EP3543366A1 - Stahlblech, stahlrohr für ein leitungsrohr und herstellungsverfahren dafür - Google Patents

Stahlblech, stahlrohr für ein leitungsrohr und herstellungsverfahren dafür Download PDF

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Publication number
EP3543366A1
EP3543366A1 EP17871656.9A EP17871656A EP3543366A1 EP 3543366 A1 EP3543366 A1 EP 3543366A1 EP 17871656 A EP17871656 A EP 17871656A EP 3543366 A1 EP3543366 A1 EP 3543366A1
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Prior art keywords
mass
less
steel plate
content
bubbles
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EP17871656.9A
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English (en)
French (fr)
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EP3543366B1 (de
EP3543366A4 (de
Inventor
Kiichiro TASHIRO
Motoki KAKIZAKI
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Kobe Steel Ltd
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Kobe Steel Ltd
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Priority claimed from PCT/JP2017/039785 external-priority patent/WO2018092605A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—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
    • C21D9/0081—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—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
    • C22C38/18—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
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron

Definitions

  • the present disclosure relates to a steel plate, a steel pipe for a line pipe, and a production method therefor.
  • HIC Hydrogen induced cracking
  • the surface layer part in the thickness direction of the steel plate is more likely to cause HIC than the center in the thickness direction of the steel plate, and thus the surface layer part is required to improve its HIC resistance.
  • Patent Document 1 discloses that the HIC resistance is improved by controlling the amount of Ar gas blown into a molten steel to a predetermined level or less to thereby reduce an amount of Ar-gas uncompressed bubbles in the steel material which would form accumulation and segregation zones of MnS, Ca-Al based, and Ca-based inclusion clusters and Ti-based and Nb-based inclusions, causing the HIC.
  • Patent Document 2 discloses that the HIC resistance is improved by controlling a Ca concentration in a slab within a predetermined range during manufacture of the slab and also by controlling the contents of Ca, S and O as well as the content of Ar gas in a steel material within respective predetermined ranges.
  • Patent Document 1 does not consider uncompressed bubbles in a steel material of the final product, even though it has considered the decrease in the number of bubbles in the slab. Consequently, defects induced by uncompressed bubbles remaining in the steel material cannot be controlled, and HIC due to the uncompressed bubbles cannot be suppressed.
  • Patent Document 2 does not consider the size of bubbles and the presence of uncompressed bubbles in a steel material, even though it has considered the decrease in the content of Ar-gas bubbles in the steel material. Thus, even in the presence of a small amount of coarse Ar bubbles, this method cannot sufficiently suppress the HIC.
  • An embodiment of the present invention has been made in view of the foregoing circumstance, and thus it is a main object of the embodiment of the present invention to provide a steel plate and a steel pipe for a line pipe that have excellent hydrogen induced cracking resistance.
  • a steel plate according to an embodiment of the present invention contains C: 0.02 to 0.15% by mass, Si: 0.02 to 0.50% by mass, Mn: 0. 6 to 2.0% by mass, P: more than 0% by mass and 0.030% by mass or less, S: more than 0% by mass and 0.003% by mass or less, Al: 0.010 to 0. 080% by mass, Ca: 0.0003 to 0.0060% by mass, N: 0.001 to 0.01% by mass, and O: more than 0% by mass and 0.0045% by mass or less, with the balance being iron and inevitable impurities, wherein the steel plate satisfies the following formulae (1) and (2) : 3.0 ⁇ Ca / S Ca ⁇ 1.25 ⁇ S / O ⁇ 1.80
  • the steel plate according to an embodiment of the present invention may further comprise one or more elements selected from the group consisting of, B: more than 0% by mass and 0.005% by mass or less, V: more than 0% by mass and 0.1% by mass or less, Cu: more than 0% by mass and 1.5% by mass or less, Ni: more than 0% by mass and 1.5% by mass or less, Cr: more than 0% by mass and 1.5% by mass or less, Mo: more than 0% by mass and 1.5% by mass or less, Nb: more than 0% by mass and 0.06% by mass or less, Ti: more than 0% by mass and 0.03% by mass or less, Mg: more than 0% by mass and 0.01% by mass or less, REM: more than 0% by mass and 0.02% by mass or less, and Zr: more than 0% by mass and 0.010% by mass or less.
  • B more than 0% by mass and 0.005% by mass or less
  • V more than 0% by mass and 0.1% by mass or less
  • Cu more than 0% by
  • the steel plate according to an embodiment of the present invention may be for use in a line pipe.
