WO2020071217A1 - サワー環境での使用に適した鋼材 - Google Patents
サワー環境での使用に適した鋼材Info
- Publication number
- WO2020071217A1 WO2020071217A1 PCT/JP2019/037747 JP2019037747W WO2020071217A1 WO 2020071217 A1 WO2020071217 A1 WO 2020071217A1 JP 2019037747 W JP2019037747 W JP 2019037747W WO 2020071217 A1 WO2020071217 A1 WO 2020071217A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- steel material
- test
- steel
- ssc resistance
- temperature
- Prior art date
Links
Images
Classifications
-
- 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
- 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
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/78—Combined heat-treatments not provided for above
-
- 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
-
- 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
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
-
- 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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
-
- 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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
-
- 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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
-
- 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
-
- 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
- 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
-
- 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
- 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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- 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
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
-
- 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
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium 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
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium 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
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium 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
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium 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
- C22C38/30—Ferrous alloys, e.g. steel alloys containing chromium with cobalt
-
- 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
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
-
- 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
-
- 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
- C21D1/62—Quenching devices
- C21D1/63—Quenching devices for bath 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/002—Bainite
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/004—Dispersions; Precipitations
-
- 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 steel material, and more particularly, to a steel material suitable for use in a sour environment.
- oil wells With the deepening of oil wells and gas wells (hereinafter, oil and gas wells are simply referred to as “oil wells”), there is a demand for higher strength of steel materials for oil wells represented by steel pipes for oil wells. Specifically, steel pipes for oil wells of 80 ksi class (yield strength is less than 80 to 95 ksi, ie, less than 552 to 655 MPa) and 95 ksi class (yield strength is less than 95 to 110 ksi, ie, less than 655 to 758 MPa) are widely used.
- yield strength is less than 80 to 95 ksi, ie, less than 552 to 655 MPa
- 95 ksi class yield strength is less than 95 to 110 ksi, ie, less than 655 to 758 MPa
- sour environment means an environment that contains hydrogen sulfide and is acidified. Note that the sour environment may contain carbon dioxide. Oil well steel pipes used in such a sour environment are required to have not only high strength but also sulfide stress cracking resistance (Sulfide / Stress / Cracking resistance: hereinafter referred to as SSC resistance).
- SSC resistance sulfide stress cracking resistance
- Patent Document 1 JP-A-2000-256784
- Patent Document 2 JP-A-2000-297344
- Patent Document 5 JP-A-2005-350754.
- Patent Document 4 Japanese Patent Application Laid-Open No. 2012-26030
- Patent Document 5 International Publication No. 2010/150915
- the steel for a high-strength oil well disclosed in Patent Document 1 is, by weight%, C: 0.2 to 0.35%, Cr: 0.2 to 0.7%, Mo: 0.1 to 0.5%. , V: 0.1 to 0.3%.
- the total amount of precipitated carbide is 2 to 5% by weight, of which the proportion of MC type carbide is 8 to 40% by weight, and the prior austenite particle size is 11 or more in the particle size number specified by ASTM.
- Patent Document 1 describes that the high-strength oil well steel is excellent in toughness and sulfide stress corrosion cracking resistance.
- the oil well steel disclosed in Patent Document 2 is, by mass%, C: 0.15 to 0.3%, Cr: 0.2 to 1.5%, Mo: 0.1 to 1%, and V: 0 It is made of a low alloy steel containing 0.05 to 0.3% and Nb: 0.003 to 0.1%.
- the total amount of precipitated carbide is 1.5 to 4% by mass, and the proportion of MC type carbide to the total amount of carbide is 5 to 45% by mass, and the proportion of M 23 C 6 type carbide is t (Mm) and (200 / t) mass% or less.
- Patent Document 2 describes that the oil well steel is excellent in toughness and sulfide stress corrosion cracking resistance.
- the low alloy steel for oil country tubular goods disclosed in Patent Document 3 is, by mass%, C: 0.20 to 0.35%, Si: 0.05 to 0.5%, Mn: 0.05 to 1.0%. , P: 0.025% or less, S: 0.010% or less, Al: 0.005 to 0.10%, Cr: 0.1 to 1.0%, Mo: 0.5 to 1.0%, Ti: 0.002 to 0.05%, V: 0.05 to 0.3%, B: 0.0001 to 0.005%, N: 0.01% or less, O (oxygen): 0.01% Contains: The half width H and the hydrogen diffusion coefficient D (10 ⁇ 6 cm 2 / s) satisfy the expression (30H + D ⁇ 19.5). Patent Document 3 describes that the low-alloy oil country tubular steel has excellent SSC resistance even when it has a high yield strength (YS) of 861 MPa or more.
- YS yield strength
- the oil well steel pipe disclosed in Patent Document 4 is, by mass%, C: 0.18 to 0.25%, Si: 0.1 to 0.3%, Mn: 0.4 to 0.8%, P : 0.015% or less, S: 0.005% or less, Al: 0.01 to 0.1%, Cr: 0.3 to 0.8%, Mo: 0.5 to 1.0%, Nb: The composition contains 0.003 to 0.015%, Ti: 0.002 to 0.05%, and B: 0.003% or less, with the balance being Fe and unavoidable impurities.
- the microstructure of the steel pipe for an oil well is M 3 C or M 2 C having a tempered martensite phase as a main phase, an aspect ratio of 3 or less contained in a 20 ⁇ m ⁇ 20 ⁇ m region, and a long diameter of 300 nm or more when the carbide shape is elliptical. Is not more than 10, M 23 C 6 is less than 1% by mass%, and needle-like M 2 C is precipitated in the grains, and the amount of Nb precipitated as carbide having a size of 1 ⁇ m or more Is less than 0.005% by mass%.
- Patent Document 4 describes that the oil well steel pipe has excellent sulfide stress cracking resistance even if the yield strength is 862 MPa or more.
- the seamless steel pipe for oil wells disclosed in Patent Document 5 is 0.15 to 0.50% C, 0.1 to 1.0% Si, and 0.3 to 1.0% Mn in mass%.
- P 0.015% or less
- S 0.005% or less
- Al 0.01 to 0.1%
- N 0.01% or less
- Cr 0.1 to 1.7%
- Mo 0 0.4 to 1.1%
- V 0.01 to 0.12%
- Nb 0.01 to 0.08%
- B 0.0005 to 0.003%
- a solid solution of Mo Mo is contained in an amount of 0.40% or more, with the balance being Fe and unavoidable impurities.
- the microstructure of the above-described seamless steel pipe for oil wells has a tempered martensite phase as a main phase, prior austenite grains having a grain size number of 8.5 or more, and 0.06 mass% of substantially particulate M 2 C-type precipitates. It has a dispersed organization.
- Patent Document 5 describes that the above-mentioned seamless steel pipe for oil wells has both high strength of 110 ksi class and excellent sulfide stress cracking resistance.
- Patent Documents 1 to 5 even when the techniques disclosed in Patent Documents 1 to 5 are applied, in a steel material having a yield strength of 95 to 125 ksi class (655 to 965 MPa) (for example, a steel pipe for an oil well), excellent SSC resistance is obtained in a low-temperature sour environment. May not be obtained in a stable manner.
- An object of the present disclosure is to provide a steel material having a yield strength of 655 to 965 MPa (95 to 140 ksi, 95 to 125 ksi class) and having excellent SSC resistance in a normal temperature sour environment and a low temperature sour environment. .
- the steel material according to the present disclosure is, by mass%, C: 0.20 to 0.35%, Si: 0.05 to 1.00%, Mn: 0.01 to 1.00%, P: 0.025% or less. , S: 0.0100% or less, Al: 0.005 to 0.100%, Cr: 0.25 to 0.80%, Mo: 0.20 to 2.00%, Ti: 0.002 to 0.
- B 0.0001 to 0.0050%, N: 0.0020 to 0.0100%, O: 0.0100% or less, V: 0 to 0.60%, Nb: 0 to 0.030% , Ca: 0 to 0.0100%, Mg: 0 to 0.0100%, Zr: 0 to 0.0100%, Co: 0 to 0.50%, W: 0 to 0.50%, Ni: 0 to 100% 0.50%, Cu: 0 to 0.50%, and rare earth element: 0 to 0.0100%, the balance being Fe and impurities, satisfying the formula (1).
- the number density of precipitates having a circle equivalent diameter of 400 nm or more in the steel material is 0.150 / ⁇ m 2 or less.
- the yield strength is 655 to 965 MPa.
- the dislocation density ⁇ is 7.0 ⁇ 10 14 m ⁇ 2 or less.
- the dislocation density ⁇ is 1.4 ⁇ 10 14 m ⁇ 2 or less.
- the dislocation density ⁇ is more than 1.4 ⁇ 10 14 to less than 3.0 ⁇ 10 14 m ⁇ 2 .
- the dislocation density ⁇ is 3.0 ⁇ 10 14 to 7.0 ⁇ 10 14 m ⁇ 2 .
- the steel material according to the present disclosure has a yield strength of 655 to 965 MPa (95 to 125 ksi class) and has excellent SSC resistance in a normal temperature sour environment and a low temperature sour environment.
- FIG. 1 is a diagram showing the relationship between Fn1 and the number density of coarse precipitates in a steel material having a yield strength of 95 ksi class.
- FIG. 2 is a diagram showing a relationship between Fn1 and the number density of coarse precipitates in a steel material having a yield strength of 110 ksi class.
- FIG. 3 is a diagram showing a relationship between Fn1 and the number density of coarse precipitates in a steel material having a yield strength of 125 ksi class.
- the present inventors have developed a method of improving SSC resistance in a normal temperature sour environment and a low temperature sour environment while maintaining a yield strength of 655 to 965 MPa (95 to 125 ksi class) in a steel material supposed to be used in a low temperature sour environment.
- a yield strength of 655 to 965 MPa 95 to 125 ksi class
- the present inventors have found that the chemical composition of the steel material is expressed in terms of mass%: C: 0.20 to 0.35%, Si: 0.05 to 1.00%, Mn: 0.01 to 1.00.
- the yield strength (Yield Strength) of the steel material is increased.
- dislocations can occlude hydrogen. Therefore, if the dislocation density of the steel material increases, the amount of hydrogen absorbed by the steel material may increase.
- the SSC resistance of the steel material decreases even though high strength is obtained. Therefore, in order to achieve both a yield strength of 95 to 125 ksi class and excellent SSC resistance, it is not preferable to use a dislocation density to increase the strength.
- the present inventors first studied reducing the dislocation density of the steel material in consideration of enhancing the SSC resistance. Specifically, the present inventors first focused on a yield strength of 655 to less than 758 MPa (95 ksi class), and considered to improve the SSC resistance by reducing the dislocation density. As a result, in the steel having the above-described chemical composition, if the dislocation density of the steel is reduced to 1.4 ⁇ 10 14 (m ⁇ 2 ) or less, the SSC resistance of the steel is improved while maintaining the yield strength of 95 ksi class. I found that it could be enhanced.
- the present inventors have also studied the case where the yield strength is different. Specifically, the present inventors have paid attention to the yield strength of 758 to less than 862 MPa (110 ksi class), and considered to improve the SSC resistance by reducing the dislocation density. As a result, it has been found that in a steel having the above-described chemical composition, if the dislocation density of the steel is reduced to less than 3.0 ⁇ 10 14 (m ⁇ 2 ), the SSC resistance of the steel may be improved. .
- a steel material having the above-described chemical composition and having a dislocation density of more than 1.4 ⁇ 10 14 to less than 3.0 ⁇ 10 14 (m ⁇ 2 ) while maintaining a 110 ksi-class yield strength, SSC resistance may be improved.
- the present inventors have further focused on the yield strength of 862 to 965 MPa (125 ksi class), and considered to reduce the dislocation density and increase the SSC resistance.
- the SSC resistance of the steel material may be improved.
- the yield strength of the 125 ksi class is maintained, and There is a possibility that the SSC property can be improved.
- the dislocation density of the steel material is reduced to 1.4 ⁇ 10 14 (m ⁇ 2 ) or less, and a yield of 110 ksi class is obtained.
- the dislocation density of the steel material is to be reduced from more than 1.4 ⁇ 10 14 to less than 3.0 ⁇ 10 14 (m ⁇ 2 ), and in order to obtain a 125 ksi-class yield strength, If the dislocation density of is reduced to 3.0 ⁇ 10 14 to 7.0 ⁇ 10 14 (m ⁇ 2 ), there is a possibility that the SSC resistance of the steel material in a normal temperature sour environment and a low temperature sour environment can be improved.
- the present inventors believe that the reason why the steel material in which a large number of coarse precipitates are precipitated does not exhibit excellent SSC resistance in a low-temperature sour environment is as follows. As described above, the sulfide stress cracking susceptibility of the steel material increases in the low temperature sour environment as compared with the normal temperature sour environment. Therefore, in the case of a steel material having the above-described chemical composition, in a low-temperature sour environment, stress concentration at an interface between a coarse precipitate and a base material becomes more apparent than in a normal-temperature sour environment, and it is considered that SSC may occur. .
- the present inventors focused on a precipitate having an equivalent circle diameter of 400 nm or more as a coarse precipitate, and studied a method of reducing the precipitate having an equivalent circle diameter of 400 nm or more.
- the present inventors have found that most of the precipitates having an equivalent circle diameter of 400 nm or more (hereinafter, also referred to as “coarse precipitates”) are carbides. That is, there is a possibility that coarse precipitates can be reduced by adjusting the contents of Cr, Mo, Ti, and V, which are alloy elements that easily form carbides. Therefore, the present inventors have studied in detail the relationship between the Cr, Mo, Ti, and V contents and the number density of coarse precipitates in a steel material having the above-described chemical composition.
- FIG. 1 is a diagram showing the relationship between Fn1 and the number density of coarse precipitates in a steel material having a yield strength of 95 ksi class.
- FIG. 1 shows a steel material having a yield strength of less than 655 to 758 MPa, a chemical composition within the range of the present embodiment, and a dislocation density of 1.4 ⁇ 10 14 (m ⁇ 2 ) or less among the examples described later.
- Fn1 is 3.00 or less for a steel material having the above-described chemical composition, a dislocation density of 1.4 ⁇ 10 14 (m ⁇ 2 ) or less, and a 95 ksi-class yield strength.
- the number density of coarse precipitates was 0.150 / ⁇ m 2 or less.
- FIG. 2 is a diagram showing a relationship between Fn1 and the number density of coarse precipitates in a steel material having a yield strength of 110 ksi class.
- FIG. 2 shows that, among the examples described later, the yield strength is less than 758 to 862 MPa, the chemical composition is within the range of the present embodiment, and the dislocation density is more than 1.4 ⁇ 10 14 to 3.0 ⁇ 10 14.
- a steel material of less than (m ⁇ 2 ) is prepared using Fn1, the number density of coarse precipitates obtained by the method described below (pieces / ⁇ m 2 ), and the evaluation result of the low-temperature SSC resistance test described below.
- “ ⁇ ” indicates a steel material having a good low-temperature SSC resistance test result.
- “ ⁇ ” in FIG. 2 indicates a steel material in which the result of the low-temperature SSC resistance test was not good.
- FIG. 3 is a diagram showing a relationship between Fn1 and the number density of coarse precipitates in a steel material having a yield strength of 125 ksi class.
