WO2012042676A1 - 高強度鋼板およびその製造方法 - Google Patents
高強度鋼板およびその製造方法 Download PDFInfo
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- WO2012042676A1 WO2012042676A1 PCT/JP2010/067611 JP2010067611W WO2012042676A1 WO 2012042676 A1 WO2012042676 A1 WO 2012042676A1 JP 2010067611 W JP2010067611 W JP 2010067611W WO 2012042676 A1 WO2012042676 A1 WO 2012042676A1
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- 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
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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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
- C21D1/76—Adjusting the composition of the atmosphere
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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
- 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
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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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/54—Furnaces for treating strips or wire
- C21D9/56—Continuous furnaces for strip or wire
- C21D9/561—Continuous furnaces for strip or wire with a controlled atmosphere or vacuum
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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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/12—Oxidising using elemental oxygen or ozone
- C23C8/14—Oxidising of ferrous surfaces
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4488—Cathodic paints
Definitions
- the present invention relates to a high-strength steel sheet having excellent chemical conversion properties and corrosion resistance after electrodeposition coating even when the Si content is large, and a method for producing the same.
- Si is oxidized even when annealing is performed in a reducing N 2 + H 2 gas atmosphere in which Fe does not oxidize (reducing Fe oxide), and Si oxide is formed on the outermost layer of the steel sheet. (SiO 2 ) is formed. Since this SiO 2 inhibits the formation reaction of the chemical conversion film during the chemical conversion treatment, a minute region (hereinafter also referred to as “ske”) where the chemical conversion film is not formed is formed, and the chemical conversion treatment performance is lowered.
- Patent Document 1 discloses a method of forming an iron coating layer of 20 to 1500 mg / m 2 on a steel sheet using an electroplating method.
- this method there is a problem that the cost is increased due to the additional steps required for the electroplating equipment.
- Patent Document 2 the Mn / Si ratio is defined, and in Patent Document 3, Ni is added to improve the phosphate processability.
- the effect depends on the Si content in the steel sheet, and it is considered that further improvement is necessary for the steel sheet having a high Si content.
- Patent Document 4 by setting the dew point during annealing to ⁇ 25 to 0 ° C., an internal oxide layer made of an Si-containing oxide is formed within a depth of 1 ⁇ m from the surface of the steel sheet substrate, and the steel sheet surface length is 10 ⁇ m. A method is disclosed in which the proportion of the Si-containing oxide is 80% or less.
- the area for controlling the dew point since the area for controlling the dew point is premised on the entire inside of the furnace, the controllability of the dew point is difficult and stable operation is difficult.
- Patent Document 5 describes a method in which a steel sheet temperature reaches 350 to 650 ° C. in an oxidizing atmosphere to form an oxide film on the steel sheet surface, and then heated and cooled to a recrystallization temperature in a reducing atmosphere.
- a steel sheet temperature reaches 350 to 650 ° C. in an oxidizing atmosphere to form an oxide film on the steel sheet surface, and then heated and cooled to a recrystallization temperature in a reducing atmosphere.
- this method there is a difference in the thickness of the oxide film formed on the surface of the steel sheet due to the oxidation method, and sufficient oxidation does not occur, or the oxide film becomes too thick, and in subsequent annealing in a reducing atmosphere. Oxide film may remain or peel off, and surface properties may deteriorate.
- a technique for oxidizing in the air is described, but oxidation in the air generates a thick oxide and subsequent reduction is difficult, or a reducing atmosphere with a high hydrogen concentration is required. There are problems such as.
- Patent Document 6 a cold-rolled steel sheet containing 0.1% or more of Si and / or 1.0% or more of Mn by mass%, the steel sheet surface in an iron oxidizing atmosphere at a steel sheet temperature of 400 ° C. or more. Describes a method in which an oxide film is formed, and then the oxide film on the surface of the steel sheet is reduced in an iron reducing atmosphere. Specifically, after oxidizing Fe on the steel sheet surface using a direct fire burner at 400 ° C. or higher and an air ratio of 0.93 or higher and 1.10 or lower, annealing is performed in an N 2 + H 2 gas atmosphere that reduces Fe oxide.
- Patent Document 6 does not specifically describe the heating temperature of an open flame burner, but when it contains a large amount of Si (approximately 0.6% or more), the amount of oxidation of Si that is easier to oxidize than Fe. As a result, the oxidation of Fe is suppressed, and the oxidation of Fe itself becomes too small. As a result, the formation of the surface Fe reduction layer after reduction may be insufficient, or SiO 2 may be present on the steel sheet surface after reduction, resulting in the occurrence of a conversion coating.
- JP-A-5-320952 JP 2004-323969 A Japanese Patent Application Laid-Open No. 6-10096 JP 2003-113441 A JP 55-145122 A JP 2006-45615 A
- the present invention has been made in view of such circumstances, and provides a high-strength steel sheet having excellent chemical conversion property and corrosion resistance after electrodeposition coating, and a method for producing the same, even when the content of Si is large. With the goal.
- the temperature in the annealing furnace By setting the temperature in the annealing furnace to a temperature range of 750 ° C. or higher and a dew point in the atmosphere of ⁇ 40 ° C. or lower, the oxygen potential at the interface between the steel sheet and the atmosphere is reduced, and an internal oxide is not formed. It is possible to suppress selective surface diffusion such as oxidation and oxidation (hereinafter referred to as surface concentration).
