EP2980238B1 - Stahlplatte mit ausgezeichneter beständigkeit gegenüber wasserstoffinduzierter rissbildung und ausgezeichneter zähigkeit, sowie leitungsstahlrohr - Google Patents

Stahlplatte mit ausgezeichneter beständigkeit gegenüber wasserstoffinduzierter rissbildung und ausgezeichneter zähigkeit, sowie leitungsstahlrohr Download PDF

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EP2980238B1
EP2980238B1 EP14773706.8A EP14773706A EP2980238B1 EP 2980238 B1 EP2980238 B1 EP 2980238B1 EP 14773706 A EP14773706 A EP 14773706A EP 2980238 B1 EP2980238 B1 EP 2980238B1
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amount
steel plate
toughness
hic
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French (fr)
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EP2980238A4 (de
EP2980238A1 (de
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Kiichirou Tashiro
Taku Kato
Shinsuke Sato
Haruya KAWANO
Takashi Miyake
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Kobe Steel Ltd
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Kobe Steel Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—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
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • 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
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—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
    • C22C38/48—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
    • 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

Definitions

  • the present invention relates to a steel plate with excellent hydrogen-induced cracking resistance and toughness, as well as the use thereof for a line pipe with excellent hydrogen-induced cracking resistance and toughness obtained using the steel plate suitable to a line pipe for transportation of natural gas and crude oil, a pressure vessel, a storage tank and the like.
  • HIC hydrogen-induced cracking
  • the hydrogen concentration of the region from the surface to 5 mm depth in the plate thickness direction (this region may be hereinafter referred to as "steel plate surface layer part") becomes higher compared to the steel plate center part, and it is known that cracking is liable to be caused from the origin of Ca-based oxide, Al-based oxide and the like of the steel plate surface layer part.
  • Patent Literature 1 a steel is disclosed in which the hydrogen-induced cracking resistance is improved by suppressing the segregation degree of Mn, Nb, and Ti of the plate thickness center part. According to this method, although the HIC property of the center segregation part can be improved, the inclusion of the portion other than the center segregation part is not controlled sufficiently, and therefore it is considered to be hard to suppress cracking of the portion other than the center segregation part.
  • Patent Literature 2 a method is disclosed in which HIC originated from the MnS and Ca-based oxy-sulfide is suppressed by a parameter expression formed of the content of Ca, O, and S.
  • HIC resistance can be secured by such a method, in the steel plate surface layer part where the hydrogen concentration becomes especially high, as described below, fine HIC is liable to be generated, and it is supposed to be hard to secure high toughness of the surface layer part as well as to secure the HIC resistance.
  • Patent Literature 3 discloses a method for producing a steel plate showing excellent hydrogen induced cracking resistance and toughness, by adjusting an optimum range of Ca-content in the steel.
  • the present invention has been developed in view of such circumstances as described above, and its object is to achieve a steel plate and a steel pipe with excellent hydrogen-induced cracking resistance and toughness in which fine HIC of approximately several ⁇ ms is also sufficiently suppressed particularly in the steel plate surface layer part in a harsh situation with a high hydrogen concentration in the sour environment.
  • the present invention relates to the following items:
  • the distribution of the Ca concentration in the plate thickness direction of the steel plate is made uniform, in the steel plate surface layer part where the hydrogen concentration becomes especially high, even fine HIC of approximately several ⁇ ms can be sufficiently suppressed. As a result, the steel plate and the steel pipe with excellent hydrogen-induced cracking resistance and toughness can be provided.
  • the present inventors made a lot of intensive studies in order to solve the problems described above.
  • HIC test National Association of Corrosion Engineers
  • NACE test National Association of Corrosion Engineers
  • This NACE test is a test for evaluating occurrence of HIC after a specimen that is a steel plate is immersed for 96 hours in a mixed aqueous solution of pH 2.7 of 5% NaCl solution and 0.5% acetic acid saturated with hydrogen sulfide gas of 1 atm.
  • the present inventors executed the Charpy test according to ASTM A370. As a result, even when the cracking was not observed in "the microscopic observation under 100 magnifications" specified in the NACE test, there was a case the result of the Charpy test after the HIC test was poor, or poor in the toughness.