  • a steel pipe for a line pipe according to an embodiment of the present invention is formed of the steel plate according to the embodiment of the present invention.
  • the steel plate according to an embodiment of the present invention may be for use in a pressure vessel.
  • a method for producing the steel plate according to an embodiment of the present invention uses a slab having a chemical composition of the steel plate according to the embodiment of the present invention, the slab having a number density of bubbles (hereinafter sometimes simply referred to as a bubble density) of 0.15 bubbles/cm 2 or less in a slab accumulation zone, the bubbles having a circular equivalent diameter of 0.2 mm or more.
  • a bubble density a number density of bubbles (hereinafter sometimes simply referred to as a bubble density) of 0.15 bubbles/cm 2 or less in a slab accumulation zone, the bubbles having a circular equivalent diameter of 0.2 mm or more.
  • the embodiments of the present invention provide a steel plate and a steel pipe for a line pipe that have excellent hydrogen induced cracking resistance, as well as a method for producing the steel plate.
  • the present inventors have conducted intensive studies about the correlation between the CLR (Crack Length Ratio, a proportion [%] of the total length of cracks to the width of a test piece, a crack length ratio) of the surface layer part measured by a HIC test and internal defects in the steel plate measured by an ultrasonic flaw detection test.
  • CLR Chip Length Ratio, a proportion [%] of the total length of cracks to the width of a test piece, a crack length ratio
  • the excellent HIC resistance can be achieved by controlling the chemical composition of the steel plate within a predetermined range such that the contents of Ca, S and O satisfy predetermined relational expressions, and also by controlling internal defects such that the area ratio of a part that has a defect echo height of 20% or more is 0.05% or less.
  • a steel plate according to an embodiment of the present invention contains, C: 0.02 to 0.15% by mass, Si: 0.02 to 0.50% by mass, Mn: 0.6 to 2.0% by mass, P: more than 0% by mass and 0.030% by mass or less, S: more than 0% by mass and 0.003% by mass or less, Al: 0.010 to 0.080% by mass, Ca: 0.0003 to 0.0060% by mass, N: 0.001 to 0.010% by mass, and O: more than 0% by mass and 0.0045% by mass or less, with the balance being iron and inevitable impurities, wherein the steel plate satisfies the following formulae (1) and (2): 3.0 ⁇ Ca / S Ca ⁇ 1.25 ⁇ S / O ⁇ 1.80 where [Ca], [S] and [O] are contents (% by mass) of Ca, S and O respectively.
  • the steel plate with excellent hydrogen induced cracking resistance can be obtained.
  • the C content is an element essential to ensure the strengths of a base material and a welded part.
  • the C content needs to be 0.02% by mass or more.
  • the C content is preferably 0.03% by mass or more, and more preferably 0.04% by mass or more.
  • an extremely high C content degrades the HAZ toughness and a weldability of the steel.
  • an excessive C content is more likely to form NbC or island-shaped martensite, which becomes a starting point of HIC or a fracture propagation route.
  • the C content needs to be 0.15% by mass or less.
  • the C content is preferably 0.12% by mass or less, and more preferably 0.10% by mass or less.
  • the Si is an element that has a deoxidation function and is effective in improving the strengths of a base material and a welded part.
  • the Si content is set at 0.02% by mass or more.
  • the Si content is preferably 0.05% by mass or more, and more preferably 0.15% by mass or more.
  • an extremely high Si content degrades the weldability and toughness of the steel.
  • an excessive Si content forms island-shaped martensite to generate and propagate HIC.
  • the Si content needs to be restricted to 0.50% by mass or less.
  • the Si content is preferably 0.45% by mass or less, and more preferably 0.35% by mass or less.
  • Mn is an element that is effective in improving the strengths of a base material and a welded.
  • the Mn content is set at 0.6% by mass or more.
  • the Mn content is preferably 0.8% by mass or more, and more preferably 1.0% by mass or more.
  • an extremely high Mn content forms MnS, degrading not only the hydrogen induced cracking resistance, but also the HAZ toughness and the weldability.
  • the upper limit of Mn content is set at 2.0% by mass.
  • the Mn content is preferably 1.8% by mass or less, more preferably 1.5% by mass or less, and further preferably 1.2% by mass or less.
  • the P content is an element inevitably contained in a steel material.
  • the P content exceeds 0.030% by mass, the toughness of a base material and a HAZ are significantly degraded, and the hydrogen induced cracking resistance of a steel plate is also degraded.