- Reference 1 (7th International Conference on Zinc and Zinc Alloy Coated Steel Sheet Galvetech 2007, Proceedings p404) converts the oxygen potential from the thermodynamic data of the oxidation reaction of Si and Mn to 800 ° C. and N 2 -5%. It has been shown that in the presence of H 2, oxidation cannot be prevented unless Si is less than ⁇ 80 ° C. and Mn is less than ⁇ 60 ° C. Therefore, when annealing a high-strength steel sheet containing Si and Mn, it has been considered that even if the hydrogen concentration is increased, surface concentration cannot be prevented unless the dew point is less than ⁇ 80 ° C. . Therefore, conventionally, no attempt has been made to perform chemical conversion treatment after annealing at a dew point of -40 to -70 ° C.
- FIG. 1 shows Si and Mn as shown below from thermodynamic data of oxidation reaction of Si and Mn shown in Reference 2 (Metal physics chemistry p72-73, published on May 20, 1996, published by the Japan Institute of Metals). It is the figure which calculated the relationship between oxidation-reduction equilibrium and a dew point, and showed it.
- the redox equilibrium of Si in a hydrogen-nitrogen atmosphere is expressed by the following equation.
- SiO 2 (solid) + 2H 2 (gas) Si + 2H 2 O (gas) (1)
- K of this reaction is as follows, assuming that the activity of Si is 1.
- K (square of H 2 O partial pressure) / (square of H 2 partial pressure) (2)
- the standard free energy ⁇ G (1) is as follows, where R is a gas constant and T is a temperature.
- ⁇ G (1) ⁇ RTlnK (3)
- the standard free energy ⁇ G (8) is as follows, where R is a gas constant and T is a temperature.
- the dew point for reducing Si and Mn to a reduced state becomes lower as the temperature decreases, and between room temperature and 800 ° C., the dew point is less than ⁇ 100 ° C. It is suggested that it is necessary, and it is strongly suggested that it would be impossible to realize an annealing environment that is heated to the annealing temperature while preventing the oxidation of Si and Mn industrially.
- the present invention is characterized in that when the steel sheet is annealed, the temperature in the annealing furnace: 750 ° C. or higher is set to a dew point in the atmosphere of ⁇ 40 ° C. or lower.
- the dew point of the annealing atmosphere of the steel sheet is ⁇ 30 ° C. or higher, in order to obtain a dew point of ⁇ 40 ° C. or lower, moisture in the annealing atmosphere must be removed, and the atmosphere of the entire annealing furnace is ⁇ 40 ° C. To do so, enormous equipment and operating costs are required.
- the dew point is set to ⁇ 40 ° C.
- predetermined characteristics can be sufficiently obtained by controlling only a limited region of 750 ° C. or higher.
- the temperature range of 600 ° C. or higher is controlled so that the dew point in the atmosphere is ⁇ 40 ° C. or lower and annealing and chemical conversion treatment are performed, better chemical conversion property can be obtained.
- a temperature range of 750 ° C. or higher or 600 ° C. or higher is set to a dew point in the atmosphere of ⁇ 45 ° C. or lower, further excellent chemical conversion property can be obtained.
- the high-strength steel plate obtained by the above method is Fe, Si, Mn, Al, P, and also B, Nb, Ti, Cr, Mo, Cu, Ni in the steel plate surface layer portion within 100 ⁇ m from the steel plate surface.
- the formation of one or more oxides selected from the above (excluding only Fe) is suppressed, and the total amount is suppressed to 0.060 g / m 2 or less per side. Thereby, it is excellent in chemical conversion property and the corrosion resistance after electrodeposition coating improves remarkably.
- the present invention is based on the above findings, and features are as follows.
- the steel sheet has a component composition in mass%, and B: 0.001 to 0.005%, Nb: 0.005 to 0.05%, Ti: 0.005 to 0.05%, One selected from Cr: 0.001 to 1.0%, Mo: 0.05 to 1.0%, Cu: 0.05 to 1.0%, Ni: 0.05 to 1.0%
- B 0.001 to 0.005%
- Nb 0.005 to 0.05%
- Ti 0.005 to 0.05%
- Mo 0.05 to 1.0%
- Cu 0.05 to 1.0%
- Ni 0.05 to 1.0%
- [4] Fe, Si, Mn, Al, P, B, Nb, Ti produced by the production method according to any one of [1] to [3] and formed on the steel sheet surface layer within 100 ⁇ m from the steel sheet surface.
- the high strength means that the tensile strength TS is 340 MPa or more.
- the unit of the content of each element of the steel component composition is “mass%”, and hereinafter, simply indicated by “%” unless otherwise specified.
- Such an effect is obtained by controlling the dew point in the atmosphere to be ⁇ 40 ° C. or lower in the temperature range of 750 ° C. or higher when annealing.
- Annealing furnace temperature By controlling the temperature range of 750 ° C. or higher so that the dew point in the atmosphere is ⁇ 40 ° C. or lower, the oxygen potential at the interface between the steel sheet and the atmosphere is lowered, and internal oxidation is not formed. Suppresses selective surface diffusion and surface concentration of Si, Mn, etc. And the favorable chemical conversion property and the corrosion resistance after electrodeposition coating without a scale and nonuniformity will be acquired.
- the reason why the temperature range for controlling the dew point is set to 750 ° C. or higher is as follows. In the temperature range of 750 ° C. or higher, surface enrichment and internal oxidation are likely to occur, causing problems such as scaling and unevenness, and deterioration of corrosion resistance. Therefore, it shall be 750 ° C or more which is a temperature range which the effect of the present invention expresses. Furthermore, when the temperature range for controlling the dew point is 600 ° C. or higher, surface concentration and internal oxidation can be more stably suppressed. There is no particular upper limit for the temperature range for dew point control to -40 ° C or lower. However, when the temperature exceeds 900 ° C., there is no problem in the effect of the present invention, but it is disadvantageous from the viewpoint of cost increase. Therefore, 900 degrees C or less is preferable.
