WO2001034862A1 - Tole d'acier galvanise trempe presentant un equilibre excellent entre resistance, ductilite et adherence entre acier et couche de placage - Google Patents
Tole d'acier galvanise trempe presentant un equilibre excellent entre resistance, ductilite et adherence entre acier et couche de placage Download PDFInfo
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- WO2001034862A1 WO2001034862A1 PCT/JP2000/007836 JP0007836W WO0134862A1 WO 2001034862 A1 WO2001034862 A1 WO 2001034862A1 JP 0007836 W JP0007836 W JP 0007836W WO 0134862 A1 WO0134862 A1 WO 0134862A1
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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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
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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
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0222—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating in a reactive atmosphere, e.g. oxidising 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0224—Two or more thermal pretreatments
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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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
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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
- 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
- C21D2211/005—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
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0447—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the heat treatment
- C21D8/0473—Final recrystallisation annealing
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0478—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing involving a particular surface treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/939—Molten or fused coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
- Y10T428/257—Iron oxide or aluminum oxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/259—Silicic material
Definitions
- the present invention relates to a hot-dip galvanized steel sheet having a sufficient strength-ductility balance and a good adhesion to the sheet, which can sufficiently withstand complicated press forming, and a method for producing the same.
- the hot-dip galvanized steel sheet in the present invention also includes a steel sheet containing an alloy element such as Fe in a zinc-coated layer.
- Mn and Si are elements that are easily oxidized, if they are added in large amounts, surface condensates such as Si and Mn precipitate on the steel sheet surface during annealing, and the wettability with molten zinc deteriorates. Is inhibited.
- JP-A-5-179356 and JP-A-5-51647 disclose a method of manufacturing a hot-rolled steel sheet. After quenching and quenching, and annealing in the two-phase region in the hot-dip galvanizing line, A method of plating has been proposed.
- the invention of the above (2) is a steel plate that can obtain high strength and has excellent plating adhesion due to the selection of the steel component.
- the structure of the base material is regulated. As a result, the required desired ductility as well as the strength cannot be obtained, which is insufficient to satisfy the performance required in the present invention.
- the invention of the above (3) is a plated steel sheet whose high strength can be obtained by selecting a steel component, similarly to the invention of the above (2), but the base material is similar to the invention of the above (1). Since the tissue of the present invention is not regulated, it cannot satisfy the required desired ductility as well as the strength, and is insufficient to satisfy the performance required in the present invention. As in the invention of (2), from the demand for stricter plating adhesion than before, the above strict L and requirements must be satisfied unless the base iron component immediately below the plating layer is controlled as disclosed in the present invention. It is difficult. Disclosure of the invention
- the present invention solves the above-mentioned problems of the prior art, and provides a high-strength solution having excellent plating adhesion and ductility even when a large amount of Si or Mn is contained in a base steel sheet (base steel).
- An object of the present invention is to provide a hot-dip galvanized steel sheet, that is, a hot-dip galvanized steel sheet excellent in both strength-ductility balance and plating adhesion.
- Another object of the present invention is to provide an advantageous method for producing a hot-dip galvanized steel sheet having the above-described excellent performance.
- the gist configuration of the present invention is as follows.
- a hot-dip galvanized steel sheet that is excellent in strength-ductility balance and plating adhesion, characterized in that it contains a martensite phase in a fraction of at least% and the balance consists of a fluoride phase and a retained austenite phase.
- an oxide containing at least one selected from these composite oxides or these oxides, and the amount of oxide formation on the surface layer of the base iron is 1 to A hot-dip galvanized steel sheet with a balance of 200mass-ppm and excellent strength and ductility balance and adhesion.
- a hot-rolled steel sheet or a cold-rolled steel sheet having a composition containing is heated to a temperature of 800 to 1000 ° C in an atmosphere satisfying the following formula, then cooled, and the pickling loss is 0.05 to 5 in terms of Fe.
- Pickling the steel sheet surface under the condition of g / m 2 then heating the steel sheet to a temperature of 700 to 850 ° C again in the continuous hot-dip galvanizing line, and then applying hot-dip galvanizing treatment.
