WO2012004889A1 - 溶融亜鉛系めっき鋼板 - Google Patents
溶融亜鉛系めっき鋼板 Download PDFInfo
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- WO2012004889A1 WO2012004889A1 PCT/JP2010/061703 JP2010061703W WO2012004889A1 WO 2012004889 A1 WO2012004889 A1 WO 2012004889A1 JP 2010061703 W JP2010061703 W JP 2010061703W WO 2012004889 A1 WO2012004889 A1 WO 2012004889A1
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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
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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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
- C23C2/0224—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
- 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
- C23C2/29—Cooling or quenching
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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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.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12611—Oxide-containing component
- Y10T428/12618—Plural oxides
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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
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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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
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
Definitions
- the present invention relates to a hot dip galvanized steel sheet.
- Alloyed hot-dip galvanized steel sheets having high spot-welding continuous spotting properties and corrosion resistance after coating are used in large quantities for applications such as automotive steel sheets.
- ⁇ phase Zn-Fe body-centered cubic metal with 20% to 28% by mass of Fe
- the intermetallic compound when there is a large amount of Fe 3 Zn 10 ) has a problem of powdering in which the plating layer is hard and is pulverized during press molding and peeled into a powder form.
- the degree of alloying is low (when there is a large amount of monoclinic intermetallic compound (FeZn 13 ) of Zn and Fe, which is called ⁇ phase and whose mass% is Fe of 5.5 to 6.2%)
- ⁇ phase a problem of damage to the plating layer
- flaking a problem of damage to the plating layer
- alloyed hot dip galvanized steel sheets are now used without any major problems.
- the basic means is to suppress the formation of the ⁇ phase at the interface between the plating and the ground iron. Further, in order to improve the anti-flaking property, it is a basic means to suppress the formation of ⁇ phase on the plating surface layer.
- Patent Document 1 discloses a hexagonal crystal having a ⁇ phase of 1.0 ⁇ m or less at the interface between the plating and the ground iron and containing 0.003% or less of Fe in mass%, which is referred to as a ⁇ phase in the plating surface layer.
- An alloyed hot-dip galvanized steel sheet having a plated layer in which no Zn phase or the ⁇ phase exists is disclosed.
- Patent Document 2 discloses an galvannealed steel sheet having a ⁇ phase thickness of 0.5 ⁇ m or less and a plating layer having no ⁇ or ⁇ phase on the plating surface layer.
- Patent Document 3 discloses an alloyed hot-dip galvanized steel sheet having a plating layer on the steel sheet surface and having a surface roughness of Rmax ⁇ 8 ⁇ m.
- Patent Document 4 discloses an alloyed hot-dip galvanized steel sheet in which the surface coverage of the ⁇ phase and the X-ray diffraction intensity ratio between the ⁇ phase and other phases are specified within a specific range.
- the plating surface layer has an anti-adhesion function, and one or more metal oxides of Mn, Mo, Co, Ni, Ca, Cr, V, W, Ti, Al, and Zn /
- a coating I mainly composed of hydroxide, and a coating II having a lubrication lubrication function and mainly composed of one or two oxygen acids of P and B, and the coating I is concentrated on the side of the iron-iron interface.
- a zinc-based plated steel sheet that is inclined and coated so as to become thicker on the surface side.
- Patent Document 6 mainly includes a Zn oxide having a flat portion on the surface of the iron-zinc alloy plating and having a thickness of 8 nm to 200 nm and an interface width of 25 nm to 500 nm.
- An alloyed hot-dip galvanized steel sheet having an oxide film is disclosed.
- Patent Document 7 discloses a zinc-based plated steel sheet in which a crystalline phosphate film is formed on the surface layer.
- Japanese Patent Laid-Open No. 01-068456 Japanese Patent Laid-Open No. 04-013855 Japanese Patent Laid-Open No. 03-191045 Japanese Patent Application Laid-Open No. 08-092714 Japanese Patent Laid-Open No. 04-176878 JP 2003-171751 A JP 2007-217784 A
- the alloyed hot-dip galvanized steel sheets of Patent Documents 1 and 2 have no ⁇ and ⁇ phases on the plating surface layer, and the ⁇ phase thickness is small. Therefore, the plating layer is formed of a single phase of Zn and Fe hexagonal intermetallic compound (FeZn 7 ), which is generally referred to as ⁇ 1 and whose Fe is 7 to 11.4% by mass. Therefore, in order to suppress both powdering and flaking, it is an ideal plating layer structure, but compared to the techniques of Patent Documents 5 to 7 in which a lubricating film is provided on the surface layer of a zinc-based plated steel sheet, Slidability during molding is poor.
- FeZn 7 Zn and Fe hexagonal intermetallic compound
- the alloyed hot-dip galvanized steel sheet of Patent Document 3 imparts a certain degree of roughness to the plating surface for the purpose of compensating for the decrease in flaking properties while the ⁇ phase is present in the plating surface layer.
- the alloyed hot-dip galvanized steel sheet of Patent Document 4 also has a ⁇ phase for the purpose of improving chemical conversion treatment properties and cationic electrodeposition coating properties.
- the alloyed hot-dip galvanized steel sheet of Patent Document 4 does not have an ideal plating layer structure.
- the galvannealed steel sheet disclosed in Patent Document 4 is inferior in slidability during press forming as compared with the techniques disclosed in Patent Documents 5, 6, and 7.
- the alloyed hot-dip galvanized steel sheet of Patent Document 5 in which a lubricating film is applied to the surface layer of the galvanized steel sheet is extremely good at the time of press forming regardless of whether or not the ⁇ phase is present in the plated surface layer.
- a large wrinkle pressing force blade holdingBforce, BHF
- wrinkles are less likely to occur, but it is necessary to apply a large wrinkle pressing force to suppress the occurrence of wrinkles. That is, although the lower limit of the wrinkle pressing force at which cracking occurs increases, the lower limit of the wrinkle pressing force that is not necessary for eliminating the wrinkle also increases. Therefore, the range of the wrinkle pressing force that does not generate both wrinkles and cracks, that is, the press-moldable range is almost the same level as the related art.
- Patent Documents 6 and 7 exhibit good slidability during press forming regardless of whether or not the ⁇ phase is present in the plating surface layer. However, the effect is inferior to the technique of Patent Document 5. Moreover, the press-moldable range is almost the same level as the related technology.
- the related technology is excellent in terms of both powdering and flaking, or slidability during press molding, but it can expand the range of wrinkle pressing force that can be taken, that is, the range in which press molding is possible. I could't. Accordingly, there has been a demand for higher press-formability, that is, an increase in the range of the wrinkle pressing force that does not cause both wrinkles and cracks, that is, the press-formable range.