- FIG. 3 shows that, among the examples described later, the yield strength was 862 to 965 MPa, the chemical composition was within the range of the present embodiment, and the dislocation density was 3.0 ⁇ 10 14 to 7.0 ⁇ 10 14 (m -2 )
- a steel material was prepared using Fn1, the number density of coarse precipitates obtained by the method described later (pieces / ⁇ m 2 ), and the evaluation result of the low-temperature SSC resistance test described later.
- “ ⁇ ” indicates a steel material having a good low-temperature SSC resistance test result.
- “ ⁇ ” in FIG. 3 indicates a steel material in which the result of the low-temperature SSC resistance test was not good.
- the dislocation density is reduced according to the yield strength (95 ksi class, 110 ksi class, and 125 ksi class) having the above-described chemical composition and Fn1 is set to 3.00 or less.
- the number density of precipitates having an equivalent circle diameter of 400 nm or more contained in the steel material is 0.150 / ⁇ m 2 or less.
- the term “equivalent circle diameter” means the diameter of a circle when the area of the observed precipitate is converted into a circle having the same area in the visual field plane in the structure observation.
- the steel material according to the present embodiment completed on the basis of the above findings is, by mass%, C: 0.20 to 0.35%, Si: 0.05 to 1.00%, and Mn: 0.01 to 1.00. %, P: 0.025% or less, S: 0.0100% or less, Al: 0.005 to 0.100%, Cr: 0.25 to 0.80%, Mo: 0.20 to 2.00% , Ti: 0.002 to 0.050%, B: 0.0001 to 0.0050%, N: 0.0020 to 0.0100%, O: 0.0100% or less, V: 0 to 0.60% , Nb: 0 to 0.030%, Ca: 0 to 0.0100%, Mg: 0 to 0.0100%, Zr: 0 to 0.0100%, Co: 0 to 0.50%, W: 0 to 0.50%, Ni: 0 to 0.50%, Cu: 0 to 0.50%, and rare earth element: 0 to 0.0100%, the balance being Fe Made fine impurities, having a chemical composition
- the number density of precipitates having a circle equivalent diameter of 400 nm or more in the steel material is 0.150 / ⁇ m 2 or less.
- the yield strength is 655 to 965 MPa.
- the dislocation density ⁇ is 7.0 ⁇ 10 14 m ⁇ 2 or less.
- the dislocation density ⁇ is 1.4 ⁇ 10 14 m ⁇ 2 or less.
- the dislocation density ⁇ is more than 1.4 ⁇ 10 14 to less than 3.0 ⁇ 10 14 m ⁇ 2 .
- the dislocation density ⁇ is 3.0 ⁇ 10 14 to 7.0 ⁇ 10 14 m ⁇ 2 .
- the steel material is not particularly limited, but is, for example, a steel pipe or a steel plate.
- the steel material according to the present embodiment exhibits a yield strength of 655 to 965 MPa (95 to 125 ksi class) and excellent SSC resistance in a normal temperature sour environment and a low temperature sour environment.
- the chemical composition may contain at least one selected from the group consisting of V: 0.01 to 0.60% and Nb: 0.002 to 0.030%.
- the chemical composition is one or two selected from the group consisting of Ca: 0.0001 to 0.0100%, Mg: 0.0001 to 0.0100%, and Zr: 0.0001 to 0.0100%. It may contain more than one species.
- the chemical composition may contain one or more selected from the group consisting of Co: 0.02 to 0.50% and W: 0.02 to 0.50%.
- the chemical composition may include one or more selected from the group consisting of Ni: 0.01 to 0.50% and Cu: 0.01 to 0.50%.
- the above chemical composition may contain rare earth elements: 0.0001 to 0.0100%.
- the steel material may have a yield strength of 655 to less than 758 MPa and a dislocation density ⁇ of 1.4 ⁇ 10 14 m ⁇ 2 or less.
- the steel material may have a yield strength of less than 758 to 862 MPa and a dislocation density ⁇ of more than 1.4 ⁇ 10 14 to less than 3.0 ⁇ 10 14 m ⁇ 2 .
- the steel material may have a yield strength of 862 to 965 MPa and a dislocation density ⁇ of 3.0 ⁇ 10 14 to 7.0 ⁇ 10 14 m ⁇ 2 .
- the steel material may be a steel pipe for an oil well.
- the steel pipe for an oil well may be a steel pipe for a line pipe or an oil well pipe.
- the shape of the oil well steel pipe is not limited, and may be, for example, a seamless steel pipe or a welded steel pipe.
- the oil country tubular goods are, for example, steel pipes used for casing and tubing applications.
- the oil well steel pipe according to the present embodiment is preferably a seamless steel pipe. If the steel pipe for an oil well according to the present embodiment is a seamless steel pipe, it has a yield strength of 655 to 965 MPa (95 to 125 ksi class), and has a normal temperature sour environment and a low temperature sour environment even if the wall thickness is 15 mm or more. Has excellent SSC resistance.
- “normal temperature sour environment” means a sour environment of 10 to 30 ° C.
- low temperature sour environment means a sour environment below 10 ° C.
- Carbon (C) enhances the hardenability of the steel material and increases the yield strength of the steel material. C further promotes spheroidization of carbides during tempering during the manufacturing process, and enhances the SSC resistance of the steel material. If the carbides are dispersed, the yield strength of the steel material further increases. If the C content is too low, these effects cannot be obtained. On the other hand, if the C content is too high, the toughness of the steel material decreases, and quenching tends to occur. If the C content is too high, coarse carbides are further generated in the steel material, and the SSC resistance of the steel material is reduced. Therefore, the C content is 0.20 to 0.35%. A preferred lower limit of the C content is 0.22%, more preferably 0.24%. The preferable upper limit of the C content is 0.33%, more preferably 0.32%, further preferably 0.30%, and further preferably 0.29%.
- Si 0.05-1.00% Silicon (Si) deoxidizes steel. If the Si content is too low, this effect cannot be obtained. On the other hand, if the Si content is too high, the SSC resistance of the steel material decreases. Therefore, the Si content is 0.05 to 1.00%.
- the lower limit of the preferred Si content is 0.15%, more preferably 0.20%.
- a preferred upper limit of the Si content is 0.85%, more preferably 0.70%.
- Mn 0.01-1.00%
- Manganese (Mn) deoxidizes steel. Mn further enhances the hardenability of the steel material and increases the yield strength of the steel material. If the Mn content is too low, these effects cannot be obtained. On the other hand, if the Mn content is too high, Mn segregates at the grain boundaries together with impurities such as P and S. In this case, the SSC resistance of the steel material decreases. Therefore, the Mn content is 0.01 to 1.00%.
- a preferred lower limit of the Mn content is 0.02%, more preferably 0.03%.
- the preferred upper limit of the Mn content is 0.90%, more preferably 0.80%.
- Phosphorus (P) is an impurity. That is, the P content is more than 0%. P segregates at the grain boundaries and lowers the SSC resistance of the steel material. Therefore, the P content is 0.025% or less.
- the preferable upper limit of the P content is 0.020%, and more preferably 0.015%.
- the P content is preferably as low as possible. However, an extreme decrease in the P content greatly increases the manufacturing cost. Therefore, in consideration of industrial production, the lower limit of the P content is preferably 0.0001%, more preferably 0.0003%, further preferably 0.001%, and still more preferably 0.002%. It is.
- S 0.0100% or less Sulfur (S) is an impurity. That is, the S content is more than 0%. S segregates at the grain boundaries and lowers the SSC resistance of the steel material. Therefore, the S content is 0.0100% or less.
- a preferred upper limit of the S content is 0.0050%, more preferably 0.0030%.
- the S content is preferably as low as possible. However, an extreme reduction in the S content greatly increases the manufacturing cost. Therefore, in consideration of industrial production, a preferable lower limit of the S content is 0.0001%, and more preferably 0.0003%.
- Al 0.005 to 0.100%
- Aluminum (Al) deoxidizes steel. If the Al content is too low, this effect cannot be obtained, and the SSC resistance of the steel material decreases. On the other hand, if the Al content is too high, coarse oxide-based inclusions are generated, and the SSC resistance of the steel material decreases. Therefore, the Al content is 0.005 to 0.100%.
- a preferred lower limit of the Al content is 0.015%, more preferably 0.020%.
- the preferable upper limit of the Al content is 0.080%, more preferably 0.060%.
- the “Al” content referred to in the present specification means “acid-soluble Al”, that is, the content of “sol. Al”.
- Chromium (Cr) enhances the hardenability of the steel material and increases the yield strength of the steel material. Cr further increases tempering softening resistance and enables high temperature tempering. As a result, the SSC resistance of the steel material increases. If the Cr content is too low, these effects cannot be obtained. On the other hand, if the Cr content is too high, coarse carbides are generated in the steel material, and the SSC resistance of the steel material decreases. Therefore, the Cr content is 0.25 to 0.80%.
- a preferred lower limit of the Cr content is 0.30%, more preferably 0.35%, and still more preferably 0.40%.
- a preferred upper limit of the Cr content is 0.78%, more preferably 0.76%.
- Mo 0.20 to 2.00% Molybdenum (Mo) enhances the hardenability of the steel material and increases the yield strength of the steel material. Mo further generates fine carbides and increases the tempering softening resistance of the steel material. As a result, the SSC resistance of the steel material increases. If the Mo content is too low, these effects cannot be obtained. On the other hand, if the Mo content is too high, the above effect is saturated. Therefore, the Mo content is 0.20 to 2.00%.
- a preferred lower limit of the Mo content is 0.30%, more preferably 0.40%, further preferably 0.50%, further preferably 0.60%, and still more preferably 0.61%. %.
- the preferable upper limit of the Mo content is 1.80%, more preferably 1.70%, and still more preferably 1.50%.
- Titanium (Ti) forms nitrides and refines crystal grains by a pinning effect. This increases the yield strength of the steel material. If the Ti content is too low, this effect cannot be obtained. On the other hand, if the Ti content is too high, the Ti nitride becomes coarse, and the SSC resistance of the steel material decreases. Therefore, the Ti content is 0.002 to 0.050%. A preferred lower limit of the Ti content is 0.003%, more preferably 0.005%. The preferable upper limit of the Ti content is 0.030%, and more preferably 0.020%.
- B 0.0001 to 0.0050% Boron (B) forms a solid solution in steel to enhance the hardenability of the steel material and increase the strength of the steel material. If the B content is too low, this effect cannot be obtained. On the other hand, if the B content is too high, coarse nitrides are generated, and the SSC resistance of the steel material decreases. Therefore, the B content is 0.0001 to 0.0050%.
- a preferred lower limit of the B content is 0.0003%, more preferably 0.0007%.
- the preferable upper limit of the B content is 0.0030%, more preferably 0.0025%, and still more preferably 0.0015%.
- N 0.0020 to 0.0100% Nitrogen (N) combines with Ti to form fine nitrides and refines crystal grains. If the N content is too low, this effect cannot be obtained. On the other hand, if the N content is too high, N forms a coarse nitride, and the SSC resistance of the steel material decreases. Therefore, the N content is 0.0020 to 0.0100%. A preferred lower limit of the N content is 0.0022%. The preferable upper limit of the N content is 0.0050%, more preferably 0.0045%.
- Oxygen (O) is an impurity. That is, the O content is more than 0%. O forms a coarse oxide and reduces the corrosion resistance of the steel material. Therefore, the O content is 0.0100% or less.
- the preferable upper limit of the O content is 0.0050%, more preferably 0.0030%, and further preferably 0.0020%.
- the O content is preferably as low as possible. However, an extreme decrease in the O content greatly increases the production cost. Therefore, in consideration of industrial production, a preferable lower limit of the O content is 0.0001%, and more preferably 0.0003%.
- the balance of the chemical composition of the steel material according to the present embodiment consists of Fe and impurities.
- the impurities are ores as raw materials, scrap, or are mixed from the production environment or the like when industrially producing the steel material, and are in a range that does not adversely affect the steel material according to the present embodiment. Means acceptable.
- the chemical composition of the above-mentioned steel material may further contain one or more selected from the group consisting of V and Nb instead of a part of Fe. These elements are all optional elements and enhance the SSC resistance and the yield strength of the steel material.
- V 0 to 0.60%
- Vanadium (V) is an optional element and may not be contained. That is, the V content may be 0%.
- V combines with C and / or N to form carbide, nitride or carbonitride (hereinafter referred to as “carbonitride or the like”).
- Carbonitrides and the like refine the substructure of the steel material by the pinning effect and increase the SSC resistance of the steel material.
- V also forms fine carbides during tempering. The fine carbides increase the tempering softening resistance of the steel and increase the yield strength of the steel. If V is contained even a little, these effects can be obtained to some extent. However, if the V content is too high, the toughness of the steel material decreases.
- the V content is 0 to 0.60%.
- a preferred lower limit of the V content is more than 0%, more preferably 0.01%, further preferably 0.02%, further preferably 0.04%, and still more preferably 0.06%. And more preferably 0.08%.
- the preferable upper limit of the V content is 0.40%, more preferably 0.30%, and further preferably 0.20%.
- Niobium (Nb) is an optional element and need not be contained. That is, the Nb content may be 0%. When contained, Nb forms a carbonitride or the like. Carbonitrides and the like refine the substructure of the steel material by the pinning effect, and enhance the SSC resistance of the steel material. Nb further combines with C to form fine carbides. As a result, the yield strength of the steel material increases. These effects can be obtained to some extent if Nb is contained at all. However, if the Nb content is too high, carbonitrides and the like are excessively generated, and the SSC resistance of the steel material decreases. Therefore, the Nb content is 0 to 0.030%. A preferable lower limit of the Nb content is more than 0%, more preferably 0.002%, further preferably 0.003%, and further preferably 0.007%. The preferable upper limit of the Nb content is 0.025%, more preferably 0.020%.
- the chemical composition of the above-mentioned steel material may further contain one or more selected from the group consisting of Ca, Mg and Zr, instead of part of Fe. These elements are all optional elements and enhance the SSC resistance of the steel material.
- Ca 0 to 0.0100%
- Calcium (Ca) is an optional element and may not be contained. That is, the Ca content may be 0%. When contained, Ca renders S in the steel material harmless as a sulfide and enhances the SSC resistance of the steel material. This effect can be obtained to some extent if Ca is contained at all. However, if the Ca content is too high, the oxides in the steel material are coarsened, and the SSC resistance of the steel material is reduced. Therefore, the Ca content is 0 to 0.0100%.
- a preferable lower limit of the Ca content is more than 0%, more preferably 0.0001%, further preferably 0.0003%, further preferably 0.0006%, and still more preferably 0.0010%. It is.
- the preferable upper limit of the Ca content is 0.0040%, more preferably 0.0030%, and further preferably 0.0025%.
- Mg 0 to 0.0100%
- Magnesium (Mg) is an optional element and may not be contained. That is, the Mg content may be 0%. When contained, Mg renders S in the steel material harmless as a sulfide and enhances the SSC resistance of the steel material. This effect can be obtained to some extent if Mg is contained at all. However, if the Mg content is too high, the oxides in the steel material are coarsened, and the SSC resistance of the steel material is reduced. Therefore, the Mg content is 0 to 0.0100%.
- a preferable lower limit of the Mg content is more than 0%, more preferably 0.0001%, further preferably 0.0003%, further preferably 0.0006%, and still more preferably 0.0010%. It is.
