EP3239320A1 - Stahlplatte mit ausgezeichnetem widerstand gegenüber wasserstoffinduzierter rissbildung und stahlrohr für leitungsrohr - Google Patents

Stahlplatte mit ausgezeichnetem widerstand gegenüber wasserstoffinduzierter rissbildung und stahlrohr für leitungsrohr Download PDF

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EP3239320A1
EP3239320A1 EP15873095.2A EP15873095A EP3239320A1 EP 3239320 A1 EP3239320 A1 EP 3239320A1 EP 15873095 A EP15873095 A EP 15873095A EP 3239320 A1 EP3239320 A1 EP 3239320A1
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Prior art keywords
steel plate
slab
less
hic
maximum opening
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EP15873095.2A
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English (en)
French (fr)
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EP3239320B1 (de
EP3239320A4 (de
Inventor
Kiichiro TASHIRO
Taku Kato
Haruya KAWANO
Yuichi OKA
Shinsuke Sato
Sei Kimura
Takashi Miyake
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Kobe Steel Ltd
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Kobe Steel Ltd
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Priority claimed from PCT/JP2015/085870 external-priority patent/WO2016104527A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • 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
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies 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
    • 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
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • 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
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • 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
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • 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

Definitions

  • the present invention relates to a steel plate having excellent hydrogen induced cracking resistance.
  • the present invention relates to a steel plate that has excellent hydrogen-induced cracking resistance and is suitable for use in line pipes for transportation and tanks for storage of natural gas and crude oil, and to a steel pipe for line pipes with excellent hydrogen-induced cracking resistance, obtained by using the steel plate.
  • HIC Hydrogen-induced cracking
  • HIC is also known to have a tendency to occur in segregation zones, including a center segregation and internal cracks of a cast strip, particularly, at an inclusion such as MnS, as a starting point. For this reason, some techniques for enhancing HIC resistance have been proposed.
  • Patent Document 1 discloses that a steel material has improved HIC resistance by suppressing segregation degrees of Mn, Nb, and Ti at the center in the thickness direction of a steel plate.
  • Patent Document 2 discloses a method for suppressing HIC that would occur in MnS or a Ca-based acid sulfide as a starting point, by using a parameter formula that includes the contents of Ca, O and S.
  • a steel plate is subjected to melting, casting, and hot-rolling, and then it undergoes an HIC test before being dispatched as a product.
  • the above-mentioned steel plate cannot be dispatched as a product with excellent hydrogen-induced cracking resistance. Because of this, the steel plate needs to be manufactured again, that is, melted again to produce a product, and then the product needs to undergo the HIC test again. This increases the manufacturing time period and might possibly result in missing the deadline or the like.
  • HIC resistance can be evaluated at the stage of a cast strip after the casting without performing the HIC test after hot rolling, the manufacturing time period can be significantly shortened.
  • HIC occurs at segregation zones (center segregation, internal cracks) or inclusions, such as MnS, as a starting point.
  • MnS inclusions
  • a long procedure A-1 from casting to dispatching is carried out in the following way.
  • the steps of "Sample Preparation (for HIC test) ⁇ HIC Test" in performing the HIC test can be omitted as illustrated in a procedure B-1, so that products can be dispatched at an early stage.
  • the conventional method would be to perform the following procedure A-2, where it takes a long time to perform steps from the casting to re-melting.
  • the HIC resistance can be evaluated at the stage of the cast strip as illustrated in the following procedure B-2, even if the evaluation result is NG, the steps of "Rolling ⁇ Sample Preparation (for the HIC Test) ⁇ HIC Test" in the procedure A-2 below can be omitted, which enables a quick start of re-melting.
  • Patent Document 3 discloses a method in which internal cracks are evaluated at the stage of the cast strip. In this method, the possibility of a hot charge rolling (HCR) operation is determined based on the evaluation result of internal cracks.
  • HCR hot charge rolling
  • the present invention has been made in view of the foregoing circumstance, and it is an object of the present invention to achieve a steel plate and a steel pipe that have excellent hydrogen-induced cracking resistance, and further to achieve a steel plate and a steel pipe that enable the evaluation of the HIC resistance by an internal quality of a cast strip without performing an HIC test.
  • a steel plate having excellent hydrogen-induced cracking resistance according to the present invention that can solve the above-mentioned problem includes, in percent by mass:
  • the threshold value t ⁇ may be a value previously determined by method including following (i) to (iii):
  • the slab cast under the same casting conditions as said slab may be the slab in which the maximum opening thickness is measured.
