WO2025033003A1 - 鋼材 - Google Patents
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- WO2025033003A1 WO2025033003A1 PCT/JP2024/023045 JP2024023045W WO2025033003A1 WO 2025033003 A1 WO2025033003 A1 WO 2025033003A1 JP 2024023045 W JP2024023045 W JP 2024023045W WO 2025033003 A1 WO2025033003 A1 WO 2025033003A1
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
Definitions
- This disclosure relates to steel materials.
- oil wells The deepening of oil and gas wells (hereinafter, oil and gas wells will be collectively referred to simply as "oil wells") has created a demand for higher strength oil well steel materials, such as oil well steel pipes.
- 80 ksi grade yield strength of 80 to less than 95 ksi, i.e., 552 to less than 655 MPa
- 95 ksi grade yield strength of 95 to less than 110 ksi, i.e., 655 to less than 758 MPa
- oil well steel materials are widely used, and recently there has been an increasing demand for 110 ksi grade (yield strength of 110 to less than 125 ksi, i.e., 758 to less than 862 MPa) oil well steel materials.
- Oil wells may further contain corrosive hydrogen sulfide gas (H 2 S) and carbon dioxide gas (CO 2 ). Therefore, steel materials expected to be used as oil well steel materials are required to have not only high strength but also excellent corrosion resistance. In addition, steel materials for oil wells are subjected to stress during use. Therefore, sulfide stress cracking resistance (hereinafter referred to as SSC resistance) has been used as an index of excellent corrosion resistance of steel materials for oil wells.
- SSC resistance sulfide stress cracking resistance
- Patent Document 1 JP 2006-28612 A
- Patent Document 2 JP 2017-166060 A
- the steel material disclosed in Patent Document 1 is a steel for steel pipes, and consists of, by mass%, C: 0.2-0.7%, Si: 0.01-0.8%, Mn: 0.1-1.5%, S: 0.005% or less, P: 0.03% or less, Al: 0.0005-0.1%, Ti: 0.005-0.05%, Ca: 0.0004-0.005%, N: 0.007% or less, Cr: 0.1-1.5%, Mo: 0.2-1.0%, with the balance being Fe and impurities.
- This steel material further has a (Ca%)/(Al%) ratio of 0.55-1.72 and a (Ca%)/(Ti%) ratio of 0.7-19 in the non-metallic inclusions containing Ca, Al, Ti, N, O, and S.
- Patent Document 1 states that this steel has a high yield strength of more than 758 MPa and excellent SSC resistance.
- This steel material further contains 0.1 M23C6 type precipitates having a grain size of 1 ⁇ m or more per mm2 or less.
- Patent Document 2 describes that this steel has a yield strength of 654 to 793 MPa and has excellent SSC resistance even in a high-pressure hydrogen sulfide environment.
- the steel material disclosed in Patent Document 3 is a material for high-strength steel pipes for oil wells, and consists, by mass%, of C: 0.20-0.45%, Si: 0.05-0.40%, Mn: 0.3-0.9%, P: 0.015% or less, S: 0.005% or less, Al: 0.005-0.10%, N: 0.001-0.006%, Cr: 0.1-0.8%, Mo: 0.1-1.6%, V: 0.02-0.2%, Nb: 0.001-0.04%, B: 0.0003-0.0030%, O (oxygen): 0.0030% or less, and the balance being Fe and unavoidable impurities.
- This steel further has a Rockwell hardness HRC that satisfies the formula (15.6 x [%C] + 29.2 ⁇ HRC ⁇ 60.5 x [%C] + 31.1).
- Patent Document 3 states that this steel can produce steel pipes with a yield strength of 758 to less than 862 MPa and excellent SSC resistance.
- JP 2006-28612 A International Publication No. 2008/123422 JP 2017-166060 A
- the purpose of this disclosure is to provide a steel material that combines high strength of the 150 ksi class (over 1034 to 1172 MPa) with excellent SSC resistance.
- the steel material according to the present disclosure is In mass percent, C: 0.15-0.45%, Si: 0.05-1.00%, Mn: 0.05-1.00%, P: 0.030% or less, S: 0.0050% or less, Al: 0.005-0.100%, Cr: 0.30-1.50%, Mo: 0.40-2.00%, Ti: 0.002 to 0.020%, Nb: 0.002-0.100%, V: 0.05-0.30%, B: 0.0005-0.0040%, N: 0.0100% or less, O: 0.0040% or less, Cu: 0 to 0.50%, Ni: 0 to 0.50%, W: 0-0.50%, Ca: 0-0.0100%, Mg: 0 to 0.0100%, Zr: 0 to 0.0100%, Rare earth elements: 0 to 0.0100%, and The balance is Fe and impurities, The yield strength is greater than 1034 to 1172 MPa; In the steel material, The Al content is 20% or more, the O content is 10% or more, and the number density of Al oxide
- the steel material disclosed herein combines high strength of 150 ksi grade (over 1034 to 1172 MPa) with excellent SSC resistance.
- FIG. 1 is a diagram showing the relationship between the number density (pieces/200 mm 2 ) of coarse Si oxides (Si oxides with a major axis of 5.0 ⁇ m or more) and the number of SSC occurrences (pieces), which is an index of SSC resistance, in this example.
- the inventors focused on the chemical composition and investigated how to obtain a steel material that combines a 150 ksi-class yield strength with excellent SSC resistance.
- the composition is, by mass%, C: 0.15-0.45%, Si: 0.05-1.00%, Mn: 0.05-1.00%, P: 0.030% or less, S: 0.0050% or less, Al: 0.005-0.100%, Cr: 0.30-1.50%, Mo: 0.40-2.00%, Ti: 0.002-0.020%, Nb: 0.002-0.100%, V: 0.05-0.30%, B: 0.0005-0.
- the inventors of the present invention investigated various methods for improving the SSC resistance of a steel material having the above-mentioned chemical composition and a 150 ksi-class yield strength. Specifically, the inventors of the present invention considered that if coarse oxide-based inclusions could be reduced, it would be possible to improve the SSC resistance while maintaining the yield strength.
- Al oxides mainly composed of Al2O3 tend to coarsen. Therefore, the inventors of the present invention first focused on the coarse Al oxides.
- Al oxides are hard oxides and tend to reduce the corrosion resistance of steel materials.
- the yield strength is increased to 150 ksi class, the effect of coarse Al oxides tends to become apparent, and SSC resistance tends to decrease significantly. Therefore, in the steel material according to this embodiment having the above-mentioned chemical composition and a yield strength of 150 ksi class, the number density of coarse Al oxides is set to less than 30 pieces/200 mm2 .
- Si oxides particles having an Al content of less than 20%, a Si content of 20% or more, and an O content of 10% or more, in mass%.
- Si oxides having a major axis of 5.0 ⁇ m or more are also referred to as “coarse Si oxides”.
- coarse Si oxides and SSC resistance will be specifically described with reference to the drawings for a steel material having the above-mentioned chemical composition, a 150 ksi-class yield strength, and a number density of coarse Al oxides of less than 30 particles/200 mm2 .
- Fig. 1 is a diagram showing the relationship between the number density (pieces/200 mm2 ) of coarse Si oxides (Si oxides with a major axis of 5.0 ⁇ m or more) in this example and the number of SSC occurrences (pieces), which is an index of SSC resistance.
- Fig. 1 was created using the number density (pieces/200 mm2 ) of coarse Si oxides determined by a method described later and the number of SSC occurrences (pieces) determined by a method described later for steel materials among the examples described later that satisfy the above-mentioned chemical composition, have a 150 ksi-class yield strength, and have a number density of coarse Al oxides of less than 30 pieces/200 mm2 .
- the steel material has the above-mentioned chemical composition and a 150 ksi-class yield strength, the number density of coarse Al oxides is less than 30/200 mm2 , and further, the number density of coarse Si oxides is 5/200 mm2 or less .
- the steel material according to this embodiment can achieve both a 150 ksi-class yield strength and excellent SSC resistance.
- the present inventors speculate that, by not only reducing the number density of coarse Al oxides to less than 30 pieces/200 mm 2 but also reducing the number density of coarse Si oxides to 5 pieces/200 mm 2 or less, excellent SSC resistance can be stably obtained even if the steel material has a yield strength of 150 ksi.
- the gist of the steel material according to this embodiment which was completed based on the above findings, is as follows:
- a steel material In mass percent, C: 0.15-0.45%, Si: 0.05-1.00%, Mn: 0.05-1.00%, P: 0.030% or less, S: 0.0050% or less, Al: 0.005-0.100%, Cr: 0.30-1.50%, Mo: 0.40-2.00%, Ti: 0.002 to 0.020%, Nb: 0.002 to 0.100%, V: 0.05-0.30%, B: 0.0005-0.0040%, N: 0.0100% or less, O: 0.0040% or less, Cu: 0 to 0.50%, Ni: 0 to 0.50%, W: 0-0.50%, Ca: 0-0.0100%, Mg: 0 to 0.0100%, Zr: 0 to 0.0100%, Rare earth elements: 0 to 0.0100%, and The balance is Fe and impurities, The yield strength is greater than 1034 to 1172 MPa; In the steel material, The Al content is 20% or more, the O content is 10% or more, and the number density of Al oxides having
- the steel material according to [1] or [2] is a seamless steel pipe. Steel.
