EP3859027A1 - Hochfestes stahlblech für säurebeständiges leitungsrohr, verfahren zur herstellung davon und hochfestes stahlrohr mit einem hochfesten stahlblech für säurebeständiges leitungsrohr - Google Patents

Hochfestes stahlblech für säurebeständiges leitungsrohr, verfahren zur herstellung davon und hochfestes stahlrohr mit einem hochfesten stahlblech für säurebeständiges leitungsrohr Download PDF

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EP3859027A1
EP3859027A1 EP19865764.5A EP19865764A EP3859027A1 EP 3859027 A1 EP3859027 A1 EP 3859027A1 EP 19865764 A EP19865764 A EP 19865764A EP 3859027 A1 EP3859027 A1 EP 3859027A1
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Prior art keywords
steel plate
temperature
sour
strength steel
high strength
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EP19865764.5A
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French (fr)
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EP3859027B1 (de
EP3859027A4 (de
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Junji Shimamura
Tomoyuki Yokota
Satoshi Ueoka
Nobuyuki Ishikawa
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JFE Steel Corp
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JFE Steel Corp
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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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • 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
    • C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C22C38/14—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
    • 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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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—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
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/002—Bainite

Definitions

  • This disclosure relates to a high strength steel plate for a sour-resistant line pipe that is excellent in material homogeneity in the steel plate and that is suitable for use in line pipes in the fields of construction, marine structure, shipbuilding, civil engineering, and construction industry machinery, and to a method for manufacturing the same.
  • This disclosure also relates to a high strength steel pipe using the high strength steel plate for a sour-resistant line pipe.
  • a line pipe is manufactured by forming a steel plate manufactured by a 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 to transport crude oil and natural gas containing hydrogen sulfide is required to have so-called sour resistance such as resistance to hydrogen-induced cracking (HIC resistance) and resistance to sulfide stress corrosion cracking (SSCC resistance), in addition to strength, toughness, weldability, and so on.
  • HIC resistance hydrogen-induced cracking
  • SSCC resistance resistance to sulfide stress corrosion cracking
  • HIC resistance hydrogen-induced cracking
  • SSCC resistance resistance to sulfide stress corrosion cracking
  • SSCC is generally known to occur in high strength seamless steel pipes for oil wells and in high hardness regions of welds, and has not been regarded as a problem in line pipes with relatively low hardness.
  • SSCC also occurs in the base metal of line pipes in environments where oil and natural gas mining environments have become increasingly severe and environments with high hydrogen sulfide partial pressure or low pH. It is also pointed out that it is important to control the hardness of the surface layer of the inner surface of a steel pipe to improve the SSCC resistance under more severe corrosion environments.
  • micro-cracks called fissures may occur, which may lead to SSCC.
  • TMCP Thermo-Mechanical Control Process
  • TMCP Thermo-Mechanical Control Process
  • it is effective to increase the cooling rate during controlled cooling.
  • the control cooling is performed at a high cooling rate, the surface layer of the steel plate is rapidly cooled, and the hardness of the surface layer becomes higher than that of the inside of the steel plate, and the hardness distribution in the plate thickness direction becomes uneven. Therefore, it is a problem in terms of ensuring the material homogeneity in the steel plate.
  • JP3951428B (PTL 1) and JP3951429B (PTL 2) describe methods for manufacturing steel plates with a reduced material property difference in the plate thickness direction by performing high-speed controlled cooling in which the surface is recuperated before completion of bainite transformation in the surface layer after rolling.
  • JP2002-327212A (PTL 3) and JP3711896B (PTL 4) describe methods for manufacturing steel plates for line pipes in which the hardness of the surface layer is reduced by heating the surface of a steel plate after accelerated cooling to a higher temperature than the inside using a high frequency induction heating device.
  • the transformation behavior differs depending on the compositions of the steel plate, a sufficient material homogenization effect by heat recuperation may not be obtained.
