WO2021193383A1 - Tôle d'acier à haute résistance pour tuyau de canalisation résistant à l'acidité, procédé de fabrication correspondant et tuyau d'acier à haute résistance utilisant une tôle d'acier à haute résistance pour tuyau de canalisation résistant à l'acidité - Google Patents

Tôle d'acier à haute résistance pour tuyau de canalisation résistant à l'acidité, procédé de fabrication correspondant et tuyau d'acier à haute résistance utilisant une tôle d'acier à haute résistance pour tuyau de canalisation résistant à l'acidité Download PDF

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WO2021193383A1
WO2021193383A1 PCT/JP2021/011238 JP2021011238W WO2021193383A1 WO 2021193383 A1 WO2021193383 A1 WO 2021193383A1 JP 2021011238 W JP2021011238 W JP 2021011238W WO 2021193383 A1 WO2021193383 A1 WO 2021193383A1
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steel sheet
less
strength
sour
temperature
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PCT/JP2021/011238
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Japanese (ja)
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大地 泉
純二 嶋村
雄太 田村
上岡　悟史
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Ｊｆｅスチール株式会社
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Priority to BR112022019204A priority Critical patent/BR112022019204A2/pt
Priority to JP2021551989A priority patent/JP7264269B2/ja
Priority to KR1020227031130A priority patent/KR20220137970A/ko
Priority to CN202180020748.6A priority patent/CN115298340B/zh
Priority to EP21774925.8A priority patent/EP4129510A1/fr
Publication of WO2021193383A1 publication Critical patent/WO2021193383A1/fr

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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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/02—Hardening articles or materials formed by forging or rolling, with no further heating beyond that required for the formation
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    • C21—METALLURGY OF IRON
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
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    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
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    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/002—Bainite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
    • C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
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    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • 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

  • the present invention provides a high-strength steel plate for sour line pipes, which is suitable for use in line pipes in the fields of construction, marine structures, shipbuilding, civil engineering, and machinery for the construction industry, and has excellent material uniformity in steel plates, and production thereof. It's about the method.
  • the present invention also relates to a high-strength steel pipe using the above-mentioned high-strength steel plate for sour-resistant pipes.
  • a line pipe is manufactured by forming a steel plate manufactured by a thick plate mill or a hot-rolling mill into a steel pipe by UOE forming, press bend forming, roll forming, or the like.
  • the line pipe used for transporting crude oil containing hydrogen sulfide and natural gas has hydrogen sulfide-induced cracking resistance (HIC (Hydrogen Induced Racing) resistance) and sulfide resistance, in addition to strength, toughness, and weldability.
  • So-called sour resistance such as stress corrosion crack resistance (SSCC (Sulfide Stress Corrosion Cracking) resistance) is required.
  • SSCC Stress Corrosion Cracking
  • HIC hydrogen ions due to the corrosion reaction are adsorbed on the steel surface, penetrate into the steel as atomic hydrogen, and diffuse and accumulate around non-metal inclusions such as MnS in the steel and the hard second phase structure.
  • TMCP Thermo-Mechanical Control Process
  • TMCP Thermo-Mechanical Control Process
  • it is effective to increase the cooling rate during controlled cooling.
  • controlled cooling is performed at a high cooling rate, the surface layer portion of the steel sheet is rapidly cooled, so that the hardness of the surface layer portion is higher than that inside the steel sheet.
  • work hardening occurs when the steel sheet is formed into a tubular shape, so that the hardness of the surface layer portion is further increased and the SSCC resistance is lowered.
  • Patent Documents 1 and 2 disclose a method of performing controlled cooling at a high cooling rate in which the surface is reheated after rolling and before the surface layer portion completes the bainite transformation.
  • Patent Documents 3 and 4 disclose a method for manufacturing a steel sheet for a line pipe, which uses a high-frequency induction heating device to heat the surface of the steel sheet after accelerated cooling to a higher temperature than the inside to reduce the hardness of the surface layer portion. Has been done.
  • Patent Documents 5 and 6 disclose a method of reducing the cooling unevenness caused by the scale thickness unevenness and improving the steel sheet shape by performing descaling immediately before cooling the steel sheet. ..
  • descaling is used to reduce surface texture defects due to scale indentation defects during hot straightening and to reduce variations in the cooling stop temperature of the steel sheet to improve the shape of the steel sheet. ..
  • the descaling conditions have not been optimized from the viewpoint of improving SSCC resistance. Further, no consideration is given to the cooling conditions for reducing the hardness of the surface layer portion of the steel sheet.