  • the inclusion composition that became the origin of generation of HIC including the fine HIC described above was investigated. More specifically, the microstructure was observed with respect to the steel plate for which the HIC test (NACE test) described in the example shown below was executed. Also, the Ca concentration of the inclusion observed was obtained. This Ca concentration in the inclusion is the rate (mass%, hereinafter shown merely as %) of Ca relative to the componential composition constituting the inclusion and excluding O and N. The rate (%) of the inclusions that became the origin of generation of HIC out of the inclusions with 50% or more of the Ca concentration in the inclusion and the rate (%) of the inclusions that became the origin of generation of HIC out of the inclusions with 20% or less of the Ca concentration in the inclusion were obtained respectively. The result is shown in Fig.
  • the Ca-based inclusions described above tend to coagulate, are merged, and gather locally during casting. It is supposed that, because much amount of these Ca-based inclusions are present in the steel plate surface layer region, much amount of fine HIC originated from these Ca-based inclusions and hardly confirmed by a method of prior art is generated locally, and causes deterioration of the toughness.
  • the ratio of the maximum Ca concentration (Cmax) and the average Ca concentration of plural positions (the average Ca concentration of a region from the surface to 5 mm depth in the plate thickness direction; Cave) (Cmax/Cave) in measuring the Ca concentration in plural positions at equal intervals from the surface to 5 mm depth in the plate thickness direction was used as the controlling factor of the amount of the Ca-based inclusions of the steel plate surface layer part.
  • the Cmax/Cave is preferably 1.19 or less, more preferably 1.18 or less, and still more preferably 1.15 or less.
  • the lower limit is approximately 1.00 at which the Ca amount of the steel plate surface layer part and inside the steel becomes equal.
  • the componential composition of steel such as a steel plate and a steel pipe obtained using the steel plate in addition to control the steel plate surface layer part described above.
  • the componential composition of the steel plate should be made as described below. Below, the reasons for determining each component will be described.
  • C is an indispensable element for securing the strength of the base plate and the weld part, and should be contained by 0.02% or more.
  • C amount is preferably 0.03% or more, and more preferably 0.05% or more.
  • C amount should be 0.15% or less.
  • C amount is preferably 0.12% or less, and more preferably 0.10% or less.
  • Si is an element having a deoxidizing action and effective in improving the strength of the base plate and the weld part.
  • Si amount is made 0.02% or more.
  • Si amount is preferably 0.05% or more, and more preferably 0.15% or more.
  • Si amount should be suppressed to 0.50% or less.
  • Si amount is preferably 0.45% or less, and more preferably 0.35% or less.
  • Mn is an element effective in improving the strength of the base plate and the weld part, and is contained by 0.6% or more in the present invention.
  • Mn amount is preferably 0.8% or more, and more preferably 1.0% or more.
  • the upper limit of Mn amount is made 2.0% or less.
  • Mn amount is preferably 1.8% or less, more preferably 1.5% or less, and still more preferably 1.2% or less.
  • P is an element inevitably included in steel.
  • P amount exceeds 0.030%, deterioration of the toughness of the base plate and the HAZ part is extreme, and the hydrogen-induced cracking resistance also deteriorates. Therefore, in the present invention, P amount is suppressed to 0.030% or less.
  • P amount is preferably 0.020% or less, and more preferably 0.010% or less.
  • S is an element that forms much amount of MnS and extremely deteriorates the hydrogen-induced cracking resistance when it is contained excessively, and therefore the upper limit of S amount is made 0.003% in the present invention.
  • S amount is preferably 0.002% or less, more preferably 0.0015% or less, and still more preferably 0.0010% or less.
  • S amount is preferable to be as little as possible.
  • Al is a strong deoxidizing element.
  • Al amount is preferably 0.020% or more, and more preferably 0.030% or more.
  • Al amount is preferably 0.08% or less.
  • Al amount is preferably 0.06% or less, and more preferably 0.05% or less.
  • Ca has an action of controlling the form of sulfide, and has an effect of suppressing formation of MnS by forming CaS.
  • Ca amount should be made 0.0003% or more.
  • Ca amount is preferably 0.0005% or more, and more preferably 0.0010% or more.
  • the upper limit of Ca amount is made 0.0060%.
  • Ca amount is preferably 0.0045% or less, more preferably 0.0035% or less, and still more preferably 0.0025% or less.
  • N is an element precipitating as TiN in the steel microstructure, suppressing coarsening of the austenitic grain of the HAZ part, promoting the ferritic transformation, and improving the toughness of the HAZ part.