- the reason for setting the dew point to ⁇ 40 ° C. or lower is as follows.
- the effect of suppressing the surface concentration is recognized at a dew point of ⁇ 40 ° C. or lower.
- the lower limit of the dew point is not particularly provided, but if it is less than -70 ° C, the effect is saturated and disadvantageous in terms of cost, so -70 ° C or higher is desirable.
- the steel component composition of the high-strength steel sheet that is the subject of the present invention will be described.
- C 0.01 to 0.18% C improves workability by forming martensite or the like as a steel structure. For that purpose, 0.01% or more is necessary. On the other hand, if it exceeds 0.18%, the elongation decreases, the material deteriorates, and the weldability deteriorates. Therefore, the C content is 0.01% or more and 0.18% or less.
- Si 0.4 to 2.0% Si is an element effective for strengthening steel and improving elongation to obtain a good material, and 0.4% or more is necessary to obtain the intended strength of the present invention. If Si is less than 0.4%, the strength within the scope of the present invention cannot be obtained, and there is no particular problem with chemical conversion treatment. On the other hand, when it exceeds 2.0%, the steel strengthening ability and the effect of improving elongation become saturated. Therefore, the Si amount is set to 0.4% or more and 2.0% or less.
- Mn 1.0 to 3.0% Mn is an element effective for increasing the strength of steel. In order to ensure mechanical properties and strength, it is necessary to contain 1.0% or more. On the other hand, if it exceeds 3.0%, it becomes difficult to ensure weldability and plating adhesion, and to ensure a balance between strength and ductility. Therefore, the Mn content is 1.0% or more and 3.0% or less.
- Al 0.001 to 1.0% Al is added for the purpose of deoxidizing molten steel, but if the content is less than 0.001%, the purpose is not achieved. The effect of deoxidation of molten steel is obtained at 0.001% or more. On the other hand, if it exceeds 1.0%, the cost increases. Furthermore, the surface concentration of Al increases and it becomes difficult to improve chemical conversion properties. Therefore, the Al content is 0.001% or more and 1.0% or less.
- P 0.005 to 0.060% or less
- P is an element inevitably contained, and in order to make it less than 0.005%, there is a concern about an increase in cost, so 0.005% or more
- P exceeds 0.060% the weldability deteriorates.
- the chemical conversion processability is greatly deteriorated, and even with the present invention, it is difficult to improve the chemical conversion processability. Therefore, the P content is 0.005% or more and 0.060% or less.
- S 0.01% S is one of the elements inevitably contained.
- the lower limit is not specified, but if it is contained in a large amount, the weldability and corrosion resistance deteriorate, so the content is made 0.01% or less.
- B 0.001 to 0.005%
- Nb 0.005 to 0.05%
- Ti 0.005 to 0.05%
- Cr 0.001
- B 0.001 to 0.005%
- B amount shall be 0.001% or more and 0.005% or less.
- Nb 0.005 to 0.05% If Nb is less than 0.005%, the effect of adjusting the strength is difficult to obtain. On the other hand, if it exceeds 0.05%, the cost increases. Therefore, when it contains, Nb amount shall be 0.005% or more and 0.05% or less.
- Ti 0.005 to 0.05% If Ti is less than 0.005%, the effect of adjusting the strength is difficult to obtain. On the other hand, if it exceeds 0.05%, chemical conversion processability is deteriorated. Therefore, when it contains, Ti amount shall be 0.005% or more and 0.05% or less.
- Cr 0.001 to 1.0%
- Cr 0.001 to 1.0%
- Mo 0.05 to 1.0% If Mo is less than 0.05%, the effect of adjusting the strength is difficult to obtain. On the other hand, if it exceeds 1.0%, cost increases. Therefore, when contained, the Mo content is 0.05% or more and 1.0% or less.
- Cu 0.05 to 1.0% If Cu is less than 0.05%, it is difficult to obtain the effect of promoting the formation of the residual ⁇ phase. On the other hand, if it exceeds 1.0%, cost increases. Therefore, when contained, the Cu content is 0.05% or more and 1.0% or less.
- Ni 0.05 to 1.0% If Ni is less than 0.05%, the effect of promoting the formation of residual ⁇ phase is difficult to obtain. On the other hand, if it exceeds 1.0%, cost increases. Therefore, when it contains, Ni amount shall be 0.05% or more and 1.0% or less.
- the balance other than the above is Fe and inevitable impurities.
- the manufacturing method of the high strength steel plate of the present invention and the reason for limitation will be described.
- steel having the above chemical components is hot-rolled, it is cold-rolled into a steel plate, and then annealed in a continuous annealing facility.
- the temperature range in the annealing furnace 750 ° C. or higher is set to the dew point in the atmosphere: ⁇ 40 ° C. or lower. This is the most important requirement in the present invention.
- the temperature range for controlling the dew point is 600 ° C. or higher, the surface concentration and internal oxidation can be more stably suppressed.
- annealing may be performed as it is without performing cold rolling.
- Hot rolling Usually, it can be performed on the conditions performed.
- the pickling treatment is preferable to perform a pickling treatment after hot pickling.
- the black scale formed on the surface in the pickling process is removed, and then cold-rolled.
- the pickling conditions are not particularly limited.
- Cold rolling is preferably performed at a rolling reduction of 40% to 80%. If the rolling reduction is less than 40%, the recrystallization temperature is lowered, and the mechanical characteristics are likely to deteriorate. On the other hand, if the rolling reduction exceeds 80%, the steel sheet is a high-strength steel plate, so that not only the rolling cost is increased, but also the surface concentration during annealing is increased, so that the chemical conversion property may be deteriorated.