- the shape of the steel material according to this embodiment is not particularly limited.
- the steel material according to this embodiment may be a steel pipe, a round bar (solid material), or a steel plate.
- round bar means a steel bar with a circular cross section perpendicular to the axial direction.
- the steel pipe may be a seamless steel pipe or a welded steel pipe.
- C 0.15-0.45% Carbon (C) improves the hardenability of steel and increases its strength. C also promotes the spheroidization of carbides during tempering in the manufacturing process, and improves the SSC resistance of the steel. If the C content is too low, the above effect cannot be sufficiently obtained even if the contents of other elements are within the range of this embodiment. On the other hand, if the C content is too high, even if the contents of other elements are within the range of this embodiment, the amount of carbides becomes too large, and the SSC resistance of the steel decreases. Therefore, the C content is 0.15 to 0.45%.
- the preferred lower limit of the C content is 0.18%, more preferably 0.20%, more preferably 0.22%, and more preferably 0.23%.
- the preferred upper limit of the C content is 0.40%, more preferably 0.38%, more preferably 0.35%, and more preferably 0.30%.
- Si 0.05-1.00% Silicon (Si) deoxidizes steel. If the Si content is too low, the above effect cannot be sufficiently obtained even if the contents of other elements are within the range of this embodiment. On the other hand, if the Si content is too high, a large number of coarse Si oxides are formed, and the SSC resistance of the steel material may decrease even if the contents of other elements are within the range of this embodiment. Therefore, the Si content is 0.05 to 1.00%.
- the preferred lower limit of the Si content is 0.10%, more preferably 0.15%, and even more preferably 0.20%.
- the preferred upper limit of the Si content is 0.85%, more preferably 0.75%, more preferably 0.60%, more preferably 0.50%, and even more preferably 0.40%.
- Mn 0.05-1.00%
- Manganese (Mn) deoxidizes steel. Mn also enhances the hardenability of steel. If the Mn content is too low, the above effects cannot be sufficiently obtained even if the contents of other elements are within the range of this embodiment. On the other hand, if the Mn content is too high, coarse sulfide-based inclusions are formed, and the SSC resistance of the steel decreases, even if the contents of other elements are within the range of this embodiment. Therefore, the Mn content is 0.05 to 1.00%.
- the preferred lower limit of the Mn content is 0.06%, more preferably 0.08%, and even more preferably 0.10%.
- the preferred upper limit of the Mn content is 0.90%, more preferably 0.80%, more preferably 0.70%, more preferably 0.60%, and even more preferably 0.50%.
- Phosphorus (P) is an impurity. That is, the lower limit of the P content is more than 0%. If the P content is too high, even if the contents of other elements are within the range of this embodiment, P will segregate at the grain boundaries, and the SSC resistance of the steel material will decrease. Therefore, the P content is 0.030% or less.
- the preferred upper limit of the P content is 0.025%, more preferably 0.020%, more preferably 0.015%, and even more preferably 0.010%.
- the P content is preferably as low as possible. However, an extreme reduction in the P content significantly increases the manufacturing cost. Therefore, in consideration of industrial production, the preferred lower limit of the P content is 0.001%, more preferably 0.002%, and even more preferably 0.003%.
- S 0.0050% or less Sulfur (S) is an impurity. That is, the lower limit of the S content is more than 0%. If the S content is too high, even if the contents of other elements are within the range of this embodiment, S will segregate at the grain boundaries, and the SSC resistance of the steel material will decrease. Therefore, the S content is 0.0050% or less.
- the preferred upper limit of the S content is 0.0040%, more preferably 0.0032%, more preferably 0.0030%, more preferably 0.0020%, and more preferably 0.0015%.
- the S content is preferably as low as possible. However, an extreme reduction in the S content significantly increases the manufacturing cost. Therefore, when considering industrial production, the preferred lower limit of the S content is 0.0001%, more preferably 0.0002%, and more preferably 0.0003%.
- Al 0.005-0.100%
- Aluminum (Al) deoxidizes steel. If the Al content is too low, the above effect is not sufficiently obtained even if the contents of other elements are within the range of this embodiment, and the SSC resistance of the steel material is reduced. On the other hand, if the Al content is too high, a large number of coarse Al oxides are formed even if the contents of other elements are within the range of this embodiment, and the SSC resistance of the steel material is reduced. Therefore, the Al content is 0.005 to 0.100%.
- the preferred lower limit of the Al content is 0.010%, more preferably 0.015%, and even more preferably 0.020%.
- the preferred upper limit of the Al content is 0.080%, more preferably 0.060%, more preferably 0.040%, and even more preferably 0.035%.
- the "Al” content in this specification means the content of "acid-soluble Al", that is, “sol. Al”.
- Chromium (Cr) enhances the hardenability of steel. Cr also enhances the temper softening resistance of steel, enabling high-temperature tempering. As a result, the SSC resistance of the steel is enhanced. If the Cr content is too low, the above effects cannot be sufficiently obtained even if the contents of other elements are within the range of this embodiment. On the other hand, if the Cr content is too high, the SSC resistance of the steel is reduced even if the contents of other elements are within the range of this embodiment. Therefore, the Cr content is 0.30 to 1.50%.
- the preferred lower limit of the Cr content is 0.35%, more preferably 0.40%, and even more preferably 0.50%.
- the preferred upper limit of the Cr content is 1.40%, more preferably 1.30%, more preferably 1.20%, more preferably 1.10%, and even more preferably 1.05%.
- Mo 0.40-2.00%
- Molybdenum (Mo) enhances the hardenability of steel. Mo also enhances the temper softening resistance of steel, enabling high-temperature tempering. As a result, the SSC resistance of steel is enhanced. If the Mo content is too low, the above effects are not sufficiently obtained even if the contents of other elements are within the range of this embodiment. On the other hand, if the Mo content is too high, the above effects are saturated. Therefore, the Mo content is 0.40 to 2.00%.
- the preferred lower limit of the Mo content is 0.45%, more preferably 0.50%, more preferably 0.51%, more preferably 0.55%, and more preferably 0.60%.
- the preferred upper limit of the Mo content is 1.80%, more preferably 1.60%, more preferably 1.40%, and more preferably 1.30%.
- Ti 0.002-0.020% Titanium (Ti) combines with N to form nitrides, and the pinning effect refines the grains of the steel material. As a result, the strength of the steel material is increased. If the Ti content is too low, the above effect cannot be sufficiently obtained even if the contents of other elements are within the range of this embodiment. On the other hand, if the Ti content is too high, even if the contents of other elements are within the range of this embodiment, the Ti nitrides become coarse, and the SSC resistance of the steel material decreases. Therefore, the Ti content is 0.002 to 0.020%. The preferred lower limit of the Ti content is 0.003%, and more preferably 0.004%. The preferred upper limit of the Ti content is 0.018%, more preferably 0.015%, more preferably 0.010%, and more preferably 0.008%.
- Niobium combines with C and/or N to form carbides, nitrides, or carbonitrides (hereinafter referred to as "carbonitrides, etc.”). Carbonitrides, etc., refine the grains of the steel material by a pinning effect, and increase the SSC resistance of the steel material. Nb also forms fine carbides during tempering to increase the temper softening resistance of the steel material and increase the strength of the steel material. If the Nb content is too low, the above effects cannot be sufficiently obtained even if the contents of other elements are within the range of this embodiment.
- the Nb content is 0.002 to 0.100%.
- the preferable lower limit of the Nb content is 0.005%, more preferably 0.010%, more preferably 0.015%, and even more preferably 0.020%.
- the upper limit of the Nb content is preferably 0.080%, more preferably 0.060%, and further preferably 0.040%.
- V 0.05-0.30% Vanadium (V) forms carbonitrides and the like. Carbonitrides and the like refine the grains of the steel material by the pinning effect, and enhance the SSC resistance of the steel material. V also forms fine carbides during tempering to enhance the temper softening resistance of the steel material and enhance the strength of the steel material. If the V content is too low, the above effects cannot be sufficiently obtained even if the contents of other elements are within the range of this embodiment. On the other hand, if the V content is too high, even if the contents of other elements are within the range of this embodiment, carbonitrides and the like are excessively formed, and the SSC resistance of the steel material decreases. Therefore, the V content is 0.05 to 0.30%. The preferred lower limit of the V content is 0.06%, more preferably 0.07%, and even more preferably 0.08%. The preferred upper limit of the V content is 0.25%, more preferably 0.20%, and even more preferably 0.15%.
- B 0.0005-0.0040% Boron (B) dissolves in steel to improve the hardenability of the steel material and increase the strength of the steel material. If the B content is too low, the above effect cannot be sufficiently obtained even if the contents of other elements are within the range of this embodiment. On the other hand, if the B content is too high, coarse nitrides are formed and the SSC resistance of the steel material decreases even if the contents of other elements are within the range of this embodiment. Therefore, the B content is 0.0005 to 0.0040%.
- the preferred lower limit of the B content is 0.0006%, and more preferably 0.0008%.
