EP2272994B1 - Acier ayant une résistance à la traction élevée et son procédé de fabrication - Google Patents

Acier ayant une résistance à la traction élevée et son procédé de fabrication Download PDF

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EP2272994B1
EP2272994B1 EP09726619.1A EP09726619A EP2272994B1 EP 2272994 B1 EP2272994 B1 EP 2272994B1 EP 09726619 A EP09726619 A EP 09726619A EP 2272994 B1 EP2272994 B1 EP 2272994B1
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mass
cooling
steel
toughness
less
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EP2272994A1 (fr
EP2272994A4 (fr
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Katsuyuki Ichimiya
Tomoyuki Yokota
Kimihiro Nishimura
Nobuo Shikanai
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JFE Steel Corp
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JFE Steel Corp
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    • 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
    • C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment 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
    • 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
    • C22C38/02—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
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • 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
    • C22C2202/00—Physical properties

Definitions

  • the present invention relates to a method of manufacturing a high-tensile strength steel that is used in ships, marine structures, line pipes, pressure vessels. Specifically, the present invention relates to a method of manufacturing a high-tensile strength steel that has a yield stress (YS) of 460 MPa or more and is not only excellent in strength and toughness of base material but also excellent in weld zone toughness (crack tip opening displacement (CTOD) properties).
  • YS yield stress
  • COD crack tip opening displacement
  • COD test crack tip opening displacement test
  • steels having large thicknesses are usually subjected to multi-pass welding.
  • multi-pass welding since the heat-affected zone experiences a complicated thermal history, there are problems that local embrittlement tends to occur and that, in particular, the bond zone (boundary between a weld metal and a base material) and the inter-critically reheated zone (region that is coarse-grained in the first cycle of welding and is heated into a two-phase region of a and y in the second cycle) are largely decreased in toughness.
  • Japanese Examined Patent Application Publication No. 03-053367 and Japanese Unexamined Patent Application Publication No. 60-184663 disclose techniques of dispersing fine particles in a steel by combined addition of a rare-earth metal (REM) and Ti for preventing the growth of austenite grains and improving the toughness of the weld zone.
  • REM rare-earth metal
  • the inter-critically reheated zone that is, a region that is exposed to a high temperature just below the melting point in the first welding and is reheated to a two-phase region of ferrite and austenite in the subsequent welding is most embrittled.
  • carbon is enriched in the austenite region by reheating to a two-phase region, and this allows the formation of a brittle bainitic structure containing island martensite during cooling, resulting in a decrease in toughness.
  • a technique of preventing the formation of island martensite by reducing the amounts of C and Si and also ensuring the base material strength by adding Cu is disclosed (for example, Japanese Unexamined Patent Application Publication No. 05-186823 ).
  • Japanese Unexamined Patent Application Publication No. 2007-231312 discloses, as a method for preventing the formation of an embrittlement structure due to reheating in welding, a technique of increasing the toughness of the welded heat-affected zone (CTOD properties) by adding Ni, while adjusting the amount of Ca added for controlling the shape of sulfide within an appropriate range.
  • CTOD properties toughness of the welded heat-affected zone
  • the present invention provides a method of manufacturing a high-tensile strength steel comprising:
  • the manufacturing method of the present invention can subject the steel after the latter cooling to tempering at 450 to 650°C.
  • the first cooling is preferably performed at a cooling rate of 5 to 20°C/sec.
  • a high-strength steel where the base material has a high strength with a yield stress of 460 MPa or more and is excellent in toughness and also the heat-affected zone after welding is excellent in toughness (CTOD properties) can be manufactured inexpensively.
  • the invention highly contributes to an increase in size of ships, marine structures, and so on.
  • the present inventors have intensively investigated methods that can increase the strength and toughness of the base material of a thick high-tensile strength steel and also improve the toughness of the welded heat-affected zone.
  • a decrease in toughness of a welded heat-affected zone is caused by formation of an embrittlement structure, in order to increase the toughness of the welded heat-affected zone, prevention of coarsening of austenite grains in a region that is heated to a high temperature in welding and also uniform and fine dispersion of transformation nuclei for accelerating ferrite transformation in cooling after the welding are effective.
  • the present inventors have further investigated methods for preventing the formation of embrittlement structures and, as a result, have found the facts that adjustment of the amount of Ca added for controlling the shape of sulfide to an appropriate range is effective and that addition of Mn is effective for increasing the toughness (CTOD properties) of a welded heat-affected zone.
