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
• • 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
  • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
• • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
  • C21D8/10—Modifying the physical properties of ferrous metals or ferrous alloys 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
  • 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

Definitions

• This disclosure relates to steel products, and more particularly to steel products suitable for use in high H2S environments.
• oil wells As oil and gas wells (hereinafter, oil and gas wells will be collectively referred to simply as "oil wells") become deeper, there is 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 oil well steel materials of 110 ksi or more (yield strength of 758 MPa or more).
• SSC resistance sulfide stress cracking resistance
• Patent Document 1 Japanese Patent Application Laid-Open No. 2006-28612
• Patent Document 2 Japanese Patent Application Laid-Open No. 2017-166060
• the steel material disclosed in Patent Document 1 is a steel for steel pipes, and consists, by mass, of 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%, and the balance being Fe and impurities.
• This steel material further contains non-metallic inclusions containing Ca, Al, Ti, N, O, and S, with a (Ca%)/(Al%) ratio of 0.55-1.72 and a (Ca%)/(Ti%) ratio of 0.7-19.
• Patent Document 1 states that this steel has a high yield strength of over 758 MPa and excellent SSC resistance.
• the steel material disclosed in Patent Document 2 is a material for high-strength oil well steel pipes, 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, with the balance being Fe and unavoidable impurities.
• this steel material has a Rockwell hardness HRC that satisfies the formula (15.6 x [%C] + 29.2 ⁇ HRC ⁇ 60.5 x [%C] + 31.1).
• Patent Document 2 states that this steel material can be used to produce steel pipes with a yield strength of 758 to less than 862 MPa and excellent SSC resistance.
• Patent Documents 1 and 2 disclose techniques for improving the SSC resistance of steel materials.
• pitting corrosion resistance oil well steel materials intended for use in high H2S environments are also required to have resistance to pitting corrosion and/or crevice corrosion (hereinafter referred to as "pitting corrosion resistance").
• pitting corrosion resistance little research has been done on the pitting corrosion resistance of oil well steel materials in high H2S environments.
• the steel material according to the present disclosure is In mass%, C: 0.20-0.35%, Si: 0.10 to 1.50%, Mn: 0.05-0.55%, P: 0.050% or less, S: 0.0100% or less, Cr: 0.20-1.00%, Mo: 0.20-1.50%, Ti: 0.003 to 0.030%, Al: 0.010-0.100%, N: 0.0100% or less, O: 0.0050% or less, Sb: 0 to 0.50%, Cu: 0 to 0.50%, Ni: 0 to 0.50%, Co: 0 to 0.50%, Zr: 0 to 0.0040%, Nb: 0 to 0.150%, V: 0 to 0.500%, B: 0 to 0.0030%, Ca: 0-0.0040%, Mg: 0 to 0.0040%, Rare earth elements: 0 to 0.0040%, and the balance being Fe and impurities;
• the yield strength is 758 to less than 965 MPa, In the microstructure, the standard deviation of the grain size
• Steels according to the present disclosure have high strength and excellent pitting corrosion resistance in high H2S environments.
• FIG. 1 is a diagram showing the relationship between the standard deviation ⁇ of the grain size number of prior austenite grains and the number of pits (number of pits), which is an index of pitting corrosion resistance, in this example.
• a steel material consisting of Cu: 0-0.50%, Ni: 0-0.50%, Co: 0-0.50%, Zr: 0-0.0040%, Nb: 0-0.150%, V: 0-0.500%, B: 0-0.0030%, Ca: 0-0.0040%, Mg: 0-0.0040%, rare earth elements: 0-0.0040%, and the remainder being Fe and impurities may be able to achieve both a yield strength of 110-140 ksi and excellent pitting corrosion resistance in a high H2
• a high H 2 S environment has a higher hydrogen sulfide concentration than an H 2 S environment at normal pressure, making it easier for a corrosion film to form on the surface of a steel material. Furthermore, the corrosion film formed on the surface of a steel material has the effect of protecting the surface of the steel material. Therefore, in a high H 2 S environment, the use of a corrosion film may effectively improve the pitting corrosion resistance of the steel material.
• the grain boundaries of a steel material have a mismatched atomic arrangement compared to the interior of the grains, making the corrosion rate more likely to be high. Therefore, if a corrosion film can be formed quickly and uniformly on the surface of a steel material, the pitting corrosion resistance in a high H 2 S environment may be improved.
• prior ⁇ grain boundaries which are grain boundaries at the time of heating to the austenite region
• the supply of metal ions for film formation may be uniform.
• prior ⁇ grain boundaries are uniformly distributed in the steel material, a uniform corrosion film can be formed quickly, potentially improving the pitting corrosion resistance of the steel material.
• the inventors speculate that, based on the above mechanism, if the standard deviation ⁇ of the prior ⁇ grain grain size number in a steel material having the above-mentioned chemical composition and yield strength is 0.80 or less, the pitting corrosion resistance in a high H2S environment will be improved. Note that it is possible that excellent pitting corrosion resistance in a high H2S environment may be achieved by a mechanism different from that speculated by the inventors. However, the fact that a steel material having the above-mentioned chemical composition and yield strength has excellent pitting corrosion resistance even in a high H2S environment if the standard deviation ⁇ of the prior ⁇ grain grain size number is 0.80 or less is proven by the examples described below.