  • the steel plate may be in an API (American Petroleum Institute) X65 Grade, and the threshold value t ⁇ may be 0.047 mm.
  • the steel plate may be in an API X70 Grade, and the threshold value t ⁇ may be 0.043 mm.
  • the steel plate may be in an ASME (American Society of Mechanical Engineers) SA516 Grade 60, and the threshold value t ⁇ may be 0.047 mm.
  • the steel plate may be in an ASME SA516 Grade 65, and the threshold value t ⁇ may be 0.047 mm.
  • the steel plate may be in an ASME SA516 Grade 70, and the threshold value t ⁇ may be 0.043 mm.
  • the steel plate may be in an ASTM (American Society for Testing and Materials) A516 Grade 60, and the threshold value t ⁇ may be 0.047 mm.
  • the steel plate may be in an ASTM A516 Grade 65, and the threshold value t ⁇ may be 0.047 mm.
  • the steel plate may be in an ASTM A516 Grade 70, and the threshold value t ⁇ may be 0.043 mm.
  • the steel plate may further contain one or more of the elements (A) and (B) below as another element:
  • the steel plate is suitable for use in line pipe and pressure container.
  • the present invention also includes a steel pipe for a line pipe formed of the steel plate.
  • the present invention can provide the steel plate and steel pipe that surely have the excellent hydrogen-induced cracking resistance. Further, the present invention can provide the steel plate and steel pipe in which the HIC resistance can be evaluated by the internal quality of the cast strip without performing an HIC test.
  • These steel plates are suitable for use in line pipe for transportation of natural gas and crude oil, pressure container, such as the storage tank, and the like.
  • the inventors have diligently studied to solve the foregoing problems.
  • the inventors have focused on the tendency for HIC to occur at a MnS inclusion as a starting point.
  • the formation of MnS can be suppressed to improve the hydrogen-induced cracking resistance.
  • an appropriate content of such a component is found to efficiently exhibit the desulfurization effect as mentioned later.
  • the component composition of the steel needs to be controlled. Furthermore, to ensure the high strength, excellent weldability, and the like, which are other properties required as, for example, the steel for line pipe, the component composition of the steel plate needs to be as follows. The reasons for specifying the contents of the respective components, including the aforesaid rare earth elements and Zr, will be described below.
  • Carbon (C) is an element essential to ensure the strength of a base metal and a weld bead.
  • the C content needs to be 0.02% or more.
  • the C content is preferably 0.03% or more, and more preferably 0.05% or more.
  • an extremely high C content degrades the heat-affected zone (HAZ) toughness and the weldability of the steel. Any excessive C content is more likely to form NbC or island-shaped martensite, which possibly becomes as the starting point of HIC or a fracture propagation route.
  • the C content needs to be 0.15% or less.
  • the C content is preferably 0.12% or less, and more preferably 0.10% or less.
  • Silicon (Si) has a deoxidation function and is effective in improving the strength of a base metal and a weld bead. To exhibit these effects, the Si content is set at 0.02% or more.
  • the Si content is preferably 0.05% or more, and more preferably 0.15% or more.
  • an extremely high Si content degrades the weldability and toughness of the steel. Any excessive Si content forms island-shaped martensite to generate and propagate HIC. Accordingly, the Si content needs to be suppressed to 0.50% or less.
  • the Si content is preferably 0.45% or less, and more preferably 0.35% or less.
  • Manganese (Mn) is an element that is effective in improving the strength of a base metal and a weld bead.
  • the Mn content is set at 0.6% or more.
  • the Mn content is preferably 0.8% or more, and more preferably 1.0% or more.
  • an extremely high Mn content forms MnS, degrading not only the hydrogen-induced cracking resistance, but also the HAZ toughness and weldability.
  • the upper limit of Mn content is set at 2.0%.
  • the Mn content is preferably 1.8% or less, more preferably 1.5% or less, and still more preferably 1.2% or less.
  • Phosphorus (P) is an element inevitably contained in steel.
  • the P content exceeds 0.030%, the roughness of a base metal and a HAZ are significantly degraded, and the hydrogen-induced cracking resistance of the steel is also degraded.
  • the P content is restricted to 0.030% or less.
  • the P content is preferably 0.020% or less, and more preferably 0.010% or less.
  • S Sulfur
  • MnS MnS
  • the upper limit of S content is 0.003%.
  • the S content is preferably 0.002% or less, more preferably 0.0015% or less, and still more preferably 0.0010% or less.
  • the S content is desirably low from the viewpoint of improving the hydrogen-induced cracking resistance.