  • the microstructure in the surface layer of the steel plate obtained by the manufacturing methods described in PTLs 1 and 2 is a dual phase structure such as a ferrite-bainite dual phase structure, the hardness value may have a large variation in a low load micro Vickers test depending on which microstructure the indenter indents.
  • the cooling rate of the surface layer in accelerated cooling is so high that the hardness of the surface layer may not be sufficiently reduced only by heating the steel plate surface.
  • the methods of PTLs 5 and 6 apply descaling to reduce the surface characteristics defects due to the scale indentation during hot leveling and to reduce the variation in the cooling stop temperature of the steel plate to improve the steel plate shape.
  • no consideration is given to the cooling conditions for obtaining a uniform material property. This is because if the cooling rate on the surface of the steel plate varies, the hardness of the steel plate will vary.
  • the present inventors repeated many experiments and examinations about the chemical compositions, microstructures, and manufacturing conditions of steel materials in order to ensure proper SSCC resistance under more severe corrosion environments.
  • the inventors discovered that in order to further improve the SSCC resistance of a high strength steel pipe, it is not sufficient to merely suppress the surface layer hardness as conventionally found, and in particular, that it is possible to reduce the increase in hardness in the coating process after pipe making by forming the outermost surface layer of the steel plate, specifically at 0.25 mm below the surface of the steel plate, with a bainite microstructure having a dislocation density of 1.0 ⁇ 10 14 to 7.0 ⁇ 10 14 (m -2 ), and as a result the SSCC resistance of the steel pipe is improved.
  • the inventors In order to provide such a steel microstructure, the inventors also discovered that it is important to strictly control the cooling rate at 0.25 mm below the surface of the steel plate, and succeeded in finding the conditions to be met. The inventors also found that Mo addition is effective in suppressing initial crack generation in environments with high hydrogen sulfide partial pressure above 1 bar, while suppressing Ni addition is effective in avoiding microcracking such as fissures in environments with low hydrogen sulfide partial pressure below 1 bar. The present disclosure was completed based on the above discoveries.
  • the high strength steel plate for a sour-resistant line pipe and the high strength steel pipe using the high strength steel plate for a sour-resistant line pipe disclosed herein are excellent not only in HIC resistance but also in SSCC resistance under more severe corrosion environments and environments with low hydrogen sulfide partial pressure below 1 bar.
  • FIG. 1 is a schematic view illustrating a method for obtaining test pieces for evaluation of SSCC resistance in Examples.
  • the C effectively contributes to the improvement in strength.
  • the content is less than 0.02 %, sufficient strength cannot be secured, while if it exceeds 0.08 %, the hardness of the surface layer and the central segregation area increases during accelerated cooling, causing deterioration in SSCC resistance and HIC resistance.
  • the toughness also deteriorates. Therefore, the C content is set in a range of 0.02 % to 0.08 %.
  • Si is added for deoxidation. However, if the content is less than 0.01 %, the deoxidizing effect is not sufficient, while if it exceeds 0.50 %, the toughness and weldability are degraded. Therefore, the Si content is in a range of 0.01 % to 0.50 %.
  • Mn effectively contributes to the improvement in strength and toughness.
  • the content is less than 0.50 %, the addition effect is poor, while if it exceeds 1.80 %, the hardness of the surface layer and the central segregation area increases during accelerated cooling, causing deterioration in SSCC resistance and HIC resistance. The weldability also deteriorates. Therefore, the Mn content is set in a range of 0.50 % to 1.80 %.
  • the upper limit is set at 0.015 %.
  • the P content is 0.008 % or less.
  • the P content is set to 0.001 % or more from the viewpoint of the refining cost.
  • S is an inevitable impurity element that forms MnS inclusions in the steel and degrades the HIC resistance, and hence a lower S content is preferable. However, up to 0.0015 % is acceptable. Although a lower S content is preferable, the S content is set to 0.0002 % or more from the viewpoint of the refining cost.
  • A1 is added as a deoxidizing agent.