  • a first aspect of the present invention is that, in order to increase the toughness of the welded heat-affected zone, crystallization of a compound (CaS) of Ca added for controlling the shape of sulfide is effectively utilized. Since the CaS is crystallized at a lower temperature compared to oxide, its uniform fine dispersion is possible. In addition, since a S solid solution is ensured even after crystallization of CaS by controlling the CaS addition amount and the dissolved oxygen amount in a molten steel when it is added to an appropriate ranges, MnS is precipitated on the surface of CaS to form complex sulfide.
  • CaS compound
  • MnS has potential for ferrite nucleus, and a Mn depleted zone is formed in the periphery of precipitated MnS. Therefore, ferrite transformation is further accelerated. This effect of the Mn depleted zone can be further effectively exhibited by increasing the amount of Mn added to the steel.
  • ferrite transformation nuclei such as TiN, BN, or AlN are precipitated on the precipitated MnS, which accelerates further ferrite transformation.
  • an increase in the Mn addition amount can effectively increase the base material strength in such a manner that island martensite, which is an embrittlement structure, is not formed as far as possible in the welded heat-affected zone. This is because that the island martensite formed during the cooling after welding tends to be decomposed to cementite by increasing the Mn addition amount thereby to reduce the island martensite in the heat-affected zone structure. As a result of these effects, the toughness of the welded heat-affected zone can be ensured without requiring addition of Ni.
  • ferrite transformation nuclei that are not dissolved even at high temperature can be finely dispersed thereby to reduce the welded heat-affected zone structure in size, and also high toughness can be obtained by preventing the formation of island martensite (M-A constituent) as far as possible.
  • M-A constituent island martensite
  • a second aspect of the present invention is that the cooling after rolling of a steel is performed by two-stage cooling of former cooling and latter cooling, wherein the cooling rate of the first cooling is higher than that of the second cooling. This point will be described on the basis of experimental results.
  • a steel slab including C: 0.08 mass%, Si: 0.2 mass%, and Mn: 1.8 mass% as basic components was heated to 1150°C and then hot-rolled in such a manner that the cumulative rolling reduction in the temperature range of 950°C or higher was 40%, the cumulative rolling reduction in the temperature range of lower than 950°C was 50%, and the finishing rolling temperature was 850°C, and then first cooling for cooling the steel from the rolling completion temperature to 500°C at a cooling rate of 5 to 45°C/sec, more preferably, 5 to 20°C/sec, and then cooling for cooling the steel to 350°C at a cooling rate of 3°C/sec were performed, followed by air cooling to give a thick steel sheet having a thickness of 10 to 50 mm.
  • the thick steel plate was examined for tensile strength properties and toughness properties at -40°C (Charpy impact absorbed energy).
  • Fig. 1 shows an effect of former cooling rate on the strength and toughness of the base material. It is confirmed that a steel excellent in strength-toughness balance such that the strength is high so as to have a yield stress of 460 MPa or more and the vE-40°C is 200 J or more can be obtained by controlling the cooling rate of the first cooling from the finishing rolling temperature to 500°C to the range of 5 to 45°C/sec.
  • the main microstructure of the steel plate thus cooled at the above-mentioned cooling rate is acicular ferrite.
  • a relatively coarse upper bainitic microstructure that contains, for example, island martensite between laths is formed, resulting in a large decrease in toughness. Accordingly, in order to achieve both high strength and high toughness, it is necessary to form a finer acicular ferrite microstructure by, for example, adjusting the rolling conditions.
  • the present inventors have found the fact that a steel sheet excellent in strength-toughness balance can be obtained by performing the cooling after rolling by two steps of former cooling and latter cooling, wherein the cooling rate of the second cooling is lower than that of the first cooling and both the cooling rates are appropriately controlled, thereby to form a structure of mainly acicular ferrite.
  • the microstructure after transformation can become a dense acicular ferrite instead of a coarse bainitic microstructure by performing the first cooling at a higher cooling rate than that of the second cooling to increase the transformation nucleation density.
  • the cooling rate of the second cooling is required to be controlled in an appropriate range because that when the cooling rate is too higher than that of the first cooling, island martensite is formed to decrease the toughness of the base material and, in contrast, that when the cooling rate of the second cooling is too low, the strength of the base material is decreased.