  • Aluminum (Al) is a strong deoxidizing element.
  • the Al content needs to be 0.010% or more.
  • the Al content is preferably 0.020% or more, and more preferably 0.030% or more.
  • the Al content needs to be 0.08% or less.
  • the Al content is preferably 0.06% or less, and more preferably 0.05% or less.
  • Ca serves to control the form of a sulfide and has an effect of suppressing the formation of MnS by forming CaS. To obtain this effect, the Ca content needs to be 0.0003% or more.
  • the Ca content is preferably 0.0005% or more, and more preferably 0.0010% or more.
  • the upper limit of Ca content is set at 0.0060%.
  • the Ca content is preferably 0.0045% or less, more preferably 0.0035% or less, and still more preferably 0.0025% or less.
  • N Nitrogen
  • the N content needs to be 0.001% or more.
  • the N content is preferably 0.003% or more, and more preferably 0.0040% or more.
  • An extremely high N content degrades the toughness of the HAZ by the presence of the solid-solute N.
  • the N content needs to be 0.01% or less.
  • the N content is preferably 0.008% or less, and more preferably 0.0060% or less.
  • a content of O i.e., oxygen is desirably low from the viewpoint of improving the cleanliness of a steel.
  • An extremely high O content degrades the toughness of the steel, 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% or less, preferably 0.0030% or less, and more preferably 0.0020% or less.
  • the sulfide-based inclusion in the steel has its form controlled as CaS by adding Ca, thereby rendering S harmless for the HIC resistance.
  • the Ca/S needs to be set at 2.0 or more.
  • the Ca/S is preferably 2.5 or more, and more preferably 3.0 or more. Note that the upper limit of Ca/S is approximately 17 based on the Ca content and S content specified by the present invention.
  • a Ca content (Ca - 1.25S) that is obtained by subtracting a content in Ca present as a sulfide (CaS) in the steel from the total Ca content in the steel must not be excessive relative to the O content.
  • CaO is more likely to be formed as an oxide-based inclusion, which makes it easier for aggregates of the CaO (coarse Ca-based inclusions) to be formed in a larger amount at a superficial layer of a steel plate.
  • the (Ca - 1.255) /O needs to be 1. 80 or less in order to obtain the excellent HIC resistance.
  • (Ca - 1.25S) /O is preferably 1.40 or less, more preferably 1.30 or less, still more preferably 1.20 or less, and particularly preferably 1.00 or less.
  • the lower limit of (Ca - 1.25S) /O is approximately 0.1.
  • a rare earth metal is an element that is effective in enhancing the hydrogen-induced cracking resistance by suppressing the formation of MnS through the desulfurization effect as mentioned above.
  • the REM content is preferably 0.0002% or more.
  • the REM content is more preferably 0.0005% or more, and still more preferably 0.0010% or more.
  • the upper limit of the REM content needs to be 0.02%.
  • the REM content is preferably 0.015% or less, more preferably 0.010% or less, and still more preferably 0.0047% or less.
  • REM means lanthanoid elements, i. e. , 15 elements from La to Lu, and scandium and yttrium.
  • Zirconium (Zr) serves to form an oxide and disperse it finely in steel, while improving the HIC resistance by the desulfurization effect, thereby contributing to improving the HAZ toughness.
  • the Zr content is preferably set at 0.0003% or more, more preferably 0.0005% or more, still more preferably 0.0010% or more, and yet more preferably 0.0015% or more.
  • any excessive Zr content forms coarse inclusions to degrade the hydrogen-induced cracking resistance and the toughness of the base metal.
  • the Zr content needs to be 0.010% or less.
  • the Zr content is preferably 0.0070% or less, more preferably 0.0047% or less, and still more preferably 0.0030% or less.
  • the steel plate and steel pipe in the present invention have been mentioned above, with the balance being iron and inevitable impurities.
  • the steel further includes:
  • B Boron
  • B enhances the hardenability of a steel and the strength of a base metal and a weld bead. Furthermore, B binds to N to precipitate BN while the heated HAZ zone is cooled in welding, thus promoting ferrite transformation from the inside of an austenite grain. In this way, B improves the HAZ toughness.
  • the B content is preferably 0.0002% or more.
  • the B content is more preferably 0.0005% or more, and still more preferably 0.0010% or more.
  • any excessive B content degrades the toughness of a base metal and a HAZ zone, thus leading to degradation in the weldability.
  • the B content is preferably 0.005% or less.
  • the B content is more preferably 0.004% or less, and still more preferably 0.0030% or less.