  • the P content is restricted to 0.030% by mass or less.
  • the P content is preferably 0.020% by mass or less, and more preferably 0.010% by mass or less.
  • the upper limit of S content is set at 0.003% by mass.
  • the S content is preferably 0.002% by mass or less, more preferably 0. 0015% by mass or less, and further preferably 0.0010% by mass or less.
  • the S content is desirably low from the viewpoint of improving the hydrogen induced cracking resistance.
  • Al is a strong deoxidizing element.
  • the Al content needs to be 0.010% by mass or more.
  • the Al content is preferably 0.020% by mass or more, and more preferably 0.030% by mass or more.
  • the Al content needs to be 0.080% by mass or less.
  • the Al content is preferably 0.060% by mass or less, and more preferably 0.050% by mass or less.
  • Ca serves to control a form of a sulfide and has an effect of suppressing formation of MnS by forming CaS.
  • the Ca content needs to be 0.0003% by mass or more.
  • the Ca content is preferably 0.0005% by mass or more, and more preferably 0.0010% by mass or more.
  • the upper limit of Ca content is set at 0.0060% by mass.
  • the Ca content is preferably 0.0045% by mass or less, more preferably 0.0035% by mass or less, and further preferably 0.0025% by mass.
  • N is an element that is precipitated as TiN in a steel microstructure to thereby suppress coarsening of austenite grains in a HAZ and to promote ferrite transformation, thus improving the toughness of the HAZ.
  • the N content needs to be 0.001% by mass or more.
  • the N content is preferably 0.003% by mass or more, and more preferably 0.0040% by mass or more.
  • An excessive N content degrades the HAZ toughness in the presence of solid-solution N.
  • the N content needs to be 0.01% by mass or less.
  • the N content is preferably 0.008% by mass or less, and more preferably 0.0060% by mass or less.
  • O content is desirably low from the viewpoint of improving cleanliness.
  • An extremely high O content degrades the toughness, and additionally causes HIC at an oxide as a starting point, thereby degrading the hydrogen induced cracking resistance.
  • the O content needs to be 0.0045% by mass or less and is preferably 0.0035% by mass or less, and more preferably 0.0030% by mass or less.
  • the steel plate according to an embodiment of the present invention satisfies the following formula (1). 3.0 ⁇ Ca / S where [Ca] and [S] are contents (% by mass) of Ca and S respectively.
  • the value of [Ca]/[S] needs to be set at 3.0 or more.
  • the value of [Ca]/[S] is preferably 3.5 or more, and more preferably 4.0 or more.
  • the upper limit of [Ca]/[S] is approximately 15. Ca ⁇ 1.25 ⁇ S / O : 1.80 or less
  • the steel plate according to an embodiment of the present invention satisfies the following formula (2).
  • the value of ([Ca] - 1.25 ⁇ [S]) / [O] is preferably 1.40 or less, more preferably 1.30 or less, further preferably 1.20 or less, and particularly preferably 1.00 or less.
  • the lower limit of ([Ca] - 1.25 ⁇ [S]) is approximately 0.1 from the viewpoint of suppressing Al 2 O 3 that easily forms aggregates, like CaO.
  • the basic components of the steel plate according to an embodiment of the present invention are as described above, with the balance is iron and inevitable impurities. It is noted that inevitable impurities, other than P and S, which are brought depending on situations, such as raw materials, other materials, or facilities, are obviously allowed to be contained in the steel.
  • the steel plate according to an embodiment of the present invention may further selectively contain the following element(s) in addition to the above-mentioned elements, and thereby will have more improved properties of the steel plate itself depending on the kinds of the elements contained.
  • B enhances the hardenability of a steel and the strengths of a base material and a welded part.
  • B binds with N in the process of cooling a heated HAZ during welding to precipitate BN, which promotes ferrite transformation from austenite grains, thereby improving the HAZ toughness.
  • the B content is preferably 0. 0002% by mass or more.
  • the B content is more preferably 0.0005% by mass or more, and further preferably 0.0010% by mass or more.
  • An excessive B content degrades the toughness of the base material and the HAZ and leads to degradation in the weldability.
  • the B content is preferably 0.005% by mass or less.
  • the B content is more preferably 0.004% by mass or less, and further preferably 0.0030% by mass or less.
  • V is an element effective in improving the strength.
  • the V content is preferably 0.003% by mass or more.
  • the V content is more preferably 0.010% by mass or more.
  • the V content is preferably 0.1% by mass or less, and more preferably 0.08% by mass or less.