- annealing furnace a heating process is performed in which the steel sheet is heated to a predetermined temperature in a preceding heating zone, and a soaking process is performed in which the temperature is maintained at a predetermined temperature for a predetermined time in a subsequent soaking zone.
- annealing and chemical conversion treatment are performed by controlling the temperature range in the annealing furnace: 750 ° C. or higher so that the dew point in the atmosphere is ⁇ 40 ° C. or lower. Since the normal dew point is higher than ⁇ 40 ° C., the dew point of ⁇ 40 ° C.
- the gas component in the annealing furnace consists of nitrogen, hydrogen and unavoidable impurities. Other gas components may be included as long as the effects of the present invention are not impaired. If the hydrogen concentration is less than 1 vol%, the activation effect due to the reduction cannot be obtained and the chemical conversion treatment performance deteriorates. The upper limit is not particularly specified, but if it exceeds 50 vol%, the cost increases and the effect is saturated. Therefore, the hydrogen concentration is preferably 1 vol% or more and 50 vol% or less. Furthermore, 5 vol% or more and 30 vol% or less are desirable. After cooling from a temperature range of 750 ° C.
- tempering is preferably performed at a temperature of 150 to 400 ° C. This is because the elongation tends to deteriorate when the temperature is less than 150 ° C., and the hardness tends to decrease when the temperature exceeds 400 ° C.
- the present invention good chemical conversion treatment can be ensured without carrying out electrolytic pickling, but a small amount of surface condensate inevitably generated during annealing is removed to ensure better chemical conversion treatment.
- the conditions of the electrolytic pickling are not particularly limited, but in order to efficiently remove the inevitably surface-enriched Si and Mn oxides formed after annealing, an alternating electrolysis with a current density of 1 A / dm 2 or more is used. It is desirable.
- the reason for alternating electrolysis is that the pickling effect is small when the steel plate is held at the cathode, and conversely, Fe that is eluted during electrolysis accumulates in the pickling solution while the steel plate is held at the anode. This is because if the Fe concentration increases and adheres to the surface of the steel sheet, problems such as dry dirt occur.
- the pickling solution used for the electrolytic pickling is not particularly limited, but nitric acid and hydrofluoric acid are not preferable because they are highly corrosive to equipment and require careful handling. Hydrochloric acid is not preferred because it may generate chlorine gas from the cathode. For this reason, use of sulfuric acid is preferable in consideration of corrosivity and environment.
- the sulfuric acid concentration is preferably 5% by mass or more and 20% by mass or less. If the sulfuric acid concentration is less than 5% by mass, the electrical conductivity will be low, so that the bath voltage during electrolysis will rise and the power load may become large. On the other hand, if it exceeds 20% by mass, the loss due to drag-out is large, which causes a cost problem.
- the temperature of the electrolytic solution is preferably 40 ° C. or higher and 70 ° C. or lower. Since the bath temperature rises due to heat generated by continuous electrolysis, it may be difficult to maintain the temperature below 40 ° C. Moreover, it is not preferable that temperature exceeds 70 degreeC from a durable viewpoint of the lining of an electrolytic cell. As described above, the high-strength steel sheet of the present invention is obtained.
- the steel plate surface has the characteristic in the structure of the steel plate surface as follows. Formation of one or more oxides selected from Fe, Si, Mn, Al, P, and B, Nb, Ti, Cr, Mo, Cu, and Ni in the steel sheet surface layer within 100 ⁇ m from the steel sheet surface Are suppressed to 0.060 g / m 2 or less per side in total. In a high-strength steel sheet in which a large amount of Si and Mn is added to the steel, in order to satisfy the corrosion resistance, it is required to minimize the internal oxidation of the steel sheet surface layer that may become a starting point of corrosion.
- the activity in the surface layer portion such as Si or Mn is reduced by lowering the oxygen potential in the annealing process in order to ensure chemical conversion treatment. And the external oxidation of these elements is suppressed and chemical conversion processability is improved as a result. Furthermore, internal oxidation formed in the surface layer portion is also suppressed, and the corrosion resistance is improved.
- Such an effect is obtained by providing at least one selected from Fe, Si, Mn, Al, P, and B, Nb, Ti, Cr, Mo, Cu, Ni on the steel sheet surface layer portion within 100 ⁇ m from the steel sheet surface.
- the hot-rolled steel sheet having the steel composition shown in Table 1 was pickled, and after removing the black scale, it was cold-rolled to obtain a cold-rolled steel sheet having a thickness of 1.0 mm. In addition, some did not carry out cold rolling, but prepared the hot-rolled steel plate (thickness 2.0 mm) after removing the black scale.
- the cold-rolled steel plate and hot-rolled steel plate obtained above were charged into a continuous annealing facility.
- the annealing facility as shown in Table 2, the dew point in the temperature range of 750 ° C. or higher in the annealing furnace was controlled and passed to perform annealing, and then tempered between 300 ° C. and 140 s after water quenching.
- electrolytic pickling was performed by alternating electrolysis in which the test material was in the order of anode and cathode for 3 seconds each in the order of the current density conditions shown in Table 2 in a sulfuric acid aqueous solution of 5% by mass at 40 ° C. Obtained.
- region which controlled the said dew point was based on -35 degreeC.
- the atmospheric gas components were nitrogen gas, hydrogen gas, and inevitable impurity gas, and the dew point was controlled by dehumidifying or absorbing and removing moisture in the atmosphere.
- the hydrogen concentration in the atmosphere was basically 10 vol%.
- TS and El were measured with respect to the obtained test material in accordance with JIS Z 2241 Metal Material Tensile Test Method.
- the chemical conversion property and corrosion resistance were investigated with respect to the obtained test material.
