WO2019189842A1 - 高強度亜鉛めっき鋼板、高強度部材およびそれらの製造方法 - Google Patents
高強度亜鉛めっき鋼板、高強度部材およびそれらの製造方法 Download PDFInfo
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- WO2019189842A1 WO2019189842A1 PCT/JP2019/014221 JP2019014221W WO2019189842A1 WO 2019189842 A1 WO2019189842 A1 WO 2019189842A1 JP 2019014221 W JP2019014221 W JP 2019014221W WO 2019189842 A1 WO2019189842 A1 WO 2019189842A1
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- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/261—After-treatment in a gas atmosphere, e.g. inert or reducing atmosphere
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/002—Bainite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
Definitions
- the present invention relates to a high-strength galvanized steel sheet, a high-strength member, and a method for producing the same, which are excellent in elongation (El) and hydrogen embrittlement resistance, which are easily deteriorated when the strength is increased, and are suitable for building materials, automobile frameworks and collision-resistant parts.
- Patent Document 1 discloses a method for providing a steel sheet having a tensile strength of 980 MPa or more and an excellent balance between strength and ductility.
- Patent Document 2 discloses a high-strength molten zinc having a plating appearance, corrosion resistance, plating peeling resistance during high processing, and workability during high processing, using a high-strength steel plate containing Si and Mn as a base material. A plated steel sheet and a method for manufacturing the same are disclosed.
- Patent Document 3 discloses a method for producing a high-strength plated steel sheet having good delayed fracture resistance.
- Patent Documents 4, 5 and 6 as steel sheets utilizing residual austenite having improved workability and hydrogen embrittlement resistance, bainitic ferrite and martensite are used as a parent phase, and residual austenite is included.
- a steel sheet is disclosed which has improved hydrogen embrittlement resistance by appropriately controlling the area ratio and dispersion form of retained austenite. Focusing on bainitic ferrite and retained austenite, which have very high hydrogen trapping capacity and hydrogen storage capacity, the form of retained austenite is in the form of fine laths on the order of submicrons, in particular, in order to fully exhibit the action of retained austenite.
- Patent Document 7 discloses a high-strength steel sheet excellent in hydrogen embrittlement at a welded portion of a steel sheet having a base material strength (TS) of about 870 MPa and a manufacturing method thereof.
- TS base material strength
- Patent Document 7 hydrogen embrittlement is improved by dispersing an oxide in steel.
- JP 2013-213232 A JP2015-151607A JP 2011-111671 A JP 2007-197819 A JP 2006-207018 A JP 2011-190474 A JP 2007-231373 A
- so-called DP steel and TRIP steel which are excellent in ductility, have low yield strength (YS) with respect to tensile strength (TS), that is, yield ratio (YR) is low.
- TS tensile strength
- YR yield ratio
- the “thin steel plate” is a steel plate having a thickness of 3.0 mm or less.
- Patent Document 1 the addition of Si that reduces plating adhesion is suppressed, but when the Mn content exceeds 2.0%, a Mn-based oxide tends to be formed on the surface of the steel sheet, which generally impairs the plateability. .
- the conditions for forming the plating layer are not particularly limited, and generally used conditions are adopted, and the plating properties are inferior. Furthermore, hydrogen embrittlement resistance is not improved.
- Patent Document 3 although the delayed fracture resistance after processing is improved, the hydrogen concentration during annealing is also high, and hydrogen remains in the base metal itself, resulting in poor hydrogen embrittlement resistance.
- Patent Documents 4 to 7 make improvements related to hydrogen embrittlement resistance. These are caused by hydrogen generated from the corrosive environment or atmosphere in the operating environment, and the hydrogen resistance of the material after manufacturing and before and during processing. It did not consider brittleness. In general, when zinc or nickel plating is applied, hydrogen does not easily release or penetrate from the material, so hydrogen that has entered the steel sheet during manufacturing tends to remain in the steel, and the material is prone to hydrogen embrittlement. Become. In Patent Document 7, the upper limit of the in-furnace hydrogen concentration of the continuous plating line is 60%, and a large amount of hydrogen is taken into the steel when annealed to a high temperature of Ac3 point or higher. Therefore, it is not possible to produce an ultrahigh strength steel sheet having excellent hydrogen embrittlement resistance with TS ⁇ 1100 MPa by the method of Patent Document 7.
- the present invention is a high-strength galvanized steel sheet with high yield strength that is excellent in plating appearance and hydrogen brittleness resistance of the material, and has a high yield ratio suitable for collision materials of building materials and automobiles,
- An object of the present invention is to provide a high-strength member and a manufacturing method thereof.
- the present inventors have used various steel sheets to have a resistance spot welded nugget as plating ability and hydrogen embrittlement resistance while having good mechanical properties in addition to good appearance.
- the study was carried out in order to achieve both crack crack overcoming.
- the optimal balance between the formation of the steel structure and mechanical properties is achieved through appropriate adjustment of the manufacturing conditions, and the amount of hydrogen in the steel is controlled to solve the above problems. It came to do.
- the present invention provides the following.
- a galvanized layer on the steel plate The amount of diffusible hydrogen in the steel is less than 0.20 mass ppm, The tensile strength is 1100 MPa or more, The relationship between the tensile strength TS (MPa), the elongation El (%) and the sheet thickness t (mm) satisfies the following formula (1): A high-strength galvanized steel sheet with a yield ratio YR of 67% or more.
- the component composition is further in mass%, Total of one or more of Ti, Nb, V and Zr: 0.005% or more and 0.10% or less, A total of one or more of Mo, Cr, Cu and Ni: 0.005% or more and 0.5% or less, and B: containing at least one of 0.0003% or more and 0.005% or less [1]
- the component composition is further in mass%, The high-strength galvanized steel sheet according to [1] or [2], which contains at least one of Sb: 0.001% to 0.1% and Sn: 0.001% to 0.1%.
- [4] The high-strength galvanized steel sheet according to any one of [1] to [3], wherein the component composition further contains, by mass%, Ca: 0.0010% or less.
- a cold-rolled steel sheet having the composition according to any one of [1] to [4] is subjected to an annealing furnace temperature T1: (A) in an annealing furnace atmosphere having a hydrogen concentration of 1 vol% or more and 13 vol% or less.
- the plated steel sheet after the plating step is heated to a temperature T2 (° C.) of 70 ° C. or higher and 450 ° C. or lower in a furnace atmosphere having a hydrogen concentration of 10 vol% or lower and a dew point of 50 ° C.
- a plated steel sheet, a high-strength member, and a manufacturing method thereof can be provided.
- the high-strength galvanized steel sheet of the present invention includes a steel sheet and a galvanized layer formed on the steel sheet. Below, it demonstrates in order of a steel plate and a zinc plating layer.
- the high strength as used in the field of this invention means that tensile strength is 1100 Mpa or more.
- excellent strength-ductility balance as used in the present invention means that the relationship between the tensile strength TS (MPa), the elongation El (%), and the sheet thickness t (mm) satisfies the following formula (1).
- the component composition of the steel sheet is as follows. In the following description, “%”, which is a unit of component content, means “mass%”.
- C 0.10% or more and 0.30% or less C is an element effective for increasing the strength of a steel sheet, and contributes to increasing the strength by forming martensite, which is one of the hard phases of the steel structure.
- the C content is 0.10% or more, preferably 0.11% or more, more preferably 0.12% or more.
- the C content exceeds 0.30%, the spot weldability is remarkably deteriorated in the present invention, and at the same time, the steel sheet becomes hard due to the increase in martensite strength and the formability such as ductility tends to be lowered. Therefore, the C content is 0.30% or less.
- the C content is preferably 0.28% or less, more preferably 0.25% or less.
- Si 1.0% or more and 2.8% or less Si is an element that contributes to strengthening by solid solution strengthening, and suppresses the formation of carbides and effectively acts on the formation of retained austenite.
- the Si content is 1.0% or more, preferably 1.2% or more.
- Si easily forms Si-based oxides on the steel sheet surface, which may cause unplating, and if excessively contained, a scale is remarkably formed at the time of hot rolling, and a scale trace is attached to the steel sheet surface. Surface properties may be deteriorated. Moreover, pickling property may fall. From these viewpoints, the Si content is set to 2.8% or less.