  • V more than 0% and 0.1% or less
  • Vanadium (V) is an element effective in improving the strength of steel. To obtain this effect, the V content is preferably 0.003% or more, and more preferably 0.010% or more. On the other hand, when the V content exceeds 0.1%, the weldability and the toughness of a base metal would be degraded. Thus, the V content is preferably 0.1% or less, and more preferably 0.08% or less.
  • Copper (Cu) is an element effective in improving the hardenability of steel.
  • the Cu content is preferably 0.01% or more.
  • the Cu content is more preferably 0.05% or more, and still more preferably 0.10% or more.
  • the toughness of steel is degraded.
  • the Cu content is preferably 1.5% or less.
  • the Cu content is more preferably 1.0% or less, and still more preferably 0.50% or less.
  • Ni more than 0% and 1.5% or less
  • Nickel (Ni) is an element effective in improving the strength and toughness of a base metal and a weld bead. To obtain these effects, the Ni content is preferably 0.01% or more. The Ni content is more preferably 0.05% or more, and still more preferably 0.10% or more. However, an extremely high Ni content leads to an excessively expensive steel for a structure. From the economical aspect, the Ni content is preferably 1.5% or less. The Ni content is more preferably 1.0% or less, and still more preferably 0.50% or less.
  • Chromium (Cr) is an element effective in improving the strength of steel.
  • the Cr content is preferably 0.01% or more.
  • the Cr content is more preferably 0.05% or more, and still more preferably 0.10% or more.
  • the Cr content is preferably 1.5% or less.
  • the Cr content is more preferably 1.0% or less, and still more preferably 0.50% or less.
  • Molybdenum (Mo) is an element effective in improving the strength and toughness of a base metal.
  • the Mo content is preferably 0.01% or more.
  • the Mo content is more preferably 0.05% or more, and still more preferably 0.10% or more.
  • the Mo content is preferably 1.5% or less, more preferably 1.0% or less, and still more preferably 0.50% or less.
  • Nb more than 0% and 0.06% or less
  • Niobium (Nb) is an element effective in enhancing the strength of steel and the toughness of a base metal without degrading its weldability. To obtain this effect, the Nb content is preferably 0.002% or more. The Nb content is more preferably 0.010% or more, and still more preferably 0.020% or more. However, when the Nb content exceeds 0.06%, the toughness of the base metal and HAZ is degraded. Thus, in the present invention, the upper limit of Nb content is preferably set at 0.06%. The Nb content is more preferably 0.047% or less, still more preferably 0.040% or less, and much more preferably 0.030% or less.
  • Titanium (Ti) precipitates as TiN in steel, thereby preventing austenite grains in a HAZ zone from being coarsened during welding and thereby promoting the ferrite transformation.
  • Ti is an element that is effective in improving the toughness of the HAZ zone.
  • Ti exhibits the desulfurization effect, and thus is an element that is effective in improving the HIC resistance.
  • the Ti content is preferably 0.003% or more.
  • the Ti content is more preferably 0.005% or more, and still more preferably 0.010% or more.
  • any excessive Ti content leads to an increase in the amount of solid-solute Ti and precipitated TiC, thus degrading the toughnesses of a base metal and a HAZ zone.
  • the Ti content is preferably 0.03% or less, and more preferably 0.02% or less.
  • Mg more than 0% and 0.01% or less
  • Magnesium (Mg) is an element that is effective in improving the toughness of steel through refinement of crystal grains, and also effective in improving the HIC resistance because of its desulfurization effect. To obtain these effects, the Mg content is preferably 0.0003% or more. The Mg content is more preferably 0.001% or more. On the other hand, an excessive Mg content saturates its effect. Thus, the upper limit of the Mg content is preferably 0.01%. The Mg content is more preferably 0.005% or less.
  • the steel plate in the present invention is a steel plate having a high hydrogen-induced cracking resistance and in which, at a stage of a slab, the slab for the steel plate has no horizontal crack or has the horizontal crack having a maximum opening thickness of a threshold value or less.
  • a threshold value means a maximum opening thickness of a horizontal crack for avoids the occurrence of HIC in the steel plate obtained by rolling the slab. The maximum opening thickness is measured in advance.
  • the horizontal crack is evaluated at the stage of the slab.
  • the maximum opening thickness of the horizontal crack at the stage of the slab is set to be the predetermined threshold value or less, thereby making it possible to produce a steel plate with higher hydrogen-induced cracking resistance and to dispatch products at an early stage, which will be mentioned below.