  • N should be contained by 0.001% or more.
  • N amount is preferably 0.003% or more, and more preferably 0.0040% or more.
  • N amount is preferably 0.008% or less, and more preferably 0.0060% or less.
  • O oxygen
  • O amount should be 0.0045% or less, is, preferably 0.0030% or less, and more preferably 0.0020% or less.
  • Ca/S When S becomes excessive relative to Ca, MnS is formed mainly in the plate thickness center part, and HIC is generated originated from MnS.
  • Ca/S should be 2.0 or more, preferably 2.5 or more, and more preferably 3.0 or more. Also, the upper limit of Ca/S becomes approximately 15 from Ca amount and S amount specified in the present invention.
  • the composition of steel (steel plate, steel pipe) of the present invention is as described above, and the remainder is iron and inevitable impurities.
  • the strength and toughness can be improved further
  • the HAZ toughness can be enhanced further, desulfurization is promoted, and the HIC resistance can be improved further.
  • B enhances the quenchability, increases the strength of the base plate and the weld part, is bonded with N in the process the HAZ part having been heated in welding is cooled to precipitate BN, promotes ferritic transformation from inside the austenitic grain, and therefore improves the HAZ toughness.
  • B amount it is preferable to contain B amount by 0.0002% or more.
  • B amount is more preferably 0.0005% or more, and still more preferably 0.0010% or more.
  • B amount is preferably 0.005% or less.
  • B amount is more preferably 0.004% or less, and still more preferably 0.0030% or less.
  • V is an element effective in improving the strength, and, in order to secure this effect, it is preferable to contain V by 0.003% or more, and more preferably 0.010% or more.
  • V content exceeds 0.1%, the weldability and the base plate toughness deteriorate. Therefore, V amount is preferably 0.1% or less, and more preferably 0.08% or less.
  • Cu is an element effective in improving the quenchability and increasing the strength. In order to secure these effects, it is preferable to contain Cu by 0.01% or more. Cu amount is more preferably 0.05% or more, and still more preferably 0.10% or more. However, because the toughness deteriorates when Cu content exceeds 1.5%, 1.5% or less is preferable. Cu amount is more preferably 1.0% or less, and still more preferably 0.50% or less.
  • Ni is an element effective in improving the strength and toughness of the base plate and the weld part. In order to secure the effect, it is preferable to make Ni amount 0.01% or more. Ni amount is more preferably 0.05% or more, and still more preferably 0.10% or more. However, when much amount of Ni is contained, the cost increases extremely as a structural steel, and therefore it is preferable to make Ni amount 1.5% or less from the economical viewpoint. Ni amount is more preferably 1.0% or less, and still more preferably 0.50% or less.
  • Cr is an element effective in improving the strength, and, in order to secure this effect, it is preferable to contain Cr by 0.01% or more. Cr amount is more preferably 0.05% or more, and still more preferably 0.10% or more. On the other hand, when Cr amount exceeds 1.5%, the HAZ toughness deteriorates. Therefore it is preferable to make Cr amount 1.5% or less. Cr amount is more preferably 1.0% or less, and still more preferably 0.50% or less.
  • Mo is an element effective in improving the strength and toughness of the base plate. In order to secure the effects, it is preferable to make Mo amount 0.01% or more. Mo amount is more preferably 0.05% or more, and still more preferably 0.10% or more. However, when Mo amount exceeds 1.5%, the HAZ toughness and weldability deteriorate. Therefore Mo amount is preferably 1.5% or less, more preferably 1.0% or less, and still more preferably 0.50% or less.
  • Nb is an element effective in enhancing the strength and base plate toughness without deteriorating the weldability. In order to secure the effects, it is preferable to make Nb amount 0.002% or more. Nb amount is more preferably 0.010% or more, and still more preferably 0.020% or more. However, when Nb amount exceeds 0.06%, the toughness of the base plate and HAZ deteriorates. Therefore, in the present invention, it is preferable that the upper limit of Nb amount is made 0.06%. Nb amount is more preferably 0.050% or less, further more preferably 0.040% or less, and still more preferably 0.030% or less.