- Mn 2.0% or more and 3.5% or less Mn is effective as an element that contributes to high strength by solid solution strengthening and martensite formation.
- the Mn content needs to be 2.0% or more, preferably 2.1% or more, more preferably 2.2% or more.
- the Mn content exceeds 3.5%, spot welded portion cracking is caused, and the steel structure is likely to be uneven due to segregation of Mn and the like, resulting in a decrease in workability.
- Mn content exceeds 3.5%, Mn tends to concentrate on the steel sheet surface as an oxide or composite oxide, which may cause non-plating. Therefore, the Mn content is 3.5% or less.
- the Mn content is preferably 3.3% or less, more preferably 3.0% or less.
- P 0.010% or less
- P is an element that is inevitably contained, and is an effective element that contributes to increasing the strength of the steel sheet by solid solution strengthening.
- the content exceeds 0.010%, workability such as weldability and stretch flangeability is deteriorated and segregates at the grain boundaries to promote grain boundary embrittlement. Therefore, the P content is 0.010% or less.
- the P content is preferably 0.008% or less, more preferably 0.007% or less.
- the lower limit of the P content is not particularly defined, but if the P content is less than 0.001%, the production efficiency may be lowered and the dephosphorization cost may be increased in the production process. Therefore, the P content is preferably 0.001% or more.
- S 0.001% or less S is an element inevitably contained in the same manner as P, and causes hot brittleness, deteriorates weldability, and exists as sulfide inclusions in steel. It is a harmful element that reduces the workability of the steel sheet. For this reason, it is preferable to reduce S content as much as possible. Therefore, the S content is set to 0.001% or less.
- the lower limit of the S content is not particularly specified, but if the S content is less than 0.0001%, the production efficiency may be lowered and the cost may be increased in the current production process. For this reason, it is preferable that S content shall be 0.0001% or more.
- Al 1% or less Al is added as a deoxidizer.
- the content is preferably 0.01% or more in order to obtain the effect.
- the Al content is more preferably 0.02% or more.
- the Al content is preferably 0.4% or less, more preferably 0.1% or less.
- the N content is 0.006% or less, preferably 0.005% or less, and more preferably 0.004% or less.
- the content is preferably as low as possible from the viewpoint of improving the ductility by cleaning the ferrite, but the lower limit of the N content is set to 0.0001% in order to reduce the production efficiency and increase the cost in the manufacturing process.
- the N content is preferably 0.0010% or more, more preferably 0.0015% or more.
- the composition of the steel sheet includes, as an optional component, at least one of Ti, Nb, V, and Zr in a total of 0.005% to 0.10%, and at least one of Mo, Cr, Cu, and Ni. A total of 0.005% or more and 0.5% or less and B: 0.0003% or more and 0.005% or less may be contained.
- Ti, Nb, V, and Zr form carbides and nitrides (may be carbonitrides) with C and N, and contribute to increasing the strength of the steel sheet, in particular, increasing YR, by forming fine precipitates. . From the viewpoint of obtaining this effect, it is preferable to contain one or more of Ti, Nb, V and Zr in a total amount of 0.005% or more. More preferably, it is 0.015% or more, More preferably, it is 0.030% or more. These elements are also effective for hydrogen trap sites (detoxification) in steel.
- the total content is preferably set to 0.10% or less. More preferably, it is 0.08% or less, More preferably, it is 0.06% or less.
- Mo, Cr, Cu and Ni are elements that contribute to increasing the strength in order to enhance the hardenability and facilitate the formation of martensite. Therefore, it is preferable to contain at least 0.005% of Mo, Cr, Cu and Ni in total.
- the total content is more preferably 0.010% or more, and still more preferably 0.050% or more.
- Mo, Cr, Cu, and Ni excessive content exceeding 0.5% leads to saturation of effects and cost increase, so the total content is preferably 0.5% or less.
- the Cu content is preferably 0.5% or less at the maximum.
- Ni is preferably contained when Cu is contained because it has an effect of suppressing the generation of surface defects due to Cu. In particular, it is preferable to contain Ni that is 1/2 or more of the Cu content.
- the B is an element that contributes to high strength in order to enhance the hardenability and facilitate the formation of martensite. Further, the B content is preferably 0.0003% or more, more preferably 0.0005% or more, and further preferably 0.0010% or more. The B content is preferably provided with the above lower limit in order to obtain the effect of suppressing the formation of ferrite that occurs in the annealing cooling process. Moreover, even if it contains B content exceeding 0.005%, since an effect is saturated, it is preferable to provide the said upper limit. Excessive hardenability also has disadvantages such as weld cracking during welding.
- the component composition of the steel sheet may contain at least one of Sb: 0.001% to 0.1% and Sn: 0.001% to 0.1% as an optional component.
- Sb and Sn are elements that are effective in suppressing the strength reduction of the steel sheet by suppressing decarburization, denitrification, deboronation, and the like. Moreover, since it is effective also in suppressing spot weld cracking, the Sn content and the Sb content are each preferably 0.001% or more. Each of the Sn content and the Sb content is more preferably 0.003% or more, and further preferably 0.005% or more. However, if Sn and Sb are each contained excessively in excess of 0.1%, workability such as stretch flangeability of the steel sheet is deteriorated. Therefore, the Sn content and the Sb content are each preferably 0.1% or less. Each of the Sn content and the Sb content is more preferably 0.030% or less, and still more preferably 0.010% or less.
- the component composition of the steel sheet may contain Ca: 0.0010% or less as an optional component.
- the Ca content is preferably 0.0010% or less.
- the Ca content is more preferably 0.0005% or less, still more preferably 0.0003% or less.
- Ca content is preferably 0.00001% or more.
- the Ca content is more preferably 0.00005% or more.
- the balance other than the above is Fe and inevitable impurities.
- the arbitrary component since the effect of this invention is not impaired when the component in which the minimum of content exists is less than the said lower limit, the arbitrary component is made into an unavoidable impurity.
- the steel structure has an area ratio of martensite of 40% or more, ferrite of 30% or less (including 0%), residual austenite of 4% to 20%, and bainite of 10% to 50%.
- the area ratio of retained austenite is not less than 4% and not more than 20% Austenite (residual austenite) that is confirmed at room temperature after the production of the steel sheet is transformed into martensite by stress induction such as processing, so that the strain easily propagates and improves the ductility of the steel sheet.
- austenite (fcc phase) has a slower diffusion of hydrogen in steel than ferrite (bcc phase), hydrogen tends to remain in the steel, and has a high hydrogen storage capacity. In that case, there is a concern of increasing the diffusible hydrogen in the steel. Therefore, the area ratio of retained austenite is set to 20% or less.
- the area ratio of retained austenite is preferably 18% or less, more preferably 15% or less.
- the area ratio of ferrite is 30% or less (including 0%)
- the presence of ferrite is not preferable from the viewpoint of obtaining high tensile strength and yield ratio, but in the present invention, the area ratio is allowed to be 30% or less from the viewpoint of compatibility with ductility.
- the area ratio of ferrite is preferably 20% or less, more preferably 15% or less.
- the lower limit of the area ratio of ferrite is not particularly limited, but the area ratio of ferrite is preferably 1% or more, more preferably 2% or more, and further preferably 3% or more. Note that bainite that does not contain carbides generated at a relatively high temperature is not distinguished from ferrite by observation with a scanning electron microscope described in Examples described later, and is regarded as ferrite.
- the area ratio of martensite is 40% or more.
- martensite includes tempered martensite (including self-tempered martensite).
- As-quenched martensite and tempered martensite are hard phases and are important in the present invention in order to obtain high tensile strength. Compared to as-quenched martensite, tempered martensite tends to soften.
- the area ratio of martensite is 40% or more, preferably 45% or more.
- the martensite area ratio is preferably 86% or less in balance with other structures. Moreover, 80% or less is more preferable from a viewpoint of ensuring ductility.
- the area ratio of bainite is 10% or more and 50% or less. Bainite is harder than ferrite and is effective in increasing the strength of the steel sheet. As described above, in the present invention, bainite that does not contain carbide is regarded as ferrite, and thus bainite here means bainite that contains carbide. On the other hand, bainite is more ductile than martensite, and the area ratio of bainite is 10% or more. However, in order to ensure the required strength, the area ratio of bainite is 50% or less, preferably 45% or less.