  • C is an element that most largely affects the strength of a steel and is necessary to be contained in an amount of 0.03 mass% or more for ensuring strength (YS ⁇ 460 MPa) required in structural steels.
  • the upper limit is determined to be 0.10 mass%.
  • Si is a component that is added as a deoxidizing material and also for highly strengthening a steel.
  • the addition amount be 0.01 mass% or more.
  • the amount has to be 0.30 mass% or less and is preferably in the range of 0.01 to 0.20 mass%.
  • Mn is an element effective for ensuring the strength of the base material, but, in the present invention, Mn is an important element that is added for accelerating the reduction of a welded heat-affected zone structure in size and also preventing the formation of an embrittlement structure as far as possible thereby to increase the toughness of the welded heat-affected zone (CTOD properties).
  • CTOD properties toughness of the welded heat-affected zone
  • an addition amount of 1.60 mass% or more is necessary.
  • the amount is 2.30 mass% or less and is preferably in the range of 1.65 to 2.15 mass%.
  • P is an impurity that is inevitably contained.
  • the amount is larger than 0.015 mass%, the toughness of the base material and the weld zone is decreased, and therefore the amount is limited to 0.015 mass% or less and preferably 0.010 mass% or less.
  • S is an impurity that is inevitably contained.
  • the amount is larger than 0.005 mass%, the toughness of the base material and the weld zone is decreased, and therefore the amount is limited to 0.005 mass% or less and preferably 0.0035 mass% or less.
  • Al is an element to be added for deoxidizing the molten steel and is required to be contained in an amount of 0.005 mass% or more.
  • an amount larger than 0.06 mass% decreases the toughness of the base material and also causes interfusion with a weld metal by dilution due to welding, which decreases the toughness. Therefore, the amount is necessarily limited to 0.06 mass% or less and preferably 0.010 to 0.055 mass%.
  • Nb enlarges a non-recrystallization zone in a low temperature range of austenite. Therefore, the base material structure can be reduced in size and increased in toughness by conducting rolling in such a temperature range. In addition, precipitation strengthening can be achieved by conducting tempering after the rolling and cooling. Therefore, Nb is an important element from the viewpoint of strengthening the steel. In order to obtain the above-described effects, Nb is necessarily contained in an amount of 0.004 mass% or more. However, when Nb is added in an excessive amount of higher than 0.05 mass%, the toughness of the weld zone is decreased. Therefore, the upper limit is determined to be 0.05 mass%.
  • Ti is precipitated as TiN when molten steel is solidified thereby to prevent the austenite in the weld zone from being coarsened and also acts as ferrite transformation nuclei thereby to contribute to an increase in toughness of the weld zone.
  • Ti is necessarily contained in an amount of 0.005 mass% or more. When the amount is less than 0.005 mass%, the effect is small, but an amount larger than 0.02 mass% causes coarsening of TiN grains, and, thereby, the effect increasing the toughness of the base material and the weld zone cannot be obtained. Therefore, the Ti addition amount is determined to be in the range of 0.005 to 0.02 mass%.
  • N is an element necessary for forming TiN that prevents the weld zone structure from being coarsened and is contained in an amount of 0.001 mass% or more.
  • the N amount is preferably in the range of 0.003 to 0.005 mass%.
  • Ca is an element that increases the toughness by fixing S. In order to realize this effect, it is necessary to be contained in an amount of at least 0.0005 mass%. However, in an amount larger than 0.003 mass%, the effect is saturated. Therefore, Ca is contained in the range of 0.0005 to 0.003 mass%. 0 ⁇ Ca - 0.18 + 130 ⁇ Ca ⁇ O / 1.25 / S ⁇ 1
  • Ca, S, and O are necessarily contained so as to satisfy the following expression (1): 0 ⁇ Ca - 0.18 + 130 ⁇ Ca ⁇ O / 1.25 / S ⁇ 1 wherein, Ca, S, and O represent the respective contents (mass%) of the elements.
  • (Ca-(0.18+130 ⁇ Ca) ⁇ O)/1.25/S) is a value showing the ratio of atomic concentrations of Ca and S for effectively controlling the shape of sulfide and suggests the shape of the sulfide ( Mochida, et al., "Tetsu to Hagane (Iron and Steel)", The Iron and Steel Institute of Japan, vol. 66 (1980), No. 3, pp. 354-362 ).
  • the value of ((Ca-(0.18+130xCa)xO)/1.25/S) is preferably in the range of 0.2 to 0.8.