  • Ti is an element required for improving the toughness of the HAZ part because Ti prevents coarsening of the austenitic grain and promotes the ferritic transformation in the HAZ part in welding by precipitating as TiN in steel. Also, because Ti exhibits the desulfurizing action, Ti is an element effective also in improving the HIC resistance. In order to secure these effects, it is preferable to contain Ti by 0.003% or more. Ti amount is more preferably 0.005% or more, and more preferably 0.010% or more. On the other hand, when Ti amount becomes excessive, the toughness of the base plate and the HAZ part deteriorates because of solid solution of Ti and precipitation of TiC, and therefore it is preferable to make Ti amount 0.03% or less. Ti amount is more preferably 0.02% or less.
  • Mg is an element effective in improving the toughness through miniaturization of the grain, and is an element exhibiting the desulfurizing action and effective also in improving the HIC resistance. In order to secure these effects, it is preferable to contain Mg by 0.0003% or more. Mg amount is more preferably 0.001% or more. On the other hand, even when Mg is contained excessively, the effects saturate, and therefore it is preferable that the upper limit of Mg amount is made 0.01%. Mg amount is more preferably 0.005% or less.
  • REM rare earth element
  • REM amount is more preferably 0.0005% or more, and still more preferably 0.0010% or more.
  • the upper limit of REM amount is made 0.02%. From the viewpoint of suppressing blockage of the immersion nozzle in casting and improving the productivity, REM amount is more preferably 0.015% or less, further more preferably 0.010% or less, and still more preferably 0.0050% or less.
  • the REM means the lanthanoid elements (15 elements from La to Lu), Sc (Scandium), and Y.
  • Zr is an element contributing to improvement of the HIC resistance by the desulfurizing action, and contributing also to improvement of the HAZ toughness by forming and finely dispersing oxide. In order to exert these effects, it is preferable to make Zr amount 0.0003% or more. Zr amount is more preferably 0.0005% or more, further more preferably 0.0010% or more, and still more preferably 0.0015% or more. On the other hand, when Zr is added excessively, coarse inclusions are formed, and the hydrogen-induced cracking resistance and the base plate toughness are deteriorated. Therefore, it is preferable to make Zr amount 0.010% or less. Zr amount is more preferably 0.0070% or less, further more preferably 0.0050% or less, and still more preferably 0.0030% or less.
  • the steel plate specified in the present invention has been described above.
  • the method for manufacturing the steel plate of the present invention is not particularly limited as far as it is a method of obtaining the steel plate surface layer part specified above.
  • a method described below can be cited.
  • the molten steel is poured to the mold through the ladle and tundish, however, in order to obtain a steel plate having the steel plate surface layer part specified in the present invention, in the step of pouring the molten steel to the tundish and performing continuous casting, it is recommendable to satisfy all of (1)-(3) below.
  • the Ca-based inclusion has high melting point and has large contact angle against molten steel, it is liable to form coagulation and is liable to become a coarse inclusion. Therefore, this Ca-based inclusion should be made to sufficiently float and be separated inside the tundish. When this floating and separating are insufficient, the coarse Ca-based inclusion is made to float for example at a curved section in continuous casting, and is liable to gather at the surface layer. In order to make the inclusion sufficiently float and be separated inside the tundish, it is better to make the average flow rate of the molten steel inside the tundish slow.
  • the floating time can be made longer, and floating and separating can be promoted by turbulence in pouring the molten steel from the ladle.
  • such tundish is used that the flow channel cross-sectional area at the molten steel pouring position to the mold in the tundish is larger than the flow channel cross-sectional area at the molten steel pouring position from the ladle.
  • the ratio expressed by (flow channel cross-sectional area at molten steel pouring position to mold)/(flow channel cross-sectional area at molten steel pouring position from ladle) only has to be over 1.00, the ratio is preferably 1.50 or more. Also, the upper limit of the ratio is approximately 5.0.
  • the Ar flow rate 0.04 L/t or more.
  • the Ar flow rate is more preferably 0.10 L/t or more, and still more preferably 0.20 L/t or more.
  • the Ar flow rate is preferably 9.7 L/t or less, more preferably 9.0 L/t or less, and still more preferably 8.0 L/t or less.
  • the inclusions which are present in the vicinity of the solidification interface are liable to be taken in to the interface when the solidifying rate is high, and a part of the inclusions is pushed out from the solidification interface to the center part not yet solidified when the solidifying rate is low.
  • the inclusions are prevented from gathering in the steel plate surface layer part. More specifically, the solidifying rate at the position of 1-3 m from the meniscus position of the molten steel inside the mold toward the drawing out direction where "the region from the surface to 5 mm depth" of the object of the present invention is solidified is made 0.26 mm/s or less.