- the steel structure may contain precipitates such as pearlite and carbide in the remainder as a structure other than the structure described above.
- precipitates such as pearlite and carbide
- These other structures are preferably 10% or less, more preferably 5% or less in terms of area ratio.
- the area ratio in the above steel structure adopts the result obtained by the method described in the examples.
- a more specific method for measuring the area ratio is described in the examples, but briefly, as follows.
- the area ratio is calculated by observing the structure in the region from the surface to the 1/4 thickness position (1/8 to 3/8) of the plate thickness.
- the above area ratio is obtained by analyzing an image taken by observing three or more fields of view at 1500 times magnification with a SEM after corroding the L section of the steel sheet (thickness section parallel to the rolling direction) with a Nital solution. Is required.
- the composition of the galvanized layer is not particularly limited and may be a general one.
- a hot-dip galvanized layer or an alloyed hot-dip galvanized layer generally, Fe: 20% by mass or less, Al: 0.001% by mass to 1.0% by mass, and further, Pb, One or more selected from Sb, Si, Sn, Mg, Mn, Ni, Cr, Co, Ca, Cu, Li, Ti, Be, Bi, and REM in total 0 to 3.5% by mass It is preferable that it is contained below and the remainder consists of Zn and inevitable impurities.
- a hot dip galvanized layer having a plating adhesion amount of 20 to 80 g / m 2 per side, and an alloyed hot dip galvanized layer obtained by alloying this.
- the Fe content in the plated layer is less than 7% by mass.
- the Fe content in the plated layer is 7 to 20% by mass. % Is preferred.
- the high-strength galvanized steel sheet of the present invention has a diffusible hydrogen content in steel obtained by measurement by the method described in the examples of less than 0.20 mass ppm. Diffusible hydrogen in steel degrades the hydrogen embrittlement resistance of the material. If the amount of diffusible hydrogen in the steel is 0.20 mass ppm or more, cracking of the welded nugget is likely to occur during welding, for example. In the present invention, it has been clarified that there is an improvement effect when the amount of diffusible hydrogen in the steel is less than 0.20 mass ppm. Preferably it is 0.15 mass ppm or less, More preferably, it is 0.10 mass ppm or less, More preferably, it is 0.08 mass ppm or less.
- the diffusible hydrogen in the steel needs to be less than 0.20 ppm by mass before the steel sheet is formed or welded.
- the diffusible hydrogen content in steel is measured by cutting a sample from the product in a general usage environment and measuring the amount of diffusible hydrogen in steel If hydrogen is less than 0.20 mass ppm, it can be considered that it was less than 0.20 mass ppm before forming and welding.
- the high-strength galvanized steel sheet of the present invention has sufficient strength. Specifically, it is 1100 MPa or more.
- the high strength galvanized steel sheet of the present invention has a high yield ratio. Specifically, the yield ratio (YR) is 67% or more.
- the balance between tensile strength (TS) and elongation (El) is adjusted in consideration of the plate thickness (t). Specifically, it is adjusted to satisfy the following expression (1).
- the unit of tensile strength TS is MPa
- the unit of elongation El is%
- the unit of sheet thickness t is mm.
- the manufacturing method of the high-strength galvanized steel sheet of the present invention includes an annealing process, a plating process, and a post heat treatment process.
- the temperature at the time of heating or cooling a slab (steel material), a steel plate, etc. shown below means the surface temperature of a slab (steel material), a steel plate, etc. unless otherwise specified.
- the cold-rolled steel sheet having the above component composition at a hydrogen concentration 1 vol% or more 13 vol% or less of the annealing furnace atmosphere, the annealing furnace temperature T1: (A c3 point -10 ° C.) or higher 900 ° C. temperature below
- the product is cooled and retained in a temperature range of 400 ° C. or more and 550 ° C. or less for 20 s or more and 1500 s or less.
- the cold rolled steel sheet used in the manufacturing method of the present invention is manufactured from a steel material.
- the steel material is manufactured by a continuous casting method generally called a slab (slab).
- the continuous casting method is used for the purpose of preventing macro segregation of alloy components.
- the steel material may be manufactured by an ingot-making method or a thin slab casting method.
- the method of hot rolling and charging into a heating furnace as it is without cooling to near room temperature Either a method of hot rolling immediately after performing a slight supplementary heat, or a method of hot rolling while maintaining a high temperature state after casting may be used.
- the hot rolling conditions are not particularly limited, but the steel material having the above component composition is heated at a temperature of 1100 ° C. or higher and 1350 ° C. or lower and subjected to hot rolling at a finish rolling temperature of 800 ° C. or higher and 950 ° C. or lower.
- the condition of winding at a temperature of from °C to 700 °C is preferable.
- these preferable conditions will be described.
- the heating temperature of the steel slab is preferably in the range of 1100 ° C to 1350 ° C. If the temperature is outside the above upper limit temperature range, the precipitates present in the steel slab are likely to be coarsened, which may be disadvantageous when securing strength by precipitation strengthening, for example. In addition, there is a possibility of adversely affecting the structure formation in the subsequent heat treatment using coarse precipitates as nuclei. Moreover, coarsening of austenite grains occurs, and the steel structure also coarsens, which may cause the strength and elongation of the steel sheet to decrease. On the other hand, it is beneficial to achieve a smooth steel plate surface by reducing cracks and irregularities on the steel plate surface by scaling off bubbles and defects on the slab surface by appropriate heating. In order to obtain such an effect, the heating temperature of the steel slab is preferably 1100 ° C. or higher.
- the hot steel slab is subjected to hot rolling including rough rolling and finish rolling.
- a steel slab becomes a sheet bar by rough rolling, and becomes a hot-rolled coil by finish rolling.
- the hot rolling conditions are preferably as follows.
- Finish rolling temperature 800 ° C. or higher and 950 ° C. or lower is preferable.
- the finish rolling temperature 800 ° C. or higher, the steel structure obtained from the hot rolled coil tends to be uniform.
- the ability to make the steel structure uniform at this stage contributes to making the steel structure of the final product uniform. If the steel structure is not uniform, workability such as elongation is reduced.
- the temperature exceeds 950 ° C. the amount of oxide (scale) generated increases, the interface between the base iron and the oxide becomes rough, and the surface quality after pickling and cold rolling may deteriorate.
- the coarse grain size in the steel structure may cause a decrease in workability such as strength and elongation of the steel plate as in the case of the steel slab.
- cooling is started within 3 seconds after finishing rolling, and the temperature range from [Finishing rolling temperature] to [Finishing rolling temperature-100 ° C]. Is preferably cooled at an average cooling rate of 10 to 250 ° C./s. This average cooling rate is the time required for cooling from [Finishing Rolling Temperature] to [Finishing Rolling Temperature—100 ° C.] by the temperature difference (° C.) between [Finishing Rolling Temperature] and [Finishing Rolling Temperature—100 ° C.]. Divide by to calculate.
- the winding temperature is preferably 450 ° C. or higher and 700 ° C. or lower. If the temperature immediately before coil winding after hot rolling, that is, the coiling temperature is 450 ° C. or higher, it is preferable from the viewpoint of fine precipitation of carbide when Nb or the like is added, and if the coiling temperature is 700 ° C. or lower. The cementite precipitate is preferable because it does not become too coarse. In addition, when the temperature range is 450 ° C. or lower or 700 ° C. or higher, the structure is likely to change during holding after being wound on the coil, and rolling due to the non-uniformity of the steel structure of the material in cold rolling in the subsequent process Troubles are likely to occur. A more preferable coiling temperature is 500 ° C. or more and 680 ° C. or less from the viewpoint of sizing the steel structure of the hot rolled sheet.
- a cold rolling process is performed. Usually, after a scale is dropped by pickling, cold rolling is performed to form a cold-rolled coil. This pickling is performed as necessary.
- Cold rolling is preferably performed at a reduction rate of 20% or more. This is to obtain a uniform and fine steel structure in the subsequent heating. If it is less than 20%, coarse grains may be easily formed during heating, and a non-uniform structure may be easily formed. As described above, there are concerns about the strength and workability of the final product plate after subsequent heat treatment, and the surface. Deteriorates properties. Although the upper limit of the rolling reduction is not particularly defined, a high strength steel sheet has a high rolling reduction, which may result in poor shape due to a reduction in productivity due to rolling load. The rolling reduction is preferably 90% or less.