  • the high-tensile strength steel of the present invention can contain one or more selected from the group consisting of B, V, Cu, Ni, Cr, and Mo for further increasing strength and toughness, in addition to the above-described essential components.
  • B segregates in an austenite grain boundary and thereby to prevent ferrite transformation that occurs from the grain boundary, which increases the fraction of a bainitic structure thereby to achieve an effect of strengthening the steel.
  • Such an effect can be achieved when the addition amount is 0.0003 mass% or more. However, when the amount is larger than 0.0025 mass%, conversely, the toughness is decreased.
  • the amount of B is more preferably in the range of 0.0005 to 0.002 mass%.
  • V 0.2 mass% or less
  • V is an element effective for increasing the strength and toughness of the base material and is precipitated as VN, which also acts as a ferrite transformation nucleus.
  • the amount to be added is preferably 0.01 mass% or more. However, when the addition amount is larger than 0.2 mass%, contrarily, a decrease in toughness is caused. Therefore, the amount to be added is preferably 0.2 mass% or less, and more preferably 0.15 mass% or less.
  • Cu is an element having an effect of increasing the strength of a steel. In order to obtain the effect, it is preferably to be contained in an amount of 0.05 mass% or more. However, when the amount is larger than 1 mass%, hot brittleness causes surface defects of the steel plate. Therefore, the addition amount is preferably in the range of 1 mass% or less and more preferably 0.8 mass% or less.
  • Ni is an element effective for increasing the strength of a steel and the CTOD properties of the welded heat-affected zone.
  • the addition amount is preferably 0.05 mass% or more.
  • Ni is an expensive element, it is preferably to determine the upper limit to be 2.0 mass%.
  • the Mn addition amount is 1.6 % or more as in this application, the amount of Ni is further preferably less than 0.3% from the viewpoint of a reduction in cost.
  • the addition amount is preferably 0.05 mass% or more.
  • the upper limit is preferably determined to be 0.7 mass%, more preferably, 0.5 mass% or less.
  • Mo is an element effective for strengthening the base material as in Cr.
  • the addition amount is preferably 0.05 mass% cr more.
  • the upper limit is preferably determined to be 0.7 mass%, more preferably, 0.5 mass% or less.
  • Microstructure of the high-tensile strength steel of the present invention is mainly composed of an acicular ferrite, and its area ratio is preferably 60% or more and more preferably 70% or more. If the area ratio of the acicular ferrite is less than 60% and a coarse upper bainite is increased, the toughness is decreased. Incidentally, the upper limit of the area ratio is not particularly limited.
  • the acicular ferrite microstructure of the high-tensile steel of the present invention is bainitic ferrite with a high dislocation density having morphology of fine needle-like or lath-like shape and is different from a polygonal ferrite or coarse upper bainite.
  • the high-tensile strength steel of the present invention be manufactured as a high-tensile strength steel having a large thickness by ingoting a molten steel having the above-described component composition of the present invention by a common method using a converter furnace, an electric furnace, a vacuum melting furnace, or the like, making a steel material such as a slab by a common step such as continuous-casting or ingot-casting-blooming, and then hot-rolling the steel material. On this occasion, it is necessary to adjust the heating temperature of the steel material to the range of 1050 to 1200°C in advance the hot-rolling.
  • a heating temperature of not lower than 1050°C is necessary for certainly pressure-bonding cast defects, which are present in the as-cast steel material, by the hot-rolling.
  • the heating temperature is necessarily regulated to 1200°C or less.
  • the steel material heated to the above-mentioned temperature is subjected to hot-rolling in such a manner that the cumulative rolling reduction in the temperature range of 950°C or higher is 30% or more and the cumulative rolling reduction in the temperature range of lower than 950°C is 30 to 70% to obtain a high-tensile strength steel having a set thickness.
  • the hot-rolling is performed at a cumulative rolling reduction of 30% in the temperature range of 950°C or higher because that the austenite grains are recrystallized to make the microstructure fine by regulating the cumulative rolling reduction in this temperature range to 30% or more, but the abnormally coarsened grains produced in the heating are left when the cumulative rolling reduction is lower than 30% to adversely affect the toughness of the base material.
  • the hot-rolling is performed at a cumulative rolling reduction of 30 to 70% in the temperature range of lower than 950°C because that since the austenite grains rolled in this temperature range are not sufficiently recrystallized thereby to hold the elongated shape after the rolling, a large amount of defects such as deformation bands are introduced, and thereby the internal strain becomes high.