  • an Al content below 0.01 % provides no addition effect, while an Al content beyond 0.08 % lowers the cleanliness of the steel and deteriorates the toughness. Therefore, the Al content is set in a range of 0.01 % to 0.08 %.
  • Mo is an effective element for improving toughness and increasing strength, it is an effective element for improving SSCC resistance regardless of the hydrogen sulfide partial pressure.
  • the Mo content needs to be 0.01 % or more, and preferably 0.10 % or more.
  • the Mo content is set to 0.50 % or less, and preferably 0.40 % or less.
  • Ca is an element effective for improving the HIC resistance by morphological control of sulfide inclusions.
  • the content is less than 0.0005 %, its addition effect is not sufficient.
  • the content exceeds 0.005 %, not only the addition effect saturates, but also the HIC resistance is deteriorated due to the reduction in the cleanliness of the steel. Therefore, the Ca content is in a range of 0.0005 % to 0.005 %.
  • Both Nb and Ti are elements effective for improving the strength and toughness of the steel plate. If the content of each added element is less than 0.005 %, the addition effect is poor, while if it exceeds 0.1 %, the toughness of the welded portion deteriorates. Therefore, at least one of Nb or Ti is added in a range of 0.005 % to 0.1 %.
  • the chemical composition of the present disclosure may also contain at least one selected from the group consisting of Cu, Ni, and Cr in the following ranges to further improve the strength and toughness of the steel plate.
  • the Cu is an element effective for improving the toughness and increasing the strength.
  • the Cu content is preferably 0.05 % or more, yet if the content is too large, the weldability deteriorates. Therefore, when Cu is added, the Cu content is up to 0.50 %.
  • Ni is an element effective for improving the toughness and increasing the strength. To obtain this effect, the Ni content is preferably 0.01 % or more. However, when Ni is added in excess of 0.10 %, microcracks called fissures easily occur in environments with low hydrogen sulfide partial pressure below 1 bar. Therefore, when Ni is added, the Ni content is up to 0.10 %. The Ni content is preferably 0.02 % or less.
  • the Cr content is preferably 0.05 % or more, yet if the content is too large, the quench hardenability becomes excessively high, causing an increase in the dislocation density to be described later and deteriorating the SSCC resistance. The weldability also deteriorates. Therefore, when Cr is added, the Cr content is up to 0.50 %.
  • the chemical composition of the present disclosure may further contain at least one selected from the group consisting of V, Zr, Mg, and REM in the following ranges.
  • V is an element that can be optionally added to increase the strength and toughness of the steel plate. If the content of each added element is less than 0.005 %, the addition effect is poor, while if it exceeds 0.1 %, the toughness of the welded portion deteriorates. Therefore, the content of each added element is preferably in a range of 0.005 % to 0.1 %.
  • Zr, Mg, and REM are elements which can be optionally added in order to enhance the toughness through grain refinement and to improve the cracking resistance through control of the inclusion properties.
  • Each of these elements is poor in the addition effect when the content is less than 0.0005 %, while the effect is saturated when the content is more than 0.02 %. Therefore, when added, the content of each added element is preferably in a range of 0.0005 % to 0.02 %.
  • the present disclosure discloses a technique for improving the SSCC resistance of the high strength steel pipe using the high strength steel plate for a sour-resistant line pipe
  • the technique disclosed herein needs to satisfy the HIC resistance at the same time as the sour resistant performance.
  • the CP value obtained by the following Expression (1) is preferably set to 1.00 or less.
  • CP 4.46 % C + 2.37 % Mn / 6 + 1.74 % Cu + 1.7 % Ni / 15 + 1.18 % Cr + 1.95 % Mo + 1.74 % V ) / 5 + 22.36 % P
  • [%X] represents the content by mass% of the element X in steel.