• 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 refers to 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 0.20-0.35% Carbon (C) improves the hardenability of steel and increases its strength. If the C content is too low, the above effects cannot be sufficiently achieved even if the contents of other elements are within the ranges of this embodiment. On the other hand, if the C content is too high, even if the contents of other elements are within the ranges of this embodiment, the amount of carbides will be too large, and the corrosion resistance of the steel will decrease. Therefore, the C content is 0.20 to 0.35%.
• the preferred lower limit of the C content is 0.21%, more preferably 0.22%, and even more preferably 0.23%.
• the preferred upper limit of the C content is 0.34%, more preferably 0.33%, and even more preferably 0.32%.
• the lower limit of the Si content is more than 0.50%. That is, the Si content is preferably more than 0.50% to 1.50%.
• a steel material having a Si content of more than 0.50% to 1.50% while satisfying the contents of other elements of this embodiment has high strength and, in a high H 2 S environment, has excellent pitting corrosion resistance as well as excellent general corrosion resistance. Therefore, the Si content is preferably more than 0.50% to 1.50%.
• a more preferable lower limit of the Si content is 0.51%, even more preferably 0.53%, even more preferably 0.55%, and even more preferably 0.60%.
• P 0.050% or less Phosphorus (P) is an impurity. That is, the lower limit of the P content is greater than 0%. If the P content is too high, even if the contents of other elements are within the ranges of this embodiment, P segregates at grain boundaries, reducing the corrosion resistance of the steel in a high H2S environment. Therefore, the P content is 0.050% or less.
• a preferred upper limit of the P content is 0.048%, more preferably 0.045%, and even more preferably 0.040%.
• the P content is preferably as low as possible. However, an extreme reduction in the P content significantly increases manufacturing costs. Therefore, considering industrial production, a preferred lower limit of the P content is 0.001%, more preferably 0.002%, and even more preferably 0.003%.
• S 0.0100% or less Sulfur (S) is an impurity. That is, the lower limit of the S content is greater than 0%. If the S content is too high, even if the contents of other elements are within the ranges of this embodiment, coarse sulfides are formed, reducing the pitting corrosion resistance of the steel in a high H2S environment. Therefore, the S content is 0.0100% or less.
• a preferred upper limit of the S content is 0.0095%, more preferably 0.0080%, even more preferably 0.0060%, and even more preferably 0.0040%.
• the S content should be as low as possible. However, an extreme reduction in the S content significantly increases production costs. Therefore, considering industrial production, a preferred lower limit of the S content is 0.0001%, more preferably 0.0003%, and even more preferably 0.0005%.
• Chromium (Cr) promotes the formation of a corrosion film on the surface of a steel material. As a result, the pitting corrosion resistance of the steel material in a high H2S environment is improved. If the Cr content is too low, the above effect cannot be sufficiently obtained even if the contents of other elements are within the ranges of this embodiment. On the other hand, if the Cr content is too high, coarse precipitates are formed, reducing the pitting corrosion resistance of the steel material, even if the contents of other elements are within the ranges of this embodiment. Therefore, the Cr content is 0.20 to 1.00%.
• the preferred lower limit of the Cr content is 0.21%, more preferably 0.23%, even more preferably 0.25%, and even more preferably 0.30%.
• the preferred upper limit of the Cr content is 0.98%, more preferably 0.96%, and even more preferably 0.95%.
• Mo 0.20 ⁇ 1.50% Molybdenum (Mo) contributes to stabilizing the corrosion film on the steel surface. As a result, the pitting corrosion resistance of the steel in a high H2S environment is improved. If the Mo content is too low, the above effects cannot be sufficiently obtained even if the contents of other elements are within the ranges of this embodiment. On the other hand, if the Mo content is too high, the above effects saturate. Therefore, the Mo content is 0.20 to 1.50%.
• the preferred lower limit of the Mo content is 0.21%, more preferably 0.24%, and even more preferably 0.30%.
• the preferred upper limit of the Mo content is 1.49%, more preferably 1.45%, even more preferably 1.40%, and even more preferably 1.30%.
• Ti 0.003 ⁇ 0.030% Titanium (Ti) bonds with N to form nitrides, which refine the grains of the steel material through a pinning effect. As a result, the pitting corrosion resistance of the steel material is improved. If the Ti content is too low, the above effect cannot be sufficiently obtained even if the contents of other elements are within the ranges of this embodiment. On the other hand, if the Ti content is too high, even if the contents of other elements are within the ranges of this embodiment, the Ti nitrides become coarse, and the pitting corrosion resistance of the steel material is reduced. Therefore, the Ti content is 0.003 to 0.030%. The preferred lower limit of the Ti content is 0.003%, and more preferably 0.005%. The preferred upper limit of the Ti content is 0.028%, and more preferably 0.025%.