  • the Cu is an element effective in improving the hardenability to enhance the strength.
  • the Cu content is preferably 0.01% by mass or more.
  • the Cu content is more preferably 0.05% by mass or more, and further preferably 0.10% by mass or more.
  • the toughness is degraded.
  • the Cu content is preferably 1.5% by mass or less.
  • the Cu content is more preferably 1.0% by mass or less, and further preferably 0.50% by mass or less.
  • Ni is an element effective in improving the strength and toughness of a base material and a welded part.
  • the Ni content is preferably 0.01% by mass or more.
  • the Ni content is more preferably 0.05% by mass or more, and further preferably 0.10% by mass or more.
  • An excessive Ni content makes the steel plate for structures extremely expensive. From the economic point of view, the Ni content is preferably 1.5% by mass or less.
  • the Ni content is more preferably 1.0% by mass or less, and further preferably 0.50% by mass or less.
  • the Cr content is an element effective in improving the strength.
  • the Cr content is preferably 0.01% by mass or more.
  • the Cr content is more preferably 0.05% by mass or more, and further preferably 0.10% by mass or more.
  • the Cr content is preferably 1.5% by mass or less .
  • the Cr content is more preferably 1. 0% by mass or less, and further preferably 0.50% by mass or less.
  • Mo is an element that is effective in improving the strength and toughness of a base material.
  • the Mo content is preferably 0.01% by mass or more.
  • the Mo content is more preferably 0.05% by mass or more, and further preferably 0.10% by mass or more.
  • the Mo content is preferably 1.5% by mass or less, more preferably 1. 0% by mass or less, and further preferably 0.50% by mass or less.
  • the Nb content is an element that is effective in enhancing the strength and the base material toughness without degrading the weldability .
  • the Nb content is preferably 0.002% by mass or more.
  • the Nb content is more preferably 0.010% by mass or more, and further preferably 0.020% by mass or more.
  • the upper limit of Nb content is preferably 0.06% by mass.
  • the Nb content is more preferably 0.050% by mass or less, more further preferably 0.040% by mass or less, and yet more preferably 0.030% by mass or less.
  • Ti is an element that is precipitated as TiN in a steel to prevent the coarsening of austenite grains at a HAZ during welding and to promote ferrite transformation, thus improving the toughness of the HAZ.
  • Ti is also the element that is effective in improving the HIC resistance of the steel plate because of its desulfurization effect.
  • the Ti content is preferably 0.003% by mass or more.
  • the Ti content is more preferably 0.005% by mass or more, and further preferably 0.010% by mass or more.
  • an excessive Ti content precipitates solid-solution Ti and TiC to degrade the toughnesses of the base material and the HAZ.
  • the Ti content is preferably 0.03% by mass or less.
  • the Ti content is more preferably 0.02% by mass or less.
  • Mg is an element that is effective in improving the toughness through refinement of crystal grains and also in improving the HIC resistance because of its desulfurization effect. To obtain these effects, the Mg content is preferably 0. 0003% by mass or more. The Mg content is more preferably 0.001% by mass or more. On the other hand, even when Mg is contained in an excessive amount, its effects are saturated. Thus, the upper limit of the Mg content is preferably 0.01% by mass. The Mg content is more preferably 0.005% by mass or less.
  • the REM are elements that are effective in enhancing the hydrogen induced cracking resistance by suppressing the formation of MnS through the desulfurization effect.
  • the REM content is preferably 0.0002% by mass or more.
  • the REM content is more preferably 0.0005% by mass or more, and further preferably 0.0010% by mass or more.
  • the upper limit of the REM content is preferably 0.02% by mass.
  • the REM content is more preferably 0.015% by mass or less, further preferably 0.010% by mass or less, and more further preferably 0.0050% by mass or less.
  • the above-mentioned REM means lanthanoid elements (15 elements from La to Lu), Sc (scandium), and Y (yttrium).
  • the Zr content is an element that contributes to improvement of the HIC resistance by the desulfurization effect and also improvement of the HAZ toughness by forming oxides and dispersing them finely.
  • the Zr content is preferably set at 0.0003% by mass or more.
  • the Zr content is more preferably 0.0005% by mass or more, further preferably 0.0010% by mass or more, and yet more preferably 0.0015% by mass or more.
  • the addition of an excessive content of Zr forms coarse inclusions to degrade the hydrogen induced cracking resistance and the toughness of a base material.
  • the Zr content is preferably 0.010% by mass or less.
