 640 605 60 24.2 842 975 Absent Present cooling Example 11 K 750 920 20 Air 25 660 610 60 0.0 836 862 Absent Present cooling Example 12 L 755 990 20 Air 25 630 605 60 15.3 906 1009 Present Comparative cooling Example 13 M 720 920 20 Air 25 625 620 60 24.1 835 965 Present Comparative cooling Example 14 N 730 930 20 Air 25 620 600 60 23.5 859 958 Present Comparative cooling Example 15 O 740 920 20 Air 25 660 595 60 0.1 852 885 Present Comparative cooling Example 16 P 730 920 20 Air 25 630 590 60 0.0 847 880 Present Comparative cooling Example 17 A 750 730 20 Air 25 640 615 60 49.8 792 866 Present Comparative cooling Example 18 C 755 920 20 Air 25 635 650 60 34.6 772 811 Present Comparative cooling Example (*1) Residual γ: Residual austenite - The martensitic stainless steel seamless pipes of the present examples all had high strength with a yield stress of 758 MPa or more, and excellent SSC resistance that did not involve cracking even under the applied stress in the H2S environment. Comparative Examples outside the range of the present invention did not show excellent SSC resistance, though the desired levels of high strength were obtained.
Claims (4)
−109.37C+7.307Mn+6.399Cr+6.329Cu+11.343Ni−13.529Mo+1.276W+2.925Nb+196.775N−2.621Ti−120.307 Formula (1)
−0.0278Mn+0.0892Cr+0.00567Ni+0.153Mo−0.0219W−1.984N+0.208Ti−1.83 Formula (2)
−1.324C+0.0533Mn+0.0268Cr+0.0893Cu+0.00526Ni+0.0222Mo−0.0132W−0.473N−0.5Ti−0.514, Formula (3)
−10≤formula (1)≤45, −0.25≤formula (2)≤−0.20, and 0.10≤formula (3)≤0.20 Formula (4)
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US20200283866A1 (en) * | 2017-09-29 | 2020-09-10 | Jfe Steel Corporation | Martensitic stainless steel seamless pipe for oil country tubular goods, and method for manufacturing same |
US11286548B2 (en) | 2017-08-15 | 2022-03-29 | Jfe Steel Corporation | High-strength stainless steel seamless pipe for oil country tubular goods, and method for manufacturing same |
US11401570B2 (en) * | 2017-09-29 | 2022-08-02 | Jfe Steel Corporation | Martensitic stainless steel seamless pipe for oil country tubular goods, and method for manufacturing same |
US11970759B2 (en) | 2018-10-02 | 2024-04-30 | Nippon Steel Corporation | Martensitic stainless seamless steel pipe |
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JP6540920B1 (en) * | 2017-09-29 | 2019-07-10 | Jfeスチール株式会社 | Martensitic stainless steel seamless steel pipe for oil well pipe and method for producing the same |
MX2020012633A (en) * | 2018-05-25 | 2021-01-29 | Jfe Steel Corp | Martensitic stainless steel seamless steel tube for oil well pipes, and method for producing same. |
BR112020023438B1 (en) * | 2018-05-25 | 2024-01-09 | Jfe Steel Corporation | MARTENSITIC STAINLESS STEEL SEAMLESS STEEL TUBE FOR OIL WELL PIPES AND METHOD FOR PRODUCING THE SAME |
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JP7060109B2 (en) * | 2018-10-02 | 2022-04-26 | 日本製鉄株式会社 | Martensitic stainless steel seamless steel pipe |
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JP2003003243A (en) * | 2001-06-22 | 2003-01-08 | Sumitomo Metal Ind Ltd | High-strength martensitic stainless steel with excellent resistance to carbon dioxide gas corrosion and sulfide stress corrosion cracking |
AR042494A1 (en) | 2002-12-20 | 2005-06-22 | Sumitomo Chemical Co | HIGH RESISTANCE MARTENSITIC STAINLESS STEEL WITH EXCELLENT PROPERTIES OF CORROSION RESISTANCE BY CARBON DIOXIDE AND CORROSION RESISTANCE BY FISURES BY SULFIDE VOLTAGES |
JP4337712B2 (en) * | 2004-11-19 | 2009-09-30 | 住友金属工業株式会社 | Martensitic stainless steel |
JP5245238B2 (en) * | 2005-11-28 | 2013-07-24 | Jfeスチール株式会社 | Stainless steel pipe for oil well pipe excellent in pipe expandability and manufacturing method thereof |
JP4978073B2 (en) | 2006-06-16 | 2012-07-18 | Jfeスチール株式会社 | High toughness ultra-high strength stainless steel pipe for oil wells with excellent corrosion resistance and method for producing the same |
RU2416670C2 (en) | 2006-08-22 | 2011-04-20 | Сумитомо Метал Индастриз, Лтд. | Martensite stainless steel |
CN101397637B (en) * | 2007-09-29 | 2010-11-24 | 宝山钢铁股份有限公司 | 13Cr high anti-carbon dioxide and trace hydrogen sulfide corrosion tubing and casing steel and method for producing the same |
JP5487689B2 (en) | 2009-04-06 | 2014-05-07 | Jfeスチール株式会社 | Manufacturing method of martensitic stainless steel seamless pipe for oil well pipe |
JP5582307B2 (en) * | 2010-12-27 | 2014-09-03 | Jfeスチール株式会社 | High strength martensitic stainless steel seamless pipe for oil wells |
EP2947167B1 (en) * | 2013-01-16 | 2016-12-07 | JFE Steel Corporation | Stainless steel seamless tube for use in oil well and manufacturing process therefor |
JP6227664B2 (en) * | 2014-05-21 | 2017-11-08 | Jfeスチール株式会社 | High strength stainless steel seamless steel pipe for oil well and method for producing the same |
MX2019011443A (en) * | 2017-03-28 | 2019-11-01 | Nippon Steel Corp | Martensitic stainless steel material. |
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US11286548B2 (en) | 2017-08-15 | 2022-03-29 | Jfe Steel Corporation | High-strength stainless steel seamless pipe for oil country tubular goods, and method for manufacturing same |
US20200283866A1 (en) * | 2017-09-29 | 2020-09-10 | Jfe Steel Corporation | Martensitic stainless steel seamless pipe for oil country tubular goods, and method for manufacturing same |
US11401570B2 (en) * | 2017-09-29 | 2022-08-02 | Jfe Steel Corporation | Martensitic stainless steel seamless pipe for oil country tubular goods, and method for manufacturing same |
US11827949B2 (en) * | 2017-09-29 | 2023-11-28 | Jfe Steel Corporation | Martensitic stainless steel seamless pipe for oil country tubular goods, and method for manufacturing same |
US11970759B2 (en) | 2018-10-02 | 2024-04-30 | Nippon Steel Corporation | Martensitic stainless seamless steel pipe |
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