  • Patent Documents 1 to 6 the conditions for avoiding fine cracks such as Fisher in an environment where the partial pressure of hydrogen sulfide is relatively low are not clear.
  • the present invention is a sour line pipe excellent not only in HIC resistance but also in SSCC resistance under a harsher corrosion environment and SSCC resistance in an environment with a low partial pressure of hydrogen sulfide of less than 1 bar. It is an object of the present invention to provide a high-strength steel plate for use together with its advantageous manufacturing method. Another object of the present invention is to propose a high-strength steel pipe using the above-mentioned high-strength steel plate for sour-resistant pipes.
  • the present inventors have determined the composition of the steel sheet and the surface of the steel sheet in order to obtain a high-strength steel sheet in which there is no locally high-hardness portion at a position of 0.25 mm below the surface of the steel sheet at the polar surface layer portion, specifically, the surface of the steel sheet. Numerous experiments were repeated on the properties of the scale present in the steel sheet and the manufacturing conditions of the steel sheet.
  • the gist structure of the present invention is as follows. [1] In terms of mass%, C: 0.020 to 0.080%, Si: 0.01 to 0.50%, Mn: 0.50 to 1.80%, P: 0.015% or less, S: 0.0015% or less, Al: 0.010 to 0.080%, N: 0.0010 to 0.0080%, Mo: 0.01 to 0.50% and Ca: 0.0005 to 0.0050%. It contains and has a component composition in which the balance consists of Fe and unavoidable impurities. The magnetite ratio in the scale existing on the surface of the steel sheet is 50% or more. The maximum value of Vickers hardness at 0.25 mm below the surface of the steel sheet is 230 HV or less. A high-strength steel plate for sour-resistant pipes having a tensile strength of 520 MPa or more.
  • the above-mentioned component composition further contains at least one selected from Cu: 0.30% or less, Ni: 0.10% or less, and Cr: 0.50% or less in mass%.
  • the component composition is, in mass%, Nb: 0.005 to 0.1%, V: 0.005 to 0.1%, Ti: 0.005 to 0.1%, Zr: 0.
  • Nb 0.005 to 0.1%
  • V 0.005 to 0.1%
  • Ti 0.005 to 0.1%
  • Zr 0.
  • the above [1] or [2] which contains at least one selected from 0005 to 0.02%, Mg: 0.0005 to 0.02% and REM: 0.0005 to 0.02%.
  • a steel piece having the component composition according to any one of the above [1] to [3] is heated to a temperature of 1000 to 1300 ° C. After that, the steel piece is hot-rolled to form a steel sheet, and at that time, descaling of a discharge pressure of 10 MPa or more is performed in a rolling pass of 50% or more of the number of rolling passes of the hot rolling.
  • the high-strength steel sheet for sour-line pipes of the present invention and the high-strength steel pipe using the high-strength steel sheet for sour-line pipes have not only HIC resistance but also SSCC resistance under more severe corrosion environment and less than 1 bar. It also has excellent SSCC resistance in an environment with low hydrogen sulfide partial pressure. Further, according to the method for producing a high-strength steel plate for sour line pipes of the present invention, not only HIC resistance but also SSCC resistance in a harsher corrosion environment and resistance in an environment with a low partial pressure of hydrogen sulfide of less than 1 bar are obtained. It is possible to manufacture a high-strength steel plate for sour line pipes having excellent SSCC properties.
  • C 0.020 to 0.080% C effectively contributes to the improvement of strength, but if the content is less than 0.020%, sufficient strength cannot be secured. Therefore, the amount of C is 0.020% or more, preferably 0.025% or more. On the other hand, if the amount of C exceeds 0.080%, the hardness of the surface layer portion and the central segregation portion increases during accelerated cooling, so that SSCC resistance and HIC resistance deteriorate. In addition, the toughness also deteriorates. Therefore, the amount of C is set to 0.080% or less, preferably 0.070% or less.
  • Si 0.01-0.50% Si is added for deoxidation, but if the content is less than 0.01%, the deoxidizing effect is not sufficient. Therefore, the amount of Si is 0.01% or more, preferably 0.05% or more. On the other hand, if the amount of Si exceeds 0.50%, the toughness and weldability deteriorate. Therefore, the amount of Si is 0.50% or less, preferably 0.45% or less.