- a first aspect of the present invention includes a steel sheet, wherein is applied to the surface of the steel sheet, as a main component Zn, plating layer deposition amount is 20 g / m 2 or more 100 g / m 2 or less, the A hot-dip galvanized steel sheet, wherein the plating layer includes an amorphous film containing an inorganic oxyacid salt and a metal-based oxide containing Zn on a surface layer thereof; and a [delta] 1 phase; the plating layer contains 8 mass% to 13 mass% of Fe; Zn contained in the metal oxide is present up to the outermost layer of the amorphous film; The value obtained by dividing the X-ray diffraction intensity after background removal at the crystal lattice plane spacing of 0.126 nm of the ⁇ phase by the X-ray diffraction intensity after background removal at the crystal lattice plane spacing of 0.127 nm of the ⁇ 1 phase.
- a certain X-ray diffraction intensity ratio I is 0.06 or more and 0.35 or less It is; a hot-dip galvanized steel sheet.
- the plating layer may have a ⁇ phase having a thickness average of 1.5 ⁇ m or less.
- the plating layer may contain 0.10 g / m 2 or more and 0.25 g / m 2 or less of Al.
- the plating layer may contain Ni exceeding 0 and not exceeding 0.40 g / m 2 .
- the plating layer may also contain 0.15 g / m 2 or more 0.45 g / m 2 or less of Al.
- the inorganic oxyacid salt may contain one or more of P or B.
- the metal oxide may further contain an oxide of one or more metals of Mn and Al. .
- the amorphous film contains a mixture of a component having an anti-adhesion function, an inorganic oxyacid salt having a roller lubrication function, and a metal oxide. Furthermore, regarding the plating layer structure, a specific amount of ⁇ phase remains in the surface layer. Therefore, a hot-dip galvanized steel sheet that is excellent in lubricity and chemical conversion processability and has a wider range that can be press-molded than the related art can be provided by the synergistic effect of such a lubricating film and the plating layer structure. As a result, in press forming of steel plates for automobile bodies, the yield is improved and production can be performed more efficiently than in related technologies.
- the design freedom of the mold is widened, and a wide variety of press molding can be performed. Therefore, the commercial value of the automobile is improved.
- the hot dip galvanized steel plate which has favorable powdering property can be provided.
- the hot dip galvanized steel sheet with a wider press forming range can be provided. .
- the hot dip galvanized steel sheet having a wider press-formable range can be provided.
- the hot dip galvanized steel plate with a wider press-moldable range can be provided.
- the lower limit ( ⁇ ) of the wrinkle pressing force that causes cracking is eliminated. It is the figure which put together the Example of Table 3, and the comparative example by making the value which remove
- the present inventors paid attention to a technique for imparting a lubricating film to the surface layer of a zinc-based plated steel sheet disclosed in Patent Document 5.
- the coating having an anti-adhesion function is thick on the interface side with the plating layer, and the coating having the collogal lubrication function is inclined to cover the coating surface side, that is, on the outer surface side of the plating layer. It was considered to be a suitable requirement for obtaining a wide press forming load range.
- the related technology is applied to alloyed hot-dip galvanized steel sheets, even if the plating layer structure is unfavorable for slidability, the technology provides excellent slidability.
- the layer structure was thought not to affect slidability.
- the present inventors are not limited to the idea in the related art with respect to these two points, and an ideal plating layer capable of expanding the range of the wrinkle holding force in which neither wrinkles nor cracks are generated, that is, the press moldable range.
- the structure and film configuration were discussed.
- a synergistic effect of a lubricating film containing a mixture of a component having an anti-adhesion function and a component having a roller lubrication function and a plating layer structure in which a specific amount of ⁇ phase remains on the surface layer is adopted. It has been found that the range of the wrinkle pressing force, that is, the press-moldable range can be expanded.
- the coating surface is processed at a low surface pressure due to the concentration of the roller lubrication component and the presence of a sliding interface between the roller friction component and the anti-adhesion component.
- High lubrication effect is also exhibited in the case of Therefore, there is a drawback that wrinkles are likely to occur.
- This disadvantage is eliminated by distributing both the roller lubrication component and the anti-adhesion component in the lubricating film.
- Patent Document 5 such a solution alone has a low limit surface pressure that causes galling when processed at a high surface pressure, which is disadvantageous for cracking during pressing. Problems arise. Therefore, we studied to have the same anti-adhesion function by forming a stronger film than the related technology.
- the Zn of the outermost coating layer can be obtained by providing a compound of oxygen-containing oxygen and zinc containing phosphorus as the main components to obtain more suitable lubricity.
- the slidability is impaired, and conversely cracking may occur. Therefore, it is important to leave an appropriate amount of ⁇ layer.
- the plating layer of this embodiment contains Zn containing Zn as a main component and a content rate of 8% by mass to 13% by mass.
- “having Zn as a main component” means that Zn is contained in an amount of 50% by mass or more.
- the Fe content is preferably 8.5% by mass or more and 12.5% by mass or less, and more preferably 9% by mass or more and 12% by mass.
- the plating layer is preferably 20 g / m 2 or more and 100 g / m 2 or less per side. When the plating layer is less than 20 g / m 2 , the corrosion resistance is insufficient, and 30 g / m 2 or more is a preferred embodiment.
- the plating layer is more than 100 g / m 2, and decreases continuously dotting property during spot welding is the preferred embodiment is 70 g / m 2 or less.
- the ⁇ phase thickness is preferably 1.5 ⁇ m or less on average.
- a more preferable ⁇ phase thickness is 1 ⁇ m or less, and a most preferable ⁇ phase thickness is 0.8 ⁇ m or less.
- the total Al concentration in the plating bath is within the range of 0.11% by mass or more and 0.15% by mass or less in order to perform alloying properly. It is preferable that If the total Al concentration in the plating bath is less than 0.11% by mass, alloying of the plating layer cannot be controlled, and the plating layer becomes overalloyed. When the total Al concentration in the plating bath is more than 0.15% by mass, the alloying of the plating layer is delayed and the production efficiency is lowered.
- the total amount of Al in the plating layer that is, the amount of Al derived from the barrier layer and the plating bath at the time of initial alloying is in the range of 0.10 g / m 2 to 0.25 g / m 2 .
- Al plating layer is preferably 0.13 g / m 2 or more 0.22 g / m 2 or less, more preferably it is desirable to control the 0.15 g / m 2 or more 0.20 g / m 2 or less.