  • the solidifying rate is preferably 0.22 mm/s or less, and more preferably 0.18 mm/s or less. Also, the lower limit value of the solidifying rate becomes approximately 0.05 mm/s from the viewpoint of productivity and the like.
  • the solidifying rate can be adjusted by controlling the water amount density of the cooling water and the casting rate.
  • the step after casting as described above is not particularly the object, and the steel plate can be manufactured by performing hot rolling according to an ordinary method, or by reheating and performing heat treatment after the hot rolling. Also, using the steel plate, a steel pipe for a line pipe can be manufactured by a method generally employed. The steel pipe for a line pipe obtained using the steel plate of the present invention is also excellent in the HIC resistance and the toughness.
  • the steel plate (plate thickness: 12-90 mm) with various componential compositions was obtained by the hot rolling/cooling method of 2 patterns as shown "TMCP" (Thermo Mechanical Control Process) or “QT” (Quenching and Tempering) in the column “hot rolling/cooling method” of Table 2.
  • TMCP Thermo Mechanical Control Process
  • QT Quenching and Tempering
  • hot rolling was performed so that the cumulative draft of 900°C or above in terms of the surface temperature of the steel plate became 30% or more, and hot rolling was further performed so that the cumulative draft of 700°C or above and below 900°C became 20% or more with the rolling finish temperature of 700°C or above and below 900°C.
  • Cmax/Cave was measured as shown below. Further, the HIC resistance was evaluated by executing the HIC test, and the toughness was evaluated by executing the Charpy impact test.
  • the distribution of the Ca concentration of the region from the surface to 5 mm depth in the plate thickness direction of the steel plate was measured by fluorescence spectroscopic analysis. More specifically, first, in order to exfoliate the scale layer of the steel plate, the portion from the steel plate surface to 0.5 mm was ground, and the Ca concentration of the ground surface that corresponded to the surface of the steel plate was measured. Next, after the steel plate was ground by 0.5 mm in the plate thickness direction, the Ca concentration of the ground surface was measured. This procedure was repeated with 0.5 mm pitch in the plate thickness direction, and the Ca concentration of 10 cross sections in total from the surface to 5 mm depth in the plate thickness direction was measured. The maximum value of the Ca concentration in 10 cross sections was made Cmax, the average value of the Ca concentration of 10 cross sections was made Cave, and Cmax/Cave was obtained.
  • the HIC test was performed for evaluation according to NACE standard TM0284-2003. More specifically, from 1/4W position and 1/2W position in the width direction of each steel plate, 3 pieces each or 6 pieces in total of the specimens (size: plate thickness ⁇ 100 mm (width) ⁇ 20 mm (rolling direction)) were taken. Also, the specimen was immersed for 96 hours in a mixed aqueous solution containing 0.5% NaCl and 0.5% acetic acid of 25°C saturated with hydrogen sulfide of 1 atm, evaluation of the cross section was executed according to NACE standard TM0284-2003 FIGURE 3, and CLR (Crack Length Ratio: the ratio (%) of the total of the crack length relative to the specimen width) was measured. Further, the case the CLR was 3% or less was evaluated to be excellent in the HIC resistance ( ⁇ ), and the case the CLR exceeded 3% was evaluated to be poor in the HIC resistance ( ⁇ ).
  • CLR Cell Length Ratio: the ratio (%) of the total of the crack length relative
  • the Charpy test specimens with 5 mm in the plate thickness direction ⁇ 10 mm in the rolling direction were taken by 3 pieces in the direction perpendicular to the rolling direction, and a notch was worked in the plate thickness direction of the steel plate.
  • the Charpy impact test was executed according to ASTM A370, the test temperature was changed variously in 0°C-80°C, and the Charpy absorption energy at 0% of the percent brittle fracture or the upper shelf energy was obtained. Also, the case this upper shelf energy was 125 J or more was evaluated to be excellent in the toughness.
  • Nos. 14 and 27 resulted to be poor in the HIC resistance because the componential composition (Ca/S) deviated from the stipulation of the present invention although Cmax/Cave of the steel plate surface layer part satisfied the range specified in the present invention.
  • the toughness became poor. In Nos. 15-19, 21, 28, 29, and 31 in particular, although the HIC resistance could be secured, the toughness became poor.