  • Mn 0.50 to 1.80% Mn effectively contributes to the improvement of strength and toughness, but if the content is less than 0.50%, the effect of adding Mn is not sufficiently exhibited. Therefore, the amount of Mn is 0.50% or more, preferably 0.80% or more. On the other hand, if the amount of Mn exceeds 1.80%, the hardness of the surface layer portion and the central segregation portion increases during accelerated cooling, so that SSCC resistance and HIC resistance deteriorate. Weldability also deteriorates. Therefore, the amount of Mn is 1.80% or less, preferably 1.70% or less.
  • P 0.015% or less
  • P is an unavoidable impurity element, which deteriorates weldability and increases the hardness of the surface layer portion and the central segregation portion, thereby deteriorating SSCC resistance and HIC resistance.
  • the amount of P is set to 0.015% or less, preferably 0.008% or less. The lower the amount of P, the better, but from the viewpoint of refining cost, it is preferably 0.001% or more.
  • S 0.0015% or less S is an unavoidable impurity element, which becomes an MnS inclusion in steel and deteriorates HIC resistance. Therefore, the amount of S is 0.0015% or less, preferably 0.0010% or less. The lower the amount of S, the better, but from the viewpoint of refining cost, it is preferably 0.0002% or more.
  • Al 0.010 to 0.080% Al is added as an antacid, but its effect is not sufficiently exhibited when the content is less than 0.010%. Therefore, the amount of Al is 0.010% or more, preferably 0.015% or more. On the other hand, when the amount of Al exceeds 0.080%, the cleanliness of the steel is lowered and the toughness is deteriorated. Therefore, the amount of Al is set to 0.080% or less, preferably 0.070% or less.
  • N 0.0010 to 0.0080% N effectively contributes to the improvement of strength, but if the content is less than 0.0010%, sufficient strength cannot be secured. Therefore, the amount of N is 0.0010% or more, preferably 0.0015% or more. On the other hand, if the amount of N exceeds 0.0080%, the hardness of the surface layer portion and the central segregation portion increases during accelerated cooling, so that SSCC resistance and HIC resistance deteriorate. In addition, the toughness also deteriorates. Therefore, the amount of N is 0.0080% or less, preferably 0.0070% or less.
  • Mo 0.01-0.50%
  • Mo is an element effective for improving toughness and increasing strength, and is an element effective for improving SSCC resistance regardless of the partial pressure of hydrogen sulfide.
  • the present inventors have found that when a steel sheet containing Mo is subjected to an SSCC test, the surface of the steel sheet after the test is smoother than the surface of the steel sheet containing no Mo after the SSCC test. The mechanism is not always clear, but it is considered that this is related to the improvement of SSCC resistance. In order to obtain this effect, the amount of Mo needs to be 0.01% or more, preferably 0.10% or more.
  • the amount of Mo is 0.50% or less, preferably 0.40% or less.
  • Ca 0.0005 to 0.0050% Ca is an element effective for improving HIC resistance by controlling the morphology of sulfide-based inclusions, but the effect is not sufficiently exhibited when the content is less than 0.0005%. Therefore, the amount of Ca is 0.0005% or more, preferably 0.0008% or more. On the other hand, when the amount of Ca exceeds 0.0050%, not only the above-mentioned effect is saturated, but also the cleanliness of the steel is lowered, so that the HIC resistance is deteriorated. Therefore, the amount of Ca is 0.0050% or less, preferably 0.0045% or less.
  • the component composition in the present invention, is one or more selected from Cu, Ni and Cr in order to further improve the strength and toughness of the steel sheet. , May be arbitrarily contained in the following range.
  • Cu 0.30% or less
  • Cu is an element effective for improving toughness and increasing strength, and the amount of Cu is preferably 0.05% or more in order to obtain this effect.
  • the amount of Cu exceeds 0.30%, fine cracks called fishers are likely to be generated in an environment where the partial pressure of hydrogen sulfide is less than 1 bar, and the SSCC resistance deteriorates. Therefore, when Cu is added, the amount of Cu is 0.30% or less, preferably 0.25% or less.
  • Ni 0.10% or less
  • Ni is an element effective for improving toughness and increasing strength, and the amount of Ni is preferably 0.01% or more in order to obtain this effect.
  • the amount of Ni exceeds 0.10%, the SSCC resistance deteriorates because fine cracks called fishers are likely to be generated in an environment where the partial pressure of hydrogen sulfide is less than 1 bar. Therefore, when Ni is added, the amount of Ni is 0.10% or less, preferably 0.05% or less.
  • Cr 0.50% or less Cr is an element effective for obtaining sufficient strength even at low C like Mn, and the amount of Cr is preferably 0.05% or more in order to obtain this effect.