  • the Zr content is more preferably 0.0070% by mass or less, further preferably 0.0050% by mass or less, and more further preferably 0.0030% by mass or less.
  • an area ratio of a part that has a defect echo height of 20% or more is 0.05% or less.
  • Ar gas needs to be blown into a molten steel, for example, in order to suppress clogging of an injection nozzle, to cause reflux for degassing in an RH, and to stir the molten steel in a tundish.
  • the slab accumulation zone is a surface part of the slab, and the part that has been cooled and solidified earlier than the center at the stage of formation of the slab.
  • bubbles caused by Ar gas blown thereinto during slab casting float, but are more likely to be trapped and remain in a solidified part of a curved portion.
  • the bubbles remaining in the slab accumulation zone are difficult to completely compress in a rolling process, so that these bubbles are more likely to remain in the steel plate accumulation zone. Since hydrogen tend to be accumulated in the bubbles remaining in the steel plate accumulation zone, HIC may occur from the remaining bubbles as a starting point. Due to this, the HIC resistance can be improved by reducing the bubbles in the steel plate accumulation zone.
  • the "slab accumulation zone” means a region of approximately t/8 to t/4 from the surface of the slab where t is a thickness of the slab
  • the "steel plate accumulation zone” means a region of approximately t'/8 to t'/4 from the surface of a steel plate where t' is a thickness of the steel plate, which is obtained by hot-rolling the above-mentioned slab having the thickness t.
  • the slab When a slab is hot-rolled, the slab is normally rolled almost uniformly (that is, the slab accumulation zone and other portions are rolled at the approximately same rolling reduction) .
  • the region of approximately t/8 to t/4 from the surface of the slab becomes a part corresponding to the region of approximately t'/8 to t'/4 from the surface of the steel plate obtained by hot-rolling the slab. That is, the "slab accumulation zone" is the part corresponding to the "steel plate accumulation zone" of the steel plate obtained by hot-rolling the slab.
  • FIG. 1 shows the result obtained by examining the relationship between the CLR of the surface layer part measured by an HIC test and an area ratio of a part that has a defect echo height of 20% or more, which is measured by an ultrasonic flaw detection test.
  • the defect echo height as used herein means a ratio [%] of an intensity of a defect echo reflected by a defect inside a test piece (taken out from a part of the steel plate) to an intensity of a bottom-surface echo reflected by the bottom surface of the steel plate (or test piece).
  • the area ratio of a part that has a defect echo height of 20% or more means a ratio [%] of the area of the part that has a defect echo height of 20% or more to the entire area of the steel plate scanned by a probe.
  • the present inventors have found a correlation between the CLR of the surface layer part and the above-mentioned area ratio. That is, it has been found that even when bubbles remain in the steel plate accumulation zone, as long as the area ratio of the part that has a defect echo height of 20% or more is 0.05% or less, the CLR of the surface layer part of the steel plate can be 10% or less, thereby the occurrence of HIC from the steel plate accumulation zone is suppressed.
  • the defect echo height is preferably 30% or less, and more preferably 25% or less
  • the area ratio of the part that has a defect echo height of 20% or more is preferably 0.04% or less, and more preferably 0.03% or less.
  • the defect echo height and the area ratio of the part that has a defect echo height of 20% or more are usually 0% or more.
  • the steel plate according to an embodiment of the present invention and a steel pipe for a line pipe formed using the steel plate may be preferably for use in line pipes for transportation, storage tanks, and pressure vessels for purification, of natural gas and crude oil.
  • a method for producing a steel plate according to an embodiment of the present invention uses a slab having the above-mentioned chemical composition, the slab having a number density of bubbles of 0.15 bubbles/cm 2 or less in a slab accumulation zone, the bubbles having a circular equivalent diameter of 0.2 mm or more. By using such a slab, the steel plate with excellent HIC resistance can be produced.
  • HIC since hydrogen tends to be accumulated in the bubbles remaining in the steel plate accumulation zone, HIC may occur from the remaining bubbles as a starting point. Thus, the HIC resistance can be improved by reducing the bubbles in the steel plate accumulation zone.
  • the "slab accumulation zone” is a part corresponding to the "steel plate accumulation zone” of the steel plate obtained by hot-rolling, as a specific means for reducing bubbles in the steel plate accumulation zone, it is effective to reduce bubbles in the slab accumulation zone so as to the bubbles in the steel plate accumulation zone of the steel plate obtained by hot-rolling. Consequently, the HIC resistance can be improved.