- the preferable upper limit of the Mg content is 0.0040%, more preferably 0.0030%, and further preferably 0.0025%.
- Zr Zirconium
- Zr Zirconium
- the Zr content may be 0%.
- Zr renders S in the steel material harmless as a sulfide and enhances the SSC resistance of the steel material. This effect can be obtained to some extent if Zr is contained at all.
- the Zr content is 0 to 0.0100%.
- a preferred lower limit of the Zr content is more than 0%, more preferably 0.0001%, further preferably 0.0003%, further preferably 0.0006%, and still more preferably 0.0010%. It is.
- the preferable upper limit of the Zr content is 0.0040%, more preferably 0.0030%, and further preferably 0.0025%.
- the total content is preferably 0.0100% or less, and is preferably 0.0050% or less. Is more preferred.
- the chemical composition of the above-mentioned steel material may further contain one or more selected from the group consisting of Co and W instead of a part of Fe.
- Each of these elements is an optional element and forms a protective corrosion film in a sour environment to suppress hydrogen intrusion. Thereby, these elements increase the SSC resistance of the steel material.
- Co is an optional element and need not be contained. That is, the Co content may be 0%. When present, Co forms a protective corrosion coating in the sour environment and inhibits hydrogen ingress. As a result, the SSC resistance of the steel material increases. This effect can be obtained to some extent if Co is contained even a little. However, if the Co content is too high, the hardenability of the steel material decreases, and the yield strength of the steel material decreases. Therefore, the Co content is 0 to 0.50%.
- a preferable lower limit of the Co content is more than 0%, more preferably 0.02%, further preferably 0.03%, and further preferably 0.05%.
- a preferred upper limit of the Co content is 0.45%, and more preferably 0.40%.
- W 0 to 0.50%
- Tungsten (W) is an optional element and need not be contained. That is, the W content may be 0%. When included, W forms a protective corrosion coating in the sour environment and inhibits hydrogen ingress. As a result, the SSC resistance of the steel material increases. This effect can be obtained to some extent if W is contained at all. However, if the W content is too high, coarse carbides are generated in the steel material, and the SSC resistance of the steel material decreases. Therefore, the W content is 0 to 0.50%.
- a preferable lower limit of the W content is more than 0%, more preferably 0.02%, further preferably 0.03%, and further preferably 0.05%.
- a preferred upper limit of the W content is 0.45%, more preferably 0.40%.
- the chemical composition of the above-mentioned steel material may further contain one or more kinds selected from the group consisting of Ni and Cu instead of part of Fe.
- Each of these elements is an optional element and enhances the hardenability of steel.
- Nickel (Ni) is an optional element and need not be contained. That is, the Ni content may be 0%. When contained, Ni enhances the hardenability of the steel material and increases the yield strength of the steel material. This effect can be obtained to some extent if Ni is contained at all. However, if the Ni content is too high, local corrosion is promoted, and the SSC resistance of the steel material decreases. Therefore, the Ni content is 0 to 0.50%.
- a preferred lower limit of the Ni content is more than 0%, more preferably 0.01%, and still more preferably 0.02%.
- the preferable upper limit of the Ni content is 0.10%, more preferably 0.08%, and further preferably 0.06%.
- Cu 0 to 0.50% Copper (Cu) is an optional element and need not be contained. That is, the Cu content may be 0%. When contained, Cu enhances the hardenability of the steel material and increases the yield strength of the steel material. This effect can be obtained to some extent as long as Cu is contained. However, if the Cu content is too high, the hardenability of the steel material becomes too high, and the SSC resistance of the steel material decreases. Therefore, the Cu content is 0 to 0.50%.
- a preferable lower limit of the Cu content is more than 0%, more preferably 0.01%, further preferably 0.02%, and further preferably 0.05%.
- a preferred upper limit of the Cu content is 0.35%, more preferably 0.25%.
- the chemical composition of the above-mentioned steel material may further contain a rare earth element instead of a part of Fe.
- the rare earth element (REM) is an optional element and may not be contained. That is, the REM content may be 0%. When contained, the REM renders S in the steel material harmless as sulfide, and enhances the SSC resistance of the steel material. REM further combines with P in the steel material to suppress segregation of P at the grain boundaries. Therefore, a decrease in the SSC resistance of the steel material due to the segregation of P is suppressed. These effects can be obtained to some extent if REM is contained at all. However, if the REM content is too high, the oxide becomes coarse and the SSC resistance of the steel material decreases. Therefore, the REM content is 0-0.0100%. A preferred lower limit of the REM content is more than 0%, more preferably 0.0001%, further preferably 0.0003%, and still more preferably 0.0006%. A preferred upper limit of the REM content is 0.0040%, more preferably 0.0025%.
- REM refers to scandium having an atomic number of 21; yttrium (Y) having an atomic number of 39; and lanthanide, lanthanum having an atomic number of 57 (La) to lutetium having an atomic number of 71 (Lu). ) Is one or more elements selected from the group consisting of: Further, the REM content in this specification is the total content of these elements.
- the steel material according to the present embodiment further satisfies Expression (1). 5 ⁇ Cr ⁇ Mo ⁇ 2 ⁇ (V + Ti) ⁇ 3.00 (1)
- the content (% by mass) of the corresponding element is substituted for the element symbol in the formula (1). If the corresponding element is not contained, “0” is substituted for the element symbol.
- the steel material according to the present embodiment has the above-described chemical composition, reduces the dislocation density according to the yield strength (95 to 125 ksi class) to be obtained, and has Fn1 of 3.00 or less.
- the steel material according to the present embodiment exhibits excellent SSC resistance even in a low temperature sour environment.
- the preferred upper limit of Fn1 is 2.90, and more preferably 2.87.
- the lower limit of Fn1 is not particularly limited, Fn1 is substantially ⁇ 2.05 or more in the above range of the chemical composition.
- the number density of precipitates having an equivalent circle diameter of 400 nm or more in the steel material is 0.150 / ⁇ m 2 or less.
- a precipitate having a circle equivalent diameter of 400 nm or more is also referred to as a “coarse precipitate”.
- the term “equivalent circle diameter” refers to the diameter of a circle when the area of the observed precipitate is converted into a circle having the same area in the visual field plane in the structure observation.
- the steel material according to the present embodiment As described above, in the steel material according to the present embodiment, as a result of reducing the dislocation density in accordance with the yield strength (95 to 125 ksi class) to be obtained, a large number of coarse precipitates may precipitate in the steel material. In this case, especially in a low-temperature sour environment, excellent SSC resistance cannot be obtained. Therefore, the steel material according to the present embodiment reduces the number density of coarse precipitates and increases the SSC resistance in addition to the above-described chemical composition and the above-described dislocation density.
- the number density of coarse precipitates in the steel material is 0.150 / ⁇ m 2 or less. If the number density of coarse precipitates in the steel material is 0.150 / ⁇ m 2 or less, the steel material has excellent SSC resistance even in a low temperature sour environment, provided that the other requirements of the present embodiment are satisfied. Is shown.
- a preferred upper limit of the number density of coarse precipitates is 0.145 / ⁇ m 2 , and more preferably 0.140 / ⁇ m 2 .
- the lower limit of the number density of the coarse precipitate is not particularly limited. That is, the number density of the coarse precipitates may be 0 / ⁇ m 2 .
- the number density of the coarse precipitate of the steel material according to the present embodiment can be obtained by the following method. From the steel material according to the present embodiment, a micro test piece for producing an extraction replica is collected. When the steel material is a steel plate, a micro test piece is collected from the center of the thickness. When the steel material is a steel pipe, a micro test piece is collected from the center of the wall thickness. After mirror polishing the surface of the micro test piece, the micro test piece is immersed in a 3% nital etching solution for 10 minutes to corrode the surface. The corroded surface is covered with a carbon deposition film. The micro test piece whose surface is covered with the deposited film is immersed in a 5% nital etching solution for 20 minutes. The deposited film is peeled off from the immersed micro test piece. The deposited film peeled off from the micro test piece is washed with ethanol, scooped with a sheet mesh, and dried.
- the deposited film (replica film) is observed with a transmission electron microscope (TEM). Specifically, three arbitrary locations are specified. Observation magnification is set to 10,000 times and the accelerating voltage is set to 200 kV for the three specified places, and a photographic image is generated. Each field of view is, for example, 8 ⁇ m ⁇ 8 ⁇ m. Image processing is performed on the photographic image of each visual field to identify the precipitate in each visual field. Precipitates can be identified from the contrast. The equivalent circle diameter of each specified precipitate is determined by image processing.
- a precipitate (coarse precipitate) having a circle equivalent diameter of 400 nm or more is specified.
- the total number of coarse precipitates specified in three visual fields is determined.
- the number density of coarse precipitates (number / ⁇ m 2 ) can be determined based on the obtained total number of coarse precipitates and the total area of three visual fields.
- the upper limit of the equivalent circle diameter of the coarse precipitate is not particularly limited, but the detection limit value is determined from the observation visual field. For example, when the observation visual field is 8 ⁇ m ⁇ 8 ⁇ m, the detection limit value of the circle equivalent diameter of the coarse precipitate is 8000 nm. In this case, the equivalent circle diameter of the coarse precipitate is substantially 400 to 8000 nm.
- the yield strength of the steel according to the present embodiment is 655 to 965 MPa (95 to 125 ksi class).
- the yield strength as used herein means a 0.2% offset proof stress obtained in a tensile test.
- the yield strength of the steel material according to the present embodiment is in the range of 95 to 125 ksi.
- the steel material according to the present embodiment satisfies the above-described chemical composition, dislocation density, and number density of coarse precipitates even if the yield strength is in the range of 95 to 125 ksi, and is excellent in a normal temperature sour environment and a low temperature sour environment. Has SSC resistance.
- the yield strength of the steel material according to the present embodiment can be obtained by the following method.
- a tensile test is performed by a method according to ASTM E8 / E8M (2013).
- a round bar test piece is collected from the steel material according to the present embodiment.
- the steel material is a steel plate
- a round bar test piece is collected from the center of the thickness.
- the steel material is a steel pipe
- a round bar test piece is collected from the center of the wall thickness.
- the size of the round bar test piece is, for example, a parallel part diameter of 4 mm and a parallel part length of 35 mm. Note that the axial direction of the round bar test piece is parallel to the rolling direction of the steel material.
- a tensile test is performed in the air at normal temperature (25 ° C.), and the obtained 0.2% offset proof stress is defined as yield strength (MPa).
- the dislocation density is 7.0 ⁇ 10 14 (m ⁇ 2 ) or less. As described above, dislocations may occlude hydrogen. Therefore, if the dislocation density is too high, the concentration of hydrogen absorbed in the steel material increases, and the SSC resistance of the steel material decreases. On the other hand, dislocations increase the yield strength of steel. Therefore, the dislocation density of the steel according to the present embodiment is reduced according to the yield strength to be obtained.
- the dislocation density of the steel material according to the present embodiment is 1.4 ⁇ 10 14 (m ⁇ 2 ) or less when the yield strength is 95 ksi class (655 to 758 MPa). As described above, if the dislocation density is too high, the SSC resistance of the steel material decreases. Therefore, when the yield strength is of the order of 95 ksi, the dislocation density of the steel material according to the present embodiment is 1.4 ⁇ 10 14 (m ⁇ 2 ) or less.
- the preferred upper limit of the dislocation density of the steel material is less than 1.4 ⁇ 10 14 (m ⁇ 2 ), more preferably 1.3 ⁇ 10 14 (m ⁇ 2 ), and still more preferably. Is 1.2 ⁇ 10 14 (m ⁇ 2 ).
- the lower limit of the dislocation density of the steel material is not particularly limited, but if the dislocation density is excessively reduced, a desired yield strength may not be obtained. Therefore, the lower limit of the dislocation density of the steel material is, for example, more than 0.1 ⁇ 10 14 (m ⁇ 2 ).
- the steel material according to the present embodiment has a dislocation density of more than 1.4 ⁇ 10 14 to less than 3.0 ⁇ 10 14 (m ⁇ 2 ) when the yield strength is 110 ksi class (less than 758 to 862 MPa). As described above, if the dislocation density is too high, the SSC resistance of the steel material decreases. On the other hand, if the dislocation density is too low, the steel cannot have a yield strength of 110 ksi class. Therefore, when the yield strength is 110 ksi class, the dislocation density of the steel material according to the present embodiment is more than 1.4 ⁇ 10 14 to less than 3.0 ⁇ 10 14 (m ⁇ 2 ).
- the preferred upper limit of the dislocation density of the steel material is 2.9 ⁇ 10 14 (m ⁇ 2 ), and more preferably 2.8 ⁇ 10 14 (m ⁇ 2 ).
- a preferable lower limit of the dislocation density of the steel material for stably obtaining a yield strength of 110 ksi class is 1.5 ⁇ 10 14 (m ⁇ 2 ).
- the steel material according to the present embodiment further has a dislocation density of 3.0 ⁇ 10 14 to 7.0 ⁇ 10 14 (m ⁇ 2 ) when the yield strength is 125 ksi class (862 to 965 MPa). As described above, if the dislocation density is too high, the SSC resistance of the steel material decreases. On the other hand, if the dislocation density is too low, the steel cannot have a yield strength of 125 ksi class. Therefore, when the yield strength is in the 125 ksi class, the dislocation density of the steel material according to the present embodiment is 3.0 ⁇ 10 14 to 7.0 ⁇ 10 14 (m ⁇ 2 ).
- a preferable upper limit of the dislocation density of the steel material is 6.5 ⁇ 10 14 (m ⁇ 2 ), and more preferably 6.3 ⁇ 10 14 (m ⁇ 2 ).
- a preferred lower limit of the dislocation density of the steel material for stably obtaining a 125 ksi-class yield strength is 3.1 ⁇ 10 14 (m ⁇ 2 ).
- the dislocation density of the steel according to the present embodiment can be obtained by the following method.
- a test piece for measuring the dislocation density is collected from the steel material according to the present embodiment.
- the steel material is a steel plate
- the test piece is collected from the center of the thickness.
- the steel material is a steel pipe
- the size of the test piece is, for example, 20 mm wide ⁇ 20 mm long ⁇ 2 mm thick.
- the thickness direction of the test piece is the thickness direction (sheet thickness direction or wall thickness direction) of the steel material.
- the observation surface of the test piece is a surface having a width of 20 mm and a length of 20 mm.
- the observation surface of the test piece is mirror-polished, and electrolytic polishing is further performed using 10% by volume of perchloric acid (acetic acid solvent) to remove surface layer distortion.
- perchloric acid acetic acid solvent
- the half-width ⁇ K of the peaks of the (110), (211), and (220) planes of the body-centered cubic structure (iron) was determined by X-ray diffraction (XRD) for the observation surface after the electrolytic polishing.
- XRD X-ray diffraction
- the half-width ⁇ K is measured with the source being CoK ⁇ radiation, the tube voltage being 30 kV, and the tube current being 100 mA. Further, in order to measure a half width derived from an X-ray diffractometer, LaB 6 (lanthanum hexaboride) powder is used.
- the non-uniform strain ⁇ of the test piece is obtained from the half width ⁇ K obtained by the above-described method and the Williamson-Hall equation (Equation (2)).