  • the amount of Cr exceeds 0.50%, the hardenability becomes excessive, so that the hardness of the surface layer portion and the central segregation portion increases during accelerated cooling, and the SSCC resistance and the HIC resistance deteriorate. Weldability also deteriorates. Therefore, when Cr is added, the amount of Cr is 0.50% or less, preferably 0.45% or less.
  • the component composition may further optionally contain one or more selected from Nb, V, Ti, Zr, Mg and REM within the following range.
  • Nb 0.005 to 0.1%
  • V 0.005 to 0.1%
  • Ti 0.005 to 0.1%
  • Zr 0.0005 to 0.02%
  • Mg 0.0005 to One or more selected from 0.02% and REM: 0.0005 to 0.02%
  • Nb, V and Ti are all elements that can be arbitrarily added in order to increase the strength and toughness of the steel sheet. If the content of each element is less than 0.005%, the effect is not sufficiently exhibited. Therefore, when these elements are added, the content of each element is preferably 0.005% or more. On the other hand, if the content of these elements exceeds 0.1%, the toughness of the welded portion deteriorates. Therefore, when these elements are added, the content of each element is preferably 0.1% or less.
  • Zr, Mg and REM are elements that can be arbitrarily added in order to enhance toughness through grain refinement and to enhance crack resistance through control of inclusion properties. If the content of each element is less than 0.0005%, the effect is not sufficiently exhibited. Therefore, when these elements are added, the content of each element is preferably 0.0005% or more. On the other hand, when the content of these elements exceeds 0.02%, the effect is saturated. Therefore, when these elements are added, the content of each element is preferably 0.02% or less.
  • the present invention relates to a technique for improving the SSCC resistance of a high-strength steel pipe using a high-strength steel plate for a sour line pipe, but it goes without saying that the sour resistance is also satisfied with the HIC resistance at the same time.
  • the CP value obtained by the following equation (1) is preferably 1.00 or less.
  • 0 may be substituted for the element which is not added.
  • the CP value is an equation devised to estimate the material of the central segregation portion from the content of each alloy element, and the higher the CP value of the above equation (1), the higher the component concentration of the central segregation portion. Increases, and the hardness of the central segregated portion increases. Therefore, by setting the CP value obtained in the above equation (1) to 1.00 or less, it is possible to suppress the occurrence of cracks in the HIC test. Further, the lower the CP value, the lower the hardness of the central segregated portion. Therefore, when higher HIC resistance is required, the upper limit thereof may be 0.95.
  • the balance other than the above elements consists of Fe and unavoidable impurities.
  • the content of other trace elements is not hindered as long as the action and effect of the present invention are not impaired.
  • O is an element unavoidably contained in steel, but if its content is 0.0050% or less, preferably 0.0040% or less, it is acceptable in the present invention.
  • the steel structure of the high-strength steel sheet for sour-resistant pipes of the present invention is preferably a bainite phase.
  • a bainite phase in order to suppress the maximum hardness of 0.25 mm below the surface of the steel sheet to a certain level or less and improve the SSCC resistance, it is preferable to use a bainite phase in the steel structure of 0.25 mm below the surface of the steel sheet.
  • the entire steel structure of the steel sheet including the portion other than the surface layer portion is a bainite phase.
  • the structure at the center of the plate thickness may be the bainite phase on behalf of the “part other than the surface layer portion”.
  • the bainite phase includes a structure called bainitic ferrite or granular ferrite that transforms during accelerated cooling or after accelerated cooling, which contributes to strengthening the transformation.
  • bainitic ferrite or granular ferrite that transforms during accelerated cooling or after accelerated cooling, which contributes to strengthening the transformation.
  • heterogeneous structures such as ferrite, martensite, pearlite, island-like martensite, and retained austenite are mixed in the bainite phase, the strength decreases, the toughness deteriorates, and the surface hardness increases. The smaller the fraction, the better.
  • the surface integral of the structure other than the bainite phase is sufficiently low, those effects can be ignored, and a certain amount is acceptable.
  • the total of steel structures other than bainite is less than 10% in area fraction, there is no significant effect, so it is permissible. It is more preferably less than 5%.
  • the magnetite ratio in the scale existing on the surface of the steel sheet after controlled cooling is 50% or more.
  • the scale present on the surface of the steel sheet after controlled cooling consists of wustite (FeO), magnetite (Fe 3 O 4 ), and hematite (Fe 2 O 3 ).
  • the magnetite ratio is less than 50%, the present inventors locally form a high hardness portion at a position 0.25 mm below the surface of the steel sheet, and as a result, the Vickers hardness at 0.25 mm below the surface of the steel sheet.