• Al 0.010-0.100%
• Aluminum (Al) deoxidizes steel. If the Al content is too low, the above effect cannot be sufficiently achieved even if the contents of other elements are within the ranges of this embodiment. On the other hand, if the Al content is too high, coarse oxide-based inclusions are formed, reducing the pitting corrosion resistance of the steel material, even if the contents of other elements are within the ranges of this embodiment. Therefore, the Al content is 0.010 to 0.100%. A preferred lower limit of the Al content is 0.015%, more preferably 0.020%, and even more preferably 0.025%. A preferred upper limit of the Al content is 0.080%, more preferably 0.070%, and even more preferably 0.060%. As used herein, the "Al" content refers to the content of "acid-soluble Al,” i.e., "sol. Al.”
• N 0.0100% or less Nitrogen (N) is unavoidably contained. That is, the lower limit of the N content is greater than 0%. N combines with Ti to form nitrides, which refine the grains of the steel material through a pinning effect. As a result, the pitting corrosion resistance of the steel material is improved. On the other hand, if the N content is too high, even if the contents of other elements are within the ranges of this embodiment, coarse nitrides are formed, and the pitting corrosion resistance of the steel material is actually reduced. Therefore, the N content is 0.0100% or less. A preferred upper limit of the N content is 0.0080%, more preferably 0.0060%, and even more preferably 0.0050%. To more effectively obtain the above effects, a preferred lower limit of the N content is 0.0005%, more preferably 0.0010%, even more preferably 0.0020%, and even more preferably 0.0025%.
• the remainder of the chemical composition of the steel material according to this embodiment consists of Fe and impurities.
• impurities refers to substances that are mixed in from raw materials such as ore or scrap, or 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, in place of a portion of Fe, one or more elements selected from the group consisting of Sb, Cu, Ni, Co, and Zr. Any of these elements suppresses the penetration of hydrogen into the steel material and improves the SSC resistance of the steel material in a high H2S environment.
• Sb 0-0.50%
• Antimony (Sb) is an optional element and does not necessarily need to be contained. That is, the Sb content may be 0%.
• Sb suppresses hydrogen penetration into the steel material in a high H 2 S environment.
• the SSC resistance of the steel material in a high H 2 S environment is improved.
• the Sb content is 0 to 0.50%.
• the preferred lower limit of the Sb content is more than 0%, more preferably 0.01%, even more preferably 0.02%, even more preferably 0.03%, and even more preferably 0.05%.
• the preferred upper limit of the Sb content is 0.45%, even more preferably 0.40%.
• 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 suppresses hydrogen penetration into the steel material in a high-H 2 S environment. As a result, the SSC resistance of the steel material in a high-H 2 S environment is improved. Even if even a small amount of Cu is contained, the above effect can be obtained to some extent. However, if the Cu content is too high, even if the contents of other elements are within the ranges of this embodiment, the hardenability of the steel material will be too high and the toughness of the steel material will decrease. Therefore, the Cu content is 0 to 0.50%.
• Nickel (Ni) is an optional element and may not be contained. That is, the Ni content may be 0%. When contained, Ni forms a corrosion film in a high-H 2 S environment, suppressing hydrogen penetration into the steel material. As a result, the SSC resistance of the steel material in a high-H 2 S environment is improved. Even if even a small amount of Ni is contained, the above effect can be obtained to some extent. However, if the Ni content is too high, localized corrosion is promoted and the corrosion resistance of the steel material decreases, even if the contents of other elements are within the ranges of this embodiment. 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%, even more preferably 0.02%, and even more preferably 0.05%.
• the preferred upper limit of the Ni content is 0.48%, even more preferably 0.45%, and even more preferably 0.40%.
• Co 0-0.50%
• Co is an optional element and may not be contained. That is, the Co content may be 0%.
• Co forms a corrosion film in a high-H 2 S environment, suppressing hydrogen penetration into the steel material.
• the SSC resistance of the steel material in a high-H 2 S environment is improved.
• the Co content is 0 to 0.50%.
• the preferred lower limit of the Co content is more than 0%, more preferably 0.01%, even more preferably 0.02%, even more preferably 0.03%, and even more preferably 0.05%.
• the preferred upper limit of the Co content is 0.48%, even more preferably 0.45%, and even more preferably 0.40%.
• the chemical composition of the above-mentioned steel may further contain, in place of a portion of the Fe, one or more elements selected from the group consisting of Nb, V, and B. All of these elements increase the strength of the steel.
• Niobium (Nb) is an optional element and may not be contained. That is, the Nb content may be 0%. When contained, Nb bonds with C or N to form carbides, nitrides, or carbonitrides (hereinafter also referred to as "carbonitrides, etc.”), and refines the grains of the steel material through a pinning effect. As a result, the strength of the steel material is increased. In this case, the corrosion resistance of the steel material is also improved. Even if even a small amount of Nb is contained, the above effects can be obtained to some extent. However, if the Nb content is too high, even if the contents of other elements are within the ranges of this embodiment, excessive carbonitrides, etc.