- ⁇ K ⁇ cos ⁇ / ⁇ 0.9 / D + 2 ⁇ ⁇ sin ⁇ / ⁇ (2)
- ⁇ diffraction angle
- ⁇ wavelength of X-ray
- D crystallite diameter
- the dislocation density ⁇ (m ⁇ 2 ) can be obtained by using the obtained non-uniform strain ⁇ and Expression (3).
- ⁇ 14.4 ⁇ ⁇ 2 / b 2
- the microstructure of the steel according to the present embodiment mainly includes tempered martensite and tempered bainite. Specifically, the microstructure has a total volume fraction of tempered martensite and tempered bainite of 90% or more. The balance of the microstructure is, for example, ferrite or pearlite. Provided that the microstructure of the steel material having the above-mentioned chemical composition contains 90% or more of the volume ratio of tempered martensite and tempered bainite, the yield strength of the steel material is satisfied on the condition that the other requirements of the present embodiment are satisfied. Is 655 to 965 MPa (95 to 125 ksi class).
- the total volume ratio of tempered martensite and tempered bainite can be determined by microstructure observation.
- the steel material is a steel plate
- a test piece having an observation surface of 10 mm in the rolling direction and 10 mm in the thickness direction is cut out from the center of the thickness.
- the steel material is a steel plate having a thickness of less than 10 mm
- a test piece having an observation surface of the thickness of the steel plate in the rolling direction of 10 mm and in the thickness direction is cut out.
- the steel material is a steel pipe
- a test piece having an observation surface of 10 mm in the pipe axis direction and 10 mm in the pipe diameter direction is cut out from the center of the wall thickness.
- the steel material is a steel pipe having a thickness of less than 10 mm
- a test piece having an observation surface of the thickness of the steel pipe in the pipe axis direction of 10 mm and the pipe diameter direction is cut out.
- the test piece is immersed in a 2% nital etchant for about 10 seconds to reveal the structure by etching.
- the etched observation surface is observed in 10 fields of view using a secondary electron image by using a scanning electron microscope (SEM: Scanning Electron Microscope).
- the viewing area is 400 ⁇ m 2 (magnification 5000 times).
- the tempered martensite and tempered bainite can be distinguished from other phases (ferrite or pearlite) by contrast.
- tempered martensite and tempered bainite are specified in each field of view.
- the sum of the area fractions of the specified tempered martensite and tempered bainite is determined.
- the arithmetic mean value of the sum of the area fractions of tempered martensite and tempered bainite, which is obtained from all visual fields, is defined as the volume fraction of tempered martensite and tempered bainite.
- the shape of the steel material according to the present embodiment is not particularly limited.
- the steel material is, for example, a steel pipe or a steel plate.
- the steel material may be a solid material (bar steel).
- the preferred thickness is 9 to 60 mm.
- the steel material according to the present embodiment is a seamless steel pipe.
- the steel material according to the present embodiment reduces the dislocation density according to the yield strength (95 to 125 ksi class) to be obtained. That is, since the dislocation density is further reduced as the steel material has lower yield strength, more excellent SSC resistance can be obtained. Therefore, the steel according to the present embodiment defines excellent SSC resistance according to the yield strength (95 to 125 ksi class) to be obtained.
- the SSC resistance of the steel material according to the present embodiment can be evaluated by the normal temperature SSC resistance test and the low temperature SSC resistance test at any yield strength. Both the normal temperature SSC resistance test and the low temperature SSC resistance test are performed by a method based on NACE TM0177-2005 ⁇ Method ⁇ A.
- the SSC resistance of the steel material can be evaluated by the following method.
- a mixed aqueous solution NACE solution A
- a round bar test piece is collected from the steel material according to the present embodiment.
- the steel material is a steel plate, a round bar test piece is collected from the center of the thickness.
- the steel material is a steel pipe, a round bar test piece is collected from the center of the wall thickness.
- the size of the round bar test piece is, for example, 6.35 mm in diameter and 25.4 mm in length of the parallel portion. Note that the axial direction of the round bar test piece is parallel to the rolling direction of the steel material. A stress equivalent to 95% of the actual yield stress is applied to the round bar test piece.
- a test solution at 24 ° C. is poured into a test container so that a stressed round bar test piece is immersed in the test container to form a test bath. After degassing the test bath, 1 atm of H 2 S gas is blown into the test bath to saturate the test bath. The test bath blown with 1 atm of H 2 S gas is held at 24 ° C. for 720 hours.
- a mixed aqueous solution (NACE solution A) of 5.0% by mass of sodium chloride and 0.5% by mass of acetic acid is used as a test solution.
- NACE solution A a mixed aqueous solution
- a round bar test piece is collected from the steel material according to the present embodiment.
- the steel material is a steel plate
- a round bar test piece is collected from the center of the thickness.
- the steel material is a steel pipe
- a round bar test piece is collected from the center of the wall thickness.
- the size of the round bar test piece is, for example, 6.35 mm in diameter and 25.4 mm in length of the parallel portion. Note that the axial direction of the round bar test piece is parallel to the rolling direction of the steel material.
- a stress equivalent to 95% of the actual yield stress is applied to the round bar test piece.
- a test solution at 4 ° C. is poured into a test vessel so that a stressed round bar test piece is immersed in the test vessel to form a test bath. After degassing the test bath, 1 atm of H 2 S gas is blown into the test bath to saturate the test bath. The test bath blown with 1 atm of H 2 S gas is held at 4 ° C. for 720 hours.
- the SSC resistance of the steel can be evaluated by the following method.
- the room temperature SSC resistance test the same as the room temperature SSC resistance test performed when the yield strength was 95 ksi class, except that the stress applied to the round bar test piece was set to 90% of the actual yield stress. carry out.
- the stress applied to the round bar test piece was set to 85% of the actual yield stress. Perform the same procedure.
- the steel material according to the present embodiment has a yield strength of 110 ksi class, no crack is observed after 720 hours in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the SSC resistance of the steel material can be evaluated by the following method. In the room temperature SSC resistance test, except that the stress applied to the round bar test piece was set to 90% of the actual yield stress, the same as the room temperature SSC resistance test performed when the yield strength was 95 ksi class described above. carry out.
- the above-mentioned low-temperature SSC resistance test was performed when the yield strength was 95 ksi class. Perform the same procedure.
- the steel material according to the present embodiment has a yield strength of 125 ksi class, no crack is observed after 720 hours in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the preparation step prepares an intermediate steel material having the above-mentioned chemical composition.
- the production method of the intermediate steel material is not particularly limited as long as it has the above chemical composition.
- the intermediate steel material here is a plate-like steel material when the final product is a steel plate, and is a raw tube when the final product is a steel pipe.
- the preparation step may include a step of preparing a raw material (raw material preparation step) and a step of hot working the raw material to produce an intermediate steel material (hot working step).
- raw material preparation step a step of preparing a raw material
- hot working step a step of hot working the raw material to produce an intermediate steel material
- a material is manufactured using molten steel having the above-described chemical composition.
- the method for producing the material is not particularly limited, and may be a known method. Specifically, a slab (slab, bloom, or billet) is manufactured by continuous casting using molten steel. An ingot may be manufactured by using a molten steel by an ingot-making method. If necessary, slabs, blooms or ingots may be slab-rolled to produce billets. The material (slab, bloom, or billet) is manufactured through the above steps.
- the prepared material is hot worked to produce an intermediate steel material.
- the steel material is a steel pipe
- the intermediate steel material corresponds to a raw pipe.
- the heating temperature is not particularly limited, but is, for example, 1100 to 1300 ° C.
- Hot working is performed on the billet extracted from the heating furnace to produce a raw pipe (seamless steel pipe).
- the hot working method is not particularly limited, and may be a known method.
- the Mannesmann method is performed as hot working to produce a raw tube. In this case, the round billet is pierced and rolled by a piercing machine.
- the piercing ratio is not particularly limited, but is, for example, 1.0 to 4.0.
- the pierced and rolled round billet is further hot-rolled by a mandrel mill, a reducer, a sizing mill or the like to form a raw tube.
- the cumulative area reduction rate in the hot working step is, for example, 20 to 70%.
- the raw pipe may be manufactured from the billet by another hot working method.
- a raw tube may be manufactured by forging such as the Erhardt method.
- a raw pipe is manufactured by the above steps.
- the wall thickness of the raw tube is not particularly limited, but is, for example, 9 to 60 mm.
- the tube manufactured by hot working may be air-cooled (As-Rolled).
- the raw tube manufactured by hot working may also be directly quenched after hot working without cooling to room temperature, and after quenching after supplementary heating (reheating) after hot working. Is also good.
- quenching is performed after direct quenching or after supplementary heat, it is preferable to stop cooling during quenching or perform gentle cooling for the purpose of suppressing quenching cracks.
- intermediate steel is prepared in the preparation process.
- the intermediate steel material may be manufactured by the above-mentioned preferred process, or may be manufactured by a third party, or another factory other than the factory in which the quenching step and the tempering step described below are performed, and other establishments. May be prepared. Hereinafter, the quenching step will be described in detail.
- quenching In the quenching step, quenching is performed on the prepared intermediate steel material (base tube). As used herein, "quenching" means to quench the three or more points A of the intermediate steel. Preferred quenching temperatures are between 800 and 1000 ° C. When direct quenching is performed after hot working, the quenching temperature corresponds to the surface temperature of the intermediate steel material measured by a thermometer installed on the outlet side of the final hot working apparatus. The quenching temperature corresponds to the temperature of the auxiliary heating furnace or the heat treatment furnace when quenching is performed using the auxiliary heating furnace or the heat treatment furnace after the hot working.
- the quenching temperature is preferably 800 to 1000 ° C.
- a more preferred upper limit of the quenching temperature is 950 ° C.
- the intermediate steel is continuously cooled from the quenching start temperature, and the temperature of the intermediate steel is continuously lowered.
- the method of continuous cooling is not particularly limited, and may be a known method.
- the continuous cooling method is, for example, a method in which an intermediate steel material is immersed in a water bath to cool it, or a method in which the intermediate steel material is accelerated and cooled by shower water cooling or mist cooling.
- the intermediate steel material (base tube) is rapidly cooled during quenching.
- the average cooling rate in the range of 800 to 500 ° C. of the intermediate steel material (base tube) during quenching is defined as a quenching cooling rate CR 800-500 (° C./sec).
- the cooling rate during quenching CR 800-500 is set at the slowest cooling position in the cross section of the intermediate steel material to be quenched (for example, when both surfaces are forcibly cooled, the center of the intermediate steel thickness). Is determined from the measured temperature.
- the preferred quenching cooling rate CR 800-500 is 8 ° C./sec or more.
- the microstructure of the quenched intermediate steel material (base tube) is mainly composed of martensite and bainite.
- a more preferred lower limit of the quenching cooling rate CR 800-500 is 10 ° C./sec.
- the preferred upper limit of the cooling rate during quenching CR 800-500 is 500 ° C./sec.
- quenching is performed after heating the intermediate steel material in the austenitic region a plurality of times.
- the SSC resistance of the steel material is further enhanced.
- heating in the austenite region may be repeated a plurality of times, or by performing normalizing and quenching, heating in the austenite region may be repeated a plurality of times.
- the tempering step will be described in detail.
- tempering is performed after the above-described quenching is performed.
- tempering means that the intermediate steel material after quenching is reheated and held at a point of A c1 or less.
- the tempering temperature is appropriately adjusted according to the chemical composition of the steel material and the yield strength to be obtained. That is, the tempering temperature of the intermediate steel material (base tube) having the chemical composition of the present embodiment is adjusted to adjust the yield strength of the steel material to a range of 655 to 965 MPa (95 to 125 ksi class).
- the tempering temperature corresponds to the temperature of the furnace when heating and holding the quenched intermediate steel material.
- the tempering time holding time means the time from when the temperature of the intermediate steel reaches a predetermined tempering temperature until it is extracted from the heat treatment furnace.
- the dislocation density is reduced by increasing the tempering temperature to 600 to 730 ° C. in order to enhance SSC resistance.
- the alloy carbide is finely dispersed in holding the tempering.
- the finely dispersed alloy carbides serve as obstacles to the dislocation movement, and thus suppress the recovery of the dislocation (that is, the disappearance of the dislocation). Therefore, there is a case where the dislocation density cannot be sufficiently reduced only by tempering at a high temperature which has been performed to reduce the dislocation density.
- the steel material according to the present embodiment is tempered at a low temperature to reduce the dislocation density to some extent in advance. Further, tempering at a high temperature is performed to further reduce the dislocation density. That is, in the tempering step according to the present embodiment, tempering is performed in two stages in the order of low-temperature tempering and high-temperature tempering. According to this method, the dislocation density can be reduced while maintaining the yield strength. That is, according to the two-stage tempering, even if the dislocation density is reduced to 1.4 ⁇ 10 14 (m ⁇ 2 ) or less, the yield strength can be adjusted to 655 to less than 758 MPa (95 ksi class).
- the yield strength is reduced to 758 to less than 862 MPa (110 ksi class). Can be adjusted.
- the yield strength is adjusted to 862 to 965 MPa (125 ksi class). be able to.
- the low-temperature tempering step and the high-temperature tempering step will be described in detail.
- the preferred tempering temperature in the low-temperature tempering step is 100 to 500 ° C. If the tempering temperature in the low-temperature tempering step is too high, the alloy carbide may be finely dispersed during the holding of the tempering, and the dislocation density may not be sufficiently reduced. In this case, the yield strength of the steel material becomes too high and / or the SSC resistance of the steel material decreases. On the other hand, if the tempering temperature in the low-temperature tempering step is too low, the dislocation density may not be reduced during the holding of the tempering. In this case, the yield strength of the steel material becomes too high and / or the SSC resistance of the steel material decreases.
- the tempering temperature in the low-temperature tempering step is preferably set to 100 to 500 ° C.
- a more preferred lower limit of the tempering temperature in the low-temperature tempering step is 150 ° C.
- a more preferable upper limit of the tempering temperature in the low-temperature tempering step is 450 ° C., and further preferably 420 ° C.
- a preferable tempering holding time is 10 to 90 minutes. If the tempering time in the low-temperature tempering step is too short, the dislocation density may not be sufficiently reduced. In this case, the yield strength of the steel material becomes too high and / or the SSC resistance of the steel material decreases. On the other hand, if the tempering time in the low-temperature tempering step is too long, the above effect is saturated. Therefore, in this embodiment, the tempering time is preferably set to 10 to 90 minutes. A more preferred upper limit of the tempering time is 80 minutes. When the steel material is a steel pipe, temperature variation of the steel pipe is more likely to occur during the soaking of the tempered steel than in other shapes. Therefore, when the steel material is a steel pipe, the tempering time is preferably 15 to 90 minutes.
- the high temperature tempering step tempering conditions are appropriately controlled according to the yield strength to be obtained.
- the preferred tempering temperature in the high-temperature tempering step is 660 to 740 ° C. If the tempering temperature in the high-temperature tempering step is too high, the dislocation density may be too low, and a desired yield strength may not be obtained. On the other hand, if the tempering temperature in the high-temperature tempering step is too low, the dislocation density may not be sufficiently reduced. In this case, the yield strength of the steel material becomes too high and / or the SSC resistance of the steel material decreases. Therefore, a preferable tempering temperature in the high temperature tempering step is 660 to 740 ° C.
- the lower limit of the more preferable tempering temperature in the high-temperature tempering step is 670 ° C, and further preferably 680 ° C.
- a more preferable upper limit of the tempering temperature in the high-temperature tempering step is 735 ° C.