  • the CP value is a formula devised to estimate the material property at the central segregation area from the content of each alloying element, and the component concentrations of the central segregation area are higher as the CP value of Expression (1) is higher, causing a rise in the hardness of the central segregation area. Therefore, by setting the CP value obtained in Expression (1) to 1.00 or less, it is possible to suppress the occurrence of cracking in the HIC test. In addition, since the hardness of the central segregation area is lower as the CP value is lower, the upper limit for the CP value may be set to 0.95 when higher HIC resistance is required.
  • N is an element which is inevitably contained in the steel, and a content of 0.007 % or less, preferably 0.006 % or less, is acceptable in the present disclosure.
  • the steel microstructure of the high strength steel plate for a sour-resistant line pipe disclosed herein will be described.
  • the steel microstructure needs to be a bainite microstructure.
  • a hard phase such as martensite or martensite austenite constituent (MA)
  • MA martensite or martensite austenite constituent
  • the surface layer hardness is increased, the variation in hardness in the steel plate is increased, and the material homogeneity is impaired.
  • the surface layer is formed with a bainite microstructure as the steel microstructure.
  • portions other than the surface layer also have a bainite microstructure, and the microstructure at the mid-thickness part representative of the portions may be a bainite microstructure.
  • the bainite microstructure includes a microstructure called bainitic ferrite or granular ferrite which contributes to transformation strengthening. These microstructures appear through transformation during or after accelerated cooling. If different microstructures such as ferrite, martensite, pearlite, martensite austenite constituent, retained austenite, and the like are mixed in the bainite microstructure, a decrease in strength, a deterioration in toughness, a rise in surface hardness, and the like occur. Therefore, it is preferable that microstructures other than the bainite phase have smaller proportions.
  • the bainite microstructure takes various forms according to the cooling rate, it is important for the present disclosure that the outermost surface layer of the steel plate, specifically at 0.25 mm below the surface of the steel plate, is formed with a bainite microstructure having a dislocation density of 1.0 ⁇ 10 14 to 7.0 ⁇ 10 14 (m -2 ). Since the dislocation density decreases in the coating process after pipe making, the hardness increase due to age hardening can be minimized if the dislocation density at 0.25 mm below the surface of the steel plate is 7.0 ⁇ 10 14 (m -2 ) or less.
  • the dislocation density at 0.25 mm below the surface of the steel plate exceeds 7.0 ⁇ 10 14 (m -2 )
  • the dislocation density does not decrease in the coating process after pipe making, and the hardness is significantly increased due to age hardening, causing deterioration in the SSCC resistance.
  • the range of dislocation density is preferably 6.0 ⁇ 10 14 (m -2 ) or less in order to obtain good SSCC resistance after pipe making.
  • the dislocation density at 0.25 mm below the surface of the steel plate is less than 1.0 ⁇ 10 14 (m -2 )
  • the strength of the steel plate deteriorates.
  • dislocation density 2.0 ⁇ 10 14 (m -2 ) or more.
  • the outermost surface layer ranging from the surface of the steel plate to a depth of 0.25 mm has an equivalent dislocation density, and consequently, the above-described SSCC resistance improving effect is obtained.
  • the HV 0.1 at 0.25 mm below the surface is 230 or less. From the viewpoint of securing the SSCC resistance of the steel pipe, it is important to suppress an increase in the surface hardness of the steel plate. However, by setting the HV 0.1 at 0.25 mm below the surface of the steel plate to 230 or less, the HV 0.1 at 0.25 mm below the surface following the coating heat treatment at 250 °C for 1 hour after pipe making can be suppressed to 260 or less, and the SSCC resistance can be secured.
  • the variation in Vickers hardness at 0.25 mm below the surface of the steel plate is 30 HV or less at 3 ⁇ , where ⁇ is a standard deviation.
  • ⁇ is a standard deviation.
  • the high strength steel plate disclosed herein is a steel plate for steel pipes having a strength of X60 grade or higher in API 5L, and thus has a tensile strength of 520 MPa or more.
  • the manufacturing method according to the present disclosure comprises: heating a slab having the above-described chemical composition, and then hot rolling the slab to form a steel plate; and then subjecting the steel plate to controlled cooling under predetermined conditions.