• the Nb content is 0 to 0.150%.
• the preferred lower limit of the Nb content is more than 0%, more preferably 0.001%, even more preferably 0.003%, even more preferably 0.005%, and even more preferably 0.010%.
• the upper limit of the Nb content is preferably 0.100%, more preferably 0.080%, and even more preferably 0.060%.
• the preferred lower limit of the V content is more than 0%, more preferably 0.001%, even more preferably 0.005%, even more preferably 0.010%, even more preferably 0.030%, and even more preferably 0.050%.
• the preferred upper limit of the V content is 0.400%, even more preferably 0.350%, and even more preferably 0.300%.
• B 0-0.0030% Boron (B) is an optional element and does not necessarily need to be contained. That is, the B content may be 0%. When contained, B dissolves in the steel to improve the hardenability and strength of the steel. Even if even a small amount of B is contained, the above effects can be obtained to some extent. However, if the B content is too high, even if the contents of other elements are within the ranges of this embodiment, coarse nitrides are formed, reducing the corrosion resistance of the steel. Therefore, the B content is 0 to 0.0030%.
• the preferred lower limit of the B content is more than 0%, more preferably 0.0001%, even more preferably 0.0005%, and even more preferably 0.0010%.
• the preferred upper limit of the B content is 0.0029%, even more preferably 0.0025%.
• the chemical composition of the above-mentioned steel may further contain, in place of a portion of the Fe, one or more elements selected from the group consisting of Ca, Mg, and rare earth elements. All of these elements are optional elements, and they neutralize the S in the steel as sulfides. As a result, all of these elements increase the corrosion resistance of the steel.
• Ca 0-0.0040% Calcium (Ca) is an optional element and does not necessarily need to be contained. That is, the Ca content may be 0%. When contained, Ca neutralizes S in the steel material by converting it into sulfides, thereby improving the corrosion resistance of the steel material. Even if even a small amount of Ca is contained, the above effect can be obtained to some extent. However, if the Ca content is too high, even if the contents of other elements are within the ranges of this embodiment, the oxides in the steel material will coarsen, and the corrosion resistance of the steel material will actually decrease. Therefore, the Ca content is 0 to 0.0040%.
• the preferred lower limit of the Ca content is more than 0%, more preferably 0.0001%, even more preferably 0.0003%, even more preferably 0.0006%, and even more preferably 0.0010%.
• the preferred upper limit of the Ca content is 0.0035%, even more preferably 0.0030%.
• Mg 0-0.0040%
• Magnesium (Mg) is an optional element and may not be contained. That is, the Mg content may be 0%. When contained, Mg neutralizes S in the steel material as sulfides, thereby improving the corrosion resistance of the steel material. Even if even a small amount of Mg is contained, the above effect can be obtained to some extent. However, if the Mg content is too high, even if the contents of other elements are within the ranges of this embodiment, the oxides in the steel material will coarsen, thereby reducing the corrosion resistance of the steel material. Therefore, the Mg content is 0 to 0.0040%.
• the preferred lower limit of the Mg content is more than 0%, more preferably 0.0001%, even more preferably 0.0003%, even more preferably 0.0006%, and even more preferably 0.0010%.
• the preferred upper limit of the Mg content is 0.0035%, even more preferably 0.0030%.
• Rare earth elements are optional elements and may not be included. That is, the REM content may be 0%. When included, REM neutralizes S in the steel material by converting it into sulfides, thereby improving the corrosion resistance of the steel material. Even if even a small amount of REM is included, the above effects can be achieved to some extent, even if the contents of other elements are within the ranges of this embodiment. However, if the REM content is too high, oxides in the steel material will coarsen, thereby reducing the corrosion resistance of the steel material, even if the contents of other elements are within the ranges of this embodiment. Therefore, the REM content is 0 to 0.0040%.
• the preferred lower limit of the REM content is greater than 0%, more preferably 0.0001%, even more preferably 0.0003%, even more preferably 0.0006%, and even more preferably 0.0010%.
• the preferred upper limit of the REM content is 0.0035%, even more preferably 0.0030%.
• 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. Furthermore, in this specification, REM content refers to the total content of these elements.
• the Si content is preferably more than 0.50% and less than 1.50%. That is, the steel material according to this embodiment contains, in mass %, C: 0.20 to 0.35%, Si: more than 0.50 to 1.50%, Mn: 0.05 to 0.55%, P: 0.050% or less, S: 0.0100% or less, Cr: 0.20 to 1.00%, Mo: 0.20 to 1.50%, Ti: 0.003 to 0.030%, Al: 0.010 to 0.100%, N: 0.0100% or less, O: 0.0050% or less, Sb: 0.
• yield strength of the steel material according to this embodiment is 758 to less than 965 MPa (110 to less than 140 ksi).
• the yield strength in this specification means the 0.2% offset proof stress obtained in a tensile test in accordance with ASTM E8/E8M (2022).