- Annealing furnace temperature T1 ( Ac3 point-10 ° C) to 900 ° C or less is not particularly limited, but the average heating rate is 10 ° C / s for the purpose of homogenizing the steel structure. Less than is preferable. In addition, the average heating rate is preferably 1 ° C./s or more from the viewpoint of suppressing a decrease in production efficiency.
- the annealing furnace temperature T1 is set to ( Ac3 point-10 ° C) or higher and 900 ° C or lower in order to secure both the material and the plating property.
- the annealing furnace temperature T1 is less than ( Ac3 point -10 ° C)
- the ferrite area ratio becomes high in the steel structure finally obtained, and it is difficult to generate the necessary amount of retained austenite, martensite, and bainite.
- the annealing furnace internal temperature T1 exceeds 900 ° C., the crystal grains are coarsened and workability such as elongation is lowered, which is not preferable.
- the annealing furnace internal temperature T1 exceeds 900 ° C.
- Mn and Si are likely to be concentrated on the surface, thereby impairing the plateability.
- the annealing furnace internal temperature T1 exceeds 900 ° C., the load on the equipment is high and there is a possibility that it cannot be stably manufactured.
- the annealing furnace temperature T1 ( Ac3 point ⁇ 10 ° C.) to 900 ° C. is heated for 5 seconds or more.
- the upper limit is not particularly limited, but 600 seconds or less is preferable because it prevents the excessive austenite grain size from coarsening.
- the hydrogen concentration in the (A c3 point -10 ° C.) or higher 900 ° C. or less of the temperature range is not less than 1 vol% 13 vol% or less.
- the in-furnace atmosphere is also controlled simultaneously with respect to the above-mentioned annealing furnace temperature T1, so that the plating property is ensured and at the same time, excessive hydrogen intrusion into the steel is prevented.
- Non-plating occurs frequently when the hydrogen concentration is less than 1 vol%.
- the hydrogen concentration exceeds 13 vol%, the effect on the plating property is saturated, and at the same time, hydrogen penetration into the steel is remarkably increased and the hydrogen embrittlement resistance of the final product is deteriorated.
- the hydrogen concentration does not have to be in the range of 1 vol% or more except in the temperature range from ( Ac3 point ⁇ 10 ° C.) to 900 ° C. above.
- the residence After the residence in the hydrogen concentration atmosphere, when cooling, the residence is performed for 20 s or more in a temperature range of 400 ° C. or more and 550 ° C. or less. This is to make it easier to form bainite and obtain retained austenite. Furthermore, this residence has the effect that hydrogen in the steel is removed. In order to produce desired amounts of bainite and retained austenite, it is necessary to retain for 20 s or more in this temperature range.
- the upper limit of the residence time is set to 1500 s or less from the viewpoint of manufacturing cost and the like. Residence at less than 400 ° C. is not preferable because it tends to be lower than the plating bath temperature that follows and deteriorates the quality of the plating bath.
- the plate temperature may be heated up to the plating bath, and thus the above temperature range. Is set to 400 ° C.
- the temperature range exceeding 550 ° C. not bainite but ferrite and pearlite are likely to be produced, and it becomes difficult to obtain retained austenite.
- the cooling rate average cooling rate
- the upper limit of the preferable cooling rate is not particularly specified.
- the cooling stop temperature may be 400 to 550 ° C., but may be once cooled to a temperature below this and retained in a temperature range of 400 to 550 ° C. by reheating. In this case, when cooled to the Ms point or lower, martensite may be generated and then tempered.
- the steel sheet after the annealing process is plated and cooled to 100 ° C. or lower at an average cooling rate of 3 ° C./s or higher.
- the method of plating treatment is preferably hot dip galvanizing treatment. Conditions may be set as appropriate. In addition, alloying treatment may be performed as necessary. When alloying, an alloying treatment is performed by heating after hot dip galvanizing. For example, the temperature at the time of alloying can be exemplified by a treatment in which a temperature range of 480 ° C. to 600 ° C. is maintained for about 1 second (s) to 60 seconds. In addition, since it becomes difficult to obtain a retained austenite when the treatment temperature exceeds 600 ° C., the treatment is preferably performed at 600 ° C. or less.
- the above plating treatment After alloying treatment in the case of alloying treatment, it is cooled to 100 ° C. or less at an average cooling rate of 3 ° C./s or more. This is to obtain martensite which is essential for increasing the strength.
- This average cooling rate is calculated by dividing the temperature difference from the cooling start temperature after the plating treatment to 100 ° C. by the time required for cooling from the cooling start temperature to 100 ° C. If it is less than 3 ° C / s, it is difficult to obtain martensite necessary for strength, and if the cooling is stopped at a temperature higher than 100 ° C, the martensite is excessively tempered (self-tempering) or austenite.
- the upper limit of the average cooling rate is not particularly specified, but is preferably 200 ° C./s or less. This is because if it is faster than this, the burden of capital investment increases. In addition, you may cool immediately after a plating process.
- the plated steel sheet after the plating step is 0.02 (hr) or higher at a temperature T2 (° C.) of 70 ° C. or higher and 450 ° C. or lower in a furnace atmosphere having a hydrogen concentration of 10 vol% or lower and a dew point of 50 ° C. or lower. Is a step of staying for at least time t (hr) satisfying the following expression (2).
- a post heat treatment step is performed to reduce the amount of diffusible hydrogen in the steel.
- the hydrogen concentration is preferably as low as possible, preferably 5 vol% or less, more preferably 2 vol% or less.
- the lower limit of the hydrogen concentration is not particularly limited, and a lower limit is preferably 1 vol% because it is preferably as small as described above.
- a dew point is 50 degrees C or less, Preferably it is 45 degrees C or less, More preferably, it is 40 degrees C or less.
- the lower limit of the dew point is not particularly limited, but is preferably ⁇ 80 ° C. or higher from the viewpoint of production cost.
- the upper limit of the temperature T2 is set to 450 ° C. at a temperature exceeding 450 ° C., because the ductility lowering, the tensile strength lowering, the plating layer deterioration, and the appearance deterioration occur due to decomposition of residual austenite.
- it is 430 degrees C or less, More preferably, it is 420 degrees C or less.
- the lower limit of the temperature T2 to retain is less than 70 degreeC, it will become difficult to fully reduce the amount of diffusible hydrogen in steel, and the crack crack of a welding part will arise. Therefore, the lower limit of the temperature T2 is set to 70 ° C.
- it is 80 degreeC or more, More preferably, it is 90 degreeC or more.
- the amount of diffusible hydrogen in the steel can be reduced by adjusting the residence time to be 0.02 hr or longer and satisfying the above formula (2).
- a cold-rolled sheet obtained by cold rolling is heated to a temperature range of A c1 point or higher (A c3 point + 50 ° C.) and lower, and a pretreatment step of pickling is performed. It is also possible.
- a c1 751-27C + 18Si-12Mn-23Cu-23Ni + 24Cr + 23Mo-40V-6Ti + 32Zr + 233Nb-169Al-895B
- a c3 910-203 (C) 1/2 + 44.7Si-30Mn-11P + 700S + 400Al + 400Ti
- the element symbol in said formula means content (mass%) of each element, and makes the component which does not contain 0.
- oxides such as Si and Mn concentrated on the surface layer of the steel sheet are removed by pickling in order to ensure plating properties in the subsequent annealing step.
- temper rolling may be performed after the plating step.
- Temper rolling is preferably performed at an elongation rate of 0.1% or more after cooling in the plating step.
- the temper rolling may not be performed.
- temper rolling is preferably performed at an elongation rate of 0.1% or more for the purpose of stably obtaining YS in addition to the purpose of shape correction and surface roughness adjustment.
- leveling may be performed instead of temper rolling.
- Excessive temper rolling reduces the evaluation value of ductility and stretch flangeability by introducing excessive strain on the steel sheet surface.
- excessive temper rolling reduces ductility and increases the equipment load due to the high strength steel sheet. Therefore, the rolling reduction of temper rolling is preferably 3% or less.