- the amount of oxide (internal oxidation amount) present in the steel sheet surface layer up to 100 ⁇ m just below the steel sheet surface layer was measured. The measurement method and evaluation criteria are shown below.
- Corrosion resistance after electrodeposition coating A test piece having a size of 70 mm x 150 mm was cut out from the test material subjected to chemical conversion treatment obtained by the above method, and cation electrodeposition was performed using PN-150G (registered trademark) manufactured by Nippon Paint Co., Ltd. Coating (baking conditions: 170 ° C. ⁇ 20 minutes, film thickness 25 ⁇ m) was performed. Thereafter, the end surface and the side not evaluated were sealed with Al tape, and a cross cut (cross angle 60 °) reaching the ground iron with a cutter knife was used as a test material.
- PN-150G registered trademark
- Coating (baking conditions: 170 ° C. ⁇ 20 minutes, film thickness 25 ⁇ m) was performed. Thereafter, the end surface and the side not evaluated were sealed with Al tape, and a cross cut (cross angle 60 °) reaching the ground iron with a cutter knife was used as a test material.
- a JIS No. 5 tensile test piece is sampled from the sample in a 90 ° direction with respect to the rolling direction, and a tensile test is performed at a constant crosshead speed of 10 mm / min in accordance with the provisions of JIS Z 2241.
- strength (TS / MPa) and elongation (El%) were measured, and TS was less than 650 MPa, TS ⁇ El ⁇ 22000 was judged good, and TS ⁇ El ⁇ 22000 was judged poor.
- TS was 650 MPa or more and 900 MPa
- TS ⁇ El ⁇ 20000 was judged good
- TS ⁇ El ⁇ 20000 was judged poor.
- TS was 900 MPa or more
- TS ⁇ El ⁇ 18000 was judged good
- TS ⁇ El ⁇ 18000 was judged poor.
- the internal oxidation amount in the region up to 100 ⁇ m of the steel sheet surface layer is measured by “impulse furnace melting-infrared absorption method”.
- the surface layer portions on both surfaces of the high-strength steel plate after continuous annealing are polished by 100 ⁇ m or more in the steel.
- Measure the oxygen concentration set the measured value as the amount of oxygen OH contained in the material, measure the oxygen concentration in the steel in the entire thickness direction of the high-strength steel sheet after continuous annealing, and measure the measured value internally.
- the subsequent oxygen amount OI was used.
- single-sided unit area i.e. 1 m 2
- the high-strength steel sheet produced by the method of the present invention is a high-strength steel sheet containing a large amount of easily oxidizable elements such as Si and Mn, but the chemical conversion treatment property, electrodeposition It can be seen that it has excellent corrosion resistance and workability after painting. On the other hand, in the comparative example, any one or more of chemical conversion property, corrosion resistance after electrodeposition coating, and workability is inferior.
- the high-strength steel sheet of the present invention is excellent in chemical conversion property, corrosion resistance, and workability, and can be used as a surface-treated steel sheet for reducing the weight and strength of an automobile body.
- the steel sheet can be applied in a wide range of fields such as home appliances and building materials as a surface-treated steel sheet provided with rust prevention.