  • the cumulative internal energy works as a driving force for the subsequent ferrite transformation to accelerate the ferrite transformation.
  • the cumulative rolling reduction is lower than 30%, the cumulative internal energy is not sufficient. Therefore, the ferrite transformation hardly occurs thereby to decrease the toughness of the base material.
  • a cumulative rolling reduction of higher than 70% accelerates the formation of polygonal ferrite and prevents the formation of acicular ferrite, and, therefore, high strength and high toughness cannot be simultaneously achieved.
  • the subsequent cooling after the completion of the hot-rolling is performed by a first cooling and a second cooling, and the cooling rate of the first cooling is relatively higher than that of the second cooling. That is, it is necessary that the first cooling is performed from the finishing rolling temperature to a cooling termination temperature of 600 to 450°C, preferably, from the finishing rolling temperature to a cooling termination temperature of 580 to 480°C at a cooling rate of 5 to 45°C/sec, preferably 5 to 20°C/sec, and further preferably 6 to 16°C/sec, and then the second cooling is performed from the first cooling termination temperature to the second cooling termination temperature of 450°C or less, preferably, from the first cooling termination temperature to the cooling termination temperature of 400 to 250°C at a cooling rate of 1°C/sec or more and less than 5°C/sec, more preferably, 2 to 4.5°C/sec.
  • the strength is hardly increased. Conversely, when the temperature is lower than the above-mentioned temperature range, the toughness is deteriorated. In addition, when the first cooling rate is lower than the lower limit of the above-mentioned range, the dominant microstructure is polygonal ferrite, and therefore an increase in the strength is not obtained. Conversely, when the rate is higher than the upper limit of the above-mentioned range, the toughness is decreased. Furthermore, when the cooling termination temperature of the second cooling is higher than the upper limit of the above-mentioned temperature range, the increase of the strength is insufficient.
  • the second cooling rate is lower than the lower limit of the above-mentioned range, the base material suffers from a shortage of strength. Conversely, when the rate is higher than the upper limit of the above-mentioned range, the toughness of the base material is decreased. In addition, when the latter cooling rate is too higher than that of the first cooling rate, island martensite is formed thereby to decrease the toughness of the base material.
  • the steel material after the cooling may be subjected to tempering in the temperature range of 450 to 650°C.
  • the temperature of the tempering is lower than 450°C, the effect removing the residual stress is small.
  • the temperature is higher than 650°C, various types of carbonitrides are precipitated thereby to cause precipitation strengthening and decrease the toughness, which is undesirable.
  • the method of manufacturing a high-tensile strength steel of the present invention it is important to appropriately control the cumulative rolling reduction according to the rolling temperature in the hot-rolling and to appropriately control the two-stage cooling conditions after the completion of the rolling.
  • the cooling rate of the first cooling to be larger than that of the second cooling, the main structure of the base material becomes acicular ferrite, and thereby a steel material excellent in strength-toughness balance can be obtained.
  • a high strength steel in which the base material has a high strength of a yield stress of 550 MPa or more and is excellent in toughness and also the heat-affected zone after welding is excellent in toughness can be inexpensively manufactured by controlling the amount of N in the chemical components to be higher than 0.0030%, the cooling rate in the former cooling to higher than 20°C/sec and not higher than 45°C/sec, the cooling termination temperature of the former cooling to 450°C or higher and lower than 500°C.
  • Thick steel sheets having thicknesses of 25 to 80 mm were manufactured using steel slabs Nos. 1 to 31 having component compositions shown in Tables 1-1 and 1-2 as materials by performing hot-rolling, former cooling, and latter cooling under conditions shown in Tables 2-1 and 2-2.
  • the temperatures shown in Tables 2-1 and 2-2 are each that of one-fourth thickness portion calculated from the steel plate surface temperature measured with a radiation thermometer. Samples prepared from the thus obtained thick steel plates were subjected to a tensile test and a Charpy impact test.
  • JIS #4 tensile test pieces were sampled from one-fourth thickness portions of the thick steel plates in such a manner that the longitudinal axis direction of each test piece was parallel to the rolling direction, and the yield stress (YS) and tensile strength (TS) of the test pieces were measured.
