CN106133194A - 镀覆钢板 - Google Patents

镀覆钢板 Download PDF

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Publication number
CN106133194A
CN106133194A CN201580016611.8A CN201580016611A CN106133194A CN 106133194 A CN106133194 A CN 106133194A CN 201580016611 A CN201580016611 A CN 201580016611A CN 106133194 A CN106133194 A CN 106133194A
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Prior art keywords
plating layer
coating
steel sheet
coated steel
adhesion amount
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CN201580016611.8A
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CN106133194B (zh
Inventor
黑崎将夫
山口伸
山口伸一
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Nippon Steel Corp
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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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/012—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of aluminium or an aluminium alloy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C12/00—Alloys based on antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • 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
    • 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
    • C23C28/02—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 only coatings only including layers of metallic material
    • 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
    • C23C28/02—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 only coatings only including layers of metallic material
    • C23C28/021—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 only coatings only including layers of metallic material including at least one metal alloy layer
    • 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
    • C23C28/02—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 only coatings only including layers of metallic material
    • C23C28/023—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 only coatings only including layers of metallic material only coatings of metal elements only
    • 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
    • C23C28/02—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 only coatings only including layers of metallic material
    • C23C28/023—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 only coatings only including layers of metallic material only coatings of metal elements only
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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
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    • 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
    • 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
    • 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
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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
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    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
    • C—CHEMISTRY; METALLURGY
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C—CHEMISTRY; METALLURGY
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • C—CHEMISTRY; METALLURGY
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • C—CHEMISTRY; METALLURGY
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
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Abstract

在镀覆钢板(1)中，包含钢板(2)、钢板(2)的至少一个表面上的包含Al、Cu、In、Zn、Sn或Sb或它们的任意的组合的预镀层(3)、和预镀层(3)上的由Ni含有率为5质量％～15质量％的Zn‑Ni合金构成的镀层(4)。预镀层(3)的附着量为0.5g/m2以上，镀层(4)的附着量为5g/m2以上。

Description

镀覆钢板
技术领域
本发明涉及具备Zn-Ni合金的镀层的镀覆钢板。
背景技术
对于汽车或双轮车等的燃料罐中使用的钢板，要求在一个表面具有相对于汽油等燃料的耐蚀性。作为燃料罐用的钢板，以往，广泛使用Sn-Pb系镀覆钢板。但是，近年来，由于对于Pb的限制，开发了替代Sn-Pb系镀覆钢板的镀覆钢板(专利文献1～4)。
关于作为Sn-Pb系镀覆钢板的替代材料之一的Zn-Ni系镀覆钢板，具有低成本、且相对于汽油发挥良好的耐蚀性这样的优点，近年来，在新兴国家中Zn-Ni系镀覆钢板的使用增加。
然而，就使用Zn-Ni系镀覆钢板制造的燃料罐而言，有时相对于燃料得不到充分的耐蚀性。特别是相对于包含醇的燃料的耐蚀性往往不足，有时在短时间内开孔。
专利文献5中记载了包含醇的生物燃料用的耐蚀性构件。然而，即使使用专利文献5中以能够再现的程度记载的材料来制造燃料罐，也无法得到充分的耐蚀性。
现有技术文献
专利文献
专利文献1：日本特开平09-241866号公报
专利文献2：日本特开2001-341228号公报
专利文献3：日本专利第3859941号公报
专利文献4：日本特开2004-360019号公报
专利文献5：日本特开2011-026669号公报
发明内容
发明所要解决的问题
本发明的目的是提供相对于各种燃料能够得到优异的耐蚀性的镀覆钢板。
用于解决问题的手段
本发明人们为了解决上述课题而进行了深入研究的结果是，详细情况在后面叙述，但发现在将镀覆钢板加工成燃料罐时在镀层中产生裂缝，以及，通过在镀层与钢板之间设置规定的预镀层，从而即使在镀层中产生裂缝也可以得到优异的耐蚀性。