- H 2 0 / H 2 partial pressure ratio of moisture and the hydrogen gas in the atmosphere
- C in the steel C content (ma ss%).
- Figure 1 shows the effect of the C concentration and the martensite phase fraction immediately below the plating layer on the strength-ductility balance and the plating adhesion.
- Figure 2 shows the effect of the C concentration immediately below the plating layer and the amount of oxide formation (oxygen conversion value) on the surface layer of the base iron on the plating adhesion.
- the steel plate after pickling was annealed at 750 ° C for 20 seconds by a vertical annealing apparatus, then rapidly cooled to 470 ° C at a speed of 10 to 80 ° CZs, and then the A1 concentration in the bath was set at 0 ° C.
- the plating treatment was performed for 1 second in a hot-dip galvanizing bath at 15 mass% and a bath temperature of 465 ° C.
- Adhesive tape is applied to the hot-dip zinc-coated steel sheet, and the adhesive tape is bent 90 ° with the side on which the adhesive tape is applied as the compression side.Then, the adhesive tape is released.
- the number of Zn counts by fluorescence X-rays per m (m): / c was measured, and those of ranks 1 and 2 were evaluated as good, and those of 3 or more were evaluated as poor according to the criteria in Table 1.
- the obtained solution is evaporated to dryness, and the amount of C in the obtained dried matter is quantified by a combustion-infrared absorption method according to the JIS standard method (G1211), and plating is performed based on the quantified result.
- the C concentration in the surface layer immediately below the bed was calculated.
- the cross section of the steel sheet embedded in the resin was etched with the following nital solution, which is a grain boundary corrosion solution.
- the ferrite phase was observed at a magnification of 1000 times using an electron microscope.
- the martensite phase is etched with the above-mentioned nital solution, polished again, the corroded layer is scraped off, etched with the following martensite etching solution, observed with an electron microscope at a magnification of 1000 times, and analyzed.
- the occupied area ratio of the martensite phase existing in a square area of 100 mm square was determined and the volume ratio of the martensite phase was determined.
- the observation area of the martensite phase, the fritite phase, and the austenite phase was set at an average position in the thickness direction other than the surface layer. However, disturbances such as center segregation were avoided.
- the amount of residual austenite was determined by polishing a specimen taken from a steel sheet to the center plane in the thickness direction and measuring the diffraction X-ray intensity at the center plane in the thickness.
- the incident X-rays were obtained using ⁇ ⁇ -rays, and the diffraction X-ray intensity ratios of the ⁇ 111 ⁇ , ⁇ 200 ⁇ , ⁇ 220 ⁇ , and ⁇ 311 ⁇ planes of the residual austenite phase in the specimen were calculated, and the average of these values was obtained.
- Fig. 1 summarizes the results obtained.
- the geological structure other than the martensite phase consisted of the second phase consisting of the ferrite phase and the retained austenite phase.
- the C concentration in the surface layer of the base iron immediately below the plating layer is limited to 0.02 mass% or less, and the martensite phase is included in the base iron structure in a fraction of 50% or more.
- the rest was limited to a structure consisting of a second phase consisting of a fritite phase and a retained austenite phase.
- composition range of the base steel sheet (base iron) in the present invention is limited to the above range.
- C is an element that is indispensable for obtaining the required strength and for forming the final structure into a composite structure of a tempered martensite and a fine martensite that can obtain high workability. It must be limited to 05 mass% or more.
- the temperature of the plating bath intrusion plate is 450-500 ° C
- the desired composite structure must be formed by the time the temperature reaches 600 ° C, the upper limit of the cooling temperature control region.It is essential that good hardenability is ensured and that the desired composite structure is formed. It is.
- the C content in steel was limited to the range of 0.05 to 0.25 mass%.
- Si is an element that promotes solid solution strengthening and a favorable composite structure, and advantageously improves the strength-elongation balance, and is a useful element for improving workability.
- the upper limit of the Si content in the steel was set to 2.0 mass%.