• the yield strength of the steel material according to this embodiment is determined by the following method. Specifically, a tensile test specimen is prepared from the steel material according to this embodiment. If the steel material is a steel plate, the tensile test specimen is prepared from the center of the plate thickness. In this case, the longitudinal direction of the tensile test specimen is parallel to the rolling direction of the steel plate. If the steel material is a steel pipe, the tensile test specimen is prepared from the center of the wall thickness. In this case, the longitudinal direction of the tensile test specimen or arc-shaped test specimen is parallel to the axial direction of the steel pipe. If the steel material is a round bar, the tensile test specimen is prepared from the R/2 position.
• the R/2 position of the round bar means the center position of the radius R in a cross section perpendicular to the axial direction of the round bar.
• the longitudinal direction of the tensile test specimen is parallel to the axial direction of the round bar.
• the tensile test specimen is, for example, a round bar specimen with a parallel section diameter of 6.0 mm and a gauge length of 30.0 mm.
• a circular arc-shaped specimen may be used as the tensile test specimen.
• the dimensions of the circular arc-shaped specimen are, for example, the full wall thickness, a width of 25.4 mm, and a gauge length of 50.8 mm.
• a tensile test is conducted in air at room temperature (25°C) in accordance with ASTM E8/E8M (2022).
• the 0.2% offset yield strength obtained from the tensile test is defined as the yield strength (MPa).
• the yield strength (MPa) is determined by rounding the obtained value to one decimal place.
• the steel material according to this embodiment has the above-mentioned chemical composition, a yield strength of 758 to less than 965 MPa, and a standard deviation ⁇ of the grain size number of the prior austenite grains (prior ⁇ grains) of 0.80 or less. As a result, the steel material according to this embodiment has excellent pitting corrosion resistance in a high H2S environment, even though it has a yield strength of 758 to less than 965 MPa.
• the standard deviation ⁇ of the grain size numbers of the prior ⁇ grains is set to 0.80 or less.
• the preferred upper limit of the standard deviation ⁇ of the grain size numbers of prior ⁇ grains is 0.79, more preferably 0.78, and even more preferably 0.77.
• the smaller the standard deviation ⁇ of the grain size numbers of prior ⁇ grains the more preferable.
• the lower limit of the standard deviation ⁇ of the grain size numbers of prior austenite grains may be 0.00, 0.05, 0.10, or 0.15.
• the grain size number of the prior ⁇ grains is not particularly limited as long as the standard deviation ⁇ is 0.80 or less.
• the grain size number of the prior ⁇ grains is, for example, 0.0 or greater.
• the lower limit of the grain size number of the prior ⁇ grains may be 0.5.
• the grain size number of the prior ⁇ grains is 5.0 or greater.
• the corrosion resistance of the steel material can be more stable.
• a more preferable lower limit of the grain size number of the prior ⁇ grains is 6.0, even more preferably 7.0, even more preferably 7.5, and even more preferably 8.0.
• the upper limit of the grain size number of the prior ⁇ grains may be 13.0, 12.0, 11.0, or 10.0.
• the standard deviation ⁇ of the crystal grain size number of prior gamma grains is determined by the following method. Specifically, test specimens for microstructure observation are prepared from the steel material according to this embodiment. If the steel material is a steel plate, the test specimen is prepared from the center of the plate thickness. If the steel material is a steel pipe, the test specimen is prepared from the center of the wall thickness. If the steel material is a round bar, the test specimen is prepared from the R/2 position.
• the size of the test specimen is not particularly limited, as long as it provides the observation surface described below.
• the observation surface of the prepared test piece is polished to a mirror finish, and then immersed for approximately 60 seconds in a solution of saturated aqueous picric acid mixed with an appropriate amount of surfactant, thereby revealing the prior gamma grain boundaries through etching.
• 10 fields of view are selected from the observation surface and observed using an optical microscope to generate photographic images.
• the magnification for microscopic observation can be set appropriately depending on the crystal grain size. Specifically, for microscopic observation, the magnification is set so that the field of view contains at least 50 crystal grains, for example.
• the steel material according to this embodiment has the above-mentioned chemical composition, a yield strength of 758 to less than 965 MPa, and a standard deviation ⁇ of the grain size numbers of prior austenite grains (prior ⁇ grains) of 0.80 or less.
• the steel material according to this embodiment has excellent pitting corrosion resistance in a high H2S environment, even though it has a yield strength of 758 to less than 965 MPa.
• having excellent pitting corrosion resistance in a high H2S environment is defined as follows.
• test specimens for four-point bending tests are prepared from the steel material according to this embodiment. If the steel material is a steel plate, the test specimen is prepared from the center of the plate thickness. If the steel material is a steel pipe, the test specimen is prepared from the center of the wall thickness. If the steel material is a round bar, the test specimen is prepared from the R/2 position. The size of the test specimen is, for example, 30 mm in length, 30 mm in width, and 3 mm in thickness.
• test specimens were sealed in an autoclave.
• a 5.0% by mass aqueous solution of sodium chloride was poured into the autoclave.
• the test specimens were not immersed in the test solution (test bath) but were kept in the gas phase region of the autoclave.
• H2S gas was pressurized and sealed into the autoclave at 15 atm to saturate the test solution and form a test bath.