  • the magnetite ratio must be at least 50% or more.
  • the upper limit of the magnetite ratio is not particularly limited, and the magnetite ratio may be 100% or less, or 95% or less.
  • the "maximum value of the Vickers hardness (HV0.5) at 0.25 mm below the surface of the steel sheet” is the Vickers hardness (HV0. 5) is measured at 100 points at equal intervals along the plate width direction, and means the highest value among the measured values.
  • HV0.5 the Vickers hardness
  • the indentation becomes smaller by measuring with HV0.5, so that the hardness information at a position closer to the surface and more sensitive to the microstructure are obtained. This is because it is possible to obtain various hardness information.
  • the indentation size becomes excessively small and the measurement variation becomes large.
  • the reason why the maximum hardness is evaluated instead of the average hardness is as follows. That is, if there is a locally hard part, cracks are likely to grow. Therefore, in order to accurately investigate the crack growth sensitivity, it is more suitable to evaluate by the maximum hardness that can detect the locally hard part. be.
  • the high-strength steel sheet of the present invention is a steel sheet for steel pipes having a strength of X60 grade or higher of API 5L, it is assumed to have a tensile strength of 520 MPa or higher.
  • the high-strength steel plate of the present invention has a thickness of 14 to 39 mm.
  • slab heating temperature 1000-1300 ° C If the slab heating temperature is less than 1000 ° C., the solid solution of the carbide becomes insufficient and the amount of solid solution strengthening becomes small, so that the required strength cannot be obtained. Therefore, the slab heating temperature is set to 1000 ° C. or higher, preferably 1030 ° C. or higher. On the other hand, when the slab heating temperature exceeds 1300 ° C., the crystal grains become extremely coarse and the toughness deteriorates. Therefore, the slab heating temperature is set to 1300 ° C. or lower, preferably 1250 ° C. or lower. It should be noted that this temperature is the temperature inside the heating furnace, and it is assumed that the slab is heated to this temperature up to the center.
  • the hot rolling step it is important to perform descaling of a discharge pressure of 10 MPa or more in a rolling pass of 50% or more of the number of hot rolling passing passes.
  • the "rolling pass” referred to here includes both a rough rolling rolling pass and a finish rolling rolling pass during the hot rolling process. Specifically, in a rolling pass of 50% or more of the number of rolling passes of hot rolling, descaling of a discharge pressure of 10 MPa or more on the surface of the slab at a position immediately before the slab (steel piece) is introduced into the rolling pass. I do.
  • This descaling condition is one of the necessary conditions for suppressing the non-uniform formation of scale and making the magnetite ratio in the scale existing on the surface of the steel sheet 50% or more after controlled cooling.
  • the "position immediately before the slab is introduced into the rolling path" is within 3 m, preferably within 1.5 m, from the position of the roll shaft of the rolling mill corresponding to the rolling path in the longitudinal direction of the hot rolling line. It shall mean the position of.
  • the number of rough rolling passes may be arbitrarily set within a general range and is not particularly limited, but is preferably 2 or more and 12 or less, for example.
  • the number of finish rolling passes may be arbitrarily set within a general range and is not particularly limited, but is preferably 5 or more and 15 or less, for example.
  • the descaling method may follow a conventional method, and can be performed, for example, by injecting high-pressure water onto the slab surface from a plurality of descaling nozzles arranged along the width direction of the hot rolling line.
  • general conditions may be adopted for conditions other than the discharge pressure (for example, the amount of water, the distance between the nozzle and the slab, and the nozzle angle).
  • the discharge pressure is 10 MPa or more, preferably 15 MPa or more.
  • the number of descaling is 50% or more, preferably 60% or more of the number of rolling passes.
  • the upper limit of the number of descaling is not particularly limited, and may be 100% of the number of rolling passes, that is, descaling may be performed immediately before all rolling passes.
  • the rolling end temperature at the steel sheet surface temperature is the required base material toughness and rolling. It is necessary to set in consideration of efficiency. From the viewpoint of improving the strength and HIC resistance, it is preferable that the rolling end temperature is equal to or higher than the Ar 3 transformation point at the surface temperature of the steel sheet.
  • the Ar 3 transformation point means the ferrite transformation start temperature during cooling, and can be obtained from the components of steel, for example, by the following formula.
  • the surface temperature of the steel sheet can be measured with a radiation thermometer or the like.
  • Ar 3 (° C.) 910-310 [% C] -80 [% Mn] -20 [% Cu] -15 [% Cr] -55 [% Ni] -80 [% Mo]
  • [% X] indicates the content (mass%) of the X element in the steel.