- the preferred upper limit of the B content is 0.0035%, more preferably 0.0030%, more preferably 0.0025%, and more preferably 0.0020%.
- N Nitrogen (N) is inevitably contained. That is, the lower limit of the N content is more than 0%. N combines with Ti to form nitrides, and the grains of the steel are refined by the pinning effect. As a result, the strength of the steel is increased. However, if the N content is too high, even if the contents of other elements are within the range of this embodiment, coarse nitrides are formed, and the SSC resistance of the steel is reduced. Therefore, the N content is 0.0100% or less.
- the preferred upper limit of the N content is 0.0080%, more preferably 0.0060%, more preferably 0.0050%, and even more preferably 0.0040%.
- the preferred lower limit of the N content to more effectively obtain the above effects is 0.0005%, more preferably 0.0010%, more preferably 0.0015%, and even more preferably 0.0020%.
- Oxygen (O) is an impurity. That is, the lower limit of the O content is more than 0%. If the O content is too high, even if the contents of other elements are within the range of this embodiment, coarse oxides are formed, and the SSC resistance of the steel material decreases. Therefore, the O content is 0.0040% or less.
- the preferred upper limit of the O content is 0.0035%, more preferably 0.0033%, more preferably 0.0030%, more preferably 0.0025%, and more preferably 0.0020%.
- the O content is preferably as low as possible. However, an extreme reduction in the O content significantly increases the manufacturing cost. Therefore, in consideration of industrial production, the preferred lower limit of the O content is 0.0001%, more preferably 0.0002%, and more preferably 0.0003%.
- the remainder of the chemical composition of the steel material according to this embodiment is composed of Fe and impurities.
- impurities refer to substances that are mixed in from raw materials such as ore and scrap, or from the manufacturing environment, during the industrial production of steel material, and are acceptable to the extent that they do not adversely affect the steel material according to this embodiment.
- the chemical composition of the steel material described above may further contain one or more elements selected from the group consisting of Cu and Ni in place of a portion of Fe. All of these elements are optional elements and enhance the hardenability of the steel material.
- Cu 0-0.50% Copper (Cu) is an optional element and may not be contained. That is, the Cu content may be 0%. When contained, Cu enhances the hardenability of the steel material and enhances the strength of the steel material. If even a small amount of Cu is contained, the above effect can be obtained to a certain extent. However, if the Cu content is too high, the SSC resistance of the steel material decreases even if the contents of other elements are within the range of this embodiment. Therefore, the Cu content is 0 to 0.50%.
- the preferred lower limit of the Cu content is more than 0%, more preferably 0.01%, and even more preferably 0.02%.
- the preferred upper limit of the Cu content is 0.35%, more preferably 0.25%, more preferably 0.15%, more preferably 0.10%, and even more preferably 0.05%.
- Ni 0-0.50%
- Nickel (Ni) is an optional element and may not be contained. That is, the Ni content may be 0%. When contained, Ni enhances the hardenability of the steel material and enhances the strength of the steel material. Ni further dissolves in the steel material to enhance the SSC resistance of the steel material. If even a small amount of Ni is contained, these effects can be obtained to a certain extent. However, if the Ni content is too high, even if the contents of other elements are within the range of this embodiment, local corrosion is promoted and the SSC resistance of the steel material is reduced. Therefore, the Ni content is 0 to 0.50%.
- the preferred lower limit of the Ni content is more than 0%, more preferably 0.01%, and more preferably 0.02%.
- the preferred upper limit of the Ni content is 0.30%, more preferably 0.20%, more preferably 0.10%, and more preferably 0.05%.
- the chemical composition of the above-mentioned steel may further contain W instead of part of the Fe.
- W 0 to 0.50%
- Tungsten (W) is an optional element and may not be contained. That is, the W content may be 0%.
- W forms a protective corrosion film in a sour environment and suppresses the penetration of hydrogen into the steel material. This enhances the SSC resistance of the steel material. If even a small amount of W is contained, the above effect can be obtained to a certain extent. However, if the W content is too high, even if the contents of other elements are within the range of this embodiment, coarse carbides are formed in the steel material, and the SSC resistance of the steel material decreases. Therefore, the W content is 0 to 0.50%.
- the preferred lower limit of the W content is more than 0%, more preferably 0.01%, more preferably 0.03%, and even more preferably 0.05%.
- the preferred upper limit of the W content is less than 0.50%, and even more preferably 0.48%.
- the chemical composition of the above-mentioned steel material may further contain, in place of a portion of Fe, one or more elements selected from the group consisting of Ca, Mg, Zr, and rare earth elements. All of these elements are optional elements, and render the S in the steel material harmless as sulfides. As a result, these elements increase the SSC resistance of the steel material.
- Ca 0 ⁇ 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 harmless as sulfides and enhances the SSC resistance of the steel. If even a small amount of Ca is contained, the above effect can be obtained to a certain extent. However, if the Ca content is too high, even if the contents of other elements are within the range of this embodiment, the oxides in the steel will coarsen and the SSC resistance of the steel will decrease. Therefore, the Ca content is 0 to 0.0100%.
- the preferred lower limit of the Ca content is more than 0%, more preferably 0.0001%, more preferably 0.0003%, and even more preferably 0.0006%.
- the preferred upper limit of the Ca content is 0.0040%, more preferably 0.0025%, and even more preferably 0.0020%.
- Mg 0-0.0100%
- 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 harmless as sulfides and enhances the SSC resistance of the steel. If even a small amount of Mg is contained, the above effect can be obtained to a certain extent. However, if the Mg content is too high, even if the contents of other elements are within the range of this embodiment, the oxides in the steel will coarsen and the SSC resistance of the steel will decrease. Therefore, the Mg content is 0 to 0.0100%.
- the preferred lower limit of the Mg content is more than 0%, more preferably 0.0001%, more preferably 0.0003%, and even more preferably 0.0006%.
- the preferred upper limit of the Mg content is 0.0040%, more preferably 0.0025%, and even more preferably 0.0020%.
- Zr Zirconium
- Zr Zirconium
- the Zr content may be 0%.
- Zr renders S in the steel harmless as sulfides and enhances the SSC resistance of the steel. If even a small amount of Zr is contained, the above effect can be obtained to a certain extent. However, if the Zr content is too high, even if the contents of other elements are within the range of this embodiment, the oxides in the steel will coarsen and the SSC resistance of the steel will decrease. Therefore, the Zr content is 0 to 0.0100%.
- the preferred lower limit of the Zr content is more than 0%, more preferably 0.0001%, more preferably 0.0003%, and even more preferably 0.0006%.
- the preferred upper limit of the Zr content is 0.0040%, more preferably 0.0025%, and even more preferably 0.0020%.
- Rare earth elements are optional elements and may not be contained. That is, the REM content may be 0%. When contained, REM renders S in the steel harmless as sulfides, and enhances the SSC resistance of the steel. REM further binds to P in the steel to suppress the segregation of P at the grain boundaries. Therefore, the decrease in the SSC resistance of the steel caused by the segregation of P is suppressed. If even a small amount of REM is contained, the above effect can be obtained to a certain extent. However, if the REM content is too high, even if the contents of other elements are within the range of this embodiment, the oxides in the steel will coarsen and the SSC resistance of the steel will decrease.
- the REM content is 0 to 0.0100%.
- the preferable lower limit of the REM content is more than 0%, more preferably 0.0001%, more preferably 0.0003%, and even more preferably 0.0006%.
- the upper limit of the REM content is preferably 0.0040%, more preferably 0.0025%, and further preferably 0.0020%.
- REM refers to one or more elements selected from the group consisting of scandium (Sc), atomic number 21; yttrium (Y), atomic number 39; and the lanthanides lanthanum (La), atomic number 57, to lutetium (Lu), atomic number 71.
- the REM content in this specification refers to the total content of these elements.
- the yield strength of the steel material according to this embodiment is more than 1034 to 1172 MPa (more than 150 to 170 ksi).
- the yield strength in this specification means the stress at 0.65% elongation (0.65% proof stress) obtained in a tensile test at room temperature (25 ° C.) in accordance with ASTM E8 / E8M (2021).
- the steel material according to this embodiment has the above-mentioned chemical composition and satisfies the number density of coarse Al oxides and the number density of coarse Si oxides described later, so that even if the yield strength is more than 1034 to 1172 MPa, it has excellent SSC resistance.
- the yield strength of the steel material according to this embodiment is determined by the following method. First, a round bar test piece is prepared from the steel material according to this embodiment. If the steel material is a steel plate, the round bar test piece is prepared from the center of the plate thickness. In this case, the axial direction of the round bar test piece is parallel to the rolling direction of the steel plate. If the steel material is a steel pipe, the round bar test piece is prepared from the center of the wall thickness. In this case, the axial direction of the round bar test piece is parallel to the axial direction of the steel pipe. If the steel material is a round bar, the round bar test piece is prepared from the R/2 position.
- the R/2 position means the center position of the radius R in a cross section perpendicular to the axial direction of the round bar.
- the axial direction of the round bar test piece is parallel to the axial direction of the round bar.