- Width trimming is preferably performed before or after the temper rolling. With this width trim, the coil width can be adjusted. Moreover, as described below, by performing the width trimming before the post heat treatment step, hydrogen in the steel can be efficiently released by the subsequent post heat treatment.
- the residence time t (hr) at the temperature T2 (° C.) of 70 ° C. or higher and 450 ° C. or lower in the post heat treatment step is set to 0.02 (hr) or more and the following (3 It is preferable that the conditions satisfy the formula. 130-17.5 ⁇ ln (t) ⁇ T2 (3) As apparent from the above equation (3), the temperature can be shortened if the temperature condition is the same as in the case of the above equation (2), and the temperature can be lowered if the residence time condition is the same. .
- the high-strength member of the present invention is obtained by subjecting the high-strength galvanized steel sheet of the present invention to at least one of forming and welding.
- the manufacturing method of the high strength member of this invention has the process of performing at least one of a shaping
- the high-strength member of the present invention has high tensile strength of 1100 MPa or higher, yield ratio of 67% or higher, excellent strength-ductility balance, excellent hydrogen brittleness resistance, and good surface properties (appearance). . Therefore, the high-strength member of the present invention can be suitably used for, for example, automobile parts.
- a general processing method such as pressing can be used without limitation.
- general welding such as spot welding and arc welding can be used without limitation.
- Example 1 Molten steel having the component composition of steel A shown in Table 1 was melted in a converter and made into a slab with a continuous casting machine. This slab was heated to 1200 ° C. to obtain a hot rolled coil at a finish rolling temperature of 840 ° C. and a winding temperature of 550 ° C. This hot-rolled coil was a cold-rolled steel sheet having a cold reduction ratio of 50% and a thickness of 1.4 mm. This cold-rolled steel sheet is heated to 810 ° C. (within ( Ac3 point ⁇ 10 ° C.) to 900 ° C.) in an annealing furnace atmosphere at various hydrogen concentrations and a dew point of ⁇ 30 ° C. for 60 seconds.
- Hydrogen content in steel was measured by the following method. First, a test piece of about 5 ⁇ 30 mm was cut out from a galvanized steel sheet subjected to post heat treatment. Next, the plating on the surface of the test piece was removed using a router (precision grinder) and placed in a quartz tube. Next, after replacing the inside of the quartz tube with Ar, the temperature was raised at 200 ° C./hr, and hydrogen generated up to 400 ° C. was measured by a gas chromatograph. In this way, the amount of released hydrogen was measured by a temperature rising analysis method. The cumulative amount of hydrogen detected in the temperature range from room temperature (25 ° C.) to less than 250 ° C. was defined as the amount of diffusible hydrogen.
- Hydrogen embrittlement resistance As an evaluation of hydrogen embrittlement resistance, a nugget crack in a resistance spot weld of a steel plate was evaluated.
- a 2 mm thick plate was sandwiched between both ends of a 30 ⁇ 100 mm plate as a spacer, and the center between the spacers was joined by spot welding to prepare a test piece as a member.
- spot welding was performed using an inverter DC resistance spot welder, and the electrode was a chrome copper dome shape with a tip diameter of 6 mm.
- the applied pressure was 380 kgf
- the energization time was 16 cycles / 50 Hz
- the holding time was 5 cycles / 50 Hz. Samples with various nugget diameters were prepared by changing the welding current value.
- FIG. 1 shows the relationship between the amount of diffusible hydrogen (mass ppm) and the minimum nugget diameter (mm).
- the steel structure and mechanical properties are also within the scope of the present invention.
- Example 2 Molten steel having the component compositions of steels A to N shown in Table 1 was melted in a converter and made into a slab with a continuous casting machine, heated to 1200 ° C. and then hot-rolled to a finish rolling temperature of 910 ° C., A hot rolled coil was formed at a winding temperature of 560 ° C. Thereafter, a cold rolled coil having a cold pressure ratio of 50% and a thickness of 1.4 mm was obtained.
- a sample of the galvanized steel sheet obtained as described above is collected, and the microstructure (area ratio), yield strength (YS), tensile strength (TS), tensile strength (TS)
- the evaluation method is as follows. As an evaluation of hydrogen embrittlement resistance, the nugget crack of the weld was evaluated.
- Microstructure observation A specimen for microstructural observation was collected from a galvanized steel sheet, and after polishing the L cross section (thickness cross section parallel to the rolling direction), it was corroded with Nital solution and near 1/4 t (t is the total thickness) from the surface with SEM. The images taken by observing three or more visual fields at a magnification of 1500 times were analyzed (the area ratio was measured for each observation visual field, and the average value was calculated). However, since the volume ratio of retained austenite (the volume ratio is regarded as the area ratio) is quantified by the X-ray diffraction intensity, the total of each structure may exceed 100%.
- F means ferrite
- M means martensite
- B bainite
- residual ⁇ means residual austenite.
- Tensile test A JIS No. 5 tensile test piece (JISZ2201) was sampled from a galvanized steel sheet in a direction perpendicular to the rolling direction, and a tensile test was performed at a constant tensile speed (crosshead speed) of 10 mm / min.
- Yield strength (YS) is the value obtained by reading the 0.2% proof stress from the slope of the 150 to 350 MPa stress range, and the tensile strength is the value obtained by dividing the maximum load in the tensile test by the initial cross-sectional area of the parallel part of the specimen. It was.
- the plate thickness in calculating the cross-sectional area of the parallel portion the plate thickness value including the plating thickness was used.
- Tensile strength (TS), yield strength (YS), and elongation (El) were measured, and yield ratio YR and equation (1) were calculated.
- Hydrogen embrittlement resistance As an evaluation of hydrogen embrittlement resistance, the hydrogen embrittlement of the resistance spot welds of steel sheets was evaluated.
- the evaluation method is the same as in Example 1.
- the welding current value was a condition for forming a nugget diameter corresponding to the strength of each steel plate.
- a nugget diameter of 3.8 mm was set at 1100 MPa or more and less than 1250 MPa, and a nugget diameter of 4.8 mm was set at 1250 MPa or more and 1400 MPa or less.
- the distance between the spacers at both ends was 40 mm, and the steel plate and the spacer were secured in advance by welding.
- the non-plating defect means an area in the order of several ⁇ m to several mm, where plating is not present and the steel sheet is exposed.
- the amount of diffusible hydrogen in steel was measured by the same method as in Example 1.
- Table 3 shows the obtained results.
- the inventive examples were all good in TS, YR, surface properties and hydrogen embrittlement resistance. Any of the comparative examples was inferior. Further, from the comparison between the inventive example and the comparative example, the relationship between the amount of diffusible hydrogen and the resistance to hydrogen embrittlement is within the range of the component composition and steel structure of the present invention, and the amount of diffusible hydrogen is 0. When the content is less than 20 ppm by mass, the resistance spot welded nugget crack is evaluated as favorable as hydrogen embrittlement resistance.
- the high-strength galvanized steel sheet of the present invention not only has high tensile strength, but also has a high yield strength ratio and good ductility, and is excellent in the hydrogen embrittlement resistance and surface properties of the material. For this reason, when a high-strength member obtained by using the high-strength galvanized steel sheet of the present invention is applied to a skeleton component of an automobile body, particularly a component around a cabin that affects collision safety, along with improvement of its safety performance, Contributes to weight reduction of vehicle body due to high strength and thinning effect. As a result, the present invention can contribute to environmental aspects such as CO 2 emission.
- the high-strength galvanized steel sheet according to the present invention has good surface properties and plating quality, it can be actively applied to places where corrosion due to rain and snow is a concern, such as undercarriage. For this reason, according to this invention, performance improvement can be expected also about the rust prevention and corrosion resistance of a vehicle body. Such characteristics are effective not only for automobile parts, but also in the fields of civil engineering / architecture and home appliances.