  • the slab heating temperature is set to 1000 °C to 1300 °C. This temperature is the temperature in the heating furnace, and the slab is heated to this temperature to the center.
  • the rolling finish temperature in terms of a temperature of the surface of the steel plate needs to be set in consideration of the required toughness for base metal and rolling efficiency. From the viewpoint of improving the strength and the HIC resistance, it is preferable to set the rolling finish temperature at or above the Ar 3 transformation temperature in terms of a temperature of the surface of the steel plate.
  • the Ar 3 transformation temperature means the ferrite transformation start temperature during cooling, and can be determined, for example, from the components of steel according to the following equation.
  • the rolling reduction ratio in a temperature range of 950 °C or lower corresponding to the austenite non-recrystallization temperature range to 60 % or more.
  • the temperature of the surface of the steel plate can be measured by a radiation thermometer or the like.
  • Ar 3 ° C 910 ⁇ 310 % C ⁇ 80 % Mn ⁇ 20 % Cu ⁇ 15 % Cr ⁇ 55 % Ni ⁇ 80 % Mo , where [%X] indicates the content by mass% of the element X in steel.
  • Cooling start temperature is (Ar 3 - 10 °C) or higher in terms of a temperature of the surface of the steel plate.
  • the temperature of the surface of the steel plate at the start of cooling is set to (Ar 3 - 10 °C) or higher. Note that the temperature of the surface of the steel plate at the start of cooling is not higher than the rolling finish temperature.
  • Average cooling rate in a temperature range from 750 °C to 550 °C in terms of a temperature at 0.25 mm below the surface of the steel plate 50 °C/s or lower
  • the average cooling rate in a temperature range from 750 °C to 550 °C in terms of a temperature at 0.25 mm below the surface of the steel plate exceeds 50 °C/s
  • the dislocation density at 0.25 mm below the surface of the steel plate exceeds 7.0 ⁇ 10 14 (m -2 ).
  • the average cooling rate is set to 50 °C/s or lower. It is preferably 45 °C/s or lower, and more preferably 40 °C/s or lower.
  • the lower limit of the average cooling rate is not particularly limited, yet if the cooling rate is excessively low, ferrite and pearlite are generated and the strength is insufficient. Therefore, from the viewpoint of preventing this, 20 °C/s or higher is preferable.
  • Average cooling rate in a temperature range from 750 °C to 550 °C in terms of an average temperature of the steel plate 15 °C/s or higher If the average cooling rate in a temperature range from 750 °C to 550 °C in terms of an average temperature of the steel plate is lower than 15 °C/s, a bainite microstructure cannot be obtained, causing deterioration in the strength and HIC resistance. Therefore, the cooling rate in terms of an average temperature of the steel plate is set to 15 °C/s or higher. From the viewpoint of variations in the strength and hardness of the steel plate, the steel plate average cooling rate is preferably 20 °C/s or higher. The upper limit of the average cooling rate is not particularly limited, yet is preferably 80 °C/s or lower such that excessive low-temperature transformation products will not be generated.
  • Average cooling rate in a temperature range from 550 °C to a cooling stop temperature in terms of a temperature at 0.25 mm below the surface of the steel plate 150 °C/s or higher
  • For cooling at a temperature of 550 °C or lower in terms of a temperature at 0.25 mm below the surface of the steel plate cooling in a stable nucleate boiling state is necessary, and it is essential to increase the water flow rate.
  • the average cooling rate is set to 150 °C/s or higher. Preferably, it is 170 °C/s or higher.
  • the upper limit of the average cooling rate is not particularly limited, yet is preferably 250 °C/s or lower in view of equipment restrictions.
  • a temperature distribution in a cross section in the plate thickness direction can be determined in real time by difference calculation using a process computer on the basis of the surface temperature at the start of cooling measured by a radiation thermometer and the target surface temperature at the end of cooling.