- the size of the round bar test piece is, for example, 8.9 mm in parallel part diameter and 35.6 mm in gauge length.
- a tensile test is performed at room temperature (25°C) in air in accordance with ASTM E8/E8M (2021), and the obtained stress at 0.65% elongation (0.65% yield strength) is defined as the yield strength (MPa).
- the yield strength (MPa) is calculated by rounding the obtained value to the nearest tenth.
- the steel material according to this embodiment has the above-mentioned chemical composition and a yield strength of more than 1034 to 1172 MPa, and furthermore, the number density of the coarse Al oxides is less than 30 particles/200 mm2 .
- particles having an Al content of 20% or more and an O content of 10% or more, in mass% are also referred to as "Al oxides”.
- Al oxides having a major axis of 5.0 ⁇ m or more are also referred to as "coarse Al oxides”.
- coarse Al oxides refer to particles having an Al content of 20% or more, an O content of 10% or more, and a major axis of 5.0 ⁇ m or more, in mass%,.
- the preferred upper limit of the number density of the coarse Al oxides is 28 pieces/200 mm2 , more preferably 25 pieces/200 mm2 , and even more preferably 22 pieces/200 mm2 .
- the lower limit of the number density of the coarse Al oxides is not particularly limited and may be 0 pieces/200 mm2 .
- the lower limit of the number density of the coarse Al oxides may be, for example, 5 pieces/200 mm2 , 7 pieces/200 mm2 , or 9 pieces/200 mm2 . A method for determining the number density of the coarse Al oxides will be described later.
- the steel material according to the present embodiment has the above-mentioned chemical composition and a yield strength of more than 1034 to 1172 MPa , the number density of the coarse Al oxides is less than 30 pieces/200 mm2, and the number density of the coarse Si oxides is 5 pieces/200 mm2 or less .
- particles having an Al content of less than 20%, a Si content of 20% or more, and an O content of 10% or more, in mass% are also referred to as "Si oxides”.
- Si oxides having a major axis of 5.0 ⁇ m or more are also referred to as "coarse Si oxides".
- coarse Si oxides refer to particles having an Al content of less than 20%, a Si content of 20% or more, an O content of 10% or more, and a major axis of 5.0 ⁇ m or more, in mass%.
- Si oxides have not been paid much attention to because of their small number.
- the steel has a high yield strength of 150 ksi class
- not only the coarse Al oxides but also the coarse Si oxides with a small number may easily cause a decrease in SSC resistance. Therefore, by making the number density of the coarse Al oxides less than 30 pieces/200 mm 2 and making the number density of the coarse Si oxides 5 pieces/200 mm 2 or less, it is possible to stably obtain excellent SSC resistance even if the yield strength is increased to 150 ksi class.
- the steel material according to this embodiment has the above-mentioned chemical composition and a yield strength of more than 1034 to 1172 MPa, and the number density of the coarse Al oxides in the steel material is less than 30 pieces/200 mm 2 , and further, the number density of the coarse Si oxides is 5 pieces/200 mm 2 or less.
- the preferred upper limit of the number density of the coarse Si oxides is 4 pieces/200 mm2 , and more preferably 3 pieces/200 mm2 .
- the lower limit of the number density of the coarse Si oxides is not particularly limited, and may be 0 pieces/200 mm2 .
- the lower limit of the number density of the coarse Si oxides may be, for example, 1 piece/200 mm2 .
- the number density of coarse Al oxides and the number density of coarse Si oxides in the steel material can be found by the following method.
- a test piece is prepared from the steel material according to this embodiment, with the observation surface being a surface including the rolling direction and the reduction direction.
- the steel material is a steel plate
- a test piece is prepared from the center of the plate thickness, with the observation surface being a surface including the rolling direction and the plate thickness direction.
- the steel material is a steel pipe
- a test piece is prepared from the center of the plate thickness, with the observation surface being a surface including the pipe axial direction and the pipe radial direction.
- the steel material is round bar
- a test piece is prepared that includes the R/2 position in the center, with the observation surface being a surface including the axial direction and the radial direction.
- the observation surface of the prepared test piece is polished to a mirror finish, and then the measurement is performed.
- the area of the observation surface is not limited, but is, for example, 300 mm 2 (20 mm ⁇ 15 mm).
- the number of Si oxides with a major axis of 5.0 ⁇ m or more is determined on the observation surface.
- the particles on the observation surface are first identified from the contrast. Element concentration analysis (EDS analysis) is performed on each identified particle.
- EDS analysis Element concentration analysis
- the acceleration voltage is set to 20 kV, and the target elements are quantified as N, O, Mg, Al, Si, P, S, Ca, Ti, Cr, Mn, Fe, Cu, Zr, and Nb.
- the particle Based on the EDS analysis results of each particle, if the Al content is 20% or more and the O content is 10% or more by mass%, the particle is identified as an "Al oxide". Based on the EDS analysis results of each particle, if the Al content is less than 20%, the Si content is 20% or more, and the O content is 10% or more, in mass%, the particle is identified as a "Si oxide".
- Al oxides identified on the observation surface Al oxides with a major axis of 5.0 ⁇ m or more (coarse Al oxides) are identified, and the total number of coarse Al oxides is calculated. Furthermore, among the Si oxides identified on the observation surface, Si oxides with a major axis of 5.0 ⁇ m or more (coarse Si oxides) are identified, and the total number of coarse Si oxides is calculated.
- the major axes of Al oxides and Si oxides can be calculated by well-known methods. In this specification, the major axis of Al oxides and Si oxides means the longest line segment ( ⁇ m) among the line segments connecting any two points on the periphery of Al oxides and Si oxides on the observation surface.
- the number density of the coarse Al oxides is calculated based on the total number of the coarse Al oxides and the total area of the observation surface. Furthermore, the number density of the coarse Si oxides (pieces/200 mm 2 ) is calculated based on the total number of the coarse Si oxides and the total area of the observation surface. In this embodiment, the number density of the coarse Al oxides (pieces/200 mm 2 ) and the number density of the coarse Si oxides (pieces/200 mm 2 ) are both calculated by rounding off the obtained values to the first decimal place.
- the number density of the coarse Al oxides and the coarse Si oxides can be measured using a device (SEM-EDS device) in which a composition analysis function is provided to a scanning electron microscope.
- SEM-EDS device for example, an automatic analyzer manufactured by FEI (ASPEX) under the product name: Metals Quality Analyzer can be used.
- the SSC resistance of the steel material according to this embodiment can be evaluated by an SSC resistance test performed in accordance with NACE TM0177-2016 Method A. Specifically, it can be evaluated by the following method.
- the test solution is a mixed aqueous solution (NACE solution D) of 5.0 mass% sodium chloride and 0.4 mass% sodium acetate, adjusted to pH 5.0 with hydrochloric acid.
- Round bar test pieces are prepared from the steel material according to this embodiment.
- the steel material is a steel plate
- the round bar test piece is prepared from the center of the plate thickness.
- the axial direction of the round bar test piece is parallel to the rolling direction of the steel plate.
- the steel material is a steel pipe
- the round bar test piece is prepared from the center of the wall thickness.
- the axial direction of the round bar test piece is parallel to the axial direction of the steel pipe.
- the round bar test piece is prepared from the R/2 position. In this case, the axial direction of the round bar test piece is parallel to the axial direction of the round steel bar.
- 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 part.
- a stress equivalent to 90% of the actual yield stress is applied to the prepared round bar test piece.
- a test solution at 24°C is poured into a test vessel so that the round bar test piece to which stress has been applied is immersed, forming a test bath. After degassing the test bath, a mixed gas of 0.01 atm H2S gas and 0.99 atm CO2 gas is blown into the test bath to saturate the test bath. The test bath saturated with the mixed gas is held at 24°C for 720 hours.
- the steel material according to this embodiment has no cracks after 720 hours. In this specification, "no cracks are observed” means that no cracks are observed when the test piece after the test is observed with the naked eye.
- the microstructure of the steel material according to this embodiment has a total volume fraction of tempered martensite and tempered bainite of 90% or more.
- the remainder of the microstructure is, for example, ferrite or pearlite. If the microstructure of the steel material having the above-mentioned chemical composition contains a total volume fraction of tempered martensite and tempered bainite of 90% or more, it can achieve both a 150 ksi-class yield strength and excellent SSC resistance, provided that other configurations of this embodiment are satisfied. That is, in this embodiment, if the steel material achieves both a 150 ksi-class yield strength and excellent SSC resistance, it is determined that the microstructure has a total volume fraction of tempered martensite and tempered bainite of 90% or more.
- a test piece having an observation surface is prepared from the steel material according to this embodiment. If the steel material is a steel plate, a test piece is prepared from the center of the plate thickness, with the observation surface being a surface including the rolling direction and the plate thickness direction. If the steel material is a steel pipe, a test piece is prepared from the center of the wall thickness, with the observation surface being a surface including the pipe axial direction and the pipe radial direction. If the steel material is round bar, a test piece is prepared that includes the R/2 position in the center, with the observation surface being a surface including the axial direction and the radial direction.
- the observation surface of the test piece is polished to a mirror finish, and then immersed in a nital etching solution for about 10 seconds to reveal the structure by etching.