- the lower limit of the Si content in the steel is preferably set to 0.1 mass%.
- the content of Si in steel is more preferably 0.1 to 2.0 mass%.
- n 1.0 to 2.5 mass%
- Mn is not only useful for obtaining the required strength and desired composite structure, but also an important element for ensuring good hardenability after CGL annealing.
- Mn content in steel is less than 1.0 mass%, the effect of addition is poor.
- Mn content in steel exceeds 2.5 mass%, the weldability deteriorates.
- the Mn content in steel was limited to the range of 1.0 to 2.5 mass%.
- A1 is a useful element that enhances the cleanliness of steel by deoxidizing.However, when the content of A1 in steel is less than 0.005% by mass, the effect of its addition is poor, and on the contrary, it exceeds 0.10% by mass. Even so, the effect saturates, and on the contrary, the elongation characteristics are deteriorated.
- the A1 content in steel was limited to the range of 0.005 to 0.10 mass%.
- a desired effect can be basically obtained as long as the amounts of C, Si, Mn and A1 satisfy a predetermined range.
- Nb at least one selected from 0.005 to 0.10 mass% and Ti: 0.01 to 0.20 mass%
- Nb and Ti are both precipitation strengthening elements, and when used in appropriate amounts, can improve strength without deteriorating weldability.
- At least one selected from Nb and Ti is contained in the above range.
- the continuous annealing line (hereinafter also referred to as CAL) increases the martensite ratio at the time of annealing and cooling, and the martensite Has the effect of making the lath structure finer. Therefore, if one or more of Cr, Ni and Mo are added, the hardenability in the two-phase region reheating / cooling process in the next step of CGL annealing is improved, and the final By improving the composite structure, various moldability can be improved.
- the upper limit is desirably 1.0 mass% in terms of the total amount of Cr, Ni and Mo from the viewpoint of manufacturing cost.
- Other impurity components are as follows.
- P is acceptable within a range of 0.015 mass% or less
- S is acceptable within a range of 0.1 OlOmass% or less.
- the preferred lower limit of the P content is 0.001 mass%
- the preferred lower limit of the S content is 0.0005 mass%.
- a continuous forged slab with a thickness of about 300 mm is heated to about 1200 ° C, finished to a thickness of about 2.3 by hot rolling, and then wound at a temperature of about 500 ° C and heated.
- Rolled steel sheet As described above, since the quenching and quenching treatment is performed in the continuous annealing line (C A L), the base steel sheet can be any type of hot-rolled steel sheet and cold-rolled steel sheet.
- cold rolling may be performed as necessary to adjust the sheet thickness according to the final use.
- the effect of the rolling at this stage is not particularly recognized, so the rolling reduction does not need to be particularly limited.
- the base steel structure mainly a tempered martensite phase and a fine martensite phase.
- the tempered martensite phase which is a soft phase, is responsible for deformation in the initial stage of processing.
- the fine martensite phase which is a hard phase
- the hard phase since the fine martensite phase, which is a hard phase, has much greater deformability, when the work hardening of the soft phase becomes comparable to the strength of the fine martensite, the hard phase also takes on the deformation. For this reason, in the subsequent stages, the soft phase and the hard phase are integrally deformed, and the hard phase does not act as a void nucleus, delaying the fracture deformation time. Workability is obtained.
- the fraction of both martensite phases in the geological structure is larger.
- the fraction of both martensite phases in the ground iron structure is specified to be 50% or more in total.
- the fine martensite phase described above refers to a martensite phase having a particle size of 5 / m or less.
- the total fraction of the two martensite phases is determined by etching the cross section of the steel sheet embedded in the resin, observing the etched surface with an electron microscope, and analyzing the image as described above. It can be determined by measurement.
- Methods for obtaining such a structure include annealing at 800 to 1000 ° C with CAL, increasing the cooling rate to 40 ° CZs or more, and setting the temperature after cooling to 300 ° C or less. There is a method.
- the remaining microstructure consisted of a frit phase and a residual austenite phase.