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Abstract
Description
C:0.10%以上0.30%以下、
Si:1.0%以上2.8%以下、
Mn:2.0%以上3.5%以下、
P:0.010%以下、
S:0.001%以下、
Al:1%以下、及び
N:0.0001%以上0.006%以下を含有し、残部がFeおよび不可避的不純物からなる成分組成と、
面積率で、残留オーステナイトが4%以上20%以下、フェライトが30%以下(0%を含む)、マルテンサイトが40%以上かつベイナイトが10%以上50%以下である鋼組織と、を有する鋼板と、
前記鋼板上の亜鉛めっき層と、を備え、
鋼中の拡散性水素量が0.20質量ppm未満であり、
引張強さが1100MPa以上であり、
引張強さTS(MPa)、伸びEl(%)および板厚t(mm)の関係が下記(1)式を満たし、
降伏比YRが67%以上である高強度亜鉛めっき鋼板。
TS×(El+3-2.5t)≧13000 (1)
[2]前記成分組成は、さらに、質量%で、
Ti、Nb、V及びZrのうち1種以上の合計:0.005%以上0.10%以下、
Mo、Cr、Cu及びNiのうち1種以上の合計:0.005%以上0.5%以下、及び
B:0.0003%以上0.005%以下のうち少なくとも1つを含有する[1]に記載の高強度亜鉛めっき鋼板。
[3]前記成分組成は、さらに、質量%で、
Sb:0.001%以上0.1%以下及びSn:0.001%以上0.1%以下のうち少なくとも1つを含有する[1]又は[2]に記載の高強度亜鉛めっき鋼板。
[4]前記成分組成は、さらに、質量%で、Ca:0.0010%以下を含有する[1]~[3]のいずれか一つに記載の高強度亜鉛めっき鋼板。
[5][1]~[4]のいずれか一つに記載の高強度亜鉛めっき鋼板が、成形加工及び溶接の少なくとも一方がされてなる高強度部材。
[6][1]~[4]のいずれか一つに記載の成分組成を有する冷延鋼板を、水素濃度1vol%以上13vol%以下の焼鈍炉内雰囲気で、焼鈍炉内温度T1:(Ac3点-10℃)以上900℃以下の温度域で5s以上加熱した後、冷却し、400℃以上550℃以下の温度域で20s以上1500s以下滞留させる焼鈍工程と、
前記焼鈍工程後の鋼板を、めっき処理し、平均冷却速度3℃/s以上で100℃以下まで冷却するめっき工程と、
前記めっき工程後のめっき鋼板を、水素濃度10vol%以下かつ露点50℃以下の炉内雰囲気で、70℃以上450℃以下の温度T2(℃)に、0.02(hr)以上で下記(2)式を満たす時間t(hr)以上滞留させる後熱処理工程と、を有する高強度亜鉛めっき鋼板の製造方法。
135-17.2×ln(t)≦ T2 (2)
[7]前記焼鈍工程前に、前記冷延鋼板を、Ac1点以上(Ac3点+50℃)以下まで加熱し、酸洗する前処理工程を有する[6]に記載の高強度亜鉛めっき鋼板の製造方法。
[8]前記めっき工程後、0.1%以上の伸長率で調質圧延を施す[6]または[7]に記載の高強度亜鉛めっき鋼板の製造方法。
[9]前記後熱処理工程後に、幅トリムをする[8]に記載の高強度亜鉛めっき鋼板の製造方法。
[10]前記後熱処理工程前に、幅トリムを行い、
前記後熱処理工程における、70℃以上450℃以下の温度T2(℃)で滞留する滞留時間t(hr)が、0.02(hr)以上かつ下記(3)式を満たす[8]に記載の高強度亜鉛めっき鋼板の製造方法。
130-17.5×ln(t)≦ T2 (3)
[11][6]~[10]のいずれか一つに記載の高強度亜鉛めっき鋼板の製造方法によって製造された高強度亜鉛めっき鋼板を、成形加工及び溶接の少なくとも一方を行う工程を有する、高強度部材の製造方法。
本発明の高強度亜鉛めっき鋼板は、鋼板と、該鋼板上に形成された亜鉛めっき層とを備える。以下では、鋼板、亜鉛めっき層の順で説明する。また、本発明でいう高強度とは、引張強さが1100MPa以上であることを意味する。また、本発明でいう強度-延性バランスに優れるとは、引張強さTS(MPa)、伸びEl(%)および板厚t(mm)の関係が下記(1)式を満たすことをいう。
鋼板の成分組成は以下の通りである。以下の説明において、成分の含有量の単位である「%」は「質量%」を意味する。
Cは鋼板の高強度化に有効な元素であり、鋼組織の硬質相の一つであるマルテンサイトを形成することで高強度化に寄与する。これらの効果を得るためには、C含有量は0.10%以上、好ましくは0.11%以上、より好ましくは0.12%以上である。一方、C含有量が0.30%を超えると、本発明ではスポット溶接性が顕著に劣化すると同時に、マルテンサイトの強度増加により鋼板が硬質化し、延性などの成形性が低下する傾向にある。したがってC含有量は0.30%以下とする。C含有量は、好ましくは0.28%以下、より好ましくは0.25%以下である。
Siは固溶強化により高強度化に寄与する元素であるとともに、炭化物の生成を抑え、残留オーステナイトの生成に有効に作用する元素である。この観点からSi含有量は1.0%以上、好ましくは1.2%以上とする。一方でSiは鋼板表面にSi系酸化物を形成しやすく、不めっきの原因となる場合があると共に、過剰に含有すると熱間圧延時にスケールが著しく形成されて鋼板表面にスケール跡疵が付き、表面性状が悪くなることがある。また、酸洗性が低下することがある。これらの観点から、Si含有量を2.8%以下とする。
Mnは固溶強化およびマルテンサイト形成により高強度化に寄与する元素として有効である。この効果を得るためにMn含有量は2.0%以上にする必要があり、好ましくは2.1%以上、より好ましくは2.2%以上である。一方、Mn含有量が3.5%を超えるとスポット溶接部割れを招くと共に、Mnの偏析などに起因して鋼組織にムラを生じやすくなり、加工性の低下を招く。また、Mn含有量が3.5%を超えると、Mnは鋼板表面に酸化物あるいは複合酸化物として濃化しやすく、不めっきの原因となる場合がある。そこで、Mn含有量は3.5%以下とする。Mn含有量は、好ましくは3.3%以下、より好ましくは3.0%以下である。
Pは、不可避的に含有する元素であると共に、固溶強化により鋼板の高強度化に寄与する有効な元素である。その含有量が0.010%を超えると溶接性や、伸びフランジ性などの加工性が低下するほか、粒界に偏析して粒界脆化を助長する。そこで、P含有量は0.010%以下とする。P含有量は、好ましくは0.008%以下、より好ましくは0.007%以下である。P含有量の下限は特に規定しないが、P含有量が0.001%未満では製造過程において生産能率低下と脱燐コストの増加を招くことがある。このため、P含有量は、好ましくは0.001%以上とする。
SもPと同様に不可避的に含有する元素であり、熱間脆性を起こす原因となったり、溶接性の低下をもたらしたり、鋼中に硫化物系介在物として存在して鋼板の加工性を低下させる有害な元素である。このため、S含有量は極力低減することが好ましい。そこで、S含有量は0.001%以下とする。S含有量の下限は特に規定しないが、S含有量が0.0001%未満では現状の製造過程において生産能率低下とコストの増加を招くことがある。このため、S含有量は0.0001%以上とすることが好ましい。
Alは脱酸剤として添加される。脱酸剤としてAlを添加する場合、その効果を得るには0.01%以上の含有が好ましい。Al含有量は、より好ましくは0.02%以上である。一方Al含有量が1%を超えると原料コストの上昇を招くほか、鋼板の表面欠陥を誘発する原因にもなるため1%を上限とする。Al含有量は、好ましくは0.4%以下、より好ましくは0.1%以下である。
N含有量が0.006%を超えると鋼中に過剰な窒化物が生成して延性や靭性を低下させるほか、鋼板の表面性状の悪化を招くことがある。このためN含有量は0.006%以下、好ましくは0.005%以下、より好ましくは0.004%以下とする。フェライトの清浄化による延性向上の観点からは含有量は極力少ない方が好ましいが、製造過程における生産能率低下とコスト増を招くためN含有量の下限は0.0001%とする。N含有量は、好ましくは0.0010%以上、より好ましくは0.0015%以上である。