- the lower limit of the more preferable tempering temperature in the high-temperature tempering step is 670 ° C.
- the upper limit of the more preferable tempering temperature in the high-temperature tempering step is 730 ° C, and further preferably 720 ° C.
- the lower limit of the more preferable tempering temperature in the high-temperature tempering step is 670 ° C.
- a more preferable upper limit of the tempering temperature in the high-temperature tempering step is 730 ° C, and further preferably 720 ° C.
- the preferred tempering time in the high temperature tempering step is 10 to 180 minutes. If the tempering time is too short, the dislocation density may not be sufficiently reduced. In this case, the yield strength of the steel material becomes too high and / or the SSC resistance of the steel material decreases. On the other hand, if the tempering time is too long, the above effect is saturated. Therefore, in the present embodiment, a preferable tempering time is 10 to 180 minutes. A more preferable upper limit of the tempering time is 120 minutes, and further preferably 90 minutes. When the steel material is a steel pipe, temperature variation is likely to occur as described above. Therefore, when the steel material is a steel pipe, the tempering time is preferably 15 to 180 minutes.
- the above-mentioned low-temperature tempering step and high-temperature tempering step can be performed as a continuous heat treatment. That is, in the low-temperature tempering step, after the above-mentioned tempering is maintained, the high-temperature tempering step may be subsequently performed by heating. At this time, the low temperature tempering step and the high temperature tempering step may be performed in the same heat treatment furnace.
- the above-mentioned low-temperature tempering step and high-temperature tempering step can be performed as discontinuous heat treatment. That is, in the low-temperature tempering step, after the above-mentioned tempering is maintained, the temperature may be once cooled to a temperature lower than the above-mentioned tempering temperature, and then the heating may be performed again to perform the high-temperature tempering step. Even in this case, the effects obtained in the low-temperature tempering step and the high-temperature tempering step are not impaired, and the steel material according to the present embodiment can be manufactured.
- the steel material according to the present embodiment can be manufactured by the above manufacturing method.
- a method of manufacturing a steel pipe has been described as an example.
- the steel material according to the present embodiment may be a steel plate or another shape.
- the method for manufacturing a steel plate or another shape also includes, for example, a preparation step, a quenching step, and a tempering step, similarly to the above-described manufacturing method.
- the above-mentioned manufacturing method is an example, and may be manufactured by another manufacturing method.
- Example 1 SSC resistance of a steel material having a yield strength of 95 ksi class (655 to less than 758 MPa) in a normal temperature sour environment and a low temperature sour environment was investigated. Specifically, 180 kg of molten steel having the chemical composition shown in Table 1 was produced. Further, Table 2 shows Fn1 obtained from the obtained chemical composition and equation (1).
- the steel sheets of test numbers 1-1 to 1-25 were hardened once. Specifically, the steel sheet after the above-mentioned cooling was reheated, the steel sheet temperature was adjusted to the quenching temperature (920 ° C.), and held for 20 minutes. Thereafter, water cooling was performed using a shower type water cooling device. The average cooling rate between 800 ° C. and 500 ° C. during quenching of the steel sheets of Test Nos. 1-1 to 1-25, that is, the cooling rate during quenching (CR 800-500 ) (° C./sec) was 10 ° C./sec. there were.
- the steel sheets of Test Nos. 1-1 to 1-25 were tempered.
- the first tempering and the second tempering were performed on the steel sheets of test numbers 1-1 to 1-19 and 1-22 to 1-25.
- the steel sheets of Test Nos. 1-20 and 1-21 were tempered only once.
- Table 2 shows the tempering temperature (° C.) and the tempering time (minute) for each of the first tempering and the second tempering.
- the tempering temperature was the temperature of the furnace in which the tempering was performed.
- the tempering time was defined as a time after the temperature of the steel sheet of each test number reached a predetermined tempering temperature and was extracted from the furnace.
- SSC resistance evaluation test of steel materials The SSC resistance was evaluated using the steel plates of Test Nos. 1-1 to 1-25 by a method based on NACE TM0177-2005 Method A. Specifically, a round bar test specimen having a diameter of 6.35 mm and a parallel part length of 25.4 mm was sampled from the central part of the steel plates of test numbers 1-1 to 1-25. A room temperature SSC resistance test was performed on three of the collected test pieces. A low-temperature SSC resistance test was performed on the other three test pieces among the collected test pieces. The axial direction of the test piece was parallel to the rolling direction.
- the normal temperature SSC resistance test was performed as follows. Tensile stress was applied to the round bar test pieces of test numbers 1-1 to 1-25 in the axial direction. At this time, the applied stress was adjusted to be 95% of the actual yield stress of each steel sheet.
- a mixed aqueous solution (NACE solution A) of 5.0% by mass of sodium chloride and 0.5% by mass of acetic acid was used.
- a test solution at 24 ° C. was poured into each of the three test containers to form test baths. Three round bar test pieces to which stress was applied were immersed in test baths of different test containers one by one. After degassing each test bath, 1 atm of H 2 S gas was blown into the test bath to saturate it. The test bath saturated with 1 atm of H 2 S gas was kept at 24 ° C. for 720 hours.
- SSC sulfide stress cracking
- the low-temperature SSC resistance test was performed in accordance with NACE TM0177-2005 ⁇ Method ⁇ A, similarly to the normal-temperature SSC resistance test.
- the applied stress was adjusted to be 95% of the actual yield stress of each steel sheet.
- NACE solution A was used as in the normal temperature SSC resistance test.
- the temperature of the test bath was 4 ° C. Other conditions were the same as in the normal temperature SSC resistance test.
- SSC sulfide stress cracking
- the chemical compositions of steel sheets of test numbers 1-1 to 1-15 are appropriate, Fn1 is 3.00 or less, and the yield strength is 655 to less than 758 MPa (95 ksi class). )Met. Further, the dislocation density ⁇ was 1.4 ⁇ 10 14 (m ⁇ 2 ) or less, and the number density of coarse precipitates was 0.150 (pieces / ⁇ m 2 ) or less. As a result, excellent SSC resistance was exhibited in the normal temperature SSC resistance test and the low temperature SSC resistance test.
- Example 2 SSC resistance in a normal temperature sour environment and a low temperature sour environment was investigated for a steel material having a yield strength of 110 ksi class (less than 758 to 862 MPa). Specifically, 180 kg of molten steel having the chemical composition shown in Table 3 was produced. Further, Table 4 shows Fn1 obtained from the obtained chemical composition and Formula (1).
- the steel sheets of Test Nos. 2-1 to 2-27 after hot rolling were allowed to cool, and the steel sheet temperature was set to normal temperature (25 ° C.). Subsequently, the steel sheets of Test Nos. 2-1 to 2-27 after cooling were quenched. The quenching temperature and the cooling rate during quenching were measured with a sheath-type K thermocouple previously inserted in the center of the thickness of the steel sheet.
- the steel sheets of Test Nos. 2-1 to 2-27 were hardened once. Specifically, the steel sheet after the above-mentioned cooling was reheated, the steel sheet temperature was adjusted to the quenching temperature (920 ° C.), and held for 20 minutes. Thereafter, water cooling was performed using a shower type water cooling device.
- the average cooling rate between 800 ° C. and 500 ° C. during quenching of the steel sheets of Test Nos. 2-1 to 2-27, that is, the cooling rate during quenching (CR 800-500 ) (° C./sec) was 10 ° C./sec. there were.
- the steel sheets of Test Nos. 2-1 to 2-27 were tempered.
- the first tempering and the second tempering were performed.
- the steel sheets of Test Nos. 2-22 and 2-23 were tempered only once.
- Table 4 shows the tempering temperature (° C.) and the tempering time (minute) for each of the first tempering and the second tempering.
- the tempering temperature was the temperature of the furnace in which the tempering was performed.
- the tempering time was defined as a time after the temperature of the steel sheet of each test number reached a predetermined tempering temperature and was extracted from the furnace.
- SSC resistance evaluation test of steel materials The SSC resistance was evaluated using the steel plates of Test Nos. 2-1 to 2-27 by a method based on NACE TM0177-2005 Method A. Specifically, a round bar test piece having a diameter of 6.35 mm and a parallel part length of 25.4 mm was sampled from the central part of the steel plates of test numbers 2-1 to 2-27. A room temperature SSC resistance test was performed on three of the collected test pieces. A low-temperature SSC resistance test was performed on the other three test pieces among the collected test pieces. The axial direction of the test piece was parallel to the rolling direction.
- the normal temperature SSC resistance test was performed as follows. A tensile stress was applied to the round bar test pieces of Test Nos. 2-1 to 2-27 in the axial direction. At this time, the applied stress was adjusted to be 90% of the actual yield stress of each steel sheet.
- a mixed aqueous solution (NACE solution A) of 5.0% by mass of sodium chloride and 0.5% by mass of acetic acid was used.
- a test solution at 24 ° C. was poured into each of the three test containers to form test baths. Three round bar test pieces to which stress was applied were immersed in test baths of different test containers one by one. After degassing each test bath, 1 atm of H 2 S gas was blown into the test bath to saturate it. The test bath saturated with 1 atm of H 2 S gas was kept at 24 ° C. for 720 hours.
- SSC sulfide stress cracking
- the low-temperature SSC resistance test was performed in accordance with NACE TM0177-2005 ⁇ Method ⁇ A, similarly to the normal-temperature SSC resistance test.
- the stress applied was adjusted so as to be 85% of the actual yield stress of each steel sheet.
- NACE solution A was used as in the normal temperature SSC resistance test.
- the temperature of the test bath was 4 ° C. Other conditions were the same as in the normal temperature SSC resistance test.
- SSC sulfide stress cracking
- the chemical compositions of the steel sheets of Test Nos. 2-1 to 2-17 are appropriate, Fn1 is 3.00 or less, and the yield strength is 758 to less than 862 MPa (110 ksi class). )Met. Further, the dislocation density ⁇ was more than 1.4 ⁇ 10 14 to less than 3.0 ⁇ 10 14 (m ⁇ 2 ), and the number density of coarse precipitates was 0.150 (particles / ⁇ m 2 ) or less. As a result, excellent SSC resistance was exhibited in the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the steel sheets of Test No. 2-22 were not subjected to low-temperature tempering. As a result, the dislocation density ⁇ became 3.0 ⁇ 10 14 (m ⁇ 2 ) or more. As a result, in the low-temperature SSC resistance test, no excellent SSC resistance was shown.
- Example 3 SSC resistance of a steel material having a yield strength of 125 ksi class (862 to 965 MPa) in a normal temperature sour environment and a low temperature sour environment was investigated. Specifically, 180 kg of molten steel having the chemical composition shown in Table 5 was produced. Further, Table 6 shows Fn1 obtained from the obtained chemical composition and Formula (1).
- the steel sheets of test numbers 3-1 to 3-25 were hardened once. Specifically, the steel sheet after the above-mentioned cooling was reheated, the steel sheet temperature was adjusted to the quenching temperature (920 ° C.), and held for 20 minutes. Thereafter, water cooling was performed using a shower type water cooling device. The average cooling rate between 800 ° C. and 500 ° C. during quenching of the steel sheets of Test Nos. 3-1 to 3-25, that is, the cooling rate during quenching (CR 800-500 ) (° C./sec) was 10 ° C./sec. there were.
- tempering was performed on the steel sheets of test numbers 3-1 to 3-25.
- the first tempering and the second tempering were performed.
- the steel sheets of Test Nos. 3-20 and 3-21 were tempered only once.
- Table 6 shows the tempering temperature (° C.) and the tempering time (minute) for each of the first tempering and the second tempering.
- the tempering temperature was the temperature of the furnace in which the tempering was performed.
- the tempering time was defined as a time after the temperature of the steel sheet of each test number reached a predetermined tempering temperature and was extracted from the furnace.
- SSC resistance evaluation test of steel materials The SSC resistance was evaluated using the steel plates of Test Nos. 3-1 to 3-25 by a method based on NACE TM0177-2005 Method A. Specifically, a round bar test piece having a diameter of 6.35 mm and a parallel part length of 25.4 mm was sampled from the central part of the steel plates having test numbers 3-1 to 3-25. A room temperature SSC resistance test was performed on three of the collected test pieces. A low-temperature SSC resistance test was performed on the other three test pieces among the collected test pieces. The axial direction of the test piece was parallel to the rolling direction.
- the normal temperature SSC resistance test was performed as follows. A tensile stress was applied to the round bar test pieces of test numbers 3-1 to 3-25 in the axial direction. At this time, the applied stress was adjusted to be 90% of the actual yield stress of each steel sheet.
- a mixed aqueous solution (NACE solution A) of 5.0% by mass of sodium chloride and 0.5% by mass of acetic acid was used.
- a test solution at 24 ° C. was poured into each of the three test containers to form test baths. Three round bar test pieces to which stress was applied were immersed in test baths of different test containers one by one. After degassing each test bath, 1 atm of H 2 S gas was blown into the test bath to saturate it. The test bath saturated with 1 atm of H 2 S gas was kept at 24 ° C. for 720 hours.
- SSC sulfide stress cracking
- the low-temperature SSC resistance test was performed in accordance with NACE TM0177-2005 ⁇ Method ⁇ A, similarly to the normal-temperature SSC resistance test.
- the applied stress was adjusted to be 80% of the actual yield stress of each steel sheet.
- NACE solution A was used as in the normal temperature SSC resistance test. At this time, the temperature of the test bath was 4 ° C. Other conditions were the same as in the normal temperature SSC resistance test.