  • Segregation of components is present at an internal crack or center segregation zone of the slab.
  • HIC segregation degree of the component becomes higher, HIC is more likely to occur, which is well known, for example, as mentioned in JP 2007-136496 A .
  • segregation forms a hard microstructure such as MA (martensite-austenite constituent so-called an island-shaped martensite), perlite band, or the like.
  • MA martensite-austenite constituent so-called an island-shaped martensite
  • perlite band or the like.
  • HIC resistance is evaluated, particularly, by taking into account the segregation degree of internal cracks.
  • Internal cracks include the "horizontal crack” and "other internal cracks". These cracks are caused by the bulging between the rolls, an imbalance of cooling water, or the deformation of steel during correction.
  • the "horizontal crack”, as shown in Fig. 1(a) is a crack present in a region ranging from the end to half the thickness D of the slab, i.e., D/2 in the width direction W of the slab.
  • the horizontal crack is the crack that propagates in the slab width direction and the casting direction.
  • “other internal cracks” as shown in Fig. 1(a) are cracks present in the slab through the entire width thereof. Such other internal cracks are cracks that propagate in the slab thickness direction and slab width direction, or in the slab thickness direction and slab casting direction.
  • the "horizontal crack” extends, while the “other internal cracks” is reduced.
  • the "horizontal crack” allows the HIC to easily propagate and extend, while the “other internal cracks” do not cause the HIC to propagate and extend, which is not problematic in terms of the quality.
  • HIC sometimes occurs at an occurrence site of the "horizontal crack", but no HIC occurs at an occurrence site of the "other internal cracks”.
  • the present invention takes into account only the "horizontal crack” among internal cracks.
  • the segregation degree of the "horizontal crack” is evaluated based on the "maximum opening thickness" to be mentioned below.
  • the occurrence position of the "horizontal crack” is illustrated in Fig. 1(a) , and is a crack that generates at a solid-liquid interface during solidification.
  • the "horizontal crack” is accompanied by a segregation line caused by propagation of concentrated, molten steel between dendritic branches. When the degree of the propagation is significant, an opening occurs along the segregation line.
  • the inventors have found that if the HIC resistance of a steel plate after rolling can be determined in advance by the use of the above-mentioned maximum opening thickness of a cast strip at a stage of a slab, i.e. , after casting and before rolling, the HIC test does not need to be performed on a steel plate as a product, thereby omitting a step therefor. Consequently, products can be dispatched at an early stage.
  • a slab obtained by casting is cut in the thickness direction, i.e., in the direction perpendicular to the casting direction as shown in Fig. 2 , and then is examined for a horizontal crack of a segregation zone.
  • the position of occurrence of a horizontal crack tends to vary not in the casting direction, but in the slab width direction and slab thickness direction.
  • a cross section perpendicular to the casting direction as an object to be examine, a part where the horizontal crack becomes worst can be examined.
  • maximum opening thicknesses t1 and t2 of horizontal cracks that are present in regions R1 and R2, respectively, ranging from both ends of the slab width W to half the slab thickness, i.e., D/2 are measured.
  • the maximum opening thickness t1 is a maximum opening thickness in the region R1
  • the maximum opening thickness t2 is a maximum opening thickness in the region R2.
  • a combination of the regions R1 and R2 will be referred to as a first range
  • a region R3 shown in Fig. 2 will be referred to as a second range in some cases.
  • the reason why the regions R1 and R2 are examined is as follows. That is, the horizontal crack occurs while solidification proceeds from both ends (narrow faces) toward the center in the width direction of the slab.
  • the regions R1 and R2, i.e., the first range are susceptible to cooling on sides of the narrow surfaces (short sides), so that the solidification proceeds toward the center in the width direction of the slab.
  • the region R3 of the width W-D, excluding D/2 from both ends in the width direction, i.e., the second region is barely susceptible to cooling on the side of the narrow surfaces (short sides), so that the solidification hardly proceeds in the width direction.
  • the horizontal cracks are examined in the regions R1 and R2 as mentioned above.
  • the maximum opening thicknesses t1 and t2 are defined as the maximum opening thicknesses among the thicknesses of a plurality of openings in the respective regions R1 and R2, respectively. For example, when three horizontal cracks are present in the region R1, one of the three horizontal cracks that has the largest opening is selected.
  • the "maximum opening thickness t1" is defined as an opening thickness of a part of the selected horizontal crack that is opened most, i.e., a part with the largest opening thickness.