- the etched observation surface is observed in 10 fields of view as secondary electron images using a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the field area is, for example, 0.01 mm 2 (magnification 1000 times).
- tempered martensite and tempered bainite are identified from the contrast.
- the area ratio of the identified tempered martensite and tempered bainite is obtained.
- the method for obtaining the area ratio is not particularly limited, and a well-known method may be used.
- the area ratio of tempered martensite and tempered bainite can be obtained by image analysis.
- the arithmetic average value of the area ratios of tempered martensite and tempered bainite obtained in all fields of view is defined as the volume ratio of tempered martensite and tempered bainite.
- a method for manufacturing a steel material according to this embodiment will be described.
- a method for manufacturing a seamless steel pipe will be described below as an example of a steel material according to this embodiment.
- the method for manufacturing a seamless steel pipe includes a process for preparing a material (steelmaking process), a process for hot working the material to manufacture a mother pipe (hot working process), and a process for quenching and tempering the mother pipe to produce a seamless steel pipe (quenching process and tempering process).
- the manufacturing method according to this embodiment is not limited to the manufacturing method described below. Each process will be described in detail below.
- Stepmaking process In the steelmaking process, first, molten pig iron produced by a known method is refined in a converter (primary refining). The molten steel produced by the primary refining is then subjected to secondary refining. In the secondary refining, alloy elements are added to adjust the composition, and molten steel satisfying the above-mentioned chemical composition is produced.
- Secondary refining involves, for example, RH (Ruhrstahl-Hausen) vacuum degassing treatment. After that, the alloy components are finally adjusted. In secondary refining, combined refining may be performed. In this case, prior to the RH vacuum degassing treatment, for example, a refining treatment using LF (Ladle Furnace) or VAD (Vacuum Arc Degassing) is performed.
- Materials are manufactured using molten steel that has undergone secondary refinement. Specifically, cast pieces (slabs, blooms, or billets) are manufactured by continuous casting using molten steel that has undergone secondary refinement. In continuous casting, molten steel is first poured from a ladle into a tundish. At this time, packing sand is usually enclosed in the nozzle of the ladle to seal it. For this reason, packing sand may be mixed in with the molten steel from the ladle to the tundish. Also, when manufacturing materials having the above-mentioned chemical composition, silicon oxides may be used as packing sand. In this case, there is a concern that silicon oxides may be introduced into the manufactured material.
- the molten steel and the Si oxide are separated.
- the method of separating the Si oxide is not particularly limited, but the following method can be used, for example.
- a tilted metal plate is placed below the nozzle of the ladle and above the opening of the tundish.
- the Si oxide is discharged from the nozzle first, followed by the molten steel.
- the Si oxide is lighter than the molten steel. Therefore, the Si oxide discharged from the nozzle is guided out of the opening of the tundish along the tilt of the metal plate.
- the tilt of the metal plate may be provided, for example, by placing a metal plate processed into a cone shape without a bottom so that its apex is directly below the nozzle of the ladle, or may be provided by other methods. Furthermore, a single metal plate may be used, or multiple metal plates may be used in a stack. Furthermore, the thickness of the metal plate is not particularly limited, but is, for example, about 1 to 10 mm.
- the metal plate in this embodiment is preferably a metal plate made of alloy elements contained in the molten steel.
- an aluminum plate can be used as a metal plate made of alloy elements contained in the molten steel.
- an aluminum plate means a metal plate made of aluminum and the remainder made of impurities.
- the metal plate is removed from below the nozzle.
- the method for removing the metal plate from below the nozzle is not particularly limited, but for example, a hole may be formed in part of the metal plate and the metal plate may be removed using a rod with a hook at its tip. In this case, the hook at the tip of the rod can be hooked into the hole in the metal plate and the rod can be pulled to remove the metal plate.
- the Si oxide can be separated from the molten steel and the molten steel can be introduced into the tundish.
- the method for separating the Si oxide from the molten steel is not limited to the above method.
- the casting method is not particularly limited, but may be, for example, a continuous casting method.
- a continuous casting method When producing the material by continuous casting, it is preferable to carry out the following method.
- the casting speed in the continuous casting machine is preferably 1.0 to 3.0 m/min. If the casting speed is too slow, an accumulation zone of Al oxides may form in the material. In this case, the produced steel material will contain a large amount of coarse Al oxides, and the SSC resistance of the steel material will decrease. On the other hand, if the casting speed is too fast, the Al oxides may not rise to the surface of the molten steel, and a large amount of Al oxide may remain in the material. In this case, the produced steel material will contain a large amount of coarse Al oxides, and the SSC resistance of the steel material will decrease. Therefore, the casting speed in the continuous casting machine is preferably 1.0 to 3.0 m/min.
- the prepared material is hot worked to produce an intermediate steel material.
- the intermediate steel material corresponds to a mother pipe.
- the heating temperature is not particularly limited, but is, for example, 1100 to 1300°C.
- the billet extracted from the heating furnace is hot worked to produce a mother pipe (seamless steel pipe).
- the method of hot working is not particularly limited, and may be a well-known method.
- the Mannesmann process may be carried out as hot working to manufacture a blank tube.
- a round billet is pierced and rolled using 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 using a mandrel mill, reducer, sizing mill, etc. to produce a blank tube.
- the cumulative reduction in area during the hot working process is, for example, 20 to 70%.
- a blank pipe from the billet.
- the blank pipe may be manufactured by forging using the Erhardt method or the like.
- the blank pipe is manufactured through the above process. There are no particular limitations on the thickness of the blank pipe, but it is, for example, 9 to 60 mm.
- the material is first heated in a heating furnace.
- the heating temperature is not particularly limited, but is, for example, 1100 to 1300°C.
- the material extracted from the heating furnace is subjected to hot processing to produce intermediate steel material with a circular cross section perpendicular to the axial direction.
- the hot processing is, for example, blooming using a blooming mill, or hot rolling using a continuous rolling mill.
- a continuous rolling mill has an alternating arrangement of horizontal stands each having a pair of grooved rolls arranged side by side in the vertical direction, and vertical stands each having a pair of grooved rolls arranged side by side in the horizontal direction.
- the material is first heated in a heating furnace.
- the heating temperature is not particularly limited, but is, for example, 1100 to 1300°C.
- the material extracted from the heating furnace is hot-rolled using a blooming mill and a continuous rolling mill to produce intermediate steel material in the shape of a steel plate.
- the blank pipe produced by hot working may be air-cooled (as-rolled).
- the blank pipe produced by hot working may be quenched directly after hot working without being cooled to room temperature, or it may be quenched after being reheated after hot working.
- SR stress relief annealing
- the prepared material is hot worked to produce intermediate steel.
- the quenching process is described in detail below.
- quenching In the quenching process, quenching is performed on the prepared intermediate steel material (blank pipe).
- quenching means rapidly cooling the intermediate steel material at the A3 point or higher.
- the preferred quenching temperature is 800 to 1000°C. If the quenching temperature is too high, the prior ⁇ grains may become coarse, and the SSC resistance of the steel material may decrease. Therefore, the quenching temperature is preferably 800 to 1000°C.
- the quenching temperature corresponds to the surface temperature of the intermediate steel material measured by a thermometer installed at the outlet of the equipment that performs the final hot processing, when quenching is performed directly after hot processing. Furthermore, the quenching temperature corresponds to the temperature of the furnace in which quenching or reheating is performed, when quenching is performed after replenishment or reheating after hot processing.
- the quenching method involves continuously cooling the intermediate steel material (bare pipe) from the quenching start temperature, and continuously lowering the surface temperature of the raw pipe.
- the method of continuous cooling is not particularly limited, and any well-known method may be used.
- the method of continuous cooling is a method of cooling the raw pipe by immersing it in a water tank, or a method of accelerating cooling the raw pipe by shower water cooling or mist cooling.
- the microstructure will not be mainly martensite and bainite, and the mechanical properties specified in this embodiment (yield strength of more than 1034 to 1172 MPa) will not be obtained. In this case, excellent SSC resistance will also not be obtained.
- the intermediate steel is quenched during quenching.
- the average cooling rate in the range of the surface temperature of the intermediate steel (blank pipe) during quenching from 800 to 500°C is defined as the cooling rate during quenching CR 800-500 .
- the cooling rate during quenching CR 800-500 is determined from the temperature measured at the location that is cooled the slowest in the cross section of the intermediate steel to be quenched (for example, the center of the thickness of the intermediate steel when both surfaces are forcibly cooled).
- the preferred cooling rate during quenching CR 800-500 is 300° C./min or more.
- the more preferred lower limit of the cooling rate during quenching CR 800-500 is 450° C./min, and the most preferred is 600° C./min.
- the upper limit of the cooling rate during quenching CR 800-500 is not particularly specified, but is, for example, 60,000° C./min.
- the blank tube is heated in the austenite region multiple times and then quenched.
- the austenite grains before quenching are refined, and the SSC resistance of the steel material is improved.
- quenching may be combined with tempering, which will be described later, and performed multiple times. In other words, quenching and tempering may be performed multiple times. In this case, the SSC resistance of the steel material is further improved.