  • FIG. 2 shows the result obtained by examining the relationship between the CLR of the surface layer part measured by the HIC test and the number density of bubbles having a circular equivalent diameter of 0.2 mm or more in a slab accumulation zone.
  • the present inventors have found that the steel plate is produced by using the slab having the number density of bubbles of 0.15 bubbles/cm 2 or less in the slab accumulation zone, the bubbles having a circular equivalent diameter of 0.2 mm or more, thereby it is possible to reduce the remaining bubbles that have remained in the rolling process without being completely compressed.
  • the area ratio of the part that has a defect echo height of 20% or more can be 0.05% or less, and the CLR of the surface layer part of the steel plate can be 10% or less, thereby HIC from the steel plate accumulation zone is suppressed.
  • the circular equivalent diameter of the bubbles in the slab accumulation zone is preferably 0.17 mm or less, and more preferably 0.15 mm or less.
  • the number density of bubbles having a circular equivalent diameter of 0.2 mm or more in the slab accumulation zone is preferably 0.10 bubbles/cm 2 or less, and more preferably 0.05 bubbles/cm 2 or less.
  • the circular equivalent diameter of the bubbles in the slab accumulation zone is normally 0 mm or more, and the number density of bubbles having a circular equivalent diameter of 0.2 mm or more in the slab accumulation zone is usually 0 bubble/cm 2 or more.
  • Methods of measuring a circular equivalent diameter of the bubble and the number density of bubbles may include, but are not particularly limited to, for example, the following methods.
  • a test piece taken out from the slab accumulation zone is observed by an optical microscope, and circular equivalent diameters of bubbles are measured with an ocular micrometer to count the number of bubbles with a circular equivalent diameter of 0.2 mm or more in the observation field of view.
  • the bubble density is calculated from the area of the observation field of view and the number of bubbles having a circular equivalent diameter of 0.2 mm or more.
  • the bubbles In order to cast the slab that has the number density of bubbles of 0.15 bubbles/cm 2 or less in the slab accumulation zone, the bubbles having a circular equivalent diameter of 0.2 mm or more, it is important to control the amount of Ar gas blown into a nozzle and the diameter of the bubble when a molten steel is supplied from the tundish to a mold during a steel making process.
  • the Ar gas needs to be blown in through a porous brick which has an inner tube diameter of 70 mm or more and 115 mm or less and an average pore diameter of 30 ⁇ m or more and 60 ⁇ m or less, at a back pressure of 1.4 kgf/cm 2 or more and 1.8 kgf/cm 2 or less and at 3 L (liter) /t (ton) or more and 10 L/t or less.
  • the inner tube diameter is preferably 75 mm or more and more preferably 80 mm or more, and is also preferably 110 mm or less and more preferably 105 mm or less.
  • the average pore diameter is preferably 35 ⁇ m or more and more preferably 40 ⁇ m or more, and is also preferably 55 ⁇ m or less and more preferably 50 ⁇ m or less.
  • the back pressure is preferably 1.45 kgf/cm 2 or more, and more preferably 1.5 kgf/cm 2 or more, and is also preferably 1.75 kgf/cm 2 or less and more preferably 1.7 kgf/cm 2 or less.
  • the amount of Ar gas blown in is preferably 5 L/t or more and more preferably 7 L/t or more, and is also preferably 12 L/t or less and 10 L/t or less.
  • the nozzle By blowing Ar gas within these ranges, the nozzle is less likely to be clogged. Furthermore, as the Ar gas flow with a large diameter is blown into the molten steel, bubbles of Ar gas are more likely to float in the mold. Consequently, the bubbles of Ar gas are easily removed from the accumulation zone, which can reduce the amount of bubbles of Ar gas trapped in the accumulation zone.
  • Conditions other than those mentioned above are not particularly limited, and a steel having the above-mentioned chemical composition may be melted according to a usual steel making method to cast a slab by a continuous casting process.
  • the method for producing the steel plate according to an embodiment of the present invention using the above-mentioned slab is not particularly limited as long as the area ratio of a part that has the defect echo height of 20% or more is 0.05% or less.
  • the steel plate can be produced by the hot-rolling, followed by cooling.
  • temperature refers to a temperature of a material.
  • the hot-rolling is recommended to be performed, for example, at a rolling reduction of 20% or less per pass for five or more passes in a range of surface temperatures of 900 °C or higher to reach a cumulative rolling reduction of 50% or more.
  • the surface layer part in the thickness direction is more preferentially deformed than the inside in the thickness direction, so that bubbles trapped in the accumulation zone can be more effectively compressed.