  • the threshold value t ⁇ to be used for the evaluation of the HIC resistance of the slab i.e., the maximum opening thickness for avoiding the occurrence of the HIC in the steel plate obtained by rolling the slab.
  • the threshold value t ⁇ is determined in advance, but its determination method is not particularly limited to the following method.
  • An example of the method for determining the threshold value t ⁇ will include the following steps (i) to (iii). The details of the method will be described below.
  • the HIC test is performed on the steel plate to examine the presence or absence of HIC occurrence.
  • the HIC test is performed by a method specified by the National Association of Corrosion and Engineer (NACE) standard TM0284-2003, as mentioned in examples below.
  • NACE National Association of Corrosion and Engineer
  • the term "same casting conditions" as used herein includes i) a casting speed is constant, ii) an abnormal state in operation, such as clogging of a nozzle, does not occur, and iii) the same cooling conditions and distance between roll are applied.
  • the threshold value t ⁇ the "segregation degree obtained by examining a slab” is related to the "HIC test result for a product”.
  • the threshold value cannot be determined.
  • the operation factors i) to iii) significantly affect the horizontal crack and center segregation, which will consequently affect the HIC resistance as well. Thus, the different operation factors lead to different HIC resistances.
  • the steel plate used in the HIC test is preferably one obtained by manufacture using a slab which has been cast on the same casting conditions (operation factors) as the slab whose maximum opening thickness is examined.
  • the slab whose maximum opening thickness is examined is preferably the same as the slab for the HIC test.
  • HIC test it is examined whether or not HIC occurs in regions of a product (steel plate), corresponding to the regions R1 and R2 of the slab shown in Fig. 2 . As illustrated in Fig. 3 , the regions to be evaluated for the HIC resistance are varied depending on the rolling direction during the rolling using the slab shown in Fig. 2 .
  • a slab width W product width W.
  • the regions of the product corresponding to the "slab regions R1 and R2" are “regions R11 and R12, ranging from both ends in the width direction of the product to half the width of the product, i.e., D/2.
  • the region of the product corresponding to the "slab region R3" is a "region R13 of the width W-D obtained by excluding half the width of the product, i.e., D/2 from both ends in the width direction of the product".
  • the width of the slab changes from W before the rolling to Wa after the rolling, and thus the slab width w is smaller than the product width Wa, i.e., slab width W ⁇ product width Wa.
  • the regions R21, R22, and R23 corresponding to the slab regions R1, R2, and R3 are determined by a rolling reduction, i.e., product width Wa/slab width W. It is confirmed whether or not HIC occurs in these regions R21 and R22.
  • a "threshold value t ⁇ of the maximum opening thickness” that avoids the occurrence of HIC is determined from the "'maximum opening thicknesses t1 and t2' obtained by examination of the slab” and "the HIC test result for the product".
  • the results obtained from the region of the slab and the corresponding region of the product are correlated to each other. For instance,
  • the threshold value t ⁇ of the maximum opening thickness serving as the criterion of the presence or absence of HIC occurrence is determined from the above-mentioned plurality of results. Specifically, for instance, in the case (I), the maximum opening thickness t2 becomes the threshold value t ⁇ . Also, in the case (II), the maximum opening thickness t2 becomes the threshold value t ⁇ .
  • the determination of the threshold value t ⁇ is preferably made by using measurement results of the horizontal cracks and their maximum opening thicknesses of a plurality of slabs, and the HIC test results thereof.
  • the measurement results of the horizontal cracks and their maximum opening thicknesses of the plurality of slabs, and the HIC test results thereof can be used to obtain the threshold value t ⁇ more precisely, thereby reducing the misjudgment of the presence or absence of HIC occurrence.
  • the segregation zone and the HIC resistance may be evaluated by examining one cross section of the slab or product, or alternatively by examining two or more cross sections thereof.
  • a description will be given on the results obtained by examining a plurality of cross sections of the slab of the same charge with reference to Fig. 4 .
  • Example 1 is an example of examining two cross sections of the slab of the same charge
  • Example 2 is an example of examining three cross sections of the slab of the same charge.
  • the result is obtained by examining the slab that is in conformity with API X65 Grade.
  • Example 1 As shown in Fig. 4 , in Example 1, at both of the two cross sections, the maximum opening thickness is 0 mm, and no HIC occurs at a horizontal crack as a starting point in the HIC test. In Example 2, the maximum opening thicknesses of the three cross sections are 0.065 mm, 0.067 mm, and 0.066 mm, which are substantially the same thickness. At all the cross sections, HIC occurs at the horizontal cracking zones as the starting points.