- the tempering process is described in detail below.
- tempering process In the tempering process, the blank pipe that has been quenched is tempered.
- tempering means reheating the quenched intermediate steel material at a temperature lower than the A c1 point and holding the temperature.
- the tempering temperature corresponds to the furnace temperature when the quenched intermediate steel material is heated and held.
- the tempering time means the time for which the intermediate steel material is held at the tempering temperature.
- the tempering temperature is adjusted appropriately depending on the chemical composition of the seamless steel pipe and the yield strength to be obtained.
- the tempering temperature is adjusted to adjust the yield strength of the seamless steel pipe to more than 1034 to 1172 MPa. It is of course possible for a person skilled in the art to adjust the yield strength of the seamless steel pipe to more than 1034 to 1172 MPa by adjusting the tempering temperature.
- the preferred tempering temperature is 640 to 660°C.
- the tempering time is preferably 10 to 90 minutes.
- a more preferable lower limit of the tempering time is 15 minutes.
- a more preferable upper limit of the tempering time is 80 minutes.
- the steel material according to this embodiment can be manufactured by the above manufacturing method.
- a method for manufacturing a seamless steel pipe has been described as one example.
- the steel material according to this embodiment may be a steel plate or other shape.
- a manufacturing method for a steel plate or other shape also includes, for example, a preparation step, a quenching step, and a tempering step.
- the above manufacturing method is one example, and the steel material may be manufactured by other manufacturing methods.
- Molten steel was produced having the chemical compositions shown in Tables 1-1 and 1-2.
- "-" means that the content of each element is at the impurity level.
- the Cu content, Ni content, and W content of Steel A were rounded off to two decimal places, meaning that they were 0%.
- the Ca content, Mg content, Zr content, and rare earth element (REM) content of Steel A were rounded off to five decimal places, meaning that they were 0%.
- the above molten steel was used to manufacture a round billet by continuous casting.
- a metal plate processed into a bottomless cone shape was placed above the opening of the tundish so that its apex was directly below the nozzle of the ladle.
- Table 2 shows whether or not a metal plate of the above shape was placed above the opening of the tundish. Specifically, when a metal plate of the above shape was placed above the opening of the tundish, "A” is indicated in the "Metal Plate” column of Table 2. When a metal plate of the above shape was not placed above the opening of the tundish, "B” is indicated in the "Metal Plate” column of Table 2.
- the metal plate of the above shape placed above the opening of the tundish was an aluminum plate. Specifically, three aluminum plates with a thickness of 2 mm were used in a stack. When a metal plate was placed, after the silicon oxide was discharged from the nozzle and before the molten steel was discharged, the metal plate was removed from below the nozzle using a rod with a hook formed at its tip. Furthermore, the molten steel was cast into a round billet at the casting speed shown in Table 2. At this time, electromagnetic stirring was performed in the mold at the current value shown in Table 2.
- the produced round billet of each test number was held at 1250°C for 1 hour, and then hot rolling was performed by the Mannesmann-mandrel method to produce a blank pipe (seamless steel pipe) of each test number. Furthermore, the blank pipe of each test number obtained was quenched. Specifically, the blank pipe of each test number was held at the temperature (°C) for the time (minutes) shown in the "Quenching process" column of Table 2, and then quenched by shower water cooling. Moreover, for test number 3, after the above-mentioned quenching, it was held at 900°C for 10 minutes, and then quenched by shower water cooling.
- the cooling rate during quenching CR 800-500 was in the range of 480 to 30000°C/min.
- the temperature (°C) of the quenching process was the temperature (°C) of the heat treatment furnace in which the blank pipe was heated.
- the time (minutes) of the quenching process was the time (minutes) in which the blank pipe was held at the quenching temperature.
- the obtained blank pipes of each test number were tempered. Specifically, the blank pipes of each test number were tempered by holding them at the temperature (°C) for the time (minutes) listed in the "Tempering process” column of Table 2.
- the tempering temperature (°C) listed in Table 2 is the temperature (°C) of the tempering furnace in which the blank pipes were heated.
- the tempering time (minutes) listed in Table 2 is the time (minutes) during which the blank pipes were held at the tempering temperature.
- the number density (pieces/200 mm 2 ) of the obtained coarse Al oxides is shown in the "coarse Al oxides (pieces/200 mm 2 )" column of Table 3.
- the number density (pieces/200 mm 2 ) of the obtained coarse Si oxides is shown in the "coarse Si oxides (pieces/200 mm 2 )" column of Table 3.
- SSC resistance test For the seamless steel pipes of each test number, an SSC resistance test was performed according to a method in accordance with NACE TM0177-2016 Method A to evaluate the SSC resistance. Specifically, a round bar test piece having a diameter of 6.35 mm and a parallel part length of 25.4 mm was prepared from the center of the wall thickness of the seamless steel pipes of each test number. The SSC resistance test was performed on three of the prepared test pieces. The axial direction of the test pieces was parallel to the tube axial direction.
- test solution used was a mixed aqueous solution of 5.0 mass% sodium chloride and 0.4 mass% sodium acetate (NACE solution D) adjusted to pH 5.0 with hydrochloric acid.
- Test solutions at 24°C were poured into three test vessels to form test baths.
- the three round bar test specimens to which stress was applied were immersed one by one in the test baths of different test vessels. After degassing each test bath, a mixed gas of 0.01 atm H2S gas and 0.99 atm CO2 gas was blown into the test bath to saturate the test bath.
- the test bath saturated with the mixed gas was held at 24°C for 720 hours.
- the round bar test pieces of each test number were observed for the occurrence of sulfide stress cracking (SSC). Specifically, the round bar test pieces after 720 hours of holding were observed with the naked eye. For each test number, the number of round bar test pieces in which SSC occurred out of the three round bar test pieces is shown in the "Number of pieces with SSC" column in Table 3.
- the seamless steel pipes of test numbers 1 to 12 had appropriate chemical compositions, and the manufacturing methods also satisfied the above-mentioned preferred conditions.
- the seamless steel pipes had a yield strength of more than 1034 to 1172 MPa, a number density of coarse Al oxides of less than 30 pieces/200 mm 2 , and a number density of coarse Si oxides of 5 pieces/200 mm 2 or less.
- the number of SSC occurrences in these seamless steel pipes was 0 in the SSC resistance test. That is, the seamless steel pipes of test numbers 1 to 12 had a yield strength of more than 1034 to 1172 MPa and excellent SSC resistance. It was determined that the sum of the volume fractions of tempered martensite and tempered bainite in the microstructure of these seamless steel pipes was 90% or more.
- the casting speed in the steelmaking process of the seamless steel pipes of test numbers 13 and 14 was too fast.
- the number density of coarse Al oxides in these seamless steel pipes was 30 pieces/200 mm2 or more .
- the number of SSC occurrences in these seamless steel pipes was one or more in the SSC resistance test, and these seamless steel pipes did not have excellent SSC resistance.
- the seamless steel pipe of test number 18 had an excessively high O content. As a result, this seamless steel pipe had more than one SSC occurrence in the SSC resistance test, and did not have excellent SSC resistance.
- the seamless steel pipe of test number 19 had too low a Mo content. As a result, this seamless steel pipe had more than one SSC occurrence in the SSC resistance test, and did not have excellent SSC resistance.
- the seamless steel pipe of test number 20 had an excessively high S content. As a result, this seamless steel pipe had more than one SSC occurrence in the SSC resistance test, and did not have excellent SSC resistance.