  • YS yield stress
  • TS tensile strength
  • JIS #4 impact test pieces were sampled from one-fourth thickness portions of the thick steel plates parallel to transverse direction, and the absorbed energy at -40°C (vE-40°C) was measured.
  • a test piece satisfying all of YS ⁇ 460 MPa, TS ⁇ 570 MPa, and vE-40°C ⁇ 200 J was determined to have satisfactory base material properties.
  • test plates prepared from the thick steel plates that satisfy all the above-mentioned criteria of YS, TS, and vE-40°C as the base material properties were each provided with a single bevel groove (bevel angle: 30°).
  • the test plate was subjected to CO 2 arc welding at a heat input amount of 25 kJ/cm to produce a weld joint.
  • a CTOD test piece provided with a notch in the straight bond zone of the single bevel groove was prepared from each weld joint and subjected to a CTOD test at -10°C.
  • the preparation of the CTOD test pieces and the test conditions were in accordance with British standard BS 7448.
  • JIS #4 impact test pieces having notches in the bond zones were prepared and were each subjected to the Charpy impact test at -40°C and measured for the absorbed energy (vE-40°C).
  • the steel plates of Nos. 11 to 17, which are steel plates according to the present invention and contain N in amounts of larger than 0.0030 mass%, are excellent such that all the CTOD values of weld zones are 0.45 mm or more due to the pinning effect of TiN.
  • the base materials have high strength such that the yield stresses are 550 MPa or more.
  • the high-tensile strength steels of the present invention can be properly used not only in ships, marine structures, line pipes, and pressure vessels but also in steel structures that are assembled by welding in the fields of constructions, civil works, and so on.
  • Table 1-1 No. Chemical Component (mass%) Notes C Si Mn P S Al Nb Ti N Ca O B V Cu Ni Cr Mo Ceq *1 ACR *2 1 0.056 0.10 2.05 0.005 0.0018 0.026 0.030 0.019 0.0015 0.0030 0.0035 - - 0.22 0.23 - - 0.428 0.447
  • Example 2 0.055 0.08 2.15 0.009 0.0015 0.044 0.029 0.017 0.0038 0.0024 0.0017 - - - - 0.11 - 0.435 0.834
  • Example 3 0.076 0.13 2.02 0.010 0.0021 0.027 0.022 0.014 0.0028 0.0014 0.0024 - - - - 0.20 0.453 0.202

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Claims (3)

  1. Procédé de fabrication d'un acier ayant une résistance à la traction élevée comprenant :
    le chauffage d'une brame d'acier ayant une composition de composants incluant C : 0,03 à 0,10 % en masse, Si : 0,30 % en masse ou moins, Mn : 1,60 à 2,30 % en masse, P : 0,015 % en masse ou moins, S : 0,005 % en masse ou moins, Al : 0,005 à 0,06 % en masse, Nb : 0,004 à 0,05 % en masse, Ti : 0,005 à 0,02 % en masse, N : 0,001 à 0,005 % en masse, Ca : 0,0005 à 0,003 % en masse, et comprenant en outre éventuellement un ou plusieurs éléments choisis dans le groupe constitué de B : 0,0003 à 0,0025 % en masse, V : 0,2 % en masse ou moins, Cu : 1 % en masse ou moins, Ni : 2 % en masse ou moins, Cr : 0,7 % en masse ou moins et Mo : 0,7 % en masse ou moins, le reste étant du fer et d'inévitables impuretés de telle sorte que Ca, S et O satisfassent l'expression (1) suivante : 0 < Ca - 0 , 18 + 130 x Ca X O / 1 , 25 / S < 1
    Figure imgb0007
    dans laquelle Ca, S et O représentent les teneurs respectives (% en masse) des éléments, à une température de 1050 à 1200°C ;
    le laminage à chaud de l'acier de telle manière que la réduction cumulative du laminage dans la plage de températures de 950° ou plus est de 30 % ou plus et la réduction cumulative du laminage dans la plage de températures inférieure à 950° est de 30 à 70 % ; et, ensuite,
    le refroidissement de l'acier de la température finale de laminage à chaud à une température de fin de refroidissement de 600 à 450°C à une vitesse de refroidissement de 5 à 45°C/s et ensuite, le refroidissement de l'acier de la première température de fin de refroidissement à une température de fin de refroidissement inférieure ou égale à 450°C à une vitesse de refroidissement de 1°C/s ou plus et inférieure à 5°C/s.