  • Cooling start temperature the steel plate surface temperature (Ar 3 -10 °C) or cooling at the start of the steel sheet surface temperature is low, becomes large ferrite amount before controlled cooling.
  • the HIC resistance may deteriorate the strength reduction is increased. Therefore, the steel sheet surface temperature of the cooling at the start and (Ar 3 -10 °C) or higher.
  • the surface temperature of the steel sheet at the start of cooling is equal to or lower than the temperature at the end of rolling.
  • Average cooling rate from 750 ° C to 550 ° C at steel plate temperature 0.25 mm below the surface of the steel plate 20 to 100 ° C / s It is important to slow down the average cooling rate from 750 ° C to 550 ° C as much as possible at the steel plate temperature 0.25 mm below the surface of the steel sheet to create a high-temperature transformation phase, and the slower the cooling rate, the lower the maximum hardness. Can be done. Since the temperature range from 750 ° C. to 550 ° C. is an important temperature range in bainite transformation, it is important to control the cooling rate in this temperature range.
  • the average cooling rate is 100 ° C./s or less, preferably 80 ° C./s or less. If the average cooling rate is less than 20 ° C./s, ferrite and pearlite are generated and the strength becomes insufficient. Therefore, the average cooling rate is set to 20 ° C./s or more.
  • the temperature of the steel sheet at 0.25 mm below the surface of the steel sheet is from 550 ° C to the cooling stop temperature.
  • the average cooling rate is preferably 110 ° C./s or higher, more preferably 150 ° C./s or higher. Further, from the viewpoint of more reliably suppressing the formation of high hardness portions, the average cooling rate is preferably 200 ° C./s or less.
  • Average cooling rate from 750 ° C to 550 ° C at average steel plate temperature 15 ° C / s or more
  • the average cooling rate at the average temperature of the steel sheet is set to 15 ° C./s or more.
  • the average cooling rate at the average temperature of the steel sheet is preferably 20 ° C./s or more.
  • the upper limit of the average cooling rate is not particularly limited, but the average cooling rate is preferably 80 ° C./s or less so that the low temperature transformation product is not excessively produced.
  • the surface temperature at the start of cooling and the surface at the target cooling stop measured by a radiation thermometer measured by a radiation thermometer.
  • the temperature distribution in the plate thickness cross section can be obtained in real time by difference calculation using a process computer.
  • the temperature at 0.25 mm below the surface of the steel sheet in the temperature distribution is defined as "the temperature of the steel sheet at 0.25 mm below the surface of the steel sheet" in the present specification, and the average value of the temperatures in the thickness direction in the temperature distribution is the "steel plate” in the present specification. "Average temperature".
  • Cooling stop temperature 250 to 550 ° C at the steel plate temperature 0.25 mm below the surface of the steel sheet
  • the cooling stop temperature is one of the necessary conditions for setting the magnetite ratio in the scale existing on the surface of the steel sheet to 50% or more after controlled cooling. If the cooling stop temperature exceeds 550 ° C., the bainite transformation is incomplete and sufficient strength cannot be obtained. If the cooling stop temperature is less than 250 ° C., the magnetite ratio cannot be 50% or more as a result of the increase in wustite. As a result, the maximum value of Vickers hardness at 0.25 mm below the surface of the steel sheet exceeds 230 HV, so that the SSCC resistance after pipe forming deteriorates.
  • the cooling stop temperature is 250 to 550 ° C., which is the temperature of the steel sheet at 0.25 mm below the surface of the steel sheet.
  • High-strength steel pipe The high-strength steel pipe of the present invention is formed into a tubular shape by press bend forming, roll forming, UOE forming, etc., and then the butt portion is welded to form a high-strength steel pipe for sour line pipes suitable for transporting crude oil and natural gas.
  • UOE steel pipe, electric resistance steel pipe, spiral steel pipe, etc. can be manufactured.
  • the end portion of a steel plate is grooved, formed into a steel pipe shape by C press, U press, and O press, and then the butt portion is seam welded by inner surface welding and outer surface welding, and further, if necessary.
  • the welding method may be any method as long as sufficient joint strength and joint toughness can be obtained, but from the viewpoint of excellent welding quality and manufacturing efficiency, submerged arc welding is preferably used.
  • the pipe can be expanded even for a steel pipe in which a steel plate is formed into a tubular shape by press bend forming and then a butt portion is seam welded.
  • the steel having the composition shown in Table 1 is made into a slab by a continuous casting method, heated to the temperature shown in Table 2, and then hot-rolled at the rolling end temperature shown in Table 2, and the steel plate having the plate thickness shown in Table 2 is subjected to hot rolling. And said.