- SSC sulfide stress cracking
- the chemical compositions of the steel sheets of Test Nos. 3-1 to 3-15 are appropriate, Fn1 is 3.00 or less, and the yield strength is 862 to 965 MPa (125 ksi class). Met. Further, the dislocation density ⁇ was 3.0 ⁇ 10 14 to 7.0 ⁇ 10 14 (m ⁇ 2 ), and the number density of coarse precipitates was 0.150 (particles / ⁇ m 2 ) or less. As a result, excellent SSC resistance was exhibited in the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the steel material according to the present invention is widely applicable to steel materials used in harsh environments such as polar regions, preferably can be used as steel materials used in oil well environments, and more preferably, casings, tubing, line pipes and the like. It can be used as a steel material.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Heat Treatment Of Steel (AREA)
Abstract
Description
降伏強度が655~758MPa未満の場合、転位密度ρが1.4×1014m-2以下である。
降伏強度が758~862MPa未満の場合、転位密度ρが1.4×1014超~3.0×1014m-2未満である。
降伏強度が862~965MPaの場合、転位密度ρが3.0×1014~7.0×1014m-2である。
5×Cr-Mo-2×(V+Ti)≦3.00 (1)
ここで、式(1)中の元素記号には、対応する元素の含有量(質量%)が代入される。対応する元素が含有されていない場合、その元素記号には「0」が代入される。
降伏強度が655~758MPa未満の場合、転位密度ρが1.4×1014m-2以下である。
降伏強度が758~862MPa未満の場合、転位密度ρが1.4×1014超~3.0×1014m-2未満である。
降伏強度が862~965MPaの場合、転位密度ρが3.0×1014~7.0×1014m-2である。
5×Cr-Mo-2×(V+Ti)≦3.00 (1)
ここで、式(1)中の元素記号には、対応する元素の含有量(質量%)が代入される。対応する元素が含有されていない場合、その元素記号には「0」が代入される。
本実施形態による鋼材の化学組成は、次の元素を含有する。
炭素(C)は、鋼材の焼入れ性を高め、鋼材の降伏強度を高める。Cはさらに、製造工程中の焼戻し時において、炭化物の球状化を促進し、鋼材の耐SSC性を高める。炭化物が分散されればさらに、鋼材の降伏強度が高まる。C含有量が低すぎれば、これらの効果が得られない。一方、C含有量が高すぎれば、鋼材の靭性が低下し、焼割れが発生しやすくなる。C含有量が高すぎればさらに、鋼材中に粗大な炭化物が生成し、鋼材の耐SSC性が低下する。したがって、C含有量は0.20~0.35%である。C含有量の好ましい下限は0.22%であり、より好ましくは0.24%である。C含有量の好ましい上限は0.33%であり、より好ましくは0.32%であり、さらに好ましくは0.30%であり、さらに好ましくは0.29%である。
シリコン(Si)は、鋼を脱酸する。Si含有量が低すぎれば、この効果が得られない。一方、Si含有量が高すぎれば、鋼材の耐SSC性が低下する。したがって、Si含有量は0.05~1.00%である。好ましいSi含有量の下限は0.15%であり、より好ましくは0.20%である。Si含有量の好ましい上限は0.85%であり、より好ましくは0.70%である。
マンガン(Mn)は、鋼を脱酸する。Mnはさらに、鋼材の焼入れ性を高め、鋼材の降伏強度を高める。Mn含有量が低すぎれば、これらの効果が得られない。一方、Mn含有量が高すぎれば、Mnは、P及びS等の不純物とともに、粒界に偏析する。この場合、鋼材の耐SSC性が低下する。したがって、Mn含有量は0.01~1.00%である。Mn含有量の好ましい下限は0.02%であり、より好ましくは0.03%である。Mn含有量の好ましい上限は0.90%であり、より好ましくは0.80%である。
燐(P)は不純物である。すなわち、P含有量は0%超である。Pは、粒界に偏析して、鋼材の耐SSC性を低下する。したがって、P含有量は0.025%以下である。P含有量の好ましい上限は0.020%であり、より好ましくは0.015%である。P含有量はなるべく低い方が好ましい。ただし、P含有量の極端な低減は、製造コストを大幅に高める。したがって、工業生産を考慮した場合、P含有量の好ましい下限は0.0001%であり、より好ましくは0.0003%であり、さらに好ましくは0.001%であり、さらに好ましくは0.002%である。
硫黄(S)は不純物である。すなわち、S含有量は0%超である。Sは、粒界に偏析して、鋼材の耐SSC性を低下する。したがって、S含有量は0.0100%以下である。S含有量の好ましい上限は0.0050%であり、より好ましくは0.0030%である。S含有量はなるべく低い方が好ましい。ただし、S含有量の極端な低減は、製造コストを大幅に高める。したがって、工業生産を考慮した場合、S含有量の好ましい下限は0.0001%であり、より好ましくは0.0003%である。
アルミニウム(Al)は、鋼を脱酸する。Al含有量が低すぎれば、この効果が得られず、鋼材の耐SSC性が低下する。一方、Al含有量が高すぎれば、粗大な酸化物系介在物が生成して、鋼材の耐SSC性が低下する。したがって、Al含有量は0.005~0.100%である。Al含有量の好ましい下限は0.015%であり、より好ましくは0.020%である。Al含有量の好ましい上限は0.080%であり、より好ましくは0.060%である。本明細書にいう「Al」含有量は「酸可溶Al」、つまり、「sol.Al」の含有量を意味する。
クロム(Cr)は、鋼材の焼入れ性を高め、鋼材の降伏強度を高める。Crはさらに、焼戻し軟化抵抗を高め、高温焼戻しを可能にする。その結果、鋼材の耐SSC性が高まる。Cr含有量が低すぎれば、これらの効果が得られない。一方、Cr含有量が高すぎれば、鋼材中に粗大な炭化物が生成し、鋼材の耐SSC性が低下する。したがって、Cr含有量は0.25~0.80%である。Cr含有量の好ましい下限は0.30%であり、より好ましくは0.35%であり、さらに好ましくは0.40%である。Cr含有量の好ましい上限は0.78%であり、より好ましくは0.76%である。
モリブデン(Mo)は、鋼材の焼入れ性を高め、鋼材の降伏強度を高める。Moはさらに、微細な炭化物を生成し、鋼材の焼戻し軟化抵抗を高める。その結果、鋼材の耐SSC性が高まる。Mo含有量が低すぎれば、これらの効果が得られない。一方、Mo含有量が高すぎれば、上記効果が飽和する。したがって、Mo含有量は0.20~2.00%である。Mo含有量の好ましい下限は0.30%であり、より好ましくは0.40%であり、さらに好ましくは0.50%であり、さらに好ましくは0.60%であり、さらに好ましくは0.61%である。Mo含有量の好ましい上限は1.80%であり、より好ましくは1.70%であり、さらに好ましくは1.50%である。
チタン(Ti)は、窒化物を形成し、ピンニング効果により、結晶粒を微細化する。これにより、鋼材の降伏強度が高まる。Ti含有量が低すぎれば、この効果が得られない。一方、Ti含有量が高すぎれば、Ti窒化物が粗大化して、鋼材の耐SSC性が低下する。したがって、Ti含有量は0.002~0.050%である。Ti含有量の好ましい下限は0.003%であり、より好ましくは0.005%である。Ti含有量の好ましい上限は0.030%であり、より好ましくは0.020%である。
ホウ素(B)は、鋼に固溶して鋼材の焼入れ性を高め、鋼材の強度を高める。B含有量が低すぎれば、この効果が得られない。一方、B含有量が高すぎれば、粗大な窒化物が生成して鋼材の耐SSC性が低下する。したがって、B含有量は0.0001~0.0050%である。B含有量の好ましい下限は0.0003%であり、より好ましくは0.0007%である。B含有量の好ましい上限は0.0030%であり、より好ましくは0.0025%であり、さらに好ましくは0.0015%である。
窒素(N)は、Tiと結合して微細窒化物を形成し、結晶粒を微細化する。N含有量が低すぎれば、この効果が得られない。一方、N含有量が高すぎれば、Nは粗大な窒化物を形成して、鋼材の耐SSC性が低下する。したがって、N含有量は0.0020~0.0100%である。N含有量の好ましい下限は0.0022%である。N含有量の好ましい上限は0.0050%であり、より好ましくは0.0045%である。
酸素(O)は不純物である。すなわち、O含有量は0%超である。Oは粗大な酸化物を形成し、鋼材の耐食性を低下する。したがって、O含有量は0.0100%以下である。O含有量の好ましい上限は0.0050%であり、より好ましくは0.0030%であり、さらに好ましくは0.0020%である。O含有量はなるべく低い方が好ましい。ただし、O含有量の極端な低減は、製造コストを大幅に高める。したがって、工業生産を考慮した場合、O含有量の好ましい下限は0.0001%であり、より好ましくは0.0003%である。
上述の鋼材の化学組成はさらに、Feの一部に代えて、V及びNbからなる群から選択される1種以上を含有してもよい。これらの元素はいずれも任意元素であり、鋼材の耐SSC性及び降伏強度を高める。
バナジウム(V)は任意元素であり、含有されなくてもよい。すなわち、V含有量は0%であってもよい。含有される場合、VはC及び/又はNと結合して、炭化物、窒化物又は炭窒化物(以下、「炭窒化物等」という)を形成する。炭窒化物等は、ピンニング効果により鋼材のサブ組織を微細化し、鋼材の耐SSC性を高める。Vはさらに、焼戻し時に微細な炭化物を形成する。微細な炭化物は鋼材の焼戻し軟化抵抗を高め、鋼材の降伏強度を高める。Vが少しでも含有されれば、これらの効果がある程度得られる。しかしながら、V含有量が高すぎれば、鋼材の靭性が低下する。したがって、V含有量は0~0.60%である。V含有量の好ましい下限は0%超であり、より好ましくは0.01%であり、さらに好ましくは0.02%であり、さらに好ましくは0.04%であり、さらに好ましくは0.06%であり、さらに好ましくは0.08%である。V含有量の好ましい上限は0.40%であり、より好ましくは0.30%であり、さらに好ましくは0.20%である。
ニオブ(Nb)は任意元素であり、含有されなくてもよい。すなわち、Nb含有量は0%であってもよい。含有される場合、Nbは炭窒化物等を形成する。炭窒化物等はピンニング効果により鋼材のサブ組織を微細化し、鋼材の耐SSC性を高める。Nbはさらに、Cと結合して微細な炭化物を形成する。その結果、鋼材の降伏強度が高まる。Nbが少しでも含有されれば、これらの効果がある程度得られる。しかしながら、Nb含有量が高すぎれば、炭窒化物等が過剰に生成して、鋼材の耐SSC性が低下する。したがって、Nb含有量は0~0.030%である。Nb含有量の好ましい下限は0%超であり、より好ましくは0.002%であり、さらに好ましくは0.003%であり、さらに好ましくは0.007%である。Nb含有量の好ましい上限は0.025%であり、より好ましくは0.020%である。
カルシウム(Ca)は任意元素であり、含有されなくてもよい。すなわち、Ca含有量は0%であってもよい。含有される場合、Caは鋼材中のSを硫化物として無害化し、鋼材の耐SSC性を高める。Caが少しでも含有されれば、この効果がある程度得られる。しかしながら、Ca含有量が高すぎれば、鋼材中の酸化物が粗大化して、鋼材の耐SSC性が低下する。したがって、Ca含有量は0~0.0100%である。Ca含有量の好ましい下限は0%超であり、より好ましくは0.0001%であり、さらに好ましくは0.0003%であり、さらに好ましくは0.0006%であり、さらに好ましくは0.0010%である。Ca含有量の好ましい上限は0.0040%であり、より好ましくは0.0030%であり、さらに好ましくは0.0025%である。
マグネシウム(Mg)は任意元素であり、含有されなくてもよい。すなわち、Mg含有量は0%であってもよい。含有される場合、Mgは鋼材中のSを硫化物として無害化し、鋼材の耐SSC性を高める。Mgが少しでも含有されれば、この効果がある程度得られる。しかしながら、Mg含有量が高すぎれば、鋼材中の酸化物が粗大化して、鋼材の耐SSC性が低下する。したがって、Mg含有量は0~0.0100%である。Mg含有量の好ましい下限は0%超であり、より好ましくは0.0001%であり、さらに好ましくは0.0003%であり、さらに好ましくは0.0006%であり、さらに好ましくは0.0010%である。Mg含有量の好ましい上限は0.0040%であり、より好ましくは0.0030%であり、さらに好ましくは0.0025%である。
ジルコニウム(Zr)は任意元素であり、含有されなくてもよい。すなわち、Zr含有量は0%であってもよい。含有される場合、Zrは鋼材中のSを硫化物として無害化し、鋼材の耐SSC性を高める。Zrが少しでも含有されれば、この効果がある程度得られる。しかしながら、Zr含有量が高すぎれば、鋼材中の酸化物が粗大化して、鋼材の耐SSC性が低下する。したがって、Zr含有量は0~0.0100%である。Zr含有量の好ましい下限は0%超であり、より好ましくは0.0001%であり、さらに好ましくは0.0003%であり、さらに好ましくは0.0006%であり、さらに好ましくは0.0010%である。Zr含有量の好ましい上限は0.0040%であり、より好ましくは0.0030%であり、さらに好ましくは0.0025%である。
コバルト(Co)は任意元素であり、含有されなくてもよい。すなわち、Co含有量は0%であってもよい。含有される場合、Coはサワー環境中で保護性の腐食被膜を形成し、水素侵入を抑制する。その結果、鋼材の耐SSC性が高まる。Coが少しでも含有されれば、この効果がある程度得られる。しかしながら、Co含有量が高すぎれば、鋼材の焼入れ性が低下して、鋼材の降伏強度が低下する。したがって、Co含有量は0~0.50%である。Co含有量の好ましい下限は0%超であり、より好ましくは0.02%であり、さらに好ましくは0.03%であり、さらに好ましくは0.05%である。Co含有量の好ましい上限は0.45%であり、より好ましくは0.40%である。
タングステン(W)は任意元素であり、含有されなくてもよい。すなわち、W含有量は0%であってもよい。含有される場合、Wはサワー環境中で保護性の腐食被膜を形成し、水素侵入を抑制する。その結果、鋼材の耐SSC性が高まる。Wが少しでも含有されれば、この効果がある程度得られる。しかしながら、W含有量が高すぎれば、鋼材中に粗大な炭化物が生成して、鋼材の耐SSC性が低下する。したがって、W含有量は0~0.50%である。W含有量の好ましい下限は0%超であり、より好ましくは0.02%であり、さらに好ましくは0.03%であり、さらに好ましくは0.05%である。W含有量の好ましい上限は0.45%であり、より好ましくは0.40%である。
ニッケル(Ni)は任意元素であり、含有されなくてもよい。すなわち、Ni含有量は0%であってもよい。含有される場合、Niは鋼材の焼入れ性を高め、鋼材の降伏強度を高める。Niが少しでも含有されれば、この効果がある程度得られる。しかしながら、Ni含有量が高すぎれば、局部的な腐食を促進させ、鋼材の耐SSC性が低下する。したがって、Ni含有量は0~0.50%である。Ni含有量の好ましい下限は0%超であり、より好ましくは0.01%であり、さらに好ましくは0.02%である。Ni含有量の好ましい上限は0.10%であり、より好ましくは0.08%であり、さらに好ましくは0.06%である。
銅(Cu)は任意元素であり、含有されなくてもよい。すなわち、Cu含有量は0%であってもよい。含有される場合、Cuは鋼材の焼入れ性を高め、鋼材の降伏強度を高める。Cuが少しでも含有されれば、この効果がある程度得られる。しかしながら、Cu含有量が高すぎれば、鋼材の焼入れ性が高くなりすぎ、鋼材の耐SSC性が低下する。したがって、Cu含有量は0~0.50%である。Cu含有量の好ましい下限は0%超であり、より好ましくは0.01%であり、さらに好ましくは0.02%であり、さらに好ましくは0.05%である。Cu含有量の好ましい上限は0.35%であり、より好ましくは0.25%である。
希土類元素(REM)は任意元素であり、含有されなくてもよい。すなわち、REM含有量は0%であってもよい。含有される場合、REMは鋼材中のSを硫化物として無害化し、鋼材の耐SSC性を高める。REMはさらに、鋼材中のPと結合して、結晶粒界におけるPの偏析を抑制する。そのため、Pの偏析に起因した、鋼材の耐SSC性の低下が抑制される。REMが少しでも含有されれば、これらの効果がある程度得られる。しかしながら、REM含有量が高すぎれば、酸化物が粗大化して、鋼材の耐SSC性が低下する。したがって、REM含有量は0~0.0100%である。REM含有量の好ましい下限は0%超であり、より好ましくは0.0001%であり、さらに好ましくは0.0003%であり、さらに好ましくは0.0006%である。REM含有量の好ましい上限は0.0040%であり、より好ましくは0.0025%である。