本发明是基于上述认识而进行的，其主旨如下所述。
(1)一种镀覆钢板，其特征在于，其具有：
钢板、
上述钢板的至少一个表面上的包含Al、Cu、In、Zn、Sn或Sb或它们的任意的组合的预镀层、和
上述预镀层上的由Ni含有率为5质量％～15质量％的Zn-Ni合金构成的镀层，
上述预镀层的附着量为0.5g/m2以上，
上述镀层的附着量为5g/m2以上。
(2)根据(1)所述的镀覆钢板，其特征在于，
其具有上述镀层上的10mg/m2以上的无铬酸盐皮膜。
(3)根据(2)所述的镀覆钢板，其特征在于，
上述无铬酸盐皮膜含有氟化合物、磷酸及钒化合物，所述氟化合物为氟钛酸或氟锆酸或它们两者。
(4)根据(2)所述的镀覆钢板，其特征在于，
上述无铬酸盐皮膜使用包含Zr或Ti或它们两者的盐的处理液、或包含硅烷偶联剂的处理液而形成。
(5)根据(4)所述的镀覆钢板，其特征在于，
上述包含硅烷偶联剂的处理液包含分子中含有1个氨基的第1硅烷偶联剂、和分子中含有1个缩水甘油基的第2硅烷偶联剂。
发明效果
根据本发明，由于包含适合的预镀层，所以相对于汽油、混合燃料等各种燃料能够得到优异的耐蚀性。
附图说明
图1是表示圆筒杯的纵壁中的镀层的状态的图。
图2是表示圆筒杯的内表面的外观的图。
图3是表示本发明的实施方式所述的镀覆钢板的结构的截面图。
图4是表示实施方式的变形例所述的镀覆钢板的结构的截面图。
图5是表示实施方式的其它变形例所述的镀覆钢板的结构的截面图。
图6是表示实施方式的其它变形例所述的镀覆钢板的结构的截面图。
图7是表示实施方式的其它变形例所述的镀覆钢板的结构的截面图。
图8是表示实施方式的其它变形例所述的镀覆钢板的结构的截面图。
具体实施方式
首先，对本发明人们想到本发明的原委进行说明。本发明中，所谓Zn-Ni合金是实质上由Zn及Ni构成的二元系合金，也可以包含杂质，但不包含有意添加的其它元素。
(第1试验)
本发明人们进行了用于确认以往的Zn-Ni系镀覆钢板中的伴随加工而产生的镀层的损伤的状况的试验(第1试验)。在第1试验中，准备含有B的极低碳Ti钢板作为母材钢板，在其两面形成Ni含有率为12质量％的Zn-Ni合金的镀层。在镀层的形成中，准备含有硫酸锌：180g/L、硫酸镍：200g/L及硫酸钠：100g/L的水溶液，使用将其pH用硫酸调整为1.2的镀覆液。镀层的附着量设定为每一面30g/m2。接着，使用包含硅烷偶联剂的处理液，在镀层的表面以每一面500mg/m2的附着量形成皮膜。这样操作，制作了镀覆钢板。之后，从镀覆钢板切取试样，将其成形为拉深比为2.2、直径为100mm的圆筒杯的形状，观察圆筒杯的纵壁中的镀层的状态。
图1中表示纵壁中的镀层的状态。如图1中所示的那样，在镀层中产生许多的裂缝，在多个地方母材钢板露出。产生了许多的裂缝是由于Zn-Ni合金的镀层由Ni5Zn21所表示的金属间化合物构成，缺乏延性。
(第2试验)
接着，本发明人们进行了用于确认成形后的Zn-Ni系镀覆钢板的耐蚀性的试验(第2试验)。在第2试验中，从第1试验中制作的镀覆钢板的其它部分重新切取试样，将其成形为拉深比为2.2、直径为100mm的圆筒杯的形状。此外，准备以体积比计汽油：乙醇：水＝69：29：2的混合燃料，每1L混合燃料在其中添加100mg的醋酸及100mg的NaCl而制作腐蚀液。然后，将100mL该腐蚀液封入成形的圆筒杯中，将封入了腐蚀液的圆筒杯在45℃下静置，经过1000小时后观察圆筒杯的内表面的外观。
图2中表示圆筒杯的内表面的外观。如图2中所示的那样，在镀层中产生了许多的裂缝的纵壁中，腐蚀显著，大量地生成孔蚀。孔蚀的深度为100μm以上。
通过这一连串的试验，确认在Zn-Ni合金的镀层中容易产生裂缝，在产生了裂缝的地方腐蚀进展。此外，这样的裂缝仅通过形成铬酸盐皮膜无法防止，例如即使通过专利文献1中记载的方法也得不到充分的耐蚀性。
本发明人们为了弄明白这种现象的原因进一步反复深入研究，结果弄明白：在从裂缝露出的母材钢板的表面，作为腐蚀反应的一部分的氧还原反应(阴极反应)快速进行，其结果是，作为成对反应的Zn-Ni合金的镀层的溶解反应(阳极反应)被促进。特别是还弄明白这些反应在燃料中包含醇的情况下显著。
进而，本发明人们基于这些认识进一步进行了深入研究，结果查明，通过在钢板与镀层之间设置规定的预镀层，能够有效地抑制Zn-Ni系镀覆钢板的腐蚀。
接着，对预镀层进行说明。
(第3试验)
本发明人们进行了用于确定预镀层中能够使用的材料的试验(第3试验)。在第3试验中，首先，与第1试验同样地，准备含有B的极低碳Ti钢板作为母材钢板，在其两面形成Al、Ag、Co、Cr、Cu、In、Mn、Ni、Zn、Sn、Sb或Pt的预镀层。预镀层的附着量设定为1g/m2。在预镀层的形成中，在以硫酸盐、氯化物盐、硝酸盐、甲酸盐或醋酸盐的形式含有Al、Ag、Co、Cr、Cu、In、Mn、Ni、Zn、Sn、Sb或Pt的溶液中进行钢板的电镀。在形成Al的预镀层时，使用有机溶剂(二甲基砜)浴，在形成其它金属的预镀层时，使用以水作为溶剂的浴。接着，在预镀层上形成含有Ni：12质量％及Zn：88质量％的Zn-Ni合金的镀层。镀层的附着量设定为每一面30g/m2。这样操作，制作了镀覆钢板。之后，与第2试验同样地操作，准备圆筒杯及腐蚀液，使用它们进行耐蚀性的评价。为了比较，对在没有形成预镀层的情况下形成Zn-Ni合金的镀层的镀覆钢板也进行了耐蚀性的评价。将它们的结果示于表1中。表1中，○表示没有侵蚀，△表示有深度为20μm以下的侵蚀，×表示有深度超过20μm的侵蚀。