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Abstract
Description
一般に自動車用鋼板は塗装して使用されており、その塗装の前処理として、リン酸塩処理と呼ばれる化成処理が施される。鋼板の化成処理は塗装後の耐食性を確保するための重要な処理の一つである。
Siの水素−窒素雰囲気での酸化還元平衡は以下の式で表される。
SiO2(solid)+2H2(gas)=Si+2H2O(gas) (1)
この反応の平衡定数Kは、Siの活量を1として、下記のようになる。
K=(H2O分圧の2乗)/(H2分圧の2乗) (2)
また、標準自由エネルギーΔG(1)は、R:気体定数、T:温度として、以下となる。
ΔG(1)=−RTlnK (3)
H2(gas)+1/2O2(gas) = H2O(gas) (4)
Si(solid)+O2(gas)=SiO2(solid) (5)
の各反応式の標準自由エネルギーΔG(4)、ΔG(5)はTの関数として、
ΔG(4)=−246000+54.8T
ΔG(5)=−902100+174T
と表される。
ΔG(1)=410100−64.4T (6)
となり、(3)=(6)より
K=exp{(1/R)(64.4−410100/T)} (7)
となる。
H2O分圧が求まり、これを露点に換算すれば、図1が得られる。
Mnについても同様に、Mnの水素−窒素雰囲気での酸化還元平衡は以下の式で表される。
MnO(solid)+H2(gas)=Mn+H2O(gas) (8)
この反応の平衡定数Kは下記のようになる。
K=(H2O分圧)/(H2分圧) (9)
ΔG(8)=−RTlnK (10)
ここで、
H2(gas)+1/2O2(gas)=H2O(gas) (11)
Mn(solid)+1/2O2(gas)=MnO(solid) (12)
の各反応式の標準自由エネルギーΔG(11)、ΔG(12)はTの関数として、
ΔG(11)=−246000+54.8T
ΔG(12)=−384700+72.8T
ΔG(8)=138700−18.0T (13)
となり、(10)=(13)より
K=exp{(1/R)(18.0−138700/T)} (14)
となる。
さらに、(9)=(14)、H2分圧=0.1気圧(10%の場合)より、各温度TでのH2O分圧が求まり、これを露点に換算すれば、図1が得られる。
通常、鋼板の焼鈍雰囲気の露点は−30℃以上であるため、−40℃以下の露点とするためには焼鈍雰囲気中の水分を除去しなければならず、焼鈍炉全体の雰囲気を−40℃とするためには莫大な設備費と操業コストを要する。しかし、本発明では焼鈍炉内温度:750℃以上の限定された領域のみ、露点を−40℃以下とするので、設備費や操業コストを低減できるという特徴がある。さらに、750℃以上の限定された領域のみの制御で充分に所定の特性が得られる。
このように限定された領域のみの雰囲気中の露点を制御することにより、内部酸化物を形成させず、表面濃化を極力抑制し、スケやムラのない、化成処理性および電着塗装後の耐食性に優れる高強度鋼板が得られることになる。なお、化成処理性に優れるとは、化成処理後のスケ、ムラのない外観を有することを言う。
焼鈍炉内温度:750℃以上の温度域を雰囲気中の露点:−40℃以下とすることを特徴とする高強度鋼板の製造方法。
先ず、本発明で最も重要な要件である、鋼板表面の構造を決定する焼鈍雰囲気条件について説明する。
鋼中に多量のSiおよびMnが添加された高強度鋼板において、耐食性を満足させるためには、腐食の起点となる可能性がある鋼板表層の内部酸化を極力少なくすることが求められる。
−40℃以下に露点制御する温度域の上限は特に設けない。しかし、900℃超えの場合、本発明の効果に何ら問題はないが、コスト増大の観点から不利となる。したがって、900℃以下が好ましい。
次いで、本発明の対象とする高強度鋼板の鋼成分組成について説明する。
Cは、鋼組織としてマルテンサイトなどを形成させることで加工性を向上させる。そのためには0.01%以上必要である。一方、0.18%を超えると伸びが低下し材質が劣化し、さらに、溶接性が劣化する。したがって、C量は0.01%以上0.18%以下とする。
Siは鋼を強化して伸びを向上させ良好な材質を得るのに有効な元素であり、本発明の目的とする強度を得るためには0.4%以上が必要である。Siが0.4%未満では本発明の適用範囲とする強度が得られず、化成処理性についても特に問題とならない。一方、2.0%を超えると鋼の強化能や伸び向上効果が飽和してくる。したがって、Si量は0.4%以上2.0%以下とする。
Mnは鋼の高強度化に有効な元素である。機械特性や強度を確保するためは1.0%以上含有させることが必要である。一方、3.0%を超えると溶接性やめっき密着性の確保、強度と延性のバランスの確保が困難になる。したがって、Mn量は1.0%以上3.0%以下とする。
Alは溶鋼の脱酸を目的に添加されるが、その含有量が0.001%未満の場合、その目的が達成されない。溶鋼の脱酸の効果は0.001%以上で得られる。一方、1.0%を超えるとコストアップになる。さらに、Alの表面濃化が多くなり、化成処理性の改善が困難になってくる。したがって、Al量は0.001%以上1.0%以下とする。
Pは不可避的に含有される元素のひとつであり、0.005%未満にするためには、コストの増大が懸念されるため、0.005%以上とする。一方、Pが0.060%を超えると溶接性が劣化する。さらに、化成処理性の劣化が激しくなり、本発明をもってしても化成処理性を向上させることが困難となる。したがって、P量は0.005%以上0.060%以下とする。
Sは不可避的に含有される元素のひとつである。下限は規定しないが、多量に含有されると溶接性および耐食性が劣化するため0.01%以下とする。
Bは0.001%未満では焼き入れ促進効果が得られにくい。一方、0.005%超えで含有すると化成処理性が劣化する。よって、含有する場合、B量は0.001%以上0.005%以下とする。
Nbは0.005%未満では強度調整の効果が得られにくい。一方、0.05%超えではコストアップを招く。よって、含有する場合、Nb量は0.005%以上0.05%以下とする。
Tiは0.005%未満では強度調整の効果が得られにくい。一方、0.05%超えでは化成処理性の劣化を招く。よって、含有する場合、Ti量は0.005%以上0.05%以下とする。
Crは0.001%未満では焼き入れ性効果が得られにくい。一方、1.0%超えではCrが表面濃化するため、溶接性が劣化する。よって、含有する場合、Cr量は0.001%以上1.0%以下とする。
Moは0.05%未満では強度調整の効果が得られにくい。一方、1.0%超えではコストアップを招く。よって、含有する場合、Mo量は0.05%以上1.0%以下とする。
Cuは0.05%未満では残留γ相形成促進効果が得られにくい。一方、1.0%超えではコストアップを招く。よって、含有する場合、Cu量は0.05%以上1.0%以下とする。
Niは0.05%未満では残留γ相形成促進効果が得られにくい。一方、1.0%超えではコストアップを招く。よって、含有する場合、Ni量は0.05%以上1.0%以下とする。
次に、本発明の高強度鋼板の製造方法とその限定理由について説明する。