  • the slabs in conformity with the API X65 Grade are used for evaluation.
  • a slab in another strength grade for example, a slab of API X70 Grade or higher grade does not differ from the API X65 Grade slab in formation or variations of internal cracks.
  • the number of cross sections to be examined is not limited.
  • the examination position (examined surface) of the slab is preferably a stationary part, but may be a non-stationary part, as shown in the examples.
  • non-stationary part means a part casted when the casting condition is varied, for example, a part casted at an initial stage of casting, such as when the casting speed increases, or a part casted at the end of casting, such as when the casting speed decreases.
  • a part adjacent to the region subjected to the HIC test is preferably examined. Such a part exhibits substantially the same HIC resistance as the HIC test result and can be evaluated more precisely.
  • the steel plate in the present invention is a steel plate in which a slab for the steel plate has no horizontal crack or has the horizontal crack having a maximum opening thickness of the threshold value t ⁇ or less, at a stage of the slab before rolling.
  • a slab for the steel plate has no horizontal crack or has the horizontal crack having a maximum opening thickness of the threshold value t ⁇ or less, at a stage of the slab before rolling.
  • the "maximum opening thickness of the horizontal crack" is used to evaluate the HIC resistance. Because of this, the internal quality of the cast strip can be precisely evaluated, so that based on this evaluation result, the HIC resistance can be evaluated at the stage of the cast strip. Consequently, the HIC test that would require several weeks can be omitted, thereby significantly shortening a time period from the manufacture to dispatching.
  • Tables 1-1 and 1-2 and Figs. 6 and 7 show the experimental conditions and results for determining the threshold value t ⁇ .
  • 21 charges were cast to obtain each of a slab corresponding to the API X65 Grade and a slab corresponding to the API X70 Grade.
  • One charge was cast to obtain each of a slab corresponding to the ASME SA516 Grade 60, a slab corresponding to the ASME SA516 Grade 65, and a slab corresponding to the ASME SA516 Grade 70. These slabs were examined for the horizontal crack in the following way.
  • X70 corresponds to API X70 Grade; "X65” to API X65 Grade; "SA516 60” to ASME SA516 Grade 60; “SA516 65” to ASME SA516 Grade 65; and "SA516 70” to ASME SA516 Grade 70.
  • the concentrations of C, Mn, Nb, P, and Ca were measured by an emission spectroscopy.
  • the S concentration was very low and thus was difficult to measure by the emission spectroscopy. Then, the S concentration was measured by using a combustion-infrared absorption method.
  • Specific Water Content (whole secondary cooling water amount per unit time from directly under the mold to a final roll of a continuous casting machine [l/min.])/(weight of cast strip production per unit time [kg/min.])
  • the casting speed is a drawing speed of the cast strip [m/min.], and calculated from the diameter (circumferential length) and the rotational speed (the number of revolutions per unit time) of a roll (major roll) in contact with the cast strip.
  • Each slab was cut at a stationary part in an entire length of 10 to 15 m, and horizontal cracks in the stationary part were then examined in the following way.
  • the term "stationary part” as used herein means a part that satisfies the following conditions.
  • the number of cross sections for examination of horizontal cracks is shown in Tables 1-1 or 1-2.
  • the hot-rolling was performed on the slab through two or more passes.
  • a surface temperature of the steel plate was set at 900°C or higher
  • a cumulative rolling reduction was 40% or more at an average steel plate temperature of 1,000°C or higher, which was determined by the calculation below, and a rolling reduction per pass was 10% or more.
  • another hot-rolling was performed such that the cumulative rolling reduction at a temperature of 700°C or higher and lower than 900°C was 20% or more, and that the rolling end temperature was 700°C or higher and lower than 900°C.
  • quenching was performed on the rolled steel plate by reheating it to a temperature of 850°C or higher and 950°C or lower, followed by tempering at a temperature of 600 to 700°C, thereby producing a steel plate with a thickness of 40 mm. Note that both types of steel plates were not subjected to rolling in the slab width direction.
  • the average steel plate temperature was determined in the following way. Specifically, based on data including a rolling pass schedule during rolling and a cooling method (water-cooling or air-cooling) between the passes, the temperature at any position of the steel plate in the thickness direction was determined by using an appropriate calculation method, such as a finite difference method. Then, the average steel plate temperature was defined as the average of the determined temperatures of the steel plate in a range from the front to back surface thereof. The definition of the "average steel plate temperature" also applied to other steel plates.