  • the hot rolling process consists of 2 to 12 passes for rough rolling and 5 to 15 passes for finish rolling, for a total of 10 to 25 passes. Scaled. Then, the steel sheet was controlled-cooled using a water-cooled control cooling device under the conditions shown in Table 2.
  • the scale was collected from the surface of the obtained steel sheet.
  • the scale was collected at a total of 9 locations at the center of the width of the steel sheet and both ends in the width direction at the tip, center, and end positions in the longitudinal direction of the steel sheet, and a scale of 0.5 g or more was collected at each location.
  • the scales collected at each site are phase-identified by the X-ray diffraction (XRD) method, and quantitative analysis (that is, measurement of the magnetite ratio) is performed using the Reference Intensity Ratio (RIR) method. went.
  • the average value of the magnetite ratios of the nine scales is shown in Table 3 as the "magnetite ratio" in the present invention.
  • the SSCC resistance was evaluated by forming a pipe using a part of each of these steel sheets.
  • Pipe making is manufactured through a pipe expansion process in which the end of the steel sheet is grooved, formed into a steel pipe shape by C press, U press, and O press, and then the butt portion of the inner and outer surfaces is seam welded by submerged arc welding. bottom.
  • a 5 ⁇ 15 ⁇ 115 mm SSCC test piece was collected from the inner surface of the steel pipe.
  • a test piece containing both the welded portion and the base material was collected.
  • the inner surface which is the surface to be inspected, was left with black skin in order to retain the state of the outermost layer.
  • a stress of 90% of the actual yield strength (0.5% YS) of each steel pipe is applied to the collected SSCC test piece, and using NACE standard TM0177 Solution A solution, hydrogen sulfide partial pressure: 1 bar, EFC 16 standard.
  • the 4-point bending SSCC test was performed in accordance with the above. Further, using a NACE standard TM0177 Solution B solution, hydrogen sulfide partial pressure: 0.1 bar + carbon dioxide partial pressure: 0.9 bar was performed in accordance with the EFC16 standard 4-point bending SSCC test.
  • the HIC resistance was examined by a 96-hour immersion HIC test at a hydrogen sulfide partial pressure of 1 bar using a NACE standard TM0177 Solution A solution.
  • hydrogen sulfide partial pressure 0.1 bar + carbon dioxide partial pressure: 0.9 bar was examined by a 96-hour immersion HIC test.
  • the HIC resistance is judged to be excellent when the crack length ratio (CLR: Crack Length Ratio) is 10% or less in the HIC test, and is judged to be good when it is more than 10% and 15% or less. If it exceeds 15%, it is judged to be insufficient and marked as ⁇ .
  • CLR Crack Length Ratio
  • the target range of the present invention is a high-strength steel plate for sour line pipes with a tensile strength of 520 MPa or more, a bainite structure at both 0.25 mm and t / 2 positions below the surface, and HV 0.5 at 0.25 mm below the surface.
  • the maximum hardness was 230 or less, no cracks were observed in the SSCC test, and the crack length ratio (CLR) was 15% or less in the HIC test.
  • Reference numeral 31 denotes an example of the invention in which the component composition and the production conditions satisfy the appropriate range of the present invention.
  • the tensile strength of the steel sheet was 520 MPa or more, and the SSCC resistance and HIC resistance were good.
  • Nos. 7 to 18 the composition of the steel sheet is outside the scope of the present invention.
  • No. 7, No. 9, and No. 12 had low strength due to insufficient solid solution strengthening.
  • No. 8, No. 10, No. 11, No. 13, No. 15, and No. 18 were inferior in SSCC resistance and HIC resistance because the maximum hardness of HV0.5 exceeded 230.
  • No. 14 since the steel sheet does not contain Mo, the SSCC resistance deteriorated in a very severe corrosion environment of hydrogen sulfide partial pressure of 2 Bar.
  • No. 16 since the amount of Cu in the steel sheet was excessive, the SSCC resistance in an environment where the partial pressure of hydrogen sulfide was low deteriorated.
  • No. 17 since the amount of Ni in the steel sheet was excessive, the SSCC resistance in an environment where the partial pressure of hydrogen sulfide was low deteriorated.
  • No. 19-No. 29 is a comparative example in which the component composition is within the range of the present invention, but the production conditions are outside the range of the present invention.
  • No. 19 since the slab heating temperature was low, the homogenization of the microstructure and the solid solution of carbides were insufficient, and the strength was low.