  2. Procédé de fabrication d'un acier ayant une résistance à la traction élevée selon la revendication 1, dans lequel l'acier, après le second refroidissement, est soumis à un traitement de trempe à une température de 450 à 650°C.
  3. Procédé de fabrication d'un acier ayant une résistance à la traction élevée selon la revendication 1 ou 2, dans lequel le premier refroidissement est effectué à une vitesse de refroidissement de 5 à 20°C/s.
EP09726619.1A 2008-03-31 2009-03-27 Acier ayant une résistance à la traction élevée et son procédé de fabrication Active EP2272994B1 (fr)

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Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5177310B2 (ja) * 2011-02-15 2013-04-03 Ｊｆｅスチール株式会社 溶接熱影響部の低温靭性に優れた高張力鋼板およびその製造方法
JP5630321B2 (ja) * 2011-02-24 2014-11-26 Ｊｆｅスチール株式会社 靭性に優れる高張力鋼板とその製造方法
JP5630322B2 (ja) * 2011-02-24 2014-11-26 Ｊｆｅスチール株式会社 靭性に優れる高張力鋼板とその製造方法
WO2012133872A1 (fr) * 2011-03-28 2012-10-04 Ｊｆｅスチール株式会社 Plaque d'acier présentant une excellente résistance à la fatigue dans le sens de l'épaisseur et son procédé de fabrication ainsi que joint soudé en angle mettant en oeuvre cette plaque d'acier
JP5906868B2 (ja) * 2011-03-28 2016-04-20 Ｊｆｅスチール株式会社 板厚方向の耐疲労特性に優れた厚鋼板およびその製造方法
JP5883257B2 (ja) * 2011-09-13 2016-03-09 株式会社神戸製鋼所 母材および溶接熱影響部の靭性に優れた鋼材、およびその製造方法
KR101608239B1 (ko) * 2011-12-14 2016-04-01 제이에프이 스틸 가부시키가이샤 대입열 용접용 강재
JP5867381B2 (ja) * 2011-12-22 2016-02-24 Ｊｆｅスチール株式会社 鋼板内の材質均一性に優れた大入熱溶接用高強度鋼板及びその製造方法
BR112014015780A8 (pt) * 2011-12-27 2017-07-04 Jfe Steel Corp chapa de aço grossa de alta resistência para construção tendo excelentes características de prevenção da difusão de fraturas frágeis e método para sua produção
JP5910219B2 (ja) * 2012-03-23 2016-04-27 Ｊｆｅスチール株式会社 鋼板内の材質均一性に優れた大入熱溶接用高強度鋼板及びその製造方法
JP5833964B2 (ja) * 2012-03-29 2015-12-16 株式会社神戸製鋼所 曲げ加工性、衝撃特性および引張特性に優れた鋼板およびその製造方法
CN104024461B (zh) * 2012-03-30 2016-04-06 新日铁住金株式会社 抗氢诱发裂纹性优良的高强度管道用钢管和其所使用的高强度管道用钢板、以及它们的制造方法
JP5958428B2 (ja) * 2012-07-30 2016-08-02 Ｊｆｅスチール株式会社 大入熱溶接用鋼板の製造方法
JP5846311B2 (ja) * 2012-09-06 2016-01-20 Ｊｆｅスチール株式会社 溶接熱影響部ｃｔｏｄ特性に優れた厚肉高張力鋼およびその製造方法
JP5732017B2 (ja) * 2012-10-03 2015-06-10 株式会社神戸製鋼所 歪時効前後の靭性変化が少ない厚鋼板
KR101435319B1 (ko) * 2013-02-27 2014-08-29 현대제철 주식회사 강판 제조 방법
EP2975148B1 (fr) * 2013-03-12 2019-02-27 JFE Steel Corporation Tôle épaisse en acier présentant d'excellentes propriétés ctod dans des joints soudés multicouches, et procédé de fabrication de tôle épaisse en acier
JP5950045B2 (ja) * 2013-12-12 2016-07-13 Ｊｆｅスチール株式会社 鋼板およびその製造方法
CN106133168B (zh) * 2014-03-31 2018-07-20 杰富意钢铁株式会社 高张力钢板及其制造方法
CN106133165B (zh) * 2014-03-31 2019-03-08 杰富意钢铁株式会社 焊接接头