  • the temperature at 0.25 mm below the surface of the steel plate in the temperature distribution is referred to as the "temperature at 0.25 mm below the surface of the steel plate", and the average value of temperatures in the thickness direction in the temperature distribution as the "average temperature of the steel plate”.
  • Cooling stop temperature 250 °C to 550 °C in terms of an average temperature of the steel plate
  • a bainite phase is generated by performing controlled cooling to quench the steel plate to a temperature range of 250 °C to 550 °C which is the temperature range of bainite transformation.
  • the cooling stop temperature exceeds 550 °C, bainite transformation is incomplete and sufficient strength cannot be obtained.
  • the cooling stop temperature is lower than 250 °C, the hardness increase in the surface layer becomes remarkable and the dislocation density at 0.25 mm below the surface of the steel plate exceeds 7.0 ⁇ 10 14 (m -2 ), causing deterioration in the SSCC resistance.
  • the cooling stop temperature of the controlled cooling is set to 250 °C to 550 °C in terms of an average temperature of the steel plate.
  • a high strength steel pipe for sour-resistant line pipes (such as a UOE steel pipe, an electric-resistance welded steel pipe, and a spiral steel pipe) that has excellent material homogeneity in the steel plate and that is suitable for transporting crude oil and natural gas can be manufactured.
  • an UOE steel pipe is manufactured by groove machining the ends of a steel plate, forming the steel plate into a steel pipe shape by C press, U-ing press, and O-ing press, then seam welding the butting portions by inner surface welding and outer surface welding, and optionally subjecting it to an expansion process.
  • Any welding method may be applied as long as sufficient joint strength and joint toughness are guaranteed, yet it is preferable to use submerged arc welding from the viewpoint of excellent weld quality and manufacturing efficiency.
  • the steels (Steels A to M) having the chemical compositions listed in Table 1 are made into slabs by continuous casting, heated to the temperatures listed in Table 2, and then hot rolled at the rolling finish temperatures and rolling reduction ratios listed in Table 2 to obtain the steel plates of the thicknesses listed in Table 2. Then, each steel plate was subjected to controlled cooling using a water-cooling type controlled-cooling device under the conditions listed in Table 2.
  • each obtained steel plate was observed by an optical microscope and a scanning electron microscope.
  • the microstructure at a position of 0.25 mm below the surface of each steel plate and the microstructure at the mid-thickness part are listed in Table 2.
  • HV 0.1 Vickers hardness
  • a sample for X-ray diffraction was taken from a position having an average hardness, the sample surface was polished to remove scale, and X-ray diffraction measurement was performed at a position of 0.25 mm below the surface of the steel plate.
  • the dislocation density was converted from the strain obtained from the half width ⁇ of X-ray diffraction measurement.
  • K ⁇ 1 and K ⁇ 2 rays having different wavelengths overlap, and are thus separated by the Rachinger's method.
  • the Williamson-Hall method described below is used for extraction of strain.
  • the strain ⁇ is calculated from the slope of the straight line by plotting ⁇ cos ⁇ / ⁇ relative to sin ⁇ / ⁇ .
  • the diffraction lines used for the calculation are (110), (211), and (220).
  • ⁇ means the peak angle calculated by the ⁇ -2 ⁇ method for X-ray diffraction
  • ⁇ means the wavelength of the X-ray used in the X-ray diffraction
  • b is a Burgers vector of Fe( ⁇ ), and is set to 0.25 nm in this embodiment.
  • the SSCC resistance was evaluated for a pipe made from a part of each steel plate.
  • Each pipe was manufactured by groove machining the ends of a steel plate, and forming the steel plate into a steel pipe shape by C press, U-ing press, and O-ing press, then seam welding the butting portions on the inner and outer surfaces by submerged arc welding, and subjecting it to an expansion process.