鋼板製造後に室温で確認されるオーステナイト(残留オーステナイト)は加工など応力誘起によりマルテンサイトに変態するため歪伝播しやすく鋼板の延性を向上させる。その効果は、残留オーステナイトの面積率が4%以上で現れ、5%以上で顕著になる。一方で、オーステナイト(fcc相)はフェライト(bcc相)に比べ、鋼中水素の拡散が遅く、鋼中に水素が残存しやすく、また水素吸蔵能が高いため、この残留オーステナイトが加工誘起変態した場合、鋼中の拡散性水素を増加させる懸念がある。そのため、残留オーステナイトの面積率は、20%以下にする。残留オーステナイトの面積率は、好ましくは18%以下、より好ましくは15%以下である。
フェライトの存在は、高い引張強さと降伏比を得る観点からは好ましくないが、本発明では延性との両立の観点から面積率で30%以下まで許容される。フェライトの面積率は、好ましくは20%以下、より好ましくは15%以下である。フェライトの面積率の下限は特に限定されないが、フェライトの面積率は1%以上が好ましく、より好ましくは2%以上、さらに好ましくは3%以上である。なお、比較的高温で生成した炭化物を含まないベイナイトは後述の実施例に記載の走査電子顕微鏡での観察ではフェライトとの区別はせず、フェライトとみなす。
ここでマルテンサイトは、焼戻しマルテンサイト(自己焼戻しマルテンサイトを含む)を含む。焼入れままマルテンサイト、焼戻しマルテンサイトは硬質相であり、高い引張強さを得るため本発明において重要である。焼入れままマルテンサイトに比べ、焼戻しマルテンサイトは軟化傾向にある。必要な強度を確保するために、マルテンサイトの面積率は40%以上、好ましくは45%以上とする。マルテンサイトの面積率の上限は特に規定していないが、他の組織とのバランスで、マルテンサイトの面積率は86%以下であることが好ましい。また、延性確保の観点から、80%以下がより好ましい。
ベイナイトはフェライトに比べ硬質であり、鋼板強度を高めるためにも有効である。上記の通り、本発明では炭化物を含まないベイナイトはフェライトとみなされるため、ここで言うベイナイトは炭化物を含むベイナイトを意味する。一方でベイナイトはマルテンサイトに比べ延性があり、ベイナイトの面積率は10%以上とする。しかしながら必要な強度を確保するために、ベイナイトの面積率は50%以下、好ましくは45%以下とする。
TS×(El+3-2.5t)≧13000 (1)
<高強度亜鉛めっき鋼板の製造方法>
本発明の高強度亜鉛めっき鋼板の製造方法は、焼鈍工程と、めっき工程と、後熱処理工程とを有する。なお、以下に示すスラブ(鋼素材)、鋼板等を加熱又は冷却する際の温度は、特に説明がない限り、スラブ(鋼素材)、鋼板等の表面温度を意味する。
鋼中の拡散性水素量を低減させるため、後熱処理工程を行う。水素濃度10vol%以下かつ露点50℃以下の炉内雰囲気にすることで、鋼中の拡散性水素量の増加を抑えることができる。水素濃度は少ない方が好ましく5vol%以下が好ましく、より好ましくは2vol%以下である。水素濃度の下限は特に限定されず、上記の通り少ない方が好ましいため、好ましい下限は1vol%である。また、上記効果を得るために、露点は、50℃以下、好ましくは45℃以下、より好ましくは40℃以下である。露点の下限は特に限定されないが、製造コストの観点からは-80℃以上が好ましい。
「Ac1点以上(Ac3点+50℃)以下の温度域に加熱」は、鋼組織の形成による高い延性とめっき性を最終製品で担保するための条件である。引続く焼鈍工程の前に、マルテンサイトを含む組織を得ておくことが材質上好ましい。さらに、めっき性の観点からもこの加熱により鋼板表層部にMnなどの酸化物を濃化させることが好ましい。その観点で、Ac1点以上(Ac3点+50℃)以下の温度域に加熱することが好ましい。ここで、上述のAc1やAc3については以下の式で得られる値を用いた。
Ac1=751-27C+18Si-12Mn-23Cu-23Ni+24Cr+23Mo-40V-6Ti+32Zr+233Nb-169Al-895B
Ac3=910-203(C)1/2+44.7Si-30Mn-11P+700S+400Al+400Tiとする。
なお、上記式における元素記号は各元素の含有量(質量%)を意味し、含有しない成分は0とする。
130-17.5×ln(t)≦T2 (3)
上記(3)式から明らかなように、上記(2)式の場合と比較して、温度条件が同じであれば短時間化でき、滞留時間の条件が同じであれば低温化することができる。
<高強度部材およびその製造方法>
本発明の高強度部材は、本発明の高強度亜鉛めっき鋼板が、成形加工及び溶接の少なくとも一方がされてなるものである。また、本発明の高強度部材の製造方法は、本発明の高強度亜鉛めっき鋼板の製造方法によって製造された高強度亜鉛めっき鋼板を、成形加工及び溶接の少なくとも一方を行う工程を有する。
表1に示す鋼Aの成分組成の溶鋼を転炉で溶製し、連続鋳造機でスラブとした。このスラブを1200℃に加熱し、仕上圧延温度840℃、巻取り温度550℃で熱延コイルとした。この熱延コイルを冷間圧下率50%で板厚1.4mmの冷延鋼板とした。この冷延鋼板を、種々の水素濃度で露点-30℃の焼鈍炉内雰囲気の焼鈍処理で、810℃((Ac3点-10℃)以上900℃以下の範囲内)まで加熱し、60秒滞留させた後、500℃まで冷却し、100秒滞留させた。その後亜鉛めっきを施して合金化処理をおこない、めっき後は水温40℃の水槽を通すことで、冷却停止温度100℃以下、平均冷却速度を3℃/s以上の条件で冷却して、高強度亜鉛めっき鋼板(製品板)を製造した。調質圧延はめっき後に実施し伸長率は0.2%とした。幅トリムは実施しなかった。
鋼中の水素量を以下の方法で測定した。先ず、後熱処理まで施した亜鉛めっき鋼板から、5×30mm程度の試験片を切り出した。次いで、ルータ(精密グラインダ)を使って試験片表面のめっきを除去して石英管中に入れた。次いで、石英管中をArで置換した後、200℃/hrで昇温し、400℃までに発生した水素をガスクロマトグラフにより測定した。このように、昇温分析法にて放出水素量を測定した。室温(25℃)から250℃未満の温度域で検出された水素量の累積値を拡散性水素量とした。
耐水素脆性の評価として、鋼板の抵抗スポット溶接部のナゲット割れを評価した。評価方法は、30×100mmの板の両端に板厚2mmの板をスペーサとして挟み、スペーサ間の中央をスポット溶接にて接合して部材としての試験片を作製した。この際、スポット溶接は、インバータ直流抵抗スポット溶接機を用い、電極はクロム銅製の先端径6mmのドーム型を用いた。加圧力は380kgf、通電時間は16サイクル/50Hz、保持時間は5サイクル/50Hzとした。溶接電流値を変化させて種々のナゲット径のサンプルを作製した。
表1に示す鋼A~Nの成分組成の溶鋼を転炉で溶製し、連続鋳造機でスラブとしたあと、1200℃に加熱してから熱間圧延を行い、仕上げ圧延温度910℃とし、巻取り温度560℃で熱延コイルとした。その後、冷圧率50%で1.4mmの板厚の冷延コイルとした。これを表2に示す種々の条件で加熱(焼鈍)、酸洗(酸洗は、酸洗液のHCl濃度を5mass%、液温を60℃に調整したものを使用した)、めっき処理、調質圧延、幅トリム、後熱処理を施し、1.4mm厚の高強度亜鉛めっき鋼板(製品板)を製造した。なお、冷却(めっき処理後の冷却)では水温50℃の水槽を通すことで、100℃以下まで冷却した。また、めっき処理では、530℃で20秒の条件で、亜鉛めっきの合金化処理を行った。
亜鉛めっき鋼板から組織観察用試験片を採取し、L断面(圧延方向に平行な板厚断面)を研磨後、ナイタール液で腐食しSEMで表面から1/4t(tは全厚)近傍の位置を1500倍の倍率で3視野以上を観察して撮影した画像を解析した(観察視野ごとに面積率を測定し、平均値を算出した)。ただし、残留オーステナイトの体積率(体積率を面積率とみなす)についてはX線回折強度により定量したため、各組織の合計が100%超える結果になる場合がある。表3のFはフェライト、Mはマルテンサイト、Bはベイナイト、残留γは残留オーステナイトを意味する。
亜鉛めっき鋼板から圧延方向に対して直角方向にJIS5号引張試験片(JISZ2201)を採取し、引張速度(クロスヘッドスピード)10mm/min一定で引張試験を行った。降伏強さ(YS)は、応力150~350MPa弾性域の傾きから0.2%耐力を読み取った値とし、引張強さは引張試験における最大荷重を初期の試験片平行部断面積で除した値とした。平行部の断面積算出における板厚はめっき厚込みの板厚値を用いた。引張強さ(TS)、降伏強さ(YS)、伸び(El)を測定し、降伏比YRと(1)式を算出した。