本実施形態による鋼材はさらに、式(1)を満たす。
5×Cr-Mo-2×(V+Ti)≦3.00 (1)
ここで、式(1)中の元素記号には、対応する元素の含有量(質量%)が代入される。対応する元素が含有されていない場合、その元素記号には「0」が代入される。
本実施形態による鋼材は、鋼材中において、円相当径400nm以上の析出物の個数密度が0.150個/μm2以下である。上述のとおり、円相当径400nm以上の析出物を「粗大析出物」ともいう。なお、上述のとおり、本明細書において円相当径とは、組織観察における視野面において、観察された析出物の面積を、同じ面積を有する円に換算した場合の円の直径を意味する。
本実施形態による鋼材の降伏強度は655~965MPa(95~125ksi級)である。本明細書でいう降伏強度は、引張試験で得られた0.2%オフセット耐力を意味する。要するに、本実施形態による鋼材の降伏強度は95~125ksi級である。本実施形態による鋼材は、降伏強度が95~125ksi級であっても、上述の化学組成、転位密度、及び、粗大析出物の個数密度を満たすことで、常温サワー環境及び低温サワー環境における優れた耐SSC性を有する。
本実施形態による鋼材では、転位密度が7.0×1014(m-2)以下である。上述のとおり、転位は水素を吸蔵する可能性がある。そのため、転位密度が高すぎれば、鋼材に吸蔵する水素濃度が高まり、鋼材の耐SSC性が低下する。一方、転位は鋼材の降伏強度を高める。したがって、本実施形態による鋼材の転位密度は、得ようとする降伏強度に応じて低減する。
具体的には、本実施形態による鋼材は、降伏強度が95ksi級(655~758MPa未満)の場合、転位密度が1.4×1014(m-2)以下である。上述のとおり、転位密度が高すぎれば、鋼材の耐SSC性が低下する。したがって、降伏強度が95ksi級の場合、本実施形態による鋼材の転位密度は1.4×1014(m-2)以下である。降伏強度が95ksi級の場合、鋼材の転位密度の好ましい上限は1.4×1014(m-2)未満であり、より好ましくは1.3×1014(m-2)であり、さらに好ましくは1.2×1014(m-2)である。鋼材の転位密度の下限は特に限定しないが、過度に転位密度を低減すると、所望の降伏強度が得られない場合がある。したがって、鋼材の転位密度の下限は、たとえば、0.1×1014(m-2)超である。
本実施形態による鋼材はさらに、降伏強度が110ksi級(758~862MPa未満)の場合、転位密度が1.4×1014超~3.0×1014(m-2)未満である。上述のとおり、転位密度が高すぎれば、鋼材の耐SSC性が低下する。一方、転位密度が低すぎれば、鋼材は110ksi級の降伏強度が得られない。したがって、降伏強度が110ksi級の場合、本実施形態による鋼材の転位密度は1.4×1014超~3.0×1014(m-2)未満である。降伏強度が110ksi級の場合、鋼材の転位密度の好ましい上限は2.9×1014(m-2)であり、より好ましくは2.8×1014(m-2)である。安定して110ksi級の降伏強度を得るための、鋼材の転位密度の好ましい下限は1.5×1014(m-2)である。
本実施形態による鋼材はさらに、降伏強度が125ksi級(862~965MPa)の場合、転位密度が3.0×1014~7.0×1014(m-2)である。上述のとおり、転位密度が高すぎれば、鋼材の耐SSC性が低下する。一方、転位密度が低すぎれば、鋼材は125ksi級の降伏強度が得られない。したがって、降伏強度が125ksi級の場合、本実施形態による鋼材の転位密度は3.0×1014~7.0×1014(m-2)である。降伏強度が125ksi級の場合、鋼材の転位密度の好ましい上限は6.5×1014(m-2)であり、より好ましくは6.3×1014(m-2)である。安定して125ksi級の降伏強度を得るための、鋼材の転位密度の好ましい下限は3.1×1014(m-2)である。
ΔK×cosθ/λ=0.9/D+2ε×sinθ/λ (2)
ここで、式(2)中において、θ:回折角度、λ:X線の波長、D:結晶子径、を意味する。
ρ=14.4×ε2/b2 (3)
ここで、式(3)中において、bは体心立方構造(鉄)のバーガースベクトル(b=0.248(nm))である。
本実施形態による鋼材のミクロ組織は、主として焼戻しマルテンサイト及び焼戻しベイナイトからなる。具体的に、ミクロ組織は、焼戻しマルテンサイト及び焼戻しベイナイトの体積率の合計が90%以上である。ミクロ組織の残部はたとえば、フェライト、又は、パーライトである。上述の化学組成を有する鋼材のミクロ組織が、焼戻しマルテンサイト及び焼戻しベイナイトの体積率の合計が90%以上を含有すれば、本実施形態の他の規定を満たすことを条件に、鋼材の降伏強度が655~965MPa(95~125ksi級)となる。
本実施形態による鋼材の形状は特に限定されない。鋼材はたとえば鋼管、鋼板である。鋼材は、中実材(棒鋼)であってもよい。鋼材が油井用鋼管である場合、好ましい肉厚は9~60mmである。より好ましくは、本実施形態による鋼材は、継目無鋼管である。本実施形態による鋼材が継目無鋼管である場合、肉厚が15mm以上の厚肉の継目無鋼管であっても、655~965MPa(95~125ksi級)の降伏強度と、常温サワー環境及び低温サワー環境における優れた耐SSC性とを示す。
上述のとおり、転位密度が高い場合、鋼材に吸蔵する水素濃度が高まり、鋼材の耐SSC性が低下する。一方、転位は降伏強度を高める。そのため、本実施形態による鋼材は、得ようとする降伏強度(95~125ksi級)に応じて、転位密度を低減させる。すなわち、降伏強度が低い鋼材であるほど、転位密度はより低減されているため、より優れた耐SSC性が得られる。したがって、本実施形態による鋼材は、得ようとする降伏強度(95~125ksi級)に応じて、優れた耐SSC性を規定する。
鋼材の降伏強度が95ksi級の場合、鋼材の耐SSC性は、次の方法で評価できる。常温耐SSC性試験では、5.0質量%塩化ナトリウムと0.5質量%酢酸との混合水溶液(NACE solution A)を、試験溶液とする。本実施形態による鋼材から、丸棒試験片を採取する。鋼材が鋼板である場合、板厚中央部から丸棒試験片を採取する。鋼材が鋼管である場合、肉厚中央部から丸棒試験片を採取する。丸棒試験片の大きさは、たとえば、径6.35mm、平行部の長さ25.4mmである。なお、丸棒試験片の軸方向は、鋼材の圧延方向と平行である。丸棒試験片に対し、実降伏応力の95%に相当する応力を負荷する。試験容器に24℃の試験溶液を、応力を付加した丸棒試験片が浸漬するように注入し、試験浴とする。試験浴を脱気した後、1atmのH2Sガスを試験浴に吹き込み、試験浴に飽和させる。1atmのH2Sガスを吹き込んだ試験浴を、24℃で720時間、保持する。
鋼材の降伏強度が110ksi級の場合、鋼材の耐SSC性は、次の方法で評価できる。常温耐SSC性試験では、丸棒試験片に対して負荷する応力を、実降伏応力の90%にすること以外、上述の降伏強度が95ksi級の場合に実施した常温耐SSC性試験と同様に実施する。
鋼材の降伏強度が125ksi級の場合、鋼材の耐SSC性は、次の方法で評価できる。常温耐SSC性試験では、丸棒試験片に対して負荷する応力を、実降伏応力の90%にすること以外、上述の降伏強度が95ksi級の場合に実施した常温耐SSC性試験と同様に実施する。
本実施形態による鋼材の製造方法を説明する。以下、本実施形態による鋼材の一例として、継目無鋼管の製造方法を説明する。なお、本実施形態による鋼材の製造方法は、以下に説明する製造方法に限定されない。
準備工程は、上述の化学組成を有する中間鋼材を準備する。中間鋼材は、上記化学組成を有していれば、製造方法は特に限定されない。ここでいう中間鋼材は、最終製品が鋼板の場合は、板状の鋼材であり、最終製品が鋼管の場合は素管である。
素材準備工程では、上述の化学組成を有する溶鋼を用いて素材を製造する。素材の製造方法は特に限定されず、周知の方法でよい。具体的には、溶鋼を用いて連続鋳造法により鋳片(スラブ、ブルーム、又は、ビレット)を製造する。溶鋼を用いて造塊法によりインゴットを製造してもよい。必要に応じて、スラブ、ブルーム又はインゴットを分塊圧延して、鋼片(ビレット)を製造してもよい。以上の工程により素材(スラブ、ブルーム、又は、ビレット)を製造する。
熱間加工工程では、準備された素材を熱間加工して中間鋼材を製造する。鋼材が鋼管である場合、中間鋼材は素管に相当する。始めに、ビレットを加熱炉で加熱する。加熱温度は特に限定されないが、たとえば、1100~1300℃である。加熱炉から抽出されたビレットに対して熱間加工を実施して、素管(継目無鋼管)を製造する。熱間加工の方法は、特に限定されず、周知の方法でよい。たとえば、熱間加工としてマンネスマン法を実施し、素管を製造する。この場合、穿孔機により丸ビレットを穿孔圧延する。穿孔圧延する場合、穿孔比は特に限定されないが、たとえば、1.0~4.0である。穿孔圧延された丸ビレットをさらに、マンドレルミル、レデューサ、サイジングミル等により熱間圧延して素管にする。熱間加工工程での累積の減面率はたとえば、20~70%である。
焼入れ工程は、準備された中間鋼材(素管)に対して、焼入れを実施する。本明細書において、「焼入れ」とは、A3点以上の中間鋼材を急冷することを意味する。好ましい焼入れ温度は800~1000℃である。焼入れ温度とは、熱間加工後に直接焼入れを実施する場合、最終の熱間加工を実施する装置の出側に設置した温度計で測定された中間鋼材の表面温度に相当する。焼入れ温度とはさらに、熱間加工後に補熱炉又は熱処理炉を用いて焼入れを実施する場合、補熱炉又は熱処理炉の温度に相当する。
焼戻し工程は、上述の焼入れを実施した後、焼戻しを実施する。本明細書において、「焼戻し」とは、焼入れ後の中間鋼材をAc1点以下で再加熱して、保持することを意味する。焼戻し温度は、鋼材の化学組成、及び、得ようとする降伏強度に応じて適宜調整する。つまり、本実施形態の化学組成を有する中間鋼材(素管)に対して、焼戻し温度を調整して、鋼材の降伏強度を655~965MPa(95~125ksi級)の範囲に調整する。ここで、焼戻し温度とは、焼入れ後の中間鋼材を加熱して、保持する際の炉の温度に相当する。焼戻し時間(保持時間)とは、中間鋼材の温度が所定の焼戻し温度に到達してから、熱処理炉から抽出されるまでの時間を意味する。
低温焼戻し工程における、好ましい焼戻し温度は100~500℃である。低温焼戻し工程における焼戻し温度が高すぎれば、焼戻しの保持中に合金炭化物が微細に分散し、転位密度を十分に低減できない場合がある。この場合、鋼材の降伏強度が高くなりすぎ、及び/又は、鋼材の耐SSC性が低下する。一方、低温焼戻し工程における焼戻し温度が低すぎれば、焼戻しの保持中に転位密度を低減することができない場合がある。この場合、鋼材の降伏強度が高くなりすぎ、及び/又は、鋼材の耐SSC性が低下する。したがって、低温焼戻し工程における焼戻し温度は100~500℃とするのが好ましい。低温焼戻し工程における焼戻し温度のより好ましい下限は150℃である。低温焼戻し工程における焼戻し温度のより好ましい上限は450℃であり、さらに好ましくは420℃である。
高温焼戻し工程では、得ようとする降伏強度に応じて、焼戻し条件を適切に制御する。高温焼戻し工程における、好ましい焼戻し温度は660~740℃である。高温焼戻し工程における焼戻し温度が高すぎれば、転位密度が低減されすぎ、所望の降伏強度が得られない場合がある。一方、高温焼戻し工程における焼戻し温度が低すぎれば、転位密度を十分に低減することができない場合がある。この場合、鋼材の降伏強度が高くなりすぎ、及び/又は、鋼材の耐SSC性が低下する。したがって、高温焼戻し工程における好ましい焼戻し温度は660~740℃である。
上記の焼戻し後の試験番号1-1~1-25の鋼板に対して、以下に説明する引張試験、転位密度測定試験、粗大析出物個数密度測定試験、及び、耐SSC性評価試験を実施した。
引張試験はASTM E8/E8M(2013)に準拠して行った。試験番号1-1~1-25の鋼板の板厚中央部から、平行部直径4mm、平行部長さ35mmの丸棒試験片を作製した。丸棒試験片の軸方向は、鋼板の圧延方向と平行であった。各丸棒試験片を用いて、常温(25℃)、大気中にて引張試験を実施して、試験番号1-1~1-25の鋼板の降伏強度(MPa)を得た。なお、本実施例では、引張試験で得られた0.2%オフセット耐力を、試験番号1-1~1-25の降伏強度と定義した。得られた降伏強度を「YS(MPa)」として表2に示す。
試験番号1-1~1-25の鋼板から、上述の方法で転位密度測定用の試験片を採取した。さらに、上述の方法で転位密度(m-2)を求めた。求めた転位密度を、転位密度ρ(×1014m-2)として表2に示す。
試験番号1-1~1-25の鋼板について、上述の測定方法により、円相当径400nm以上の析出物(粗大析出物)の個数密度を測定及び算出した。なお、TEMは日本電子(株)製JEM-2010で、加速電圧は200kVとした。試験番号1-1~1-25の鋼板の、粗大析出物の個数密度(個/μm2)を表2に示す。
試験番号1-1~1-25の鋼板を用いて、NACE TM0177-2005 Method Aに準拠した方法によって、耐SSC性を評価した。具体的には、試験番号1-1~1-25の鋼板の板厚中央部から、径6.35mm、平行部の長さ25.4mmの丸棒試験片を採取した。採取した試験片のうち3本に対して、常温耐SSC性試験を実施した。採取した試験片のうち、他の3本に対して、低温耐SSC性試験を実施した。なお、試験片の軸方向は、圧延方向に平行であった。
表2に試験結果を示す。
上記の焼戻し後の試験番号2-1~2-27の鋼板に対して、以下に説明する引張試験、転位密度測定試験、粗大析出物個数密度測定試験、及び、耐SSC性評価試験を実施した。
引張試験はASTM E8/E8M(2013)に準拠して行った。試験番号2-1~2-27の鋼板の板厚中央部から、平行部直径4mm、平行部長さ35mmの丸棒試験片を作製した。丸棒試験片の軸方向は、鋼板の圧延方向と平行であった。各丸棒試験片を用いて、常温(25℃)、大気中にて引張試験を実施して、試験番号2-1~2-27の鋼板の降伏強度(MPa)を得た。なお、本実施例では、引張試験で得られた0.2%オフセット耐力を、試験番号2-1~2-27の降伏強度と定義した。得られた降伏強度を「YS(MPa)」として表4に示す。
試験番号2-1~2-27の鋼板から、上述の方法で転位密度測定用の試験片を採取した。さらに、上述の方法で転位密度(m-2)を求めた。求めた転位密度を、転位密度ρ(×1014m-2)として表4に示す。
試験番号2-1~2-27の鋼板について、上述の測定方法により、円相当径400nm以上の析出物(粗大析出物)の個数密度を測定及び算出した。なお、TEMは日本電子(株)製JEM-2010で、加速電圧は200kVとした。試験番号2-1~2-27の鋼板の、粗大析出物の個数密度(個/μm2)を表4に示す。
試験番号2-1~2-27の鋼板を用いて、NACE TM0177-2005 Method Aに準拠した方法によって、耐SSC性を評価した。具体的には、試験番号2-1~2-27の鋼板の板厚中央部から、径6.35mm、平行部の長さ25.4mmの丸棒試験片を採取した。採取した試験片のうち3本に対して、常温耐SSC性試験を実施した。採取した試験片のうち、他の3本に対して、低温耐SSC性試験を実施した。なお、試験片の軸方向は、圧延方向に平行であった。
表4に試験結果を示す。
上記の焼戻し後の試験番号3-1~3-25の鋼板に対して、以下に説明する引張試験、転位密度測定試験、粗大析出物個数密度測定試験、及び、耐SSC性評価試験を実施した。
引張試験はASTM E8/E8M(2013)に準拠して行った。試験番号3-1~3-25の鋼板の板厚中央部から、平行部直径4mm、平行部長さ35mmの丸棒試験片を作製した。丸棒試験片の軸方向は、鋼板の圧延方向と平行であった。各丸棒試験片を用いて、常温(25℃)、大気中にて引張試験を実施して、試験番号3-1~3-25の鋼板の降伏強度(MPa)を得た。なお、本実施例では、引張試験で得られた0.2%オフセット耐力を、試験番号3-1~3-25の降伏強度と定義した。得られた降伏強度を「YS(MPa)」として表6に示す。
試験番号3-1~3-25の鋼板から、上述の方法で転位密度測定用の試験片を採取した。さらに、上述の方法で転位密度(m-2)を求めた。求めた転位密度を、転位密度ρ(×1014m-2)として表6に示す。
試験番号3-1~3-25の鋼板について、上述の測定方法により、円相当径400nm以上の析出物(粗大析出物)の個数密度を測定及び算出した。なお、TEMは日本電子(株)製JEM-2010で、加速電圧は200kVとした。試験番号3-1~3-25の鋼板の、粗大析出物の個数密度(個/μm2)を表6に示す。
試験番号3-1~3-25の鋼板を用いて、NACE TM0177-2005 Method Aに準拠した方法によって、耐SSC性を評価した。具体的には、試験番号3-1~3-25の鋼板の板厚中央部から、径6.35mm、平行部の長さ25.4mmの丸棒試験片を採取した。採取した試験片のうち3本に対して、常温耐SSC性試験を実施した。採取した試験片のうち、他の3本に対して、低温耐SSC性試験を実施した。なお、試験片の軸方向は、圧延方向に平行であった。
表6に試験結果を示す。
Claims (10)
- 質量%で、
C:0.20~0.35%、