• the test bath was kept at 24°C and the test specimens were kept in the test bath for 720 hours while stirring.
• the surface of a 30 mm long and 30 mm wide test piece is observed to check for the presence or absence of pitting corrosion.
• Pitting corrosion is defined as corrosion with a depth of 50 ⁇ m or more and an equivalent circle diameter of 40 ⁇ m or more.
• the surface of the test piece is observed with a magnifying glass at a magnification of 10 times to check for the presence or absence of pitting corrosion. If pitting corrosion is confirmed, the number of pits is counted. In this embodiment, if the number of pits is 10 or less as a result of the pitting corrosion resistance test under the above conditions, the test piece is evaluated as having excellent pitting corrosion resistance even in a high H2S environment.
• the steel material according to this embodiment has the above-described chemical composition, a Si content of more than 0.50% and less than 1.50%, a yield strength of 758 to less than 965 MPa, and a standard deviation ⁇ of the grain size number of prior austenite grains (prior ⁇ grains) of 0.80 or less.
• a yield strength of 758 to less than 965 MPa it has excellent pitting corrosion resistance in a high H2S environment and also has excellent general corrosion resistance in a high H2S environment.
• having excellent general corrosion resistance in a high H2S environment is defined as follows.
• a corrosion test is performed on the steel material according to this embodiment. Specifically, a test specimen is prepared in the same manner as in the pitting corrosion resistance test described above. The test specimen is sealed in an autoclave. A 5.0 mass % sodium chloride aqueous solution is poured into the autoclave. The test specimen is immersed in the test solution (test bath). After sealing the autoclave under the same environment, the test bath is maintained at 24°C, and the test specimen is maintained for 720 hours while stirring the test bath. The difference between the mass of the test specimen before the test and the mass of the test specimen after 720 hours of immersion, from which corrosion scale has been removed, is calculated.
• the corrosion rate (mm/year) of the test specimen is calculated by dividing the obtained mass difference by the surface area, density, and immersion time of the test specimen. In this embodiment, if the corrosion rate obtained as a result of the corrosion test under the above conditions is 0.40 mm/year or less, the test specimen is evaluated as having excellent general corrosion resistance even in a high H2S environment.
• 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 a steel material having the above-described chemical composition contains a total volume fraction of tempered martensite and tempered bainite of 90% or more, the steel material will have a yield strength of 758 to less than 965 MPa (110 to less than 140 ksi) and excellent pitting corrosion resistance in a high-H 2 S environment, provided that the other configurations of this embodiment are satisfied.
• the microstructure is determined to have 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 plane 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 plane including the pipe axial direction and the pipe radial direction. If the steel material is a round bar, a test piece is prepared with the R/2 position in the center, with the observation surface being a plane including the axial and radial directions.
• the observation surface of the test specimen is polished to a mirror finish, and then immersed in a nital etching solution for approximately 10 seconds to reveal the structure by etching.
• the etched observation surface is observed using a scanning electron microscope (SEM) to obtain secondary electron images from 10 fields of view.
• the field area is, for example, 0.01 mm 2 (magnification: 1000x).
• tempered martensite and tempered bainite are identified based on contrast.
• the area fractions of the identified tempered martensite and tempered bainite are calculated.
• the method for calculating the area fractions is not particularly limited, and any known method may be used.
• the area fractions of tempered martensite and tempered bainite can be calculated by image analysis.
• the arithmetic mean value of the area fractions of tempered martensite and tempered bainite calculated in all fields of view is defined as the volume fraction 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 step of preparing a mother pipe (preparation step) and a step of quenching and tempering the mother pipe to form a seamless steel pipe (quenching step and tempering step). Note that the manufacturing method according to this embodiment is not limited to the manufacturing method described below. Each step will be described in detail below.
• an intermediate steel material having the above-mentioned chemical composition is prepared.
• the intermediate steel material referred to here is a plate-shaped steel material if the final product is a steel plate, a blank pipe if the final product is a steel pipe, or a steel bar having a circular cross section perpendicular to the axial direction if the final product is a round steel bar.
• the preparation process may include a process of preparing a raw material (raw material preparation process) and a process of hot-working the raw material to produce an intermediate steel material (hot-working process).
• raw material preparation process a process of preparing a raw material
• hot-working process a process of hot-working the raw material to produce an intermediate steel material
• a material is produced using molten steel having the above-described chemical composition.
• the method for producing the material is not particularly limited and may be a well-known method. Specifically, a cast piece (slab, bloom, or billet) may be produced using the molten steel by a continuous casting method. An ingot may be produced using the molten steel by an ingot casting method. If necessary, the slab, bloom, or ingot may be subjected to blooming to produce a billet.
• the material (slab, bloom, or billet) is produced by the above steps.
• the prepared material is hot worked to produce an intermediate steel material.
• the intermediate steel material corresponds to a mother pipe.
• a billet is heated in a heating furnace.
• the billet extracted from the heating furnace is then hot worked to produce a mother pipe (seamless steel pipe).
• the billet is preferably heated under the following conditions.