  • Fig. 2 is a drawing showing the relationship between Cmax/Cave and the upper shelf energy obtained using the result of the Table 2. From this Fig. 2 , it is known that Cmax/Cave only has to be made 1.20 or less in order to secure excellent toughness of 125 J or more of the upper shelf energy.
  • the steel plates related to the present invention are excellent in the hydrogen-induced cracking resistance and the toughness, they are used suitably to a line pipe for transportation, a pressure vessel, a storage tank and the like of natural gas and crude oil.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)

Claims (3)

  1. Stahlplatte oder -blech mit hervorragender Beständigkeit gegen eine wasserstoffinduzierte Rissbildung und Zähigkeit, bestehend aus:
    C: 0,02-0,15 % (% bedeutet Massen-%, nachstehend gilt das Gleiche);
    Si: 0,02-0,50 %;
    Mn: 0,6-2,0 %;
    P: 0,030 % oder weniger;
    S: 0,003 % oder weniger;
    Al: 0,010-0,08 %;
    Ca: 0,0003-0,0060 %;
    N: 0,001-0,01 % und
    O (Sauerstoff): 0,0045 % oder weniger,
    und gegebenenfalls
    mindestens einem Element, ausgewählt aus mindestens einer der Gruppe (a) und der Gruppe (b), die nachstehend angegeben sind;
    (a) eine Gruppe, bestehend aus:
    B: 0,0002 %-0,005 %;
    V: 0,003 %-0,1%;
    Cu: 0,01 %-1,5%;
    Ni: 0,01 %-1,5%;
    Cr: 0,01 %-1,5%;
    Mo: 0,01 %-1,5% und
    Nb: 0,002 %-0,06%
    (b) eine Gruppe, bestehend aus:
    Ti: 0,003 %-0,03 %;
    Mg: 0,0003 %-0,01 %;
    wobei der Rest aus Eisen und unvermeidbaren Verunreinigungen besteht;
    wobei
    das Verhältnis von Ca und S (Ca/S) 2,0 oder mehr beträgt und
    das Verhältnis der maximalen Ca-Konzentration (Cmax) eines Bereichs von der Oberfläche bis zu einer Tiefe von 5 mm in der Platten- oder Blechdickenrichtung und der durchschnittlichen Ca-Konzentration (Cave) in dem Bereich (Cmax/Cave) 1,20 oder weniger beträgt.
  2. Verwendung einer Stahlplatte oder eines Stahlblechs nach Anspruch 1 für ein Leitungsrohr.
  3. Verwendung einer Stahlplatte oder eines Stahlblechs nach Anspruch 1 für einen Druckbehälter.
EP14773706.8A 2013-03-29 2014-03-25 Stahlplatte mit ausgezeichneter beständigkeit gegenüber wasserstoffinduzierter rissbildung und ausgezeichneter zähigkeit, sowie leitungsstahlrohr Not-in-force EP2980238B1 (de)

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JP6343472B2 (ja) * 2014-03-28 2018-06-13 株式会社神戸製鋼所 低温靭性に優れた高強度ラインパイプ用鋼板および高強度ラインパイプ用鋼管
JP2016125140A (ja) * 2014-12-26 2016-07-11 株式会社神戸製鋼所 耐水素誘起割れ性と靭性に優れた鋼板およびラインパイプ用鋼管
WO2016104528A1 (ja) * 2014-12-26 2016-06-30 株式会社神戸製鋼所 耐水素誘起割れ性と靭性に優れた鋼板およびラインパイプ用鋼管
WO2016104529A1 (ja) * 2014-12-26 2016-06-30 株式会社神戸製鋼所 耐水素誘起割れ性に優れた鋼板およびラインパイプ用鋼管
JP2016125137A (ja) * 2014-12-26 2016-07-11 株式会社神戸製鋼所 耐水素誘起割れ性に優れた鋼板およびラインパイプ用鋼管
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CN105102652B (zh) 2017-11-21
EP2980238A4 (de) 2016-11-23
JP6169025B2 (ja) 2017-07-26
EP2980238A1 (de) 2016-02-03
KR101709034B1 (ko) 2017-02-21
CN105102652A (zh) 2015-11-25
WO2014157165A1 (ja) 2014-10-02
KR20150121193A (ko) 2015-10-28
JP2014208892A (ja) 2014-11-06

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