表1
金属 耐蚀性
Al ○
Ag △
Co △
Cr △
Cu ○
In ○
Mn △
Ni △
Zn ○
Sn ○
Sb ○
Pt ×
无 △
如表1中所示的那样，在形成Al、Cu、In、Zn、Sn或Sb的预镀层的情况下，与没有形成预镀层的情况相比得到优异的耐蚀性。
(第4试验、第5试验)
进而，本发明人们为了弄明白适于预镀层的上述的金属的特性，进行了关于氧还原反应的试验及关于加工后的镀层的状态的试验。
在关于氧还原反应的试验(第4试验)中，首先，与第1试验同样地准备含有B的极低碳Ti钢板作为母材钢板，在其两面形成Al、Ag、Co、Cr、Cu、Fe、In、Mn、Ni、Zn、Sn、Sb或Pt的预镀层。预镀层的附着量设定为1g/m2。接着，使用将Na2SO4以50g/L溶解并通过鼓泡30分钟以上空气而使溶存氧饱和的水溶液，以-600mV(Ag/AgCl电极对照)的电位测定氧还原电流。-600mV(Ag/AgCl电极对照)的电位相当于含有Ni：12质量％及Zn：88质量％的Zn-Ni合金的腐蚀电位。将其结果示于表2中。表2中，○表示氧还原电流与在预镀层中使用Fe的情况相比小一个数量级以上，×表示大一个数量级以上，△表示为它们之间。
在关于加工后的镀层的状态的试验(第5试验)中，首先，与第4试验同样地在母材钢板的两面形成预镀层。接着，从形成有预镀层的母材钢板切取试样，将其成形为拉深比为2.2、直径为100mm的圆筒杯的形状。然后，测定残存于圆筒杯的纵壁上的预镀层的面积率。将其结果示于表2中。表2中，○表示残存的预镀层的面积率为95％以上，△表示为90％以上且低于95％，×表示低于90％。
表2
金属 氧还原电流 面积率
AI ○ ○
Ag △ ○
Co △ ×
Cr △ ×
Cu ○ ○
Fe △ ○
In ○ ○
Mn △ ×
Ni △ ×
Zn ○ ○
Sn ○ ○
Sb ○ ○
Pt × ○
如表2中所示的那样，在第3实验中弄明白了被用于预镀层中而使耐蚀性提高的金属(表1中为○)的氧还原电流比Fe的氧还原电流小一个数量级以上，加工后残存的预镀层的面积率为95％以上。
(第6试验)
本发明人们进行了关于预镀层所需的附着量的试验(第6试验)。在第6试验中，首先，与第5试验同样地在母材钢板的两面形成预镀层。此时，元素使用耐蚀性良好的Al、Cu、In、Zn、Sn或Sb，使附着量在0g/m2～1.0g/m2的范围内变化。接着，从形成有预镀层的母材钢板切取试样，将其成形为拉深比为2.2、直径为100mm的圆筒杯的形状。然后，测定残存于圆筒杯的纵壁上的预镀层的面积率。将关于Al得到的结果示于表3中。表3中，○表示残存的预镀层的面积率为95％以上，△表示为90％以上且低于95％，×表示低于90％。此外，关于Cu、In、Zn、Sn、Sb，也得到同样的结果。
表3
如表3中所示的那样，弄明白了为了在加工后以95％以上的面积率残存预镀层，必须将附着量设定为0.5g/m2以上。
由这些试验弄明白，通过设置Al、Cu、In、Zn、Sn或Sb的预镀层，从而即使通过加工而在Zn-Ni合金的镀层中产生裂缝，也可以维持母材钢板被预镀层被覆的状态，可以抑制母材钢板从裂缝露出，以及通过该露出的抑制，氧还原反应(阴极反应)的进行变慢，可以抑制镀层的溶解反应(阳极反应)。
接着，对本发明的实施方式进行说明。图3是表示本发明的实施方式所述的镀覆钢板的截面图。
如图3中所示的那样，在本实施方式所述的镀覆钢板1中，包含钢板(母材钢板)2、钢板2的一个表面上的预镀层3、及预镀层3上的镀层4。预镀层3包含Al、Cu、In、Zn、Sn或Sb或它们的任意的组合，其附着量为0.5g/m2以上。镀层4由Ni：5质量％～15质量％及Zn：85质量％～95质量％的Zn-Ni合金构成，其附着量为5g/m2以上。
钢板2的钢种及组成没有特别限定。例如可以将IF(interstitial free，无间隙原子)钢、含有Ti及少量的Nb的极低碳Ti钢、极低碳Ti-Nb钢等通常使用的极低碳钢用于钢板2。也可以将包含Si、Mn及P等强化元素的钢、作为晶界强化元素包含B的钢用于钢板2。也可以将不锈钢等含有Cr的钢用于钢板2。含有Cr的钢适合于在户外等以在端面容易生锈的形态使用镀覆钢板1的情况。