- the limit of the wrinkle pressing force at which cracks occur due to the insufficient amount of Zn taken into the amorphous film containing the metal oxide and the metal-based oxide is reduced, and the formable range is narrowed. If the X-ray diffraction intensity ratio I is greater than 0.35, the slipping property is insufficient, and the lower limit ( ⁇ ) of the wrinkle pressing force necessary to eliminate wrinkles is lowered, but wrinkle pressers that cause more cracks are generated. Since the lower limit ( ⁇ ) of the force is also lowered, the moldable range is narrowed also in this case.
- the X-ray diffraction intensity ratio is more preferably in the range of 0.10 to 0.35, and most preferably in the range of 0.15 to 0.30.
- the background removal method is shown in FIG.
- the horizontal axis in FIG. 1 indicates the X-ray incident angle, and the vertical axis indicates the diffraction intensity.
- K1 is a line representing the background of the peak 19 corresponding to the ⁇ 1 phase
- K2 is a line representing the background of the peak 20 corresponding to the ⁇ phase.
- Plating layer of this embodiment the a main component Zn, of not more than 13 wt% 8 wt% or more containing Fe and 0.15 g / m 2 or more 0.45 g / m 2 or less Al, 0 g / m 2 More than 0.40 g / m 2 Ni.
- the method is immersed in a hot dip galvanizing bath having a higher Al concentration in the plating bath than in the case of the first embodiment described above.
- Plating with. The purpose is to further suppress the formation of the ⁇ phase.
- the higher the Al concentration in the plating bath the less the formation of the ⁇ phase and the more the formation of the ⁇ 1 phase.
- the Al concentration in the plating bath is simply increased, a large amount of Fe—Al barrier layer is formed at the interface of the iron base, so that alloying is delayed and production efficiency decreases.
- Ni is pre-plated on the surface of the steel plate in advance, and Ni is pre-plated in the vicinity of the steel plate interface when immersed in the bath to react with Al in the bath, thereby reducing the Al concentration in the vicinity of the interface and generating it at the interface. Control is performed so that there are not too many Fe—Al barrier layers. On the other hand, since a high concentration of Al exists in the deposited plating layer, a ⁇ phase is difficult to be generated during alloying.
- Ni in the plating layer is more than 0 g / m 2 and not more than 0.40 g / m 2 depends on the appropriate range of Ni to be pre-plated.
- the appropriate amount of Ni to be pre-plated is 0.10 g / m 2 or more and 0.50 g / m 2 or less.
- a part is dissolved and lost in the plating bath, so that the amount of Ni remaining in the plating layer exceeds 0 g / m 2 , preferably 0.07 g / m 2.
- the range is 0.40 g / m 2 or less.
- Ni to pre-plate is 0.10 g / m ⁇ 2 > or more.
- Ni to be pre-plated exceeds 0.50 g / m 2 , the reaction with Al in the bath is violent, and the formation of the barrier layer becomes non-uniform, which impairs the appearance after alloying.
- the the Al in the coating layer was defined as 0.15 g / m 2 or more 0.45 g / m 2 or less, by proper range of Al concentration in the plating bath.
- the Al concentration in the plating bath is preferably in the range of 0.16% by mass to 0.20% by mass.
- the Al concentration in the plating bath is less than 0.16% by mass, alloying cannot be controlled and an overalloy is formed.
- the Al concentration in the plating bath is more than 0.20% by mass, alloying is delayed and production efficiency is lowered.
- the total of Al in the plating layer that is, Al derived from the barrier layer and the plating bath at the time of initial alloying is 0.15 g / m 2 or more.
- the range is 0.45 g / m 2 or less.
- the ⁇ phase is less likely to be generated. Since one phase is easily generated, the value of the X-ray diffraction intensity ratio I can be controlled to be lower.
- the lubricious film formed on the plating surface is an amorphous film composed of an inorganic oxyacid salt and a metal-based oxide in both cases of the first embodiment and the second embodiment.
- oxygen acid containing P and these salts are preferably used for film formation. It is done.
- boric acid which is an oxygen acid containing B, and salts thereof are also applicable. These may be used alone or in combination. When mixed and used, it is preferable to contain an oxygen acid containing P.
- the metal oxide is an oxide or hydroxide of Zn, Al, Ni, Mn, Mo, Co, Ni, Ca, V, W, Ti, Ce, or the like. These are added to the reaction solution, and Zn, Al, and Ni are components incorporated into the lubricating film by dissolving in the reaction solution from the hot-dip plating layer. These, particularly Zn, are important as a component that reinforces the function of preventing adhesion between the mold and the plating layer.
- the incorporation of these components into the lubricating film can be determined by elemental analysis in the depth direction by Auger electron spectroscopy. The presence of Zn in the outermost layer of the coating can be confirmed by detecting Zn when elemental analysis of the sample surface is performed without sputtering by Auger electron spectroscopy or X-ray photoelectron spectroscopy.
- the proper amount of the inorganic oxyacid salt is the sum of P and B, and the proper amount of the metal-based oxide is Zn, Al, Ni, Mn, Mo, Co, Ni, Ca, V, W, Ti,
- the total amount of Ce is preferably 1 mg / m 2 or more and 250 mg / m 2 or less. When each component is less than 1 mg / m 2 , there is no effect, and when it exceeds 250 mg / m 2 , the chemical conversion treatment property is adversely affected. More preferably, any component is 3 mg / m 2 or more and 150 mg / m 2 or less.
- a major feature different from the related art is that an inorganic oxyacid salt and a metal-based oxide containing Zn are contained, and that Zn oxide exists in the film up to the outermost layer.
- the above-described preferred technique in Patent Document 5 is a technique in which a P-containing component having a roller lubrication function is concentrated toward the surface layer in the coating, and a Mn-containing component having an adhesion preventing function is inclinedly coated so as to be strong at the interface of the steel.
- the results of glow discharge spectroscopic analysis are disclosed.
- FIG. 2A and FIG. 2B show the results of depth analysis by Auger electron spectroscopic analysis corresponding to the first and second embodiments.
- Patent Document 5 The analysis result according to Patent Document 5 is compared with the analysis results of the first and second embodiments.
- the technique of Patent Document 5 that is, the related technique, it can be seen that the P-containing component and the Mn-containing component have peaks at different positions. It can also be seen that Zn is present only in the inner layer of the lubricating film.