  • Figs. 6 and 7 show the relationships between the "presence or absence of HIC occurrence" confirmed by the HIC test and the "'Opening Thickness of Horizontal Crack' and 'Cmax (Mn)/C 0 (Mn)'".
  • Fig. 6 shows the examination results of threshold values t ⁇ at which HIC occurred in components of the steels shown in Table 1-2 and belonging to strength classes corresponding to API X65 Grade, ASME SA516 Grade 60, or ASME SA516 Grade 65.
  • Fig. 7 shows the examination results of threshold values t ⁇ at which HIC occurred in the components of the steels shown in Table 1-1 or 1-2 and belonging to strength classes corresponding to API X70 Grade or ASME SA516 Grade 70.
  • the threshold value t ⁇ of the maximum opening thickness was set at 0.047 mm, and thereby the determination was made as follows. When maximum opening thickness is 0. 047 mm or less ( ⁇ 0.047 mm), HIC is determined not to occur. When maximum opening thickness is more than 0.047 mm (> 0.047 mm), HIC is determined to occur.
  • the threshold value t ⁇ of the maximum opening thickness was set at 0.043 mm, and thereby the determination was made as follows. When maximum opening thickness is 0.043 mm or less ( ⁇ 0.043 mm), HIC is determined not to occur. When maximum opening thickness is more than 0.043 mm (> 0. 043 mm), HIC is determined to occur.
  • the HIC resistance of each slab as the determination target was evaluated using the threshold value t ⁇ in the following procedure.
  • the steel with the component composition shown in Table 2 was melted and subjected to continuous casting, thereby producing a slab as the determination target that had a slab thickness D of 280 mm and a slab width W of 2100 mm.
  • the HIC resistance was evaluated by using the slab in the following procedure.
  • each slab was processed by either of two types of hot-rolling and cooling methods, denoted as “TMCP” or “QT” in a “hot-rolling and cooling method” column shown in Table 3. Consequently, steel plates (each having 9 to 90 mm in thickness x 2000 to 3500 mm in width x 12000 to 35000 mm in length) with various component compositions were produced.
  • TMCP hot-rolling and cooling methods
  • the "TMCP” was a method that involved: hot-rolling through two or more passes, in each of which a surface temperature of the steel plate was set at 900°C or higher, a cumulative rolling reduction was 40% or more at an average steel plate temperature of 1000°C or higher, determined by the calculation, and a rolling reduction per pass was 10% or more; and then another hot-rolling such that a cumulative rolling reduction was 20% or more at a temperature of 700°C or higher and lower than 900°C and that the surface temperature at the end of the rolling was 850°C.
  • the "TMCP” method further involved: starting to cool the rolled steel plate from a cooling start surface temperature of 950°C at an average cooling rate of 10°C/s and then stopping the cooling at a temperature of 350 to 600°C, followed by air-cooling to the room temperature.
  • the "QT” was a method that involved: hot-rolling such that the rolling end temperature was 850°C or higher, followed by air-cooling to the room temperature; quenching by reheating the rolled steel plate to a temperature of 850°C or higher and 950°C or lower; and tempering the steel plate at 600 to 700°C.
  • the HIC test was performed using the steel plates.
  • the HIC test was performed according to the method specified by the NACE standard TM0284-2003. After the HIC test, each sample was cut at three sites, and then respective cross sections (three cross sections) were observed with the microscope to confirm the presence or absence of HIC. The results are shown in Fig. 3 .
  • Tables 2 and 3 show the following.
  • Each of steel types Nos. 1 to 7, 10, 12, and 14 to 17 satisfied the specified component composition and had the maximum opening thickness of a horizontal crack in its slab restrained to the threshold value t ⁇ or less.
  • These steel plates are the steel plates with excellent HIC resistance according to the present invention.
  • a time period required from starting of casting to completion of a production of the steel plate that is, a time period until dispatching the steel plate with the sour resistance (casting ⁇ rolling ⁇ dispatching) was 19 days.
  • a time period required from starting of casting to dispatching (casting ⁇ rolling ⁇ HIC test ⁇ dispatching) was 28 days, which was a long duration.
  • the HIC test after the rolling was able to be omitted, which could significantly shorten the time period from starting of the casting to dispatching, e.g., from 28 days to 19 days.
  • the HIC resistance can be evaluated at the stage of the slab as the cast strip without conducting the HIC test after the rolling, thereby making it possible to significantly shorten the manufacturing lead time.
  • the same HIC test is used for both the determination of the threshold value t ⁇ for evaluating the HIC resistance of a slab and the confirmation of HIC.
  • the determination method of the present invention has high accuracy.

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