• Heating temperature T 1150-1300°C Holding time t: 30 to 500 minutes
• the heating temperature T (° C.) and the holding time t (minutes) satisfy the following formula (A). 30000 ⁇ (273+T) ⁇ (20+Log(t/60)) ⁇ 32000 (A)
• the heating temperature T of the billet refers to the temperature (°C) of the heat treatment furnace when heating the billet.
• the holding time t when heating the billet refers to the time (minutes) for which the billet is held at the heating temperature T. If the heating temperature T is too high, the austenite grains may become coarse. On the other hand, if the heating temperature T is too low, the billet may not be heated enough, which may place too much strain on the hot working equipment. Furthermore, if the holding time t when heating the billet is too short, the billet may not be heated enough, which may place too much strain on the hot working equipment. On the other hand, if the holding time t is too long, the heating effect will saturate.
• LMP is defined as (273 + T) ⁇ (20 + Log(t/60)). If the LMP is too low, the billet may not be heated sufficiently, resulting in temperature variations in the material during hot working. In this case, the variation in prior gamma grains increases, and the standard deviation ⁇ of the prior gamma grain grain size number increases. On the other hand, if the LMP is too high, Ostwald ripening of pinning particles, such as Ti nitrides, may be promoted, resulting in variations in the size and distribution of the pinning particles.
• the hot working process according to this embodiment it is preferable to set the LMP when heating the billet to a value between 30,000 and 32,000.
• the raw material extracted from the heating furnace is hot-worked to produce an intermediate steel material.
• the intermediate steel material is a blank pipe, it is preferable to use the Mannesmann process to produce the blank pipe.
• the round billet is pierced and rolled using a piercing mill.
• piercing and rolling there are no particular restrictions on the piercing ratio, but it 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 pipe.
• the time between piercing and rolling and hot rolling (elongation) using a mandrel mill is also referred to as the "piercing-elongation hold time.”
• the time between piercing and rolling and the start of elongation is also referred to as the "piercing-elongation hold time.”
• the piercing-elongation hold time is too long, the temperature of the intermediate steel may drop, making it impossible to achieve hot workability. Furthermore, in this case, the austenite grains may grow too much, increasing the standard deviation ⁇ of the prior- ⁇ grain grain size number. Therefore, in the hot working process according to this embodiment, it is preferable to set the piercing-elongation hold time to 30 to 180 seconds.
• Intermediate steel produced by hot working may be air-cooled (as-rolled), or may be quenched directly after hot working without being cooled to room temperature, or may be reheated after hot working and then quenched.
• the quenching process is described in detail below.
• quenching means rapidly cooling the intermediate steel material at the A3 point or above.
• the preferred quenching temperature is 850 to 1000°C. If the quenching temperature is too high, the prior ⁇ grains may become coarse, and corrosion resistance may not be obtained. Therefore, the quenching temperature is preferably 850 to 1000°C.
• the quenching temperature corresponds to the surface temperature of the intermediate steel material measured with a thermometer installed at the outlet of the equipment that performs the final hot processing, when quenching is performed directly after hot processing. Furthermore, when quenching is performed after supplementary heating or reheating following hot processing, the quenching temperature corresponds to the temperature of the furnace in which supplementary heating or reheating is performed.
• the quenching method involves, for example, continuously cooling the intermediate steel material (raw pipe) from the quenching start temperature, thereby continuously lowering the surface temperature of the raw pipe.
• continuous cooling There are no particular restrictions on the method of continuous cooling, and any well-known method may be used. Examples of continuous cooling methods include immersing the raw pipe in a water tank for cooling, or accelerating the cooling of the raw pipe by shower water cooling or mist cooling.
• the resulting microstructure may not be primarily martensite and bainite.
• the mechanical properties specified in this embodiment yield strength of 110 to less than 140 ksi
• the intermediate steel is rapidly cooled during quenching.
• the average cooling rate in the range of 800 to 500°C in the surface temperature of the intermediate steel (blank pipe) during quenching 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 within the cross section of the intermediate steel to be quenched that cools the slowest (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 lower limit of the cooling rate during quenching, CR 800-500 is more preferably 450°C/min, and even more preferably 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 mother pipe is heated multiple times in the austenite region and then quenched.
• the austenite grains before quenching are refined, thereby improving the pitting corrosion resistance of the steel material.
• heating in the austenite region may be repeated multiple times, or by normalizing and quenching, heating in the austenite region may be repeated multiple times.
• Quenching and tempering which will be described later, may also be combined and performed multiple times. In other words, quenching and tempering may be performed multiple times. In this case, the pitting corrosion resistance of the steel material is further improved.
• the tempering process is described in detail below.
• tempering process In the tempering process, the intermediate steel material that has been quenched as described above is tempered.
• tempering means reheating the quenched intermediate steel material to a temperature below the A c1 point and holding it there.
• the tempering temperature corresponds to the furnace temperature when heating and holding the quenched intermediate steel material.
• the tempering time means the time from when the temperature of the intermediate steel material reaches a predetermined tempering temperature until it is extracted from the heat treatment furnace.