  • FIG. 1 after a coupon cut out from each obtained steel pipe was flattened, an SSCC test piece of 5 mm ⁇ 15 mm ⁇ 115 mm was collected from the inner surface of the steel pipe. At this time, the inner surface to be tested was left intact without removing the scale in order to leave the state of the outermost layer.
  • Each collected SSCC test piece was loaded with 90 % stress of the actual yield strength (0.5 % YS) of the corresponding steel pipe, and evaluation was made using a NACE standard TM0177 Solution A solution, at a hydrogen sulfide partial pressure of 1 bar, in accordance with the 4-point bending SSCC test specified by the EFC 16 standard.
  • evaluation was made using a NACE standard TM0177 Solution B solution in accordance with the 4-point bending SSCC test specified by the EFC 16 standard.
  • HIC resistance was determined by performing HIC test at a hydrogen sulfide partial pressure of 1 bar and with an immersion time of 96 hours using a NACE standard TM0177 Solution A solution. In addition, HIC resistance was determined by performing HIC test at a hydrogen sulfide partial pressure of 0.1 bar and a carbon-dioxide partial pressure of 0.9 bar and with an immersion time of 96 hours using a NACE standard TM0177 Solution B solution. The HIC resistance was judged as "Good” when the crack length ratio (CLR) was 15 % or less in the HIC test, or "Poor" when the CLR exceeded 15 %. The results are listed in Table 2.
  • CLR crack length ratio
  • Nos. 1 to 15 are our examples in which the chemical compositions and the production conditions satisfy the appropriate ranges of the present disclosure.
  • the tensile strength as a steel plate was 520 MPa or more
  • the microstructure at both positions of 0.25 mm below the surface and of t/2 was a bainite microstructure
  • the HV 0.1 at 0.25 mm below the surface was 230 or less
  • the SSCC resistance and HIC resistance were also good in the high strength steel pipe made from the steel plate.
  • Nos. 16 to 23 are comparative examples whose chemical compositions are within the scope of the present disclosure but whose production conditions are outside the scope of the present disclosure.
  • the slab heating temperature was low, the homogenization of the microstructure and the solid solution state of carbides were insufficient and the strength was low.
  • the cooling start temperature was low and the microstructure was formed in a layered manner with precipitation of ferrite, the strength was low and the HIC resistance after pipe making deteriorated.
  • No. 16 since the slab heating temperature was low, the homogenization of the microstructure and the solid solution state of carbides were insufficient and the strength was low.
  • the cooling start temperature was low and the microstructure was formed in a layered manner with precipitation of ferrite, the strength was low and the HIC resistance after pipe making deteriorated.
  • the SSCC resistance after pipe making was inferior.
  • the dislocation density at 0.25 mm below the surface was high, and the HV 0.1 exceeded 230, the SSCC resistance after pipe making was inferior.
  • the HIC resistance was also inferior because the hardness of the central segregation area increased.
  • the amount of Ni in the steel plate was excessive, and the SSCC resistance in environments with low hydrogen sulfide partial pressure deteriorated.
  • the steel plate was Mo-free, and the SSCC resistance deteriorated in a very severe corrosion environment with a hydrogen sulfide partial pressure of 2 bar.
  • the average cooling rate in a temperature range from 750 °C to 550 °C in terms of a temperature at 0.25 mm below the surface of the steel plate exceeded 50 °C/s, and the SSCC resistance deteriorated under a very severe corrosion environment with a hydrogen sulfide partial pressure of 2 bar.
  • steel pipes such as electric-resistance welded steel pipes, spiral steel pipes, and UOE steel pipes
  • steel pipes manufactured by cold-forming the disclosed steel plate can be suitably used for transportation of crude oil and natural gas that contain hydrogen sulfides where sour resistance is required.
EP19865764.5A 2018-09-28 2019-09-25 Hochfeste stahlplatte für sauergas-resistente leitungsrohre und verfahren zu ihrer herstellung, und hochfestes stahlrohr unter verwendung von hochfesten stahlplatten für sauergas-resistente leitungsrohre Active EP3859027B1 (de)

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