例えば、上記化学成分を有する鋼を熱間圧延した後、冷間圧延し鋼板とし、次いで、連続焼鈍設備において焼鈍を行う。なお、焼鈍時、本発明においては、焼鈍炉内温度:750℃以上の温度域を雰囲気中の露点:−40℃以下とする。これは本発明において、最も重要な要件である。更に、露点を制御する温度域を600℃以上とすると前記表面濃化や内部酸化はより安定して抑制できる。また、上記において、熱間圧延終了後、冷間圧延を施さずに、そのまま焼鈍を行う場合もある。
通常、行われる条件にて行うことができる。
熱間圧延後は酸洗処理を行うのが好ましい。酸洗工程で表面に生成した黒皮スケールを除去し、しかる後冷間圧延する。なお、酸洗条件は特に限定しない。
40%以上80%以下の圧下率で行うことが好ましい。圧下率が40%未満では再結晶温度が低温化するため、機械特性が劣化しやすい。一方、圧下率が80%超えでは高強度鋼板であるため、圧延コストがアップするだけでなく、焼鈍時の表面濃化が増加するため、化成処理性が劣化する場合がある。
焼鈍炉では、前段の加熱帯で鋼板を所定温度まで加熱する加熱工程を行い、後段の均熱帯で所定温度に所定時間保持する均熱工程を行う。
そして、上述したように、焼鈍炉内温度:750℃以上の温度域を雰囲気中の露点:−40℃以下となるように制御して焼鈍、化成処理を行う。通常の露点は、−40℃より高いため、炉内の水分を除湿装置や吸収剤で吸収除去することにより−40℃以下の露点とする。
焼鈍炉内の気体成分は、窒素、水素及び不可避的不純物からなる。本発明効果を損するものでなければ他の気体成分を含有してもよい。なお、水素濃度が1vol%未満では還元による活性化効果が得られず化成処理性が劣化する。上限は特に規定しないが、50vol%超えではコストアップし、かつ効果が飽和する。よって、水素濃度は1vol%以上50vol%以下が好ましい。更には、5vol%以上30vol%以下が望ましい。
750℃以上の温度域から冷却後、必要に応じて焼入れ、焼き戻しを行っても良い。この条件は特に限定しないが、焼き戻しは150~400℃の温度で行うのが望ましい。150℃未満では伸びが劣化傾向にあり、400℃超えでは硬度が低下する傾向にあるためである。
電解酸洗の条件は特に限定しないが、焼鈍後に形成された不可避的に表面濃化したSiやMnの酸化物を効率的に除去するため、電流密度が1A/dm2以上の交番電解とすることが望ましい。交番電解とする理由は、鋼板を陰極に保持したままでは酸洗効果が小さく、逆に鋼板を陽極に保持したままでは電解時に溶出するFeが酸洗液中に蓄積し、酸洗液中のFe濃度が増大してしまい、鋼板表面に付着すると乾き汚れ等の問題が発生してしまうためである。
以上により、本発明の高強度鋼板が得られる。
鋼板表面から100μm以内の鋼板表層部では、Fe、Si、Mn、Al、P、さらには、B、Nb、Ti、Cr、Mo、Cu、Niのうちから選ばれる1種以上の酸化物の形成が合計で片面あたり0.060g/m2以下に抑制される。
鋼中に多量のSi及びMnが添加された高強度鋼板において、耐食性を満足させるためには、腐食の起点になる可能性がある鋼板表層の内部酸化を極力少なくすることが求められる。
さらに、表層部に形成する内部酸化も抑制され、耐食性が改善することになる。このような効果は、鋼板表面から100μm以内の鋼板表層部に、Fe、Si、Mn、Al、P、さらには、B、Nb、Ti、Cr、Mo、Cu、Niのうちから選ばれる少なくとも1種以上の酸化物の形成量を合計で0.060g/m2以下に抑制することで認められる。酸化物形成量の合計(以下、内部酸化量と称す)が0.060g/m2超えでは、耐食性が劣化する。また、内部酸化量を0.0001g/m2未満に抑制しても、耐食性向上効果は飽和するため、内部酸化量の下限は0.0001g/m2以上が好ましい。
表1に示す鋼組成からなる熱延鋼板を酸洗し、黒皮スケールを除去した後、冷間圧延し、厚さ1.0mmの冷延鋼板を得た。なお、一部は冷間圧延を実施せず、黒皮スケール除去後の熱延鋼板(厚さ2.0mm)ままのものも用意した。
得られた供試材に対してJIS Z 2241 金属材料引張試験方法 に従い、TS、Elを測定した。また、得られた供試材に対して、化成処理性及び耐食性を調査した。鋼板表層直下の100μmまので鋼板表層部に存在する酸化物の量(内部酸化量)を測定した。測定方法および評価基準を下記に示す。
化成処理性の評価方法を以下に記載する。
化成処理液は日本パーカライジング(株)製の化成処理液(パルボンドL3080(登録商標))を用い、下記方法で化成処理を施した。
日本パーカライジング(株)製の脱脂液ファインクリーナー(登録商標)で脱脂したのち、水洗し、次に日本パーカライジング(株)製の表面調整液プレパレンZ(登録商標)で30s表面調整を行い、43℃の化成処理液(パルボンドL3080)に120s浸漬した後、水洗し、温風乾燥した。
○:10%以下
×:10%超
上記の方法で得られた化成処理を施した供試材より寸法70mm×150mmの試験片を切り出し、日本ペイント(株)製のPN−150G(登録商標)でカチオン電着塗装(焼付け条件:170℃×20分、膜厚25μm)を行った。その後、端部と評価しない側の面をAlテープでシールし、カッターナイフにて地鉄に達するクロスカット(クロス角度60°)を入れ、供試材とした。
○:剥離幅が片側2.5mm未満
×:剥離幅が片側2.5mm以上
加工性は、試料から圧延方向に対して90°方向にJIS 5号引張試験片を採取し、JIS Z 2241の規定に準拠してクロスヘッド速度10mm/min一定で引張試験を行い、引張り強度(TS/MPa)と伸び(El%)を測定し、TSが650MPa未満の場合は、TS×El≧22000のものを良好、TS×El<22000のものを不良とした。TSが650MPa以上900MPaの場合は、TS×El≧20000のものを良好、TS×El<20000のものを不良とした。TSが900MPa以上の場合は、TS×El≧18000のものを良好、TS×El<18000のものを不良とした。
内部酸化量は、「インパルス炉溶融−赤外線吸収法」により測定する。ただし、素材(すなわち焼鈍を施す前の高強度鋼板)に含まれる酸素量を差し引く必要があるので、本発明では、連続焼鈍後の高強度鋼板の両面の表層部を100μm以上研磨して鋼中酸素濃度を測定し、その測定値を素材に含まれる酸素量OHとし、また、連続焼鈍後の高強度鋼板の板厚方向全体での鋼中酸素濃度を測定して、その測定値を内部酸化後の酸素量OIとした。このようにして得られた高強度鋼板の内部酸化後の酸素量OIと、素材に含まれる酸素量OHとを用いて、OIとOHの差(=OI−OH)を算出し、さらに片面単位面積(すなわち1m2)当たりの量に換算した値(g/m2)を内部酸化量とした。
以上により得られた結果を製造条件と併せて表2に示す。
Claims (4)
- 質量%で、C:0.01~0.18%、Si:0.4~2.0%、Mn:1.0~3.0%、Al:0.001~1.0%、P:0.005~0.060%、S≦0.01%を含有し、残部がFeおよび不可避的不純物からなる鋼板に、連続焼鈍を施す際に、
焼鈍炉内温度:750℃以上の温度域を雰囲気中の露点:−40℃以下とすることを特徴とする高強度鋼板の製造方法。 - 前記鋼板は、成分組成として、質量%で、さらに、B:0.001~0.005%、Nb:0.005~0.05%、Ti:0.005~0.05%、Cr:0.001~1.0%、Mo:0.05~1.0%、Cu:0.05~1.0%、Ni:0.05~1.0%の中から選ばれる1種以上の元素を含有することを特徴とする請求項1に記載の高強度鋼板の製造方法。
- 前記連続焼鈍を行った後、硫酸を含む水溶液中で電解酸洗を行うことを特徴とする請求項1または2に記載の高強度鋼板の製造方法。