• the tempering temperature is adjusted appropriately depending on the chemical composition of the steel and the yield strength to be achieved. In other words, for intermediate steel having the chemical composition of this embodiment, the tempering temperature is adjusted to adjust the yield strength of the steel to 758 to less than 965 MPa. In the tempering process of this embodiment, the preferred tempering temperature is 660 to 740°C. Furthermore, in the tempering process of this embodiment, the preferred tempering time is 20 to 180 minutes.
• the steel material according to this embodiment can be manufactured using the above manufacturing method.
• a method for manufacturing a seamless steel pipe has been described as an example.
• the steel material according to this embodiment may be in the form of a steel plate or other shapes.
• the above manufacturing method is only an example, and the steel material may be manufactured using other manufacturing methods.
• the present invention will be explained in more detail using examples. Note that the conditions in the following examples are one example of conditions adopted to confirm the feasibility and effects of the steel material according to this embodiment. Therefore, the steel material according to this embodiment is not limited to this one example of conditions.
• Molten steel was produced having the chemical compositions shown in Tables 1A and 1B. Note that a "-" in Table 1B indicates that the content of each element was at the impurity level. Specifically, the Sb content, Cu content, Ni content, and Co content of Test No. 1 were rounded to two decimal places to mean 0%. The Nb content and V content of Test No. 1 were rounded to four decimal places to mean 0%. Furthermore, the Zr content, B content, Ca content, Mg content, and REM content of Test No. 1 were rounded to five decimal places to mean 0%.
• Round billets were produced using the continuous casting method using the molten steel of each test number.
• the round billets of each test number were heated in a heating furnace and hot-worked.
• the heated round billet was subjected to piercing and elongation rolling.
• the time from the end of piercing and rolling to the start of elongation rolling is shown in Table 2.
• a (Appropriate)” in the piercing-elongation holding time column means that the piercing-elongation holding time was 30 to 180 seconds.
• S (Short) in the piercing-elongation holding time column means that the piercing-elongation holding time was less than 30 seconds.
• “L (Long)” in the piercing-elongation holding time column means that the piercing-elongation holding time exceeded 180 seconds.
• the manufactured blank pipes were then quenched and tempered. Specifically, the blank pipes of each test number were quenched by holding them at the temperature (°C) listed in Table 2 for the time (minutes) listed in Table 2, followed by water cooling. The quenched blank pipes of each test number were then tempered by holding them at the temperature (°C) listed in Table 2 for the time (minutes) listed in Table 2. Through the above manufacturing process, seamless steel pipes of each test number were obtained.
• the seamless steel pipes of test numbers 1, 3 to 5, 7, 8, 10, 13 to 16, 18, and 20 to 25 further satisfied the Si content of more than 0.50 to 1.50%. As a result, it was determined that these seamless steel pipes had a corrosion rate of 0.40 mm/year or less and had excellent general corrosion resistance even in a high H2S environment.
• the seamless steel pipe of test number 26 had an excessively low Si content, and as a result, the number of pitting corrosion in this seamless steel pipe exceeded 10, and it was determined that this seamless steel pipe did not have excellent pitting corrosion resistance in a high H2S environment.
• the seamless steel pipe of test number 27 had an excessively low Cr content, resulting in more than 10 pits, and was therefore judged not to have excellent pitting corrosion resistance in a high H2S environment.
• the seamless steel pipe of test number 28 had an excessively low Mo content, and as a result, the number of pits in this seamless steel pipe exceeded 10, and it was determined that this seamless steel pipe did not have excellent pitting corrosion resistance in a high H2S environment.
• the seamless steel pipe of test number 29 had a holding time of too short a time after piercing and drawing. As a result, the standard deviation of the prior ⁇ grain size number of this seamless steel pipe exceeded 0.80. As a result, the number of pits in this seamless steel pipe exceeded 10, and it was determined that this seamless steel pipe did not have excellent pitting corrosion resistance in a high H2S environment.
• the seamless steel pipe of test number 30 had a piercing-drawing holding time that was too long. As a result, the standard deviation of the prior ⁇ grain size number of this seamless steel pipe exceeded 0.80. As a result, the number of pits in this seamless steel pipe exceeded 10, and it was determined that this seamless steel pipe did not have excellent pitting corrosion resistance in a high H2S environment.
• the seamless steel pipe of test number 31 had an LMP of more than 32,000 when heated before hot working. As a result, the standard deviation of the prior ⁇ grain size number of this seamless steel pipe exceeded 0.80. As a result, the number of pits in this seamless steel pipe exceeded 10, and it was determined that this seamless steel pipe did not have excellent pitting corrosion resistance in a high H2S environment.
• the seamless steel pipe of test number 32 had an LMP of less than 30,000 when heated before hot working. As a result, the standard deviation of the prior ⁇ grain size number of this seamless steel pipe exceeded 0.80. As a result, the number of pits in this seamless steel pipe exceeded 10, and it was determined that this seamless steel pipe did not have excellent pitting corrosion resistance in a high H2S environment.

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