耐水素脆性の評価として、鋼板の抵抗スポット溶接部の水素脆性を評価した。評価方法は、実施例1と同様である。溶接電流値は、それぞれの鋼板強度に応じたナゲット径を形成する条件とした。1100MPa以上1250MPa未満では3.8mmのナゲット径とし、1250MPa以上1400MPa以下では4.8mmのナゲット径とした。実施例1同様、両端のスペーサ間隔は40mmとし、鋼板とスペーサは、予め溶接により固縛した。溶接後24時間放置したのち、スペーサ部を切り落として、溶接ナゲットの断面観察をおこない、割れ(亀裂)の有無の評価をおこなった。表3の溶接割れの欄で、亀裂なしを「○」、亀裂ありを「×」であらわした。
めっき後、後熱処理したのちの外観を目視観察し、不めっき欠陥が全くないものを「良好」、不めっき欠陥が発生したものを「不良」、不めっき欠陥はないがめっき外観ムラなどが生じたものは「やや良好」とした。なお、不めっき欠陥とは数μm~数mm程度のオーダーで、めっきが存在せず鋼板が露出している領域を意味する。
鋼中の拡散性水素量の測定は、実施例1と同様の方法で行った。
Claims (11)
- 質量%で、
C:0.10%以上0.30%以下、
Si:1.0%以上2.8%以下、
Mn:2.0%以上3.5%以下、
P:0.010%以下、
S:0.001%以下、
Al:1%以下、及び
N:0.0001%以上0.006%以下を含有し、残部がFeおよび不可避的不純物からなる成分組成と、
面積率で、残留オーステナイトが4%以上20%以下、フェライトが30%以下(0%を含む)、マルテンサイトが40%以上かつベイナイトが10%以上50%以下である鋼組織と、を有する鋼板と、
前記鋼板上の亜鉛めっき層と、を備え、
鋼中の拡散性水素量が0.20質量ppm未満であり、
引張強さが1100MPa以上であり、
引張強さTS(MPa)、伸びEl(%)および板厚t(mm)の関係が下記(1)式を満たし、
降伏比YRが67%以上である高強度亜鉛めっき鋼板。
TS×(El+3-2.5t)≧13000 (1) - 前記成分組成は、さらに、質量%で、
Ti、Nb、V及びZrのうち1種以上の合計:0.005%以上0.10%以下、
Mo、Cr、Cu及びNiのうち1種以上の合計:0.005%以上0.5%以下、及び
B:0.0003%以上0.005%以下のうち少なくとも1つを含有する請求項1に記載の高強度亜鉛めっき鋼板。 - 前記成分組成は、さらに、質量%で、
Sb:0.001%以上0.1%以下及びSn:0.001%以上0.1%以下のうち少なくとも1つを含有する請求項1又は2に記載の高強度亜鉛めっき鋼板。 - 前記成分組成は、さらに、質量%で、Ca:0.0010%以下を含有する請求項1~3のいずれか一項に記載の高強度亜鉛めっき鋼板。
- 請求項1~4のいずれか一項に記載の高強度亜鉛めっき鋼板が、成形加工及び溶接の少なくとも一方がされてなる高強度部材。
- 請求項1~4のいずれか一項に記載の成分組成を有する冷延鋼板を、水素濃度1vol%以上13vol%以下の焼鈍炉内雰囲気で、焼鈍炉内温度T1:(Ac3点-10℃)以上900℃以下の温度域で5s以上加熱した後、冷却し、400℃以上550℃以下の温度域で20s以上1500s以下滞留させる焼鈍工程と、
前記焼鈍工程後の鋼板を、めっき処理し、平均冷却速度3℃/s以上で100℃以下まで冷却するめっき工程と、
前記めっき工程後のめっき鋼板を、水素濃度10vol%以下かつ露点50℃以下の炉内雰囲気で、70℃以上450℃以下の温度T2(℃)に、0.02(hr)以上で下記(2)式を満たす時間t(hr)以上滞留させる後熱処理工程と、を有する高強度亜鉛めっき鋼板の製造方法。
135-17.2×ln(t)≦ T2 (2) - 前記焼鈍工程前に、前記冷延鋼板を、Ac1点以上(Ac3点+50℃)以下まで加熱し、酸洗する前処理工程を有する請求項6に記載の高強度亜鉛めっき鋼板の製造方法。
- 前記めっき工程後、0.1%以上の伸長率で調質圧延を施す請求項6または7に記載の高強度亜鉛めっき鋼板の製造方法。
- 前記後熱処理工程後に、幅トリムをする請求項8に記載の高強度亜鉛めっき鋼板の製造方法。
- 前記後熱処理工程前に、幅トリムを行い、
前記後熱処理工程における、70℃以上450℃以下の温度T2(℃)で滞留する滞留時間t(hr)が、0.02(hr)以上かつ下記(3)式を満たす請求項8に記載の高強度亜鉛めっき鋼板の製造方法。
130-17.5×ln(t)≦ T2 (3) - 請求項6~10のいずれか一項に記載の高強度亜鉛めっき鋼板の製造方法によって製造された高強度亜鉛めっき鋼板を、成形加工及び溶接の少なくとも一方を行う工程を有する、高強度部材の製造方法。
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| WO2022014172A1 (ja) * | 2020-07-14 | 2022-01-20 | Jfeスチール株式会社 | 鋼材及び鋼製品の脱水素方法、並びに、鋼材及び鋼製品の製造方法 |
| WO2022014131A1 (ja) * | 2020-07-14 | 2022-01-20 | Jfeスチール株式会社 | 連続焼鈍装置及び連続溶融亜鉛めっき装置、並びに鋼板の製造方法 |
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| WO2022264585A1 (ja) * | 2021-06-15 | 2022-12-22 | Jfeスチール株式会社 | 高強度亜鉛めっき鋼板および部材ならびにそれらの製造方法 |
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| JP7151948B1 (ja) * | 2021-06-15 | 2022-10-12 | Jfeスチール株式会社 | 高強度亜鉛めっき鋼板および部材ならびにそれらの製造方法 |
| EP4375389A4 (en) * | 2021-07-21 | 2024-11-13 | Nippon Steel Corporation | Cold-rolled steel sheet and manufacturing method thereof |
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| WO2023181821A1 (ja) * | 2022-03-25 | 2023-09-28 | Jfeスチール株式会社 | 脱水素装置及び鋼板の製造システム、並びに鋼板の製造方法 |
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| CN115216716B (zh) * | 2022-05-30 | 2023-09-08 | 山东嘉隆新型材料有限公司 | 一种高强度抗压镀锌板 |
| CN115216716A (zh) * | 2022-05-30 | 2022-10-21 | 山东嘉隆新型材料有限公司 | 一种高强度抗压镀锌板 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3757243B1 (en) | 2022-05-04 |
| MX2020010228A (es) | 2020-11-06 |
| JP2020045568A (ja) | 2020-03-26 |
| CN111936651A (zh) | 2020-11-13 |
| JP6631760B1 (ja) | 2020-01-15 |
| KR20200124740A (ko) | 2020-11-03 |
| EP3757243A1 (en) | 2020-12-30 |
| CN115404406A (zh) | 2022-11-29 |
| EP3757243A4 (en) | 2020-12-30 |
| JP6787466B2 (ja) | 2020-11-18 |
| US20210010115A1 (en) | 2021-01-14 |
| US11795531B2 (en) | 2023-10-24 |
| KR102400445B1 (ko) | 2022-05-20 |
| JPWO2019189842A1 (ja) | 2020-04-30 |
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