- 請求項1~3に記載のいずれかの製造方法により製造され、鋼板表面から100μm以内の鋼板表層部に生成したFe、Si、Mn、Al、P、B、Nb、Ti、Cr、Mo、Cu、Niのうちから選ばれる1種以上の酸化物が、片面あたり0.060g/m2以下であることを特徴とする高強度鋼板。
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020137008044A KR20130049821A (ko) | 2010-09-30 | 2010-09-30 | 고강도 강판 및 그 제조 방법 |
PCT/JP2010/067611 WO2012042676A1 (ja) | 2010-09-30 | 2010-09-30 | 高強度鋼板およびその製造方法 |
BR112013007154A BR112013007154A2 (pt) | 2010-09-30 | 2010-09-30 | folha de aço de alta resistência e método para fabricação da mesma |
KR1020157030335A KR101692179B1 (ko) | 2010-09-30 | 2010-09-30 | 고강도 강판 및 그 제조 방법 |
US13/822,832 US9534270B2 (en) | 2010-09-30 | 2010-09-30 | High strength steel sheet and method for manufacturing the same |
CN2010800693359A CN103140597A (zh) | 2010-09-30 | 2010-09-30 | 高强度钢板及其制造方法 |
EP10857889.9A EP2623630B1 (en) | 2010-09-30 | 2010-09-30 | Method for producing high-strength steel sheet |
CA2810989A CA2810989C (en) | 2010-09-30 | 2010-09-30 | High strength steel sheet and method for manufacturing the same |
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EP (1) | EP2623630B1 (ja) |
KR (2) | KR101692179B1 (ja) |
CN (1) | CN103140597A (ja) |
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Cited By (3)
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US9534270B2 (en) | 2010-09-30 | 2017-01-03 | Jfe Steel Corporation | High strength steel sheet and method for manufacturing the same |
US9598743B2 (en) | 2010-09-29 | 2017-03-21 | Jfe Steel Corporation | High strength steel sheet and method for manufacturing the same |
JP2019084546A (ja) * | 2017-11-02 | 2019-06-06 | 新日鐵住金株式会社 | コイル状鋼板の冷却方法 |
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JP5962541B2 (ja) * | 2012-07-23 | 2016-08-03 | Jfeスチール株式会社 | 高強度鋼板の製造方法 |
DE102012024616A1 (de) * | 2012-12-17 | 2014-06-18 | GM Global Technology Operations LLC (n. d. Gesetzen des Staates Delaware) | Stahlblech und Formteil daraus |
JP5794284B2 (ja) * | 2013-11-22 | 2015-10-14 | Jfeスチール株式会社 | 高強度鋼板の製造方法 |
WO2019092467A1 (en) * | 2017-11-08 | 2019-05-16 | Arcelormittal | A galvannealed steel sheet |
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2010
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- 2010-09-30 EP EP10857889.9A patent/EP2623630B1/en active Active
- 2010-09-30 CN CN2010800693359A patent/CN103140597A/zh active Pending
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US9598743B2 (en) | 2010-09-29 | 2017-03-21 | Jfe Steel Corporation | High strength steel sheet and method for manufacturing the same |
US9534270B2 (en) | 2010-09-30 | 2017-01-03 | Jfe Steel Corporation | High strength steel sheet and method for manufacturing the same |
JP2019084546A (ja) * | 2017-11-02 | 2019-06-06 | 新日鐵住金株式会社 | コイル状鋼板の冷却方法 |
Also Published As
Publication number | Publication date |
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CA2810989C (en) | 2017-02-07 |
KR20150124456A (ko) | 2015-11-05 |
CA2810989A1 (en) | 2012-04-05 |
KR20130049821A (ko) | 2013-05-14 |
US20130306203A1 (en) | 2013-11-21 |
US9534270B2 (en) | 2017-01-03 |
KR101692179B1 (ko) | 2017-01-02 |
EP2623630A4 (en) | 2016-11-23 |
BR112013007154A2 (pt) | 2016-06-14 |
CN103140597A (zh) | 2013-06-05 |
EP2623630B1 (en) | 2020-07-01 |
EP2623630A1 (en) | 2013-08-07 |
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