  • the cooling conditions taken after the hot-rolling are recommended in which cooling is performed, for example, from a cooling start temperature of Ar3 transformation point or higher at an average cooling rate of 10 °C/s or more.
  • a steel pipe for a line pipe can be produced by a general method, using the steel plate according to an embodiment of the present invention.
  • the steel pipe for a line pipe obtained by using the steel plate according to an embodiment of the present invention also has excellent HIC resistance and toughness.
  • the steel plate according to an embodiment of the present invention may be for use in a pressure vessel by a general method.
  • the steel plate and production method therefor according to the embodiments of the present invention have been described by focusing, especially, on the slab accumulation zone and the steel plate accumulation zone.
  • the amount of bubbles located in a part other than the accumulation zone is normally less than that located in the accumulation zone.
  • the HIC resistance of the accumulation zone is improved, so that the part other than the accumulation zone can also have excellent HIC resistance. That is, it should be noted that the effect of the present invention is not limited to the accumulation zone only, but can be exhibited across the whole of the steel plate.
  • the notation "O” indicates a method in which Ar gas was blown into a tundish through a porous brick with an inner tube diameter of 90 mm and an average pore diameter of 45 ⁇ m, at a back pressure of 1.4 to 1.8 kgf/cm 2 and at 5 to 9 L/t, thereby obtaining a slab with a thickness of 280 mm by continuous casting.
  • the notation "x" indicates a method in which Ar gas was blown into the tundish through a porous brick with an inner tube diameter of 120 to 150 mm and an average pore diameter of 45 ⁇ m, at a back pressure of 1.4 to 1.8 kgf/cm 2 and at 5 to 9 L/t, thereby obtaining a slab with a thickness of 280 mm by the continuous casting.
  • the obtained slabs were reheated to a temperature between 1,050°C and 1,250°C, and then subjected to one of two patterns of processes shown in Table 2, and thus the steel plates of tests Nos. 1 to 12 were produced.
  • the process "TMCP” refers to a method which includes (1) hot-rolling the steel plate at a rolling reduction of 20% or less per pass for five or more passes in a range of temperatures of 900 °C or higher so as to reach a cumulative rolling reduction of 50% or more, (2) hot-rolling the steel plate in a range of temperatures of 850 °C or higher and lower than 900 °C so as to reach a cumulative rolling reduction of 20% or more and a rolling end temperature of 850 to 900 °C, and (3) cooling from a cooling start temperature of 750 to 850 °C at an average cooling rate of 10 to 50 °C/s and then stopping the cooling in a range of temperatures of 350 to 600 °C, followed by air-cooling to the room temperature.
  • the process "QT” refers to a method which includes (1) hot-rolling the steel plate at a rolling reduction of 20% or less per pass for five or more passes in a range of temperatures of 900 °C or higher so as to reach a cumulative rolling reduction of 50% or more and a rolling end temperature of 850 °C or higher, (2) air-cooling to the room temperature, (3) reheating to a temperature between the 850 °C to 950 °C and then hardening, and (4) tempering at a temperature between 600 °C and 700 °C.
  • the number density of bubbles having a circular equivalent diameter of 0.2 mm or more in the slab accumulation zone, as well as the area ratio of the part that had a defect echo height of 20% or more were measured, and the HIC test was performed on the steel plates, according to the following procedures.
  • the L cross section of each test piece was polished using emery polishing paper (#320 to #1500), followed by mirror finishing through buffing.
  • the L cross section of the test piece was observed using an optical microscope (magnification: 5 times), and circular equivalent diameters of the bubbles were measured using an ocular micrometer (magnification: 5 times), whereby the number of bubbles having a circular equivalent diameter of 0.2 mm or more was counted in the observation field of view.
  • the density of bubbles was calculated from the area of the observation field and the number of bubbles having the circle equivalent diameter of 0.2 mm or more.
  • the maximum value of the densities obtained from the above-mentioned two sites was referred to as the number density of bubbles having the circular equivalent diameter of 0.2 mm or more in the slab accumulation zone.
  • Test pieces were respectively taken from two sites (steel plate accumulation zones) of the steel plate, located at positions corresponding to 1/4 and 1/2 of the width of the steel plate along its width direction (direction perpendicular to the rolling direction), depending on the thickness of the steel plate in the following ways.