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Abstract
Description
質量%で、
C:0.15~0.45%、
Si:0.05~1.00%、
Mn:0.05~1.00%、
P:0.030%以下、
S:0.0050%以下、
Al:0.005~0.100%、
Cr:0.30~1.50%、
Mo:0.40~2.00%、
Ti:0.002~0.020%、
Nb:0.002~0.100%、
V:0.05~0.30%、
B:0.0005~0.0040%、
N:0.0100%以下、
O:0.0040%以下、
Cu:0~0.50%、
Ni:0~0.50%、
W:0~0.50%、
Ca:0~0.0100%、
Mg:0~0.0100%、
Zr:0~0.0100%、
希土類元素:0~0.0100%、及び、
残部がFe及び不純物からなり、
降伏強度が1034超~1172MPaであり、
前記鋼材中において、
質量%で、Al含有量が20%以上であり、O含有量が10%以上であり、長径が5.0μm以上のAl酸化物の個数密度が、30個/200mm2未満であり、
質量%で、Al含有量が20%未満であり、Si含有量が20%以上であり、O含有量が10%以上であり、長径が5.0μm以上のSi酸化物の個数密度が、5個/200mm2以下である。
鋼材であって、
質量%で、
C:0.15~0.45%、
Si:0.05~1.00%、
Mn:0.05~1.00%、
P:0.030%以下、
S:0.0050%以下、
Al:0.005~0.100%、
Cr:0.30~1.50%、
Mo:0.40~2.00%、
Ti:0.002~0.020%、
Nb:0.002~0.100%、
V:0.05~0.30%、
B:0.0005~0.0040%、
N:0.0100%以下、
O:0.0040%以下、
Cu:0~0.50%、
Ni:0~0.50%、
W:0~0.50%、
Ca:0~0.0100%、
Mg:0~0.0100%、
Zr:0~0.0100%、
希土類元素:0~0.0100%、及び、
残部がFe及び不純物からなり、
降伏強度が1034超~1172MPaであり、
前記鋼材中において、
質量%で、Al含有量が20%以上であり、O含有量が10%以上であり、長径が5.0μm以上のAl酸化物の個数密度が、30個/200mm2未満であり、
質量%で、Al含有量が20%未満であり、Si含有量が20%以上であり、O含有量が10%以上であり、長径が5.0μm以上のSi酸化物の個数密度が、5個/200mm2以下である、
鋼材。
[1]に記載の鋼材であって、
Cu:0.01~0.50%、
Ni:0.01~0.50%、
W:0.01~0.50%、
Ca:0.0001~0.0100%、
Mg:0.0001~0.0100%、
Zr:0.0001~0.0100%、及び、
希土類元素:0.0001~0.0100%からなる群から選択される1元素以上を含有する、
鋼材。
[1]又は[2]に記載の鋼材であって、
前記鋼材は継目無鋼管である、
鋼材。
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、鋼材の強度を高める。Cはさらに、製造工程中の焼戻しにおいて、炭化物の球状化を促進し、鋼材の耐SSC性を高める。C含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、C含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、炭化物が多くなりすぎ、鋼材の耐SSC性が低下する。したがって、C含有量は0.15~0.45%である。C含有量の好ましい下限は0.18%であり、さらに好ましくは0.20%であり、さらに好ましくは0.22%であり、さらに好ましくは0.23%である。C含有量の好ましい上限は0.40%であり、さらに好ましくは0.38%であり、さらに好ましくは0.35%であり、さらに好ましくは0.30%である。
ケイ素(Si)は、鋼を脱酸する。Si含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、Si含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、粗大Si酸化物が多数形成され、鋼材の耐SSC性が低下する場合がある。したがって、Si含有量は0.05~1.00%である。Si含有量の好ましい下限は0.10%であり、さらに好ましくは0.15%であり、さらに好ましくは0.20%である。Si含有量の好ましい上限は0.85%であり、さらに好ましくは0.75%であり、さらに好ましくは0.60%であり、さらに好ましくは0.50%であり、さらに好ましくは0.40%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る。Mn含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、Mn含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、粗大な硫化物系介在物が形成され、鋼材の耐SSC性が低下する。したがって、Mn含有量は0.05~1.00%である。Mn含有量の好ましい下限は0.06%であり、さらに好ましくは0.08%であり、さらに好ましくは0.10%である。Mn含有量の好ましい上限は0.90%であり、さらに好ましくは0.80%であり、さらに好ましくは0.70%であり、さらに好ましくは0.60%であり、さらに好ましくは0.50%である。
燐(P)は不純物である。すなわち、P含有量の下限は0%超である。P含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、Pが粒界に偏析し、鋼材の耐SSC性が低下する。したがって、P含有量は0.030%以下である。P含有量の好ましい上限は0.025%であり、さらに好ましくは0.020%であり、さらに好ましくは0.015%であり、さらに好ましくは0.010%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0.001%であり、さらに好ましくは0.002%であり、さらに好ましくは0.003%である。
硫黄(S)は不純物である。すなわち、S含有量の下限は0%超である。S含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、Sが粒界に偏析し、鋼材の耐SSC性が低下する。したがって、S含有量は0.0050%以下である。S含有量の好ましい上限は0.0040%であり、さらに好ましくは0.0032%であり、さらに好ましくは0.0030%であり、さらに好ましくは0.0020%であり、さらに好ましくは0.0015%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、さらに好ましくは0.0002%であり、さらに好ましくは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、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られず、鋼材の耐SSC性が低下する。一方、Al含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、粗大Al酸化物が多数形成され、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0.010%であり、さらに好ましくは0.015%であり、さらに好ましくは0.020%である。Al含有量の好ましい上限は0.080%であり、さらに好ましくは0.060%であり、さらに好ましくは0.040%であり、さらに好ましくは0.035%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る。Crはさらに、鋼材の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、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、Cr含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、鋼材の耐SSC性が低下する。したがって、Cr含有量は0.30~1.50%である。Cr含有量の好ましい下限は0.35%であり、さらに好ましくは0.40%であり、さらに好ましくは0.50%である。Cr含有量の好ましい上限は1.40%であり、さらに好ましくは1.30%であり、さらに好ましくは1.20%であり、さらに好ましくは1.10%であり、さらに好ましくは1.05%である。
モリブデン(Mo)は鋼材の焼入れ性を高める。Moはさらに、鋼材の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。Mo含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。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0.40~2.00%である。Mo含有量の好ましい下限は0.45%であり、さらに好ましくは0.50%であり、さらに好ましくは0.51%であり、さらに好ましくは0.55%であり、さらに好ましくは0.60%である。Mo含有量の好ましい上限は1.80%であり、さらに好ましくは1.60%であり、さらに好ましくは1.40%であり、さらに好ましくは1.30%である。
チタン(Ti)はNと結合して窒化物を形成し、ピンニング効果により鋼材の結晶粒を微細化する。その結果、鋼材の強度が高まる。Ti含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、Ti含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、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0.002~0.020%である。Ti含有量の好ましい下限は0.003%であり、さらに好ましくは0.004%である。Ti含有量の好ましい上限は0.018%であり、さらに好ましくは0.015%であり、さらに好ましくは0.010%であり、さらに好ましくは0.008%である。
ニオブ(Nb)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、鋼材の結晶粒を微細化し、鋼材の耐SSC性を高める。Nbはさらに、焼戻し時に微細な炭化物を形成して鋼材の焼戻し軟化抵抗を高め、鋼材の強度を高める。Nb含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、Nb含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、炭窒化物等が過剰に形成され、鋼材の耐SSC性が低下する。したがって、Nb含有量は0.002~0.100%である。Nb含有量の好ましい下限は0.005%であり、さらに好ましくは0.010%であり、さらに好ましくは0.015%であり、さらに好ましくは0.020%である。Nb含有量の好ましい上限は0.080%であり、さらに好ましくは0.060%であり、さらに好ましくは0.040%である。
バナジウム(V)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、鋼材の結晶粒を微細化し、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して鋼材の焼戻し軟化抵抗を高め、鋼材の強度を高める。V含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、V含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、炭窒化物等が過剰に形成され、鋼材の耐SSC性が低下する。したがって、V含有量は0.05~0.30%である。V含有量の好ましい下限は0.06%であり、さらに好ましくは0.07%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0.25%であり、さらに好ましくは0.20%であり、さらに好ましくは0.15%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、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、B含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、粗大な窒化物が形成され、鋼材の耐SSC性が低下する。したがって、B含有量は0.0005~0.0040%である。B含有量の好ましい下限は0.0006%であり、さらに好ましくは0.0008%である。B含有量の好ましい上限は0.0035%であり、さらに好ましくは0.0030%であり、さらに好ましくは0.0025%であり、さらに好ましくは0.0020%である。
窒素(N)は不可避に含有される。すなわち、N含有量の下限は0%超である。NはTiと結合して窒化物を形成し、ピンニング効果により、鋼材の結晶粒を微細化する。その結果、鋼材の強度が高まる。しかしながら、N含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、粗大な窒化物が形成され、鋼材の耐SSC性が低下する。したがって、N含有量は0.0100%以下である。N含有量の好ましい上限は0.0080%であり、さらに好ましくは0.0060%であり、さらに好ましくは0.0050%であり、さらに好ましくは0.0040%である。上記効果をより有効に得るためのN含有量の好ましい下限は0.0005%であり、さらに好ましくは0.0010%であり、さらに好ましくは0.0015%であり、さらに好ましくは0.0020%である。
酸素(O)は不純物である。すなわち、O含有量の下限は0%超である。O含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、粗大な酸化物が形成され、鋼材の耐SSC性が低下する。したがって、O含有量は0.0040%以下である。O含有量の好ましい上限は0.0035%であり、さらに好ましくは0.0033%であり、さらに好ましくは0.0030%であり、さらに好ましくは0.0025%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、さらに好ましくは0.0002%であり、さらに好ましくは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、Cu、及び、Niからなる群から選択される1元素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、鋼材の焼入れ性を高める。