WO2016009595A1 (fr) * 2014-07-15 2016-01-21 Ｊｆｅスチール株式会社 Procédé de fabrication d'une tôle d'acier pour soudage à apport de chaleur élevé
US10450627B2 (en) 2014-09-05 2019-10-22 Jfe Steel Corporation Thick steel plate having good multipass weld joint CTOD characteristics and method for manufacturing the same
KR101676143B1 (ko) * 2014-12-25 2016-11-15 주식회사 포스코 저온충격인성이 우수한 저항복비형 고강도 강재 및 그 제조방법
CN106048412B (zh) * 2016-06-29 2018-04-27 宝山钢铁股份有限公司 一种相变强化冷加工高强度钢、钢管及钢管的制造方法
JP6819830B2 (ja) * 2019-01-31 2021-01-27 Ｊｆｅスチール株式会社 突起付きｈ形鋼およびその製造方法
SG11202108242RA (en) * 2019-01-31 2021-08-30 Jfe Steel Corp H-beam having protrusions, and manufacturing method for same
CN113366138A (zh) * 2019-03-19 2021-09-07 杰富意钢铁株式会社 高锰钢铸片的制造方法、高锰钢钢片及高锰钢钢板的制造方法
KR102357082B1 (ko) 2019-12-20 2022-02-03 주식회사 포스코 용접 열영향부 인성이 우수한 고강도 강판 및 그 제조방법

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS601929B2 (ja) * 1980-10-30 1985-01-18 新日本製鐵株式会社 強靭鋼の製造法
JPS5877529A (ja) * 1981-10-31 1983-05-10 Nippon Steel Corp 厚肉高張力鋼の製造法
JPS60152626A (ja) 1984-01-20 1985-08-10 Kawasaki Steel Corp 溶接構造用高張力鋼のじん性安定化方法
JPS60184663A (ja) 1984-02-29 1985-09-20 Kawasaki Steel Corp 大入熱溶接用低温用高張力鋼
JPH0694569B2 (ja) * 1987-02-27 1994-11-24 新日本製鐵株式会社 溶接熱影響部の低温靭性が優れた鋼の製造法
JP3045856B2 (ja) 1991-11-13 2000-05-29 川崎製鉄株式会社 高靱性Ｃｕ含有高張力鋼の製造方法
JP3699657B2 (ja) * 2000-05-09 2005-09-28 新日本製鐵株式会社 溶接熱影響部のＣＴＯＤ特性に優れた４６０ＭＰａ以上の降伏強度を有する厚鋼板
JP2002235114A (ja) * 2001-02-05 2002-08-23 Kawasaki Steel Corp 大入熱溶接部靱性に優れた厚肉高張力鋼の製造方法
JP5145616B2 (ja) * 2001-04-19 2013-02-20 Ｊｆｅスチール株式会社 溶接熱影響部靭性の優れた低温用溶接構造用高張力鋼
JP3869747B2 (ja) * 2002-04-09 2007-01-17 新日本製鐵株式会社 変形性能に優れた高強度鋼板、高強度鋼管および製造方法
WO2004022807A1 (fr) * 2002-09-04 2004-03-18 Jfe Steel Corporation Acier pour soudures a fort apport thermique et son procede de production
JP4997805B2 (ja) * 2005-03-31 2012-08-08 Ｊｆｅスチール株式会社 高強度厚鋼板およびその製造方法、ならびに高強度鋼管
CN100513611C (zh) * 2005-03-31 2009-07-15 杰富意钢铁株式会社 高强度厚钢板及其制造方法、以及高强度钢管
EP1918398B1 (fr) * 2005-08-22 2012-10-31 Sumitomo Metal Industries Limited Tuyau d acier sans joint pour tuyau d oléoduc et procédé de fabrication idoine
JP4946092B2 (ja) * 2006-02-28 2012-06-06 Ｊｆｅスチール株式会社 高張力鋼およびその製造方法
JP4673784B2 (ja) * 2006-04-11 2011-04-20 新日本製鐵株式会社 優れた溶接熱影響部靭性を有する高強度鋼板およびその製造方法

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JP2009263777A (ja) 2009-11-12
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KR20100116701A (ko) 2010-11-01
CN102124133A (zh) 2011-07-13
EP2272994A1 (fr) 2011-01-12
KR20150094793A (ko) 2015-08-19
WO2009123292A1 (fr) 2009-10-08
EP2272994A4 (fr) 2014-01-08
KR20130035277A (ko) 2013-04-08

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