Si:0.05~1.00%、
Mn:0.01~1.00%、
P:0.025%以下、
S:0.0100%以下、
Al:0.005~0.100%、
Cr:0.25~0.80%、
Mo:0.20~2.00%、
Ti:0.002~0.050%、
B:0.0001~0.0050%、
N:0.0020~0.0100%、
O:0.0100%以下、
V:0~0.60%、
Nb:0~0.030%、
Ca:0~0.0100%、
Mg:0~0.0100%、
Zr:0~0.0100%、
Co:0~0.50%、
W:0~0.50%、
Ni:0~0.50%、
Cu:0~0.50%、及び、
希土類元素:0~0.0100%を含有し、残部がFe及び不純物からなり、式(1)を満たす化学組成を有し、
鋼材中において、円相当径400nm以上の析出物の個数密度が0.150個/μm2以下であり、
降伏強度が655~965MPaであり、
転位密度ρが、7.0×1014m-2以下であり、
前記降伏強度が655~758MPa未満の場合、前記転位密度ρが1.4×1014m-2以下であり、
前記降伏強度が758~862MPa未満の場合、前記転位密度ρが1.4×1014超~3.0×1014m-2未満であり、
前記降伏強度が862~965MPaの場合、前記転位密度ρが3.0×1014~7.0×1014m-2である、鋼材。
5×Cr-Mo-2×(V+Ti)≦3.00 (1)
ここで、式(1)中の元素記号には、対応する元素の含有量(質量%)が代入される。対応する元素が含有されていない場合、その元素記号には「0」が代入される。 - 請求項1に記載の鋼材であって、
前記化学組成は、
V:0.01~0.60%、及び、
Nb:0.002~0.030%からなる群から選択される1種以上を含有する、鋼材。 - 請求項1又は請求項2に記載の鋼材であって、
前記化学組成は、
Ca:0.0001~0.0100%、
Mg:0.0001~0.0100%、及び、
Zr:0.0001~0.0100%からなる群から選択される1種又は2種以上を含有する、鋼材。 - 請求項1~請求項3のいずれか1項に記載の鋼材であって、
前記化学組成は、
Co:0.02~0.50%、及び、
W:0.02~0.50%からなる群から選択される1種以上を含有する、鋼材。 - 請求項1~請求項4のいずれか1項に記載の鋼材であって、
前記化学組成は、
Ni:0.01~0.50%、及び、
Cu:0.01~0.50%からなる群から選択される1種以上を含有する、鋼材。 - 請求項1~請求項5のいずれか1項に記載の鋼材であって、
前記化学組成は、
希土類元素:0.0001~0.0100%を含有する、鋼材。 - 請求項1~請求項6のいずれか1項に記載の鋼材であって、
前記降伏強度が655~758MPa未満であり、
前記転位密度ρが1.4×1014m-2以下である、鋼材。 - 請求項1~請求項6のいずれか1項に記載の鋼材であって、
前記降伏強度が758~862MPa未満であり、
前記転位密度ρが1.4×1014超~3.0×1014m-2未満である、鋼材。 - 請求項1~請求項6のいずれか1項に記載の鋼材であって、
前記降伏強度が862~965MPaであり、
前記転位密度ρが3.0×1014~7.0×1014m-2である、鋼材。 - 請求項1~請求項9のいずれか1項に記載の鋼材であって、
前記鋼材は油井用鋼管である、鋼材。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112021000070-4A BR112021000070B1 (pt) | 2018-10-04 | 2019-09-26 | Material de aço adequado para uso em ambiente ácido |
EP19869014.1A EP3862453A4 (en) | 2018-10-04 | 2019-09-26 | STEEL MATERIAL FOR USE IN AN ACID ENVIRONMENT |
MX2021001897A MX2021001897A (es) | 2018-10-04 | 2019-09-26 | Material de acero adecuado para uso en ambientes agrios. |
US17/253,229 US11492688B2 (en) | 2018-10-04 | 2019-09-26 | Steel material suitable for use in sour environment |
JP2020550343A JP6958746B2 (ja) | 2018-10-04 | 2019-09-26 | サワー環境での使用に適した鋼材 |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018188777 | 2018-10-04 | ||
JP2018188868 | 2018-10-04 | ||
JP2018-188841 | 2018-10-04 | ||
JP2018-188777 | 2018-10-04 | ||
JP2018-188868 | 2018-10-04 | ||
JP2018188841 | 2018-10-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020071217A1 true WO2020071217A1 (ja) | 2020-04-09 |
Family
ID=70055044
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/037747 WO2020071217A1 (ja) | 2018-10-04 | 2019-09-26 | サワー環境での使用に適した鋼材 |
Country Status (6)
Country | Link |
---|---|
US (1) | US11492688B2 (ja) |
EP (1) | EP3862453A4 (ja) |
JP (1) | JP6958746B2 (ja) |
BR (1) | BR112021000070B1 (ja) |
MX (1) | MX2021001897A (ja) |
WO (1) | WO2020071217A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4245866A4 (en) * | 2020-11-11 | 2024-07-31 | Nippon Steel Corp | STEEL MATERIAL FOR USE IN AN ACIDIC ENVIRONMENT |
JP7564498B1 (ja) | 2023-04-06 | 2024-10-09 | 日本製鉄株式会社 | 鋼材 |
WO2024209910A1 (ja) * | 2023-04-06 | 2024-10-10 | 日本製鉄株式会社 | 鋼材 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114672632A (zh) * | 2022-03-21 | 2022-06-28 | 山东建筑大学 | 一种44GPa·%高强塑积冷轧中锰钢及其制备方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000256783A (ja) | 1999-03-11 | 2000-09-19 | Sumitomo Metal Ind Ltd | 靭性と耐硫化物応力腐食割れ性に優れる高強度油井用鋼およびその製造方法 |
JP2000297344A (ja) | 1999-04-09 | 2000-10-24 | Sumitomo Metal Ind Ltd | 靭性と耐硫化物応力腐食割れ性に優れる油井用鋼およびその製造方法 |
JP2005350754A (ja) | 2004-06-14 | 2005-12-22 | Sumitomo Metal Ind Ltd | 耐硫化物応力割れ性に優れた低合金油井管用鋼 |
WO2010150915A1 (ja) | 2009-06-24 | 2010-12-29 | Jfeスチール株式会社 | 耐硫化物応力割れ性に優れた油井用高強度継目無鋼管およびその製造方法 |
JP2012026030A (ja) | 2010-06-21 | 2012-02-09 | Jfe Steel Corp | 耐硫化物応力割れ性に優れた油井用鋼管及びその製造方法 |
WO2016059763A1 (ja) * | 2014-10-17 | 2016-04-21 | 新日鐵住金株式会社 | 低合金油井用鋼管 |
WO2018066689A1 (ja) * | 2016-10-06 | 2018-04-12 | 新日鐵住金株式会社 | 鋼材、油井用鋼管、及び、鋼材の製造方法 |
WO2018074109A1 (ja) * | 2016-10-17 | 2018-04-26 | Jfeスチール株式会社 | 油井用高強度継目無鋼管およびその製造方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10233520B2 (en) * | 2014-06-09 | 2019-03-19 | Nippon Steel & Sumitomo Metal Corporation | Low-alloy steel pipe for an oil well |
WO2017200033A1 (ja) * | 2016-05-20 | 2017-11-23 | 新日鐵住金株式会社 | 継目無鋼管及びその製造方法 |
RU2707845C1 (ru) * | 2016-09-01 | 2019-11-29 | Ниппон Стил Корпорейшн | Стальной материал и стальная труба для нефтяной скважины |
-
2019
- 2019-09-26 MX MX2021001897A patent/MX2021001897A/es unknown
- 2019-09-26 EP EP19869014.1A patent/EP3862453A4/en active Pending
- 2019-09-26 WO PCT/JP2019/037747 patent/WO2020071217A1/ja unknown
- 2019-09-26 BR BR112021000070-4A patent/BR112021000070B1/pt active IP Right Grant
- 2019-09-26 JP JP2020550343A patent/JP6958746B2/ja active Active
- 2019-09-26 US US17/253,229 patent/US11492688B2/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000256783A (ja) | 1999-03-11 | 2000-09-19 | Sumitomo Metal Ind Ltd | 靭性と耐硫化物応力腐食割れ性に優れる高強度油井用鋼およびその製造方法 |
JP2000297344A (ja) | 1999-04-09 | 2000-10-24 | Sumitomo Metal Ind Ltd | 靭性と耐硫化物応力腐食割れ性に優れる油井用鋼およびその製造方法 |
JP2005350754A (ja) | 2004-06-14 | 2005-12-22 | Sumitomo Metal Ind Ltd | 耐硫化物応力割れ性に優れた低合金油井管用鋼 |
WO2010150915A1 (ja) | 2009-06-24 | 2010-12-29 | Jfeスチール株式会社 | 耐硫化物応力割れ性に優れた油井用高強度継目無鋼管およびその製造方法 |
JP2015038247A (ja) * | 2009-06-24 | 2015-02-26 | Jfeスチール株式会社 | 耐硫化物応力割れ性に優れた油井用高強度継目無鋼管およびその製造方法 |
JP2012026030A (ja) | 2010-06-21 | 2012-02-09 | Jfe Steel Corp | 耐硫化物応力割れ性に優れた油井用鋼管及びその製造方法 |
WO2016059763A1 (ja) * | 2014-10-17 | 2016-04-21 | 新日鐵住金株式会社 | 低合金油井用鋼管 |
WO2018066689A1 (ja) * | 2016-10-06 | 2018-04-12 | 新日鐵住金株式会社 | 鋼材、油井用鋼管、及び、鋼材の製造方法 |
WO2018074109A1 (ja) * | 2016-10-17 | 2018-04-26 | Jfeスチール株式会社 | 油井用高強度継目無鋼管およびその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3862453A4 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4245866A4 (en) * | 2020-11-11 | 2024-07-31 | Nippon Steel Corp | STEEL MATERIAL FOR USE IN AN ACIDIC ENVIRONMENT |
JP7564498B1 (ja) | 2023-04-06 | 2024-10-09 | 日本製鉄株式会社 | 鋼材 |
WO2024209910A1 (ja) * | 2023-04-06 | 2024-10-10 | 日本製鉄株式会社 | 鋼材 |
Also Published As
Publication number | Publication date |
---|---|
US11492688B2 (en) | 2022-11-08 |
BR112021000070A2 (pt) | 2021-07-13 |
JPWO2020071217A1 (ja) | 2021-09-02 |
MX2021001897A (es) | 2021-04-28 |
JP6958746B2 (ja) | 2021-11-02 |
US20210269902A1 (en) | 2021-09-02 |
EP3862453A4 (en) | 2022-07-13 |
EP3862453A1 (en) | 2021-08-11 |
BR112021000070B1 (pt) | 2023-11-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2020071217A1 (ja) | サワー環境での使用に適した鋼材 | |
JP7036238B2 (ja) | サワー環境での使用に適した鋼材 | |
JP6747524B2 (ja) | 鋼材、及び、鋼材の製造方法 | |
WO2021210564A1 (ja) | マルテンサイト系ステンレス鋼材、及び、マルテンサイト系ステンレス鋼材の製造方法 | |
WO2021039431A1 (ja) | サワー環境での使用に適した鋼材 | |
JP7211554B2 (ja) | サワー環境での使用に適した鋼材 | |
JP6981527B2 (ja) | サワー環境での使用に適した鋼材 | |
US11155893B2 (en) | Steel material suitable for use in sour environment | |
JP7088305B2 (ja) | 鋼材、及び、鋼材の製造方法 | |
JP6206423B2 (ja) | 低温靭性に優れた高強度ステンレス厚鋼板およびその製造方法 | |
JP7036237B2 (ja) | サワー環境での使用に適した鋼材 | |
US11174539B2 (en) | Steel material suitable for use in sour environment | |
WO2020071219A1 (ja) | サワー環境での使用に適した継目無鋼管 | |
WO2024185411A1 (ja) | サワー環境での使用に適した鋼材 | |
JP6950819B2 (ja) | サワー環境での使用に適した鋼材 | |
JP7486012B1 (ja) | サワー環境での使用に適した鋼材 | |
JP2019112681A (ja) | 鋼材、油井用鋼管、及び、鋼材の製造方法 | |
WO2024147238A1 (ja) | サワー環境での使用に適した鋼材 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19869014 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2020550343 Country of ref document: JP Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112021000070 Country of ref document: BR |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2019869014 Country of ref document: EP Effective date: 20210504 |
|
ENP | Entry into the national phase |
Ref document number: 112021000070 Country of ref document: BR Kind code of ref document: A2 Effective date: 20210104 |