- the composite microstructure including a frit phase and a residual austenite phase reduced other mechanical properties such as lowering the yield ratio. This is because it contributes to the improvement of. Such features cannot be obtained in complex organizations including veneers and perlites.
- the second phase other than the martensite phase was assumed to consist of the fluoride phase and the residual austenite phase.
- these structures are reheated in the CGL within a temperature range of 700 to 850 ° C, more preferably 725 to 840 ° C, and the cooling rate is 2 ° CZs or more.
- the subsequent temperature is set to 600 ° C or lower, a fine austenite phase is formed in the lath portion of the portion where the structure was originally martensite.
- the surface part of the base iron immediately below the plating layer is an area within at least 5 in the depth direction from the surface of the base iron after the separation of the plating layer (within 5 / m in the depth direction from the surface of the base steel). And the region that is considered to be involved in the alloying reaction during the heating alloying performed as necessary.
- the C concentration in the surface layer of the base iron immediately below the plating layer is 0.02 mass% or less, the above-mentioned precipitates are not generated, and the average C content of the base iron is 0.05 mass% or more. It is considered that even with a C-containing steel sheet, the plating adhesion is improved and improved.
- the method of reducing the C concentration only in the surface layer portion of the base iron as described above is not particularly limited.
- One example is a method of decarburizing the surface layer portion by annealing a steel sheet in a high dew point atmosphere.
- the C concentration in steel immediately below the plating layer (C concentration in the surface layer of ground iron) can be measured by any of the following methods (1) to (3).
- the front and back surfaces of the base steel are heated at 60 ° C—5 mass% HC1 Using an aqueous solution, dissolve 5 m based on the gravimetric method for estimating the thickness reduction using the weight before and after pickling as an index.
- the presence or absence of cementite precipitation can be easily determined by etching the cross section of the steel sheet and observing it with an optical microscope or an electron microscope. Furthermore, in the above-mentioned region where the C concentration in the surface layer of the base iron is 0.02 niass% or less, oxides containing the elements Si, Mn, and Fe in the steel, ie, Si oxides, Mn oxides, Fe oxides or If these composite oxides, or oxides containing at least one selected from these oxides, are present at at least one of the crystal grain boundaries and within the crystal grains, the metal oxides will be formed during the bending of the plating film. The stress is alleviated by the introduction of fine cracks at the plating layer / base iron interface.
- the presence or absence of oxide formation on the surface of the ground iron is determined by etching the cross section of the steel sheet with a picral solution (: 4 g of picric acid ZlOOcc ethanol) and observing the etched surface with a scanning electron microscope (SEM). You can find out this In this case, it can be considered that an oxide layer has been formed if at least one oxide layer is formed on at least one of the grain boundary and the inside of the grain.
- a picral solution 4 g of picric acid ZlOOcc ethanol
- the type of oxide can be identified by analyzing the extract using inductively coupled plasma atomic emission spectrometry (ICP emission spectrometry).
- ICP emission spectrometry inductively coupled plasma atomic emission spectrometry
- the amount of oxides generated in the surface layer of the base iron be about 1 to 200 mass-ppm in terms of the amount of oxygen.
- the reason for this is that if the amount of oxides generated is less than l mass-ppm in terms of oxygen, the amount of oxides generated is too small to achieve a sufficient plating adhesion improvement effect. On the other hand, if the amount of generated oxide exceeds 200 mass-ppni in terms of oxygen, the amount of generated oxide is excessive, which leads to deterioration of plating adhesion.
- the oxygen conversion value of the amount of oxides generated in the surface layer of the base steel is the oxygen content of the steel sheet after peeling and removing the plating layer with an alkaline aqueous solution to which an inhibitor has been added, and the peeling and removal of the plating layer.
- Each of the oxygen content of the steel sheet obtained by polishing the front and back surfaces of the steel sheet after mechanical treatment by about 100 // m using an inert gas melting infrared absorption method, the oxygen content of the former and the oxygen content of the latter were measured. Is determined from the difference between
- Heating temperature of hot-rolled steel sheet-cold-rolled steel sheet must be 800-1000 ° C.