  • Step plate having a thickness of 30 mm or less (Steel plate having a thickness of 30 mm or less)
  • test pieces each having a thickness of the steel plate ⁇ 20 mm width ⁇ 100 mm length (in the rolling direction), were taken from each of the above-mentioned two positions. Consequently, the six test pieces in total were prepared.
  • test pieces each having 30 mm thickness ⁇ 20 mm width ⁇ 100 mm length, were taken (i) from the surface of the steel plate in the direction perpendicular to the surface, (ii) from the position of 1/2 of the thickness of the steel plate, and (iii) from the back surface of the steel plate in the direction perpendicular to the back surface. Consequently, the six test pieces in total were prepared.
  • Each test piece was subjected to an ultrasonic flaw detection test at a pitch of 0.4 mm ⁇ 0.4 mm using an ultrasonic flaw detector "GSONIC SCAN 8AX1500SR" manufactured by GNES Corporation, and a water immersion probe (frequency: 10 MHz, diameter: 0.5 inches, focal depth: 4.5 inches).
  • An area ratio of a part of the test piece that had a defect echo height of 20% or more was measured, and an average of the measured area ratios was referred to as an area ratio of the part that had the defect echo height of 20% or more.
  • the HIC test was performed on the test piece used in the above-mentioned ultrasonic flaw detection test, according to the method specified by the NACE standard TM0284-2003.
  • the test piece was immersed in an aqueous solution (5.0% NaCl + 0.5% acetic acid) with 1 atm of hydrogen sulfide saturated therein, at 25°C for 96 hours.
  • the cross section of each test piece was evaluated (according to NACE standard TM0284-2003 FIGURES 2 to 8 ), depending on the thickness of the steel plate to thereby measure a CLR of each test piece in the following way.
  • the cross section is a plane defined by the thickness direction and the width direction of the test piece.
  • Step plate having a thickness of 30 mm or less (Steel plate having a thickness of 30 mm or less)
  • the cross section of each test piece was equally divided into three pieces in the thickness direction, namely, three cross sections on the surface side, the center, and the back surface side.
  • the CLRs of the cross section on the surface side were measured, and an average of the measured CLRs was referred to as a "CLR of the surface layer part".
  • the CLRs of the cross section at its center were measured, and an average of the measured CLRs was referred to as a "CLR of the center”.
  • CLR of the surface layer part The CLRs of the test piece taken from the surface of the steel plate in the direction perpendicular to the surface were measured, and an average of the measured CLRs was referred to as a "CLR of the surface layer part".
  • CLR of the center the CLRs of the test piece taken from the position located at 1/2 of the thickness of the steel plate in its thickness direction were measured, and an average of the measured CLRs was referred to as a "CLR of the center”.
  • the steel plate in which each of the CLR of the surface layer part and the CLR of the center was 10% or less was evaluated to be a practical standard one and to have excellent HIC resistance.
  • Table 2 shows the measurement results of the number density of bubbles having the circular equivalent diameter of 0.2 mm or more in the slab accumulation zone, the area ratio of the part that had a defect echo height of 20% or more, the CLR of the surface layer part, and the CLR of the center.
  • the test pieces in which each of the CLR of the surface layer part and the CLR of the center was 10% or less were indicated by the notation "O".
  • tests Nos. 6 to 11 are examples that did not satisfy any one of the requirements specified by the embodiments of the present invention.
  • the tests Nos. 6 and 7 are examples of the steel plate in which the casting conditions were not appropriate and each of the used slabs had the large number density of bubbles having a circular equivalent diameter of 0.2 mm or more in the slab accumulation zone. Consequently, in the steel plates of these tests, the area ratio of the part that had the defect echo height of 20% or more was large, thus the CLR of the surface layer part was deteriorated, so that the desired HIC resistance could not be achieved.
  • the tests Nos. 8 and 9 are examples of the steel plate in which the steel plates were produced using steel materials of the steel types G and H, respectively, that had small ratios of [Ca]/[S]. Consequently, in the steel plates of these tests, a large amount of MnS was generated to deteriorate the CLR of the center, so that the desired HIC resistance could not be achieved. In the test No. 8, the CLR of the center was deteriorated, and thus the number density of bubbles was not evaluated.
  • the tests Nos. 10 and 11 are examples of the steel plate in which the steel plates were produced using the steels of the steel types I and J, respectively, that had large ratios of ([Ca] - 1.25 ⁇ [S])/[O]. Consequently, in the steel plates of these tests, coarse Ca inclusions were formed in the steel plate accumulation zone, thus the CLR of the surface layer part was deteriorated, so that the desired HIC resistance could not be achieved.

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