  • a high-strength steel plate for sour line pipes which is excellent not only in HIC resistance but also in SSCC resistance under a harsher corrosion environment and SSCC resistance in an environment with a low partial pressure of hydrogen sulfide of less than 1 bar.
  • steel pipes electrostrength steel pipes, spiral steel pipes, UOE steel pipes, etc. manufactured by cold forming this steel sheet can be suitably used for transporting crude oil and natural gas containing hydrogen sulfide, which requires sour resistance. ..

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  • Mechanical Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne une tôle d'acier à haute résistance destinée à un tuyau de canalisation résistant à l'acidité qui présente non seulement une excellente résistance à la fissuration induite par l'hydrogène (HIC) mais également une excellente résistance à la fissuration par corrosion sous contrainte associée aux sulfures (SSCC) dans des environnements très corrosifs et une excellente résistance à la SSCC dans des environnements présentant une faible pression partielle en sulfure d'hydrogène inférieure à 1 bar. Cette tôle d'acier à haute résistance pour tuyau résistant à l'acidité est caractérisée en ce qu'elle présente une composition de composant contenant, en termes de % en masse, de 0,020 à 0,080 % de C, de 0,01 à 0,50 % de Si, de 0,50 à 1,80 % de Mn, pas plus de 0,015 % de P, pas plus de 0,0015 % de S, de 0,010 à 0,080 % d'Al, de 0,0010 à 0,0080 % de N, de 0,01 à 0,50 % de Mo et de 0,0005 à 0,0050 % de Ca, le reste comprenant du Fe et des impuretés inévitables, le rapport de magnétite à l'échelle qui est présent sur la surface de la feuille d'acier étant de 50 % ou plus, la valeur maximale de la dureté Vickers à 0,25 mm au-dessous de la surface de la tôle d'acier étant de 230 HV ou moins, et la résistance à la traction de la tôle d'acier étant de 520 MPa ou plus.
PCT/JP2021/011238 2020-03-26 2021-03-18 Tôle d'acier à haute résistance pour tuyau de canalisation résistant à l'acidité, procédé de fabrication correspondant et tuyau d'acier à haute résistance utilisant une tôle d'acier à haute résistance pour tuyau de canalisation résistant à l'acidité WO2021193383A1 (fr)

Priority Applications (5)

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BR112022019204A BR112022019204A2 (pt) 2020-03-26 2021-03-18 Chapa de aço de alta resistência para tubo de linha resistente a ácidos e método para fabricação do mesmo, e tubo de aço de alta resistência usando chapa de aço de alta resistência para tubo de linha resistente a ácidos
JP2021551989A JP7264269B2 (ja) 2020-03-26 2021-03-18 耐サワーラインパイプ用高強度鋼板およびその製造方法並びに耐サワーラインパイプ用高強度鋼板を用いた高強度鋼管
KR1020227031130A KR20220137970A (ko) 2020-03-26 2021-03-18 내사워 라인 파이프용 고강도 강판 및 그 제조 방법 그리고 내사워 라인 파이프용 고강도 강판을 사용한 고강도 강관
CN202180020748.6A CN115298340B (zh) 2020-03-26 2021-03-18 耐酸管线用高强度钢板及其制造方法以及使用耐酸管线用高强度钢板的高强度钢管
EP21774925.8A EP4129510A1 (fr) 2020-03-26 2021-03-18 Tôle d'acier à haute résistance pour tuyau de canalisation résistant à l'acidité, procédé de fabrication correspondant et tuyau d'acier à haute résistance utilisant une tôle d'acier à haute résistance pour tuyau de canalisation résistant à l'acidité

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JP7332078B1 (ja) * 2022-06-03 2023-08-23 Ｊｆｅスチール株式会社 サワーガス設備用高強度鋼板及びそれを用いた高強度鋼管
WO2023233734A1 (fr) * 2022-06-03 2023-12-07 Ｊｆｅスチール株式会社 Tôle d'acier à haute résistance pour installation de gaz acide, et tuyau en acier à haute résistance l'utilisant

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WO2023233734A1 (fr) * 2022-06-03 2023-12-07 Ｊｆｅスチール株式会社 Tôle d'acier à haute résistance pour installation de gaz acide, et tuyau en acier à haute résistance l'utilisant

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EP4129510A1 (fr) 2023-02-08
BR112022019204A2 (pt) 2022-11-08
CN115298340A (zh) 2022-11-04
KR20220137970A (ko) 2022-10-12
JP7264269B2 (ja) 2023-04-25
CN115298340B (zh) 2023-10-31

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