- the hydrogen concentration in the atmosphere during the heat treatment (annealing) be 1 to 100 vol%.
- H 2 0 / H 2 partial pressure ratio of moisture and the hydrogen gas in the atmosphere
- C in the steel C content (ma ss%) shown o
- CO generated at the time of decarburization simultaneously promotes the internal oxidation reaction, so that oxide formation is promoted at the grain boundaries and in the grains.
- the steel sheet After annealing by the above-described heat treatment, the steel sheet is cooled, and then the surface of the steel sheet is pickled under conditions where the pickling loss is 0.05 to 5 g / m 2 in terms of Fe to remove oxides.
- pickling weight loss is less than 0. 05G / m 2 in terms of Fe
- pickling is left is insufficient excess oxides, lead to coating adhesion deterioration, conversely, pickling weight loss
- pickling weight loss If There exceeding 5 g / m 2 in terms of Fe and rough surface of the steel sheet, hot-dip zinc plated well appearance of the steel sheet Ru impaired after, the extreme case is internally oxidized layer or decarburized layer be removed It is because.
- the above-mentioned Fe-converted value of the pickling loss can be obtained from the weight of the steel sheet before and after the pickling.
- Hydrochloric acid is particularly preferred as the acid used for pickling, but sulfuric acid, nitric acid, phosphoric acid, or the like may also be used. These acids may be used in combination with hydrochloric acid, and the acid may be used. Is not particularly limited.
- Conditions for hot-dip galvanizing By subjecting the steel sheet prepared as described above to a hot-dip galvanizing line, it is possible to obtain a hot-dip galvanized steel sheet having excellent strength-ductility balance and excellent adhesion.
- the steel sheet is heated again to a temperature of 700 to 850 in a reducing atmosphere and then hot-dip galvanizing is performed. If the heating temperature is lower than 700 ° C, reduction of oxides generated on the steel sheet surface by pickling becomes insufficient, and the plating adhesion deteriorates.On the other hand, if the heating temperature exceeds 850 ° C, Si Degradation of plating adhesion is inevitable due to the surface thickening of the metal.
- molten zinc plating bath a molten zinc plating bath containing 0.01 to 0.2 mass% of A1 is preferable, and the bath temperature is preferably 450 to 500 ° C.
- the temperature of the steel sheet when entering the bath is preferably 450 to 500 ° C.
- the coating weight of the hot-dip galvanized steel sheet is preferably 20 to L20 g / m 2 per one side of the steel sheet, that is, per unit area of the coated steel sheet.
- the hot-dip galvanized steel sheet thus obtained can be subjected to a heat alloying treatment if necessary.
- Heat alloying is particularly preferable for improving the weldability, and is divided into cases where heat alloying is performed and cases where heat alloying is not performed according to the purpose of use.
- the heat alloying be carried out within a temperature range of 450 to 550 ° C, particularly within a temperature range of 480 to 520 ° C.
- the heating alloying temperature is lower than 450 ° C, alloying hardly progresses, and if it exceeds 550 ° C, on the other hand, alloying proceeds excessively and the plating adhesion deteriorates. This is because pearlite is generated and a desired tissue cannot be obtained. Further, it is desirable that the amount of Fe diffusion in the plated layer after alloying, that is, the Fe content in the plated layer, be regulated in the range of 8 to 12 mass%.
- the amount of Fe diffusion in the plated layer after alloying is more preferably 9 to 10 mass%.
- a gas heating furnace, an induction heating furnace, or the like may be used, and a conventionally known method may be used.
- a continuous green slab having a thickness of 300 mm with the composition shown in Table 2 was heated to 1200 ° C, and then hot-rolled into a hot-rolled steel sheet having a thickness of 2.3 mm and then wound at 500 ° C. .
- Table 3-1 shows the annealing temperature, annealing atmosphere, and cooling conditions after annealing in CAL.
- the annealed steel sheet was pickled using an aqueous hydrochloric acid solution while adjusting the pickling loss.
- Adjustment of the pickling loss was performed by adjusting the concentration of HC1 in the pickling solution to 3 to 10 mass% and the temperature of the pickling solution to 50 to 80 ° C.
- Table 2-2 shows the above pickling loss in terms of Fe.
- the Fe conversion value of the pickling loss was determined from the weight of the steel sheet before and after pickling.
- the pickled steel sheet is passed through a continuous hot-dip galvanizing line (CGL), It was heated and reduced in a reducing atmosphere with a hydrogen concentration of 5 vol%, cooled, and then subjected to molten zinc plating.
- CGL continuous hot-dip galvanizing line
- Table 3-2 shows the heating temperature in CGL and the cooling conditions after thermal reduction.
- the coating weight of the hot-dip galvanized coating was 40 g / m 2 per unit area of the coating on both sides of the steel sheet.
- Alloying temperature (plate temperature): 490 to 600 ° C
- the hot-dip galvanized steel sheet or the alloyed hot-dip galvanized steel sheet obtained above as described above, the following methods were used to (1) the C concentration in the surface layer of the ground iron immediately below the plating layer, and (2) The fraction of the martensite phase in the base metal structure and the base metal structure (total fraction of the tempered martensite phase and the fine martensite phase) and (3) the amount of oxide formation (oxygen conversion value) in the surface layer of the base iron Measured and observed.
- Quantification was performed by the above-mentioned inhibitor-containing alkaline solution, 60 ° C-5 mass% HCl aqueous solution and combustion-infrared absorption method.
- the melt thickness of the surface layer of the base steel was set to 5 / im.
- the steel layer after separating and removing the plating layer and the surface of the steel sheet after peeling and removing the plating layer are polished by mechanical method to about 100 zm with an alkaline aqueous solution containing the following inhibitors.
- the oxygen content of each of the obtained steel sheets was measured by an inert gas fusion infrared absorption method (JIS Z 2613), and the difference between the former oxygen content and the latter oxygen content was determined.
- the oxide in the above-mentioned oxide generation amount indicates Si oxide, Mn oxide, Fe oxide or a composite oxide thereof, and the oxide generation amount is the total amount of these oxides (oxygen amount). (Equivalent value).
- the cross section of the steel sheet embedded in the resin was etched with a picral solution (4 g ethanolic picophosphate ZlOOcc ethanol), and the locations of the grain boundaries and within grains were confirmed. Further, the mechanical properties and the adhesion of the hot-dip galvanized steel sheet or alloyed hot-dip galvanized steel sheet obtained above were investigated.
- the plating adhesion was determined by bending the coated steel sheet by 90 °, separating the compression side plating layer with an adhesive tape, and measuring the Zn force by fluorescent X-rays per unit length (m) of the adhesive tape. c was measured and evaluated according to the criteria in Table 1 described above.
- Table 4 shows the properties, mechanical properties and plating adhesion of the plated steel sheet obtained above.
- Fig. 2 shows the effect of the C concentration in the surface layer of the base iron immediately below the plating layer and the amount of oxides generated (in terms of oxygen content) on the surface of the base iron on the adhesion.
- the steel sheets of the invention examples did not have any problem in mechanical properties and plating adhesion, whereas in the comparative examples, the plating adhesion was good even if the mechanical properties were good. The mechanical properties were inferior even if the plating properties were poor or the plating adhesion was good.
- Heating alloying experiment Experiment Heating reduction furnace Cooling conditions after heat reduction Melting zinc plating bath
- a hot-dip galvanized steel sheet having both excellent strength-ductility balance and excellent adhesion can be obtained.
- the hot-dip galvanized steel sheet of the present invention it is possible to reduce the weight and fuel consumption of automobiles, and thus to greatly contribute to improving the global environment.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Coating With Molten Metal (AREA)
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/869,903 US6558815B1 (en) | 1999-11-08 | 2000-11-08 | Hot dip Galvanized steel plate excellent in balance of strength and ductility and in adhesiveness between steel and plating layer |
AU13019/01A AU771011B2 (en) | 1999-11-08 | 2000-11-08 | Hot dip galvanized steel plate excellent in balance of strength and ductility and in adhesiveness between steel and plating layer |
DE60006068T DE60006068T2 (de) | 1999-11-08 | 2000-11-08 | Feuerverzinktes galvanisiertes stahlblech mit hervorragendem gleichgewicht zwischen festigkeit und dehnbarkeit und adhäsion zwischen stahl und beschichtung |
EP00974818A EP1149928B1 (en) | 1999-11-08 | 2000-11-08 | Hot dip galvanized steel plate excellent in balance of strength and ductility and in adhesiveness between steel and plating layer |
CA002360070A CA2360070C (en) | 1999-11-08 | 2000-11-08 | Hot dip galvanized steel plate excellent in balance of strength and ductility and in adhesiveness between steel and plating layer |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31643999 | 1999-11-08 | ||
JP11/316439 | 1999-11-08 | ||
JP2000214713 | 2000-07-14 | ||
JP2000-214713 | 2000-07-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001034862A1 true WO2001034862A1 (fr) | 2001-05-17 |
Family
ID=26568658
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/007836 WO2001034862A1 (fr) | 1999-11-08 | 2000-11-08 | Tole d'acier galvanise trempe presentant un equilibre excellent entre resistance, ductilite et adherence entre acier et couche de placage |
Country Status (9)
Country | Link |
---|---|
US (1) | US6558815B1 (ja) |
EP (1) | EP1149928B1 (ja) |
KR (1) | KR100561893B1 (ja) |
CN (1) | CN1188534C (ja) |
AU (1) | AU771011B2 (ja) |
CA (1) | CA2360070C (ja) |
DE (1) | DE60006068T2 (ja) |
TW (1) | TW504519B (ja) |
WO (1) | WO2001034862A1 (ja) |
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- 2000-11-06 TW TW089123403A patent/TW504519B/zh not_active IP Right Cessation
- 2000-11-08 KR KR1020017008598A patent/KR100561893B1/ko not_active IP Right Cessation
- 2000-11-08 AU AU13019/01A patent/AU771011B2/en not_active Ceased
- 2000-11-08 US US09/869,903 patent/US6558815B1/en not_active Expired - Lifetime
- 2000-11-08 EP EP00974818A patent/EP1149928B1/en not_active Expired - Lifetime
- 2000-11-08 CA CA002360070A patent/CA2360070C/en not_active Expired - Fee Related
- 2000-11-08 DE DE60006068T patent/DE60006068T2/de not_active Expired - Lifetime
- 2000-11-08 CN CNB008047073A patent/CN1188534C/zh not_active Expired - Lifetime
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7294412B2 (en) * | 2003-01-15 | 2007-11-13 | Nippon Steel Corporation | High-strength hop-dip galvanized steel sheet |
US7736449B2 (en) | 2003-01-15 | 2010-06-15 | Nippon Steel Corporation | High-strength hot-dip galvanized steel sheet and method for producing the same |
JP2013117043A (ja) * | 2011-12-02 | 2013-06-13 | Nippon Steel & Sumitomo Metal Corp | 合金化溶融亜鉛めっき鋼帯およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN1343262A (zh) | 2002-04-03 |
EP1149928B1 (en) | 2003-10-22 |
AU1301901A (en) | 2001-06-06 |
EP1149928A4 (en) | 2002-06-05 |
AU771011B2 (en) | 2004-03-11 |
CA2360070C (en) | 2008-04-01 |
KR20010101411A (ko) | 2001-11-14 |
EP1149928A1 (en) | 2001-10-31 |
TW504519B (en) | 2002-10-01 |
KR100561893B1 (ko) | 2006-03-16 |
CA2360070A1 (en) | 2001-05-17 |
US6558815B1 (en) | 2003-05-06 |
DE60006068D1 (de) | 2003-11-27 |
DE60006068T2 (de) | 2004-07-22 |
CN1188534C (zh) | 2005-02-09 |
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