- the amount of Zn in the lubricating film is overwhelmingly higher in the present invention than in the related art, and the presence of Zn can be confirmed in the outermost layer of the lubricating film. That is, unlike the related art, the hot dip galvanized steel sheet according to the present embodiment has Zn present in the lubricating film up to the outermost layer. Taking such a film configuration leads to an expansion of the press-moldable range.
- the outermost Zn layer may be formed so as to exist mainly (50% or more) in the form of a phosphorus-containing oxygen acid and zinc compound (salt).
- the Zn state of the film is identified by X-ray photoelectron spectroscopy.
- FIG. 4 shows a 2p spectrum of P and a 3s spectrum of Zn in a region from the outermost layer to a depth of 18 nm.
- the horizontal axis represents the binding energy (eV).
- the main component is a compound of oxygen-containing acid and zinc containing phosphorus, and at a depth of 4 nm, the compound of oxygen-containing acid and zinc containing zinc and zinc oxide / metal zinc are almost the same, from a depth of 6 nm. It can be seen that at 18 nm, the main components are zinc oxide and metallic zinc.
- FIG. 5 is a 2p spectrum of Zn of the same sample. The horizontal axis represents the binding energy (eV).
- the main component is an oxygen acid and zinc compound containing phosphorus, and at a depth of 4 nm, the oxygen acid and zinc compound containing phosphorus and zinc oxide / metal zinc are almost equivalent, and the depth is 6 nm to 18 nm. Then, it turns out that zinc oxide and metallic zinc are the main components.
- the manufacturing conditions of the plated steel sheet according to one embodiment of the present invention will be described first from the conditions regarding the plating layer.
- a specific amount of ⁇ phase remains in the plating layer, and the ⁇ phase thickness is 1.5 ⁇ m or less, more preferably 1 ⁇ m or less, and most preferably 0.8 ⁇ m or less.
- the first aspect is that the total Al concentration in the plating bath is 0.11% by mass or more and 0.15% by mass or less, and an alloy heater or the like is used in alloying to rapidly heat at a high temperature and then release. Take a heat pattern to cool by cooling or air-water cooling.
- the alloying top temperature is higher than the peritectic temperature of the ⁇ phase and lower than the peritectic temperature when allowed to cool.
- the peritectic temperature of the ⁇ phase is 530 ° C., but in the bath containing Al, the ⁇ phase hardly forms as an initial crystal when the temperature is 500 ° C. or higher.
- the alloying temperature is 470 ° C. or higher and 600 ° C. or lower, more preferably 500 ° C. or higher and 530 ° C.
- isothermal holding is within 25 seconds, more preferably within 5 seconds, and the cooling rate during cooling is 25 ° C./sec or lower. More preferably, it is preferably 4 ° C./sec or more and 8 ° C./sec or less and is cooled to around 350 ° C.
- the total Al concentration in the plating bath is 0.16% by mass or more and 0%.
- an induction heater or the like is used in alloying, and after heating rapidly at a high temperature, the heat pattern is cooled by standing or cooling with air or water. Since the Al concentration in the bath is high, the alloying temperature is also set to a high value of 510 ° C. or higher and 560 ° C. or lower, isothermal holding is within 3 seconds, and the cooling rate is 2 ° C./sec to 4 ° C./sec. It is preferable to cool to mist and further to mist. Note that according to the second aspect, the ⁇ phase can be reduced even if the ⁇ phase has the same thickness as in the first aspect. Therefore, the press range in which neither wrinkles nor cracks occur is expanded.
- the lubricating film is present in the lubricating film in a state where the inorganic oxyacid salt and the metal oxide are mixed.
- a coating structure uses a treatment liquid containing inorganic oxyacid salt and metal oxide components, and performs roll coating treatment after controlling the concentration and the plate temperature of the hot-dip galvanized steel sheet to an appropriate range. This is preferably realized.
- a reverse type can be selected for the roll coating treatment.
- the component for generating the inorganic oxyacid salt P-containing oxygen acids (phosphoric acid, phosphorous acid, hypophosphorous acid, etc.), boric acid and the like and salts thereof are preferably used.
- an oxide colloid made of Si, Al, Ti or the like may be added.
- an inorganic salt such as manganese sulfate, manganese nitrate, permanganate or the like is preferably used.
- oxides / hydroxides of Zn, Al, Ni, Mo, Co, Ni, Ca, V, W, Ti, and Ce may be included. Salts, ammonium salts, sulfates and the like are applicable.
- sulfuric acid or nitric acid can be added as necessary.
- the total concentration of the treatment liquid is in the range of 5 g / l to 30 g / l.
- the total concentration means the total concentration of elements other than oxygen, such as P, B, Zn, and Mn. If it is less than 5 g / l, the production efficiency of the lubricating film is poor, and the sheet feeding speed must be lowered. When it exceeds 30 g / l, the lubricating film tends to have an excessively inclined structure.
- the temperature of the treatment liquid is preferably 10 to 50 ° C.
- the plate temperature of the hot dip galvanized steel sheet immediately before the film formation treatment is preferably 30 ° C or higher and 70 ° C or lower.
- the concentration of oxygen acid containing P in the treatment liquid is increased, and the drying temperature of the film is lowered as much as possible. It is better to shorten the time.
- the oxygen acid alone containing P is preferably 10 g / l or more, the drying temperature is 60 ° C. or less, and the drying time is 5 seconds or less. If this condition is not met, the amount of zinc oxide produced increases.
- the steel plate that can be used in the present embodiment is not particularly limited, but an ultra-low carbon steel plate excellent in deep drawability and ductility is preferable considering that it is used for good press formability.
- a steel sheet in which solid solution C is reduced by adding Ti, Nb, or the like is suitable, and the effect of the present invention can be achieved by using a steel sheet having increased strength by adding P, Mn, Si, B, or the like as necessary.
- a trump element such as Cr, Cu, Ni, or Sn may be included.
- a lubricating film containing a mixture of a component having an anti-adhesion function and a component having a roller lubrication function, and a plating layer in which a specific amount of ⁇ phase remains on the surface layer Synergistic with the structure, the range of wrinkle pressing force that can be taken, that is, the range where press forming is possible, is expanded as compared with steel plates by related technology.
- a value obtained by dividing the lower limit ( ⁇ ) of the wrinkle pressing force causing cracking by the lower limit ( ⁇ ) of the wrinkle pressing force necessary for eliminating the wrinkle is 1.21, and more preferably 1.25.
- Particularly preferred is a steel plate of more than 1.27, most preferably greater than 1.30.
- Test materials Table 1 shows the components of the steel plates tested. A cold rolled material having a thickness of 0.7 mm was used.
- (2) Plating conditions After degreasing the test material, it was heated to 800 ° C. in a 4% H 2 —N 2 atmosphere, held for 60 s, air cooled to 470 ° C., and then immersed in a hot dip galvanizing bath at 460 ° C. for 3 s. The basis weight was adjusted by wiping. This was heated and alloyed under the conditions shown in Table 2 to be described later, then air-cooled to 350 ° C., and further cooled by mist.
- (4) Film treatment conditions A treatment solution containing the components shown in Table 2 was used. After the plated steel plate was preheated to a predetermined temperature, it was processed by the following three methods.
- a range of about 3 ⁇ m ⁇ 3 ⁇ m is selected from a flat portion where the unevenness of the plating surface layer is not severe as shown in FIG. 3, and sputtering is performed for 0.1 min at a sputtering rate of about 10 nm / min by Auger electron spectroscopy. While conducting elemental analysis, a total depth of about 10 nm was analyzed for the surface layer. As shown in FIG. 2A and FIG. 2B, when P, Mn, and Zn were contained in a state of being mixed without intentional deviation and Zn was present even in the surface layer of the film, it was classified as A type. On the other hand, as shown in FIG.
- the P-containing component and the Mn-containing component have peaks at clearly different positions, P has a peak on the surface layer side, Mn has a peak on the inner layer side, Those without Zn were classified as B type.
- the spectra corresponding to FIGS. 4 and 5 were obtained by X-ray photoelectron spectroscopy, whether Zn was present up to the outermost layer of the coating, and whether the outermost layer Zn was an oxygen acid containing phosphorus. It was investigated whether the compound was mainly composed of zinc (P-Zn) or zinc oxide (ZnO).
- Friction coefficient The sample after the film formation treatment was cut into a width of 17 mm and a length of 300 mm, and after applying 1 g / m 2 of Noxlast 550HN (Parker Kosan), a draw bead test was performed at a pulling speed of 500 mm / min.
- the pull-out load was measured by changing the holding load from 200 to 800 kgf (1.96 ⁇ 10 3 to 7.84 ⁇ 10 3 N), and the slope was obtained from the plot with the holding load as the horizontal axis. The coefficient of friction was multiplied.
- Comparative material Comparative materials were not subjected to film formation treatment (in Table 3, numbers 32 and 33), and instead of film formation treatment, Fe—Zn electroplating (Fe 80%) was used. The one provided with 3 g / m 2 (34 in the number column in Table 3) was used.
- Table 3 shows the performance evaluation results.
- 1 to 24 in the number column are plated steel sheets according to the present invention, and 25 to 34 are related to comparative examples.
- the X-ray diffraction intensity ratio I of ⁇ phase and [delta] 1 phase regarding the ratio of ⁇ phase and [delta] 1 phase in the coating layer on the horizontal axis, to eliminate the wrinkles of the lower limit (beta) of the blank-holding force generated by the cracking
- the values divided by the lower limit ( ⁇ ) of the wrinkle presser force required for the above are plotted on the vertical axis, and the examples and comparative examples in Table 3 are summarized and shown in FIG.
- All the plated steel sheets according to the present invention have a low coefficient of friction, excellent slidability, and good chemical conversion properties. Furthermore, compared with the prior art, the moldable range between the wrinkle generation limit and the crack generation limit is wide.
- Comparative Examples 25, 26, 27, and 29 since the film structure of the lubricating film is the B type, the wrinkle generation limit is high, and the moldable range is narrower than that according to the present invention.
- Comparative Examples 28, 30, and 31 the film structure is the A type, but the film amount is too large and the chemical conversion treatment property is inferior, or the plating layer structure is ⁇ in the plating layer of the present invention described above.
- the formula relating to the X-ray diffraction intensity ratio I of the ⁇ 1 phase and the ⁇ 1 phase is not satisfied, and the cracking limit is low, so that the moldable range is narrower than the product of the present invention. (Example 2)
- Example 2 in which the plating method is different from Example 1 will be described.
- Test materials Table 1 shows the components of the steel plates tested. A cold rolled material having a thickness of 0.7 mm was used.
- (2) Plating conditions After degreasing and pickling the test material, Ni was pre-plated by electroplating using a Watt bath. After that, it was heated to 470 ° C. in a 4% H 2 —N 2 atmosphere, immersed in a hot dip galvanizing bath at 460 ° C. for 3 s, and the basis weight was adjusted by wiping. This was heated and alloyed under the conditions shown in Table 4 to be described later, then air-cooled to 450 ° C., and further cooled by mist.
- Table 4 shows the performance evaluation results.
- 35 to 50 in the number column are plated steel sheets according to the present invention
- 51 to 57 are plated steel sheets according to comparative examples.
- FIG. 8 summarizes the examples and comparative examples in Table 4 with the value divided by the lower limit ( ⁇ ) of the wrinkle presser force required for the above as the vertical axis.
- All the plated steel sheets according to the present invention have a low coefficient of friction, excellent slidability, and good chemical conversion properties. Furthermore, compared with the comparative example (related technology), the moldable range between the wrinkle generation limit and the crack generation limit is wide. Moreover, even if compared with the plated steel plate which concerns on this invention of Table 3 (Example 1), it turns out that a shapeable range is wide.
- a component having an anti-adhesion function and a component having a roller lubrication function are present in the lubricating film in a state of being mixed up to the outermost layer in the entire lubricating film, and Zn is further added to the outermost layer. Existed until. In addition, a specific amount of ⁇ phase remained on the surface of the plating layer. Due to the synergistic effect of the lubricating film and the plating layer, the press forming range of hot dip galvanized steel sheet could be expanded. As a result, in press forming of steel plates for automobile bodies, the yield is improved and production can be performed more efficiently than in related technologies. In addition, the design flexibility of the mold is expanded, and press molding with a wide range of designs can be performed, leading to an improvement in the product value of automobiles. Therefore, its industrial utility value is extremely large.
- K1 Line representing the background of the peak 19 corresponding to the ⁇ 1 phase
- K2 Line representing the background of the peak 20 corresponding to the ⁇ phase
- Line M representing 127 nm
- Line representing the strength ⁇ (d 0.126 nm) after removal of the background of the ⁇ phase 1:
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Abstract
Description
(1)本発明の第1の態様は、鋼板と、前記鋼板の表面に付与され、Znを主成分とし、付着量が20g/m2以上100g/m2以下であるめっき層と、を備える溶融亜鉛系めっき鋼板であって、前記めっき層は、その表層に、無機酸素酸塩とZnを含む金属系酸化物とを含有する非晶質皮膜を含有し;前記めっき層は、ζ相とδ1相とを有し;前記めっき層は、8質量%以上13質量%以下のFeを含有し;前記金属酸化物に含まれるZnは、前記非晶質皮膜の最表層にまで存在し;前記ζ相の結晶格子面間隔0.126nmにおけるバックグラウンド除去後のX線回折強度を、前記δ1相の結晶格子面間隔0.127nmにおけるバックグラウンド除去後のX線回折強度で除した値であるX線回折強度比Iが、0.06以上0.35以下である;溶融亜鉛系めっき鋼板である。
(2)前記(1)に記載の溶融亜鉛系めっき鋼板では、前記めっき層が、厚さ平均1.5μm以下のΓ相を有しても良い。
(3)前記(1)に記載の溶融亜鉛系めっき鋼板では、前記めっき層が、0.10g/m2以上0.25g/m2以下のAlを含有しても良い。
(4)前記(1)に記載の溶融亜鉛系めっき鋼板では、前記めっき層が、0を越え0.40g/m2以下のNiを含有しても良い。
(5)前記(4)に記載の溶融亜鉛系めっき鋼板では、前記めっき層が、0.15g/m2以上0.45g/m2以下のAlを含有しても良い。
(6)前記(1)~(5)のいずれかに記載の溶融亜鉛系めっき鋼板では、前記無機酸素酸塩が、PまたはBの一種以上を含有しても良い。
(7)前記(1)~(5)のいずれかに記載の溶融亜鉛系めっき鋼板では、前記金属系酸化物が、さらにMn及びAlのうち一種以上の金属の酸化物を含有しても良い。
(8)前記(1)~(5)のいずれかに記載の溶融亜鉛系めっき鋼板では、前記無機酸素酸塩のうちでPおよびBの量が合計でlmg/m2以上250mg/m2以下であり;前記Znを含む金属系酸化物のうちでMn、Mo、Co、Ni、Ca、V、W、Ti、Ceの量が合計でlmg/m2以上250mg/m2以下であっても良い。
(9)前記(1)~(5)のいずれかに記載の溶融亜鉛系めっき鋼板では、前記非晶質皮膜に存在するZnは、りんを含む酸素酸と、亜鉛との化合物が主成分となるように生成されても良い。
また、上記(2)に記載の構成によれば、良好なパウダリング性を有する溶融亜鉛めっき鋼板が提供できる。
また、上記(3)に記載の構成によれば、(1)に記載のめっき層構造をより得やすくなり、プレス成形可能範囲の広い溶融亜鉛系めっき鋼板が提供できる。
また、上記(4)、(5)に記載の構成によれば、めっき層中のζ相の生成をより抑制することが出来るため、更にプレス成形可能範囲の広い溶融亜鉛系めっき鋼板が提供できる。
また、上記(6)、(7)、(8)に記載の構成によれば、(1)に記載のめっき層構造がより得やすくなるため、更にプレス成形可能範囲の広い溶融亜鉛系めっき鋼板が提供できる。
また、(9)に記載の構成によれば、好適な潤滑性が得られるため、更にプレス成形可能範囲の広い溶融亜鉛系めっき鋼板が提供できる。
まず、本発明の第1の実施形態に係るめっき鋼板に関する構成要件について詳述する。この実施の形態のめっき層は、Znを主成分とし、含有率が8質量%以上13質量%以下のFeを含有している。尚、「Znを主成分とする」とは、Znが50質量%以上含まれることを意味する。
めっき層のFe含有率が8質量%未満の場合、未合金のために塗装後耐食性が不良となり、またζ相が多いために摺動性が不良となって加工時にフレーキングを起こす。逆に、Fe含有率が13質量%を越える場合、Γ相が厚くなってパウダリング性が劣化する。フレーキング性とパウダリング性、塗装後耐食性をより高度に満足するためには、Fe含有率は8.5質量%以上12.5質量%以下であることが好ましく、9質量%以上12質量%以下であることがより好ましい。
自動車用鋼板として用いる場合には、めっき層が片面あたり20g/m2以上100g/m2以下であることが好適である。めっき層が20g/m2未満の場合、耐食性が不足し、30g/m2以上が好ましい実施態様である。めっき層が100g/m2を超える場合、スポット溶接時の連続打点性が低下し、70g/m2以下が好ましい実施態様である。
パウダリング性を良好に保つためには、Γ相厚みが平均1.5μm以下であることが好ましい。より好適なΓ相厚みは1μm以下であり、最も好適なΓ相厚みは0.8μm以下である。
I = ζ(d=0.126nm)/δ1(d=0.127nm) ・・・(1)
の式で表した場合、X線回折強度比Iを、0.06以上0.35以下の範囲とする。なお、上記式中のζ(d=0.126nm)は結晶格子面間隔d=0.126nmにおけるζ相のX線回折強度の値を示す。また、δ1(d=0.127nm)は結晶格子面間隔d=0.127nmにおけるδ1相のX線回折強度の値を示す。
ζ相はδ1相に比べて亜鉛量が多いので、Iが小さいと、めっき層中の亜鉛量が少なく、また、その結果、金型との凝着が減りすべりが良くなる。X線回折強度比Iが0.06より少ない場合、すべり性が良すぎてしわを消滅するのに必要なしわ押え力の下限(α)が上がる一方、めっき表層から溶解して無機酸素酸塩と金属系酸化物とを含有する非晶質皮膜中に取り込まれるZnの量が不足して割れの発生するしわ押え力の限界は下がるため、成形可能範囲が狭まる。X線回折強度比Iが0.35より多いと、すべり性が不足して、しわを消滅するのに必要なしわ押え力の下限(α)が下がるが、それ以上に割れの発生するしわ押え力の下限(β)も下がるため、この場合も成形可能範囲は狭まる。より好適には、X線回折強度比0.10以上0.35以下の範囲であり、最も好適には、0.15以上0.30以下の範囲である。
図1中、K1は、δ1相に相当するピーク19のバックグラウンドを表す線であり、K2はζ相に相当するピーク20のバックグラウンドを表す線である。また、Lはδ1相のバックグラウンド除去後の強度δ1(d=0.127nm)を表す線であり、Mはζ相のバックグラウンド除去後の強度ζ(d=0.126nm)を表す線である。
このうち、無機酸素酸塩に関し、上記第1及び第2の実施の形態に適用可能な無機酸素酸塩の種類として、皮膜生成にはPを含有する酸素酸、およびこれらの塩が好適に用いられる。これら以外にBを含有する酸素酸であるほう酸およびこれらの塩もまた適用可能である。これらは単独で用いても良いし、混合して用いても良い。混合して用いる場合には、Pを含有する酸素酸を含有することが好適である。なお、Si、Al、Ti等からなる酸化物コロイドを含有しても良い。これらはプレス加工時に破壊された粒子が転がることによる潤滑機能を主として発揮するものと考えられる。
上述した特許文献5における好適技術は、コロガリ潤滑機能を有するP含有成分が皮膜において表層方向に向かって濃く、凝着防止機能を有するMn含有成分が地鉄界面に強くなるよう傾斜被覆させた技術であり、図にはグロー放電分光分析の結果が開示されている。
これに対して、第1の実施の形態および第2の実施の形態に相当するオージェ電子分光分析による深さ分析のそれぞれの結果を、図2A、図2Bに示す。特許文献5に係る分析結果と第1及び第2の実施の形態の分析結果とを比較する。まず、特許文献5の技術、即ち関連技術においてはP含有成分とMn含有成分とが明瞭に異なる位置にピークを有していることがわかる。またZnは潤滑性皮膜の内層にしか存在しないことがわかる。これに対し、潤滑性皮膜中のZnは、関連技術に比べて本発明の方が圧倒的に多く、潤滑性皮膜の最表層においてもZnの存在が確認できる。
すなわち、本実施形態に係る溶融亜鉛系めっき鋼板は、関連技術と異なり、Znが潤滑性皮膜中に最表層にまで存在している。このような皮膜構成をとることが、プレス成形可能範囲の拡大につながっている。
本実施形態では、めっき層中にζ相を特定量残存させ、かつΓ相厚みを1.5μm以下、より好適には1μm以下、最も好適には0.8μm以下とする。
そのための第一の様態は、めっき浴中の全Al濃度を0.11質量%以上0.15質量%以下としたうえで、合金化においてインダクションヒーター等を使用し高温で急速に加熱後、放冷又は気水冷却等により冷却するヒートパターンをとる。合金化トップ温度はζ相の包晶温度よりも高温とし、放冷時に包晶温度以下にするのが効果的である。ζ相の包晶温度はZn-Fe二元合金状態図では530℃となっているが、Alを含む浴では500℃以上になるとζ相は初晶として生成しにくい。
また、加熱後にはなるべく等温保持時間を短くし、直ちに冷却するのが、Γ相の成長抑制の観点から好ましい。具体的には、合金化温度470℃以上600℃以下、より好ましくは500℃以上530℃以下、等温保持25秒以内、より好ましくは5秒以内、放冷時の冷却速度25℃/sec以下、より好ましくは4℃/sec以上8℃/sec以下で、350℃前後まで冷却するのが好ましい。
(実施例1)
(1)供試材
表1に、供試した鋼板の成分を示す。板厚は0.7mmの冷延材を用いた。
(2)めっき条件
供試材を脱脂後、4%H2-N2雰囲気中で800℃まで加熱して60s保持し、470℃まで空冷したのち、460℃の溶融亜鉛めっき浴に3s浸漬し、ワイピングにより目付量を調整した。これを後述する表2に示す条件で加熱・合金化後350℃まで空冷し、さらにミスト冷却して取り出した。
(3)めっき層の分析
めっき層中のZn、Fe、Al量は、WAKO社製ヘキサメチレンテロラミンを0.6%添加したインヒビター入り塩酸でめっき層を溶解後、ICP発光分光分析法により測定した。これらを合計して全付着量とした。めっき層中のζ相とδ1相の比率に関するこれらζ相とδ1相のX線回折強度比Iに係る上述の式の値は、X線回折により得られた結果を、図1の方法でバックグラウンド除去後に算出した。Γ層厚みは、めっき断面をナイタール(アルコール+硝酸)等でエッチングして、地鉄界面近傍を光学顕微鏡で観察することで求めた。サンプルはN=3とし、各サンプルごとに、十分離れた平均的な視野10箇所を観察して厚みを測定し、全体の平均をΓ相厚みとした。
(4)皮膜処理条件
表2に示す成分を含む処理液を使用した。めっき後の鋼板を所定温度まで予熱してから、下記の3通りの方法で処理した。
RC:ロールコーティング後、乾燥(板温50℃)
Dip:浸漬処理後、水洗し、乾燥(板温50℃)
EC:電解処理後、水洗し、乾燥(板温50℃)
(5)皮膜の分析
クロム酸水溶液で皮膜を溶解後、各元素をICP発光分光分析法にて定量した。ここで、表3に示す無機酸素酸塩量とはP、B量の合計、金属系酸化物量とはMn、Zn、Al、Ce、Ti量の合計である。
皮膜構造については、図3に示すようなめっき表層の凹凸が激しくない平坦部分から約3μm×3μmの範囲を選んで、オージェ電子分光法により、スパッタ速度約10nm/minで0.1minスパッタするごとに元素分析を行いながら、合計で表層10nm程度を深さ分析した。図2A、図2Bに示すようにP、Mn、Znが意図的な偏り無く混ぜ合わされた状態で含有されており、かつ皮膜表層にまでZnが存在している場合はAタイプと分類した。一方、特許文献5の図5のように、P含有成分とMn含有成分が明瞭に異なる位置にピークを有していて、Pが表層側、Mnが内層側にピークを持ち、皮膜表層にはZnが存在しないものはBタイプと分類した。
皮膜最表層のZnについては、X線光電子分光法により図4、図5に相当するスペクトルを得て、皮膜最表層までZnが存在するかどうか、および最表層のZnがりんを含む酸素酸と亜鉛の化合物主体(P-Zn)か酸化亜鉛主体(ZnO)かを調べた。
(6)摩擦係数
皮膜形成処理後のサンプルを幅17mm、長さ300mmに切り出し、ノックスラスト550HN(パーカー興産)を1g/m2塗油後に、引張り速度500mm/minでドロービード試験を行った。押さえ荷重を200~800kgf(1.96×103~7.84×103N)と変化させて引き抜き荷重を測定し、押さえ荷重を横軸としたプロットから傾きを求め、これを1/2倍して、摩擦係数とした。
(7)しわ、割れ発生限界
皮膜形成処理後のサンプルを90mmφに打ち抜き、ポンチ径50mm(4R)、ダイス径54mm(4R)で円筒成形試験を行った。しわ押さえ荷重を3~7ton(2.94×104~6.93×104N)の間で変化させ、しわの消滅する下限荷重(α)と割れの発生する下限荷重(β)とを求めた。
(8)化成処理性
皮膜形成処理後のサンプルを市販の化成処理液(SD5000:日本ペイント)で、処方通り脱脂、表面調整を行ったのちに化成処理を行った。これをSEMにより観察し、均一に皮膜が形成されているものはGood、面積率10%以内で皮膜が形成されない領域があるものはFairとした。
(9)比較材
比較材として、皮膜形成処理を行っていないもの(表3中、番号欄の32、33のもの)、および皮膜形成処理のかわりに、Fe-Zn電気めっき(Fe80%)を3g/m2付与したもの(表3中、番号欄の34のもの)を用いた。
(実施例2)
(1)供試材
表1に、供試した鋼板の成分を示す。板厚は0.7mmの冷延材を用いた。
(2)めっき条件
供試材を脱脂、酸洗後、Watt浴を用いて電気めっきによりNiを予備めっきした。こののち、4%H2-N2雰囲気中で470℃まで加熱し、そのまま460℃の溶融亜鉛めっき浴に3s浸漬し、ワイピングにより目付量を調整した。これを後述する表4に示す条件で加熱・合金化後450℃まで空冷し、さらにミスト冷却して取り出した。
(3)めっき層の分析
めっき層中のZn、Fe、Al、Ni付着量は、WAKO社製ヘキサメチレンテロラミンを0.6%添加したインヒビター入り塩酸でめっき層を溶解後、ICP発光分光分析法により測定した。これらを合計して全付着量とした。他は実施例1と同様に行った。
(4)皮膜処理条件および皮膜分析
実施例1と同様に行った。
(5)性能評価試験
摩擦係数、しわ、割れ発生限界、化成処理性は実施例1と同様に評価した。
K2: ζ相に相当するピーク20のバックグラウンドを表す線
L : δ1相のバックグラウンド除去後の強度δ1(d=0.127nm)を表す線
M : ζ相のバックグラウンド除去後の強度ζ(d=0.126nm)を表す線
1: 溶融亜鉛めっき鋼板
2: 鋼板
3: めっき層
4: 非晶質皮膜(潤滑性皮膜)
Claims (9)
- 鋼板と、
前記鋼板の表面に付与され、Znを主成分とし、付着量が20g/m2以上100g/m2以下であるめっき層と、
を備える溶融亜鉛系めっき鋼板であって、
前記めっき層は、その表層に、無機酸素酸塩と金属系酸化物とを含有する非晶質皮膜を含有し;
前記めっき層は、ζ相とδ1相とを有し;
前記めっき層は、8質量%以上13質量%以下のFeを含有し;
前記金属酸化物に含まれるZnは、前記非晶質皮膜の最表層にまで存在し;
前記ζ相の結晶格子面間隔0.126nmにおけるバックグラウンド除去後のX線回折強度を、前記δ1相の結晶格子面間隔0.127nmにおけるバックグラウンド除去後のX線回折強度で除した値であるX線回折強度比Iが、0.06以上0.35以下である;
ことを特徴とする溶融亜鉛系めっき鋼板。 - 前記めっき層が、厚さ平均1.5μm以下のΓ相を有することを特徴とする請求項1に記載の溶融亜鉛系めっき鋼板。
- 前記めっき層が、0.10g/m2以上0.25g/m2以下のAlを含有することを特徴とする請求項1に記載の溶融亜鉛系めっき鋼板。
- 前記めっき層が、0を越え0.40g/m2以下のNiを含有することを特徴とする請求項1に記載の溶融亜鉛系めっき鋼板。
- 前記めっき層が、0.15g/m2以上0.45g/m2以下のAlを含有することを特徴とする請求項4に記載の溶融亜鉛系めっき鋼板。
- 前記無機酸素酸塩が、PまたはBの一種以上を含有することを特徴とする請求項1~請求項5のいずれか1項に記載の溶融亜鉛系めっき鋼板。
- 前記金属系酸化物が、さらにMn及びAlのうち一種以上の金属の酸化物を含有することを特徴とする請求項1~請求項5のいずれか1項に記載の溶融亜鉛系めっき鋼板。
- 前記無機酸素酸塩のうちでPおよびB量が合計でlmg/m2以上250mg/m2以下であり;
前記Znを含む金属系酸化物のうちでMn、Mo、Co、Ni、Ca、V、W、Ti、Ce量が合計でlmg/m2以上250mg/m2以下である;
ことを特徴とする請求項1~請求項5のいずれか1項に記載の溶融亜鉛系めっき鋼板。 - 前記非晶質皮膜に存在するZnは、りんを含む酸素酸と、亜鉛との化合物が主成分となるように生成されることを特徴とする請求項1~請求項5のいずれか1項に記載の溶融亜鉛系めっき鋼板。
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WO2016159298A1 (ja) * | 2015-03-31 | 2016-10-06 | 新日鐵住金株式会社 | 溶融亜鉛系めっき鋼板 |
US10987695B2 (en) | 2015-03-31 | 2021-04-27 | Nippon Steel Corporation | Hot-dip zinc-based plated steel sheet |
CN112534079A (zh) * | 2018-07-30 | 2021-03-19 | 日本制铁株式会社 | 热浸镀锌处理方法、利用该热浸镀锌处理方法的合金化热浸镀锌钢板的制造方法、利用该热浸镀锌处理方法的热浸镀锌钢板的制造方法、合金化热浸镀锌钢板、以及热浸镀锌钢板 |
Also Published As
Publication number | Publication date |
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BRPI1011500A2 (pt) | 2016-03-22 |
CN102753730A (zh) | 2012-10-24 |
US8852753B2 (en) | 2014-10-07 |
JPWO2012004889A1 (ja) | 2013-09-02 |
EP2527493A4 (en) | 2014-01-08 |
EP2527493B1 (en) | 2018-09-05 |
JP4970632B2 (ja) | 2012-07-11 |
MX2012009298A (es) | 2012-09-07 |
KR101456346B1 (ko) | 2014-11-03 |
EP2527493A1 (en) | 2012-11-28 |
PL2527493T3 (pl) | 2019-02-28 |
US20120288734A1 (en) | 2012-11-15 |
ES2698392T3 (es) | 2019-02-04 |
CN102753730B (zh) | 2015-04-29 |
CA2786639C (en) | 2015-10-27 |
KR20120105048A (ko) | 2012-09-24 |
BRPI1011500B1 (pt) | 2019-12-03 |
CA2786639A1 (en) | 2012-01-12 |
BRPI1011500A8 (pt) | 2016-10-11 |
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