像上述那样，预镀层3包含Al、Cu、In、Zn、Sn或Sb或它们的任意的组合。即，预镀层3可以单独包含Al、Cu、In、Zn、Sn或Sb，也可以包含它们中的2种以上。预镀层3中也可以包含Cr、Mo、Nb、Fe等金属。然而，若Cr、Mo、Nb、Fe等金属的总量超过10质量％，则预镀层3脆，在加工时容易剥落。例如，若进行与第5试验同样的试验，则残存的预镀层的面积率容易变低。因此，除Al、Cu、In、Zn、Sn或Sb以外的金属的总量优选为10质量％以下。形成预镀层3的方法没有特别限定，但优选电解处理法。这是由于，在现状下，电解处理法的均匀性最优异，最有效地体现耐蚀性的提高效果。电解处理液中包含的上述6种金属的盐没有特别限定，例如使用硫酸盐、氯化物盐、硝酸盐、甲酸盐或醋酸盐。
预镀层3的附着量为0.5g/m2以上。预镀层3的附着量低于0.5g/m2时，会在镀覆钢板中产生得不到充分的耐蚀性的部位。为了得到更优异的耐蚀性，预镀层3的附着量优选为0.8g/m2以上。预镀层3的附着量的上限没有特别限定，预镀层3的附着量的效果在5.0g/m2左右时饱和，超过100.0g/m2时预镀层3变得容易剥落。因此，预镀层3的附着量从抑制剥落的观点出发优选为100.0g/m2以下，从经济性的观点出发优选为5.0g/m2以下。
构成镀层4的Zn-Ni合金的Ni含有率为5质量％～15质量％。Ni含有率低于5质量％时，Zn含有率超过95质量％，与通常的Zn镀覆同样地，得不到相对于劣化汽油的充分的耐蚀性，在早期产生红锈，产生孔蚀。因此，Ni含有率为5质量％以上。为了得到相对于劣化汽油的更优异的耐蚀性，Ni含有率优选为7质量％以上。另一方面，Ni含有率超过15质量％时，镀层4变得过硬，在加工时产生剥离，得不到充分的耐蚀性。因此，Ni含有率为15质量％以下。为了进一步抑制加工时的剥离，Ni含有率优选为13质量％以下。
镀层4的附着量为5g/m2以上。镀层4的附着量低于5g/m2时，相对于劣化汽油以及汽油及醇的混合燃料中的任一者均得不到充分的耐蚀性。为了得到更优异的耐蚀性，镀层4的附着量优选为10g/m2以上。镀层4的附着量的上限没有特别限定，镀层4的附着量的效果在60g/m2左右时饱和，超过100g/m2时镀层4变得容易剥落。因此，镀层4的附着量从抑制剥落的观点出发优选为100g/m2以下，从经济性的观点出发优选为60g/m2以下。
这样的镀覆钢板1在按照预镀层3及镀层4成为内表面的方式成形的燃料罐中，相对于汽油以及汽油及醇的混合燃料发挥优异的耐蚀性。
如图4中所示的那样，在镀覆钢板1中也可以包含钢板2的另一个表面上的预镀层5、及预镀层5上的镀层6。若预镀层5具备与预镀层3同样的构成，镀层6具备与镀层4同样的构成，则在按照预镀层5及镀层6成为内表面的方式成形的燃料罐中也发挥优异的耐蚀性。如图5中所示的那样，也可以在不形成预镀层5的情况下形成镀层6。如图6中所示的那样，也可以形成预镀层5，而没有形成镀层6。在图5或图6中所示的例子中，镀覆钢板1在按照预镀层3及镀层4成为内表面的方式成形的燃料罐中发挥优异的耐蚀性。
如图7中所示的那样，在图3中所示的镀覆钢板1中也可以包含镀层4上的无铬酸盐皮膜7。无铬酸盐皮膜7有助于防锈效果。无铬酸盐皮膜7的附着量低于10mg/m2时，得不到充分的防锈效果。因此，无铬酸盐皮膜7的附着量优选为10mg/m2以上，为了得到更优异的防锈效果，更优选为15mg/m2以上。另一方面，无铬酸盐皮膜7的防锈效果在1000mg/m2左右时饱和。因此，无铬酸盐皮膜7的附着量从经济性的观点出发优选为1000mg/m2以下，更优选为900mg/m2以下。
无铬酸盐皮膜7可以通过无铬酸盐处理(非铬酸盐处理)而形成。作为无铬酸盐处理中使用的处理液，可列举出不含有环境上有害的六价铬的处理液、例如包含Zr或Ti或它们两者的盐的处理液、或包含硅烷偶联剂的处理液等。通过使用了这些处理液的无铬酸盐处理，能够在镀层4上形成含有5质量％以上的Ti、Zr、P、Ce、Si、Al、Li等作为主要成分、且不含有铬的无铬酸盐皮膜(化成处理皮膜)7。即，无铬酸盐皮膜7例如包含Ti、Zr、P、Ce、Si、Al或Li或它们的任意的组合。
在无铬酸盐皮膜7的形成中，包含硅烷偶联剂的处理液特别有效。例如，优选使用包含分子中含有1个氨基的第1硅烷偶联剂、分子中含有1个缩水甘油基的第2硅烷偶联剂、氟化合物、磷酸及钒化合物的处理液，所述氟化合物为氟钛酸或氟锆酸或它们两者。通过使用该处理液，能够形成含有氟化合物、磷酸及钒化合物的复合皮膜作为无铬酸盐皮膜7，所述氟化合物为氟钛酸或氟锆酸或它们两者。
关于上述处理液中的配合比，当设第1硅烷偶联剂的固体成分质量为A、设第2硅烷偶联剂的固体成分质量为B、设氟化合物的固体成分质量为X、设磷酸的固体成分质量为Y、设钒化合物的固体成分质量为Z时，优选成立下面的4个关系。
0.5≤A/B≤1.7
0.02≤X/(A+B)≤0.07
0.03≤Y/(A+B)≤0.12
0.05≤Z/(A+B)≤0.17
如图8中所示的那样，在图4中所示的镀覆钢板1中也可以包含镀层6上的无铬酸盐皮膜8。同样地，在