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、鋼材の強度を高める。Cuが少しでも含有されれば、上記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、他の元素含有量が本実施形態の範囲内であっても、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、さらに好ましくは0.01%であり、さらに好ましくは0.02%である。Cu含有量の好ましい上限は0.35%であり、さらに好ましくは0.25%であり、さらに好ましくは0.15%であり、さらに好ましくは0.10%であり、さらに好ましくは0.05%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、鋼材の強度を高める。Niはさらに、鋼に固溶して、鋼材の耐SSC性を高める。Ni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、Ni含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、局部的な腐食が促進され、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、さらに好ましくは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0.30%であり、さらに好ましくは0.20%であり、さらに好ましくは0.10%であり、さらに好ましくは0.05%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はサワー環境において、保護性の腐食被膜を形成し、鋼材への水素の侵入を抑制する。これにより、鋼材の耐SSC性を高める。Wが少しでも含有されれば、上記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、他の元素含有量が本実施形態の範囲内であっても、鋼材中に粗大な炭化物が形成され、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、さらに好ましくは0.01%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0.50%未満であり、さらに好ましくは0.48%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、上記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、他の元素含有量が本実施形態の範囲内であっても、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、さらに好ましくは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。Ca含有量の好ましい上限は0.0040%であり、さらに好ましくは0.0025%であり、さらに好ましくは0.0020%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、上記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、他の元素含有量が本実施形態の範囲内であっても、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、さらに好ましくは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。Mg含有量の好ましい上限は0.0040%であり、さらに好ましくは0.0025%であり、さらに好ましくは0.0020%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、上記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、他の元素含有量が本実施形態の範囲内であっても、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、さらに好ましくは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。Zr含有量の好ましい上限は0.0040%であり、さらに好ましくは0.0025%であり、さらに好ましくは0.0020%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、上記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、他の元素含有量が本実施形態の範囲内であっても、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、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、さらに好ましくは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、さらに好ましくは0.0025%であり、さらに好ましくは0.0020%である。
本実施形態による鋼材の降伏強度は1034超~1172MPa(150超~170ksi)である。本明細書でいう降伏強度は、ASTM E8/E8M(2021)に準拠した常温(25℃)での引張試験で得られた0.65%伸び時の応力(0.65%耐力)を意味する。本実施形態による鋼材は、上述の化学組成を有し、後述する粗大Al酸化物の個数密度、及び、粗大Si酸化物の個数密度を満たすことで、降伏強度が1034超~1172MPaであっても、優れた耐SSC性を有する。
本実施形態による鋼材は、上述の化学組成と、1034超~1172MPaの降伏強度を有し、さらに、粗大Al酸化物の個数密度が30個/200mm2未満である。上述のとおり、本明細書では、質量%で、Al含有量が20%以上であり、O含有量が10%以上の粒子を「Al酸化物」ともいう。上述のとおり、本明細書ではさらに、長径が5.0μm以上のAl酸化物を「粗大Al酸化物」ともいう。つまり、粗大Al酸化物とは、質量%で、Al含有量が20%以上であり、O含有量が10%以上であり、長径が5.0μm以上の粒子を意味する。
本実施形態による鋼材は、上述の化学組成と、1034超~1172MPaの降伏強度を有し、粗大Al酸化物の個数密度が30個/200mm2未満であり、さらに、粗大Si酸化物の個数密度が5個/200mm2以下である。上述のとおり、本明細書では、質量%で、Al含有量が20%未満であり、Si含有量が20%以上であり、O含有量が10%以上の粒子を「Si酸化物」ともいう。上述のとおり、本明細書ではさらに、長径が5.0μm以上のSi酸化物を「粗大Si酸化物」ともいう。つまり、粗大Si酸化物とは、質量%で、Al含有量が20%未満であり、Si含有量が20%以上であり、O含有量が10%以上であり、長径が5.0μm以上の粒子を意味する。
本実施形態による鋼材の耐SSC性は、NACE TM0177-2016 Method Aに準拠した方法で実施する耐SSC性試験によって評価できる。具体的に、次の方法で評価することができる。
本実施形態による鋼材のミクロ組織は、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、本実施形態の他の構成を満たすことを条件に、150ksi級の降伏強度と、優れた耐SSC性とを両立できる。すなわち、本実施形態では、鋼材が150ksi級の降伏強度と、優れた耐SSC性とを両立していれば、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%以上であると判断する。
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。継目無鋼管の製造方法は、素材を準備する工程(製鋼工程)と、素材を熱間加工して素管を製造する工程(熱間加工工程)と、素管に対して焼入れ及び焼戻しを実施して、継目無鋼管とする工程(焼入れ工程及び焼戻し工程)とを備える。なお、本実施形態による製造方法は、以下に説明する製造方法に限定されない。以下、各工程について詳述する。
製鋼工程では、初めに、周知の方法で製造された溶銑に対して、転炉での精錬(一次精錬)を実施する。一次精錬された溶鋼に対して、二次精錬を実施する。二次精錬において、成分調整の合金元素の添加を実施して、上述の化学組成を満たす溶鋼を製造する。
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。鋼材が継目無鋼管である場合、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。
焼入れ工程では、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。焼入れ温度が高すぎれば、旧γ粒の結晶粒が粗大になり、鋼材の耐SSC性が低下する場合がある。したがって、焼入れ温度は800~1000℃であるのが好ましい。
焼戻し工程では、上述の焼入れが実施された素管に対して、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点未満の温度で再加熱して、保持することを意味する。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。焼戻し時間とは、中間鋼材を焼戻し温度で保持する時間を意味する。
上記の焼戻し後の各試験番号の継目無鋼管に対して、以下に説明する引張試験、粗大Al酸化物及び粗大Si酸化物の個数密度測定試験、及び、耐SSC性試験を実施した。
各試験番号の継目無鋼管に対して、引張試験を実施して、降伏強度を求めた。引張試験はASTM E8/E8M(2021)に準拠して行った。各試験番号の継目無鋼管の肉厚中央部から、平行部直径8.9mm、標点距離35.6mmの丸棒試験片を作製した。丸棒試験片の軸方向は、継目無鋼管の管軸方向と平行であった。作製した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、各試験番号の継目無鋼管の降伏強度(MPa)を得た。なお、本実施例では、引張試験で得られた0.65%伸び時の応力(0.65%耐力)を、降伏強度と定義した。得られた降伏強度(MPa)を「YS(MPa)」として表3に示す。
各試験番号の継目無鋼管に対して、粗大Al酸化物及び粗大Si酸化物の個数密度測定試験を実施して、長径5.0μm以上のAl酸化物(粗大Al酸化物)、及び、長径5.0μm以上のSi酸化物(粗大Si酸化物)の個数密度を求めた。各試験番号の継目無鋼管の肉厚中央部から作製した試験片を用いて、上述の方法で、粗大Al酸化物及び粗大Si酸化物の個数密度を求めた。得られた粗大Al酸化物の個数密度(個/200mm2)を、表3の「粗大Al酸化物(個/200mm2)」欄に示す。得られた粗大Si酸化物の個数密度(個/200mm2)を、表3の「粗大Si酸化物(個/200mm2)」欄に示す。
各試験番号の継目無鋼管に対して、NACE TM0177-2016 Method Aに準拠した方法で耐SSC性試験を実施して、耐SSC性を評価した。具体的には、各試験番号の継目無鋼管の肉厚中央部から、径6.35mm、平行部の長さ25.4mmの丸棒試験片を作製した。作製した試験片のうち3本に対して、耐SSC性試験を実施した。なお、試験片の軸方向は、管軸方向に平行であった。
表1-1、表1-2、表2、及び、表3を参照して、試験番号1~12の継目無鋼管の化学組成は適切であり、製造方法も上述の好ましい条件を満たしていた。その結果、これらの継目無鋼管は、降伏強度が1034超~1172MPaであり、粗大Al酸化物の個数密度が30個/200mm2未満であり、さらに、粗大Si酸化物の個数密度が5個/200mm2以下であった。その結果、これらの継目無鋼管は、耐SSC性試験において、SSC発生本数が0本となった。すなわち、試験番号1~12の継目無鋼管は、1034超~1172MPaの降伏強度と、優れた耐SSC性とを有していた。なお、これらの継目無鋼管は、ミクロ組織において、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%以上であると判断した。
Claims (3)
- 鋼材であって、
質量%で、
C:0.15~0.45%、
Si:0.05~1.00%、
Mn:0.05~1.00%、
P:0.030%以下、
S:0.0050%以下、
Al:0.005~0.100%、
Cr:0.30~1.50%、
Mo:0.40~2.00%、
Ti:0.002~0.020%、
Nb:0.002~0.100%、
V:0.05~0.30%、
B:0.0005~0.0040%、
N:0.0100%以下、
O:0.0040%以下、
Cu:0~0.50%、
Ni:0~0.50%、
W:0~0.50%、
Ca:0~0.0100%、
Mg:0~0.0100%、
Zr:0~0.0100%、
希土類元素:0~0.0100%、及び、
残部がFe及び不純物からなり、
降伏強度が1034超~1172MPaであり、
前記鋼材中において、
質量%で、Al含有量が20%以上であり、O含有量が10%以上であり、長径が5.0μm以上のAl酸化物の個数密度が、30個/200mm2未満であり、
質量%で、Al含有量が20%未満であり、Si含有量が20%以上であり、O含有量が10%以上であり、長径が5.0μm以上のSi酸化物の個数密度が、5個/200mm2以下である、
鋼材。 - 請求項1に記載の鋼材であって、
Cu:0.01~0.50%、
Ni:0.01~0.50%、
W:0.01~0.50%、
Ca:0.0001~0.0100%、
Mg:0.0001~0.0100%、
Zr:0.0001~0.0100%、及び、
希土類元素:0.0001~0.0100%からなる群から選択される1元素以上を含有する、
鋼材。 - 請求項1又は請求項2に記載の鋼材であって、
前記鋼材は継目無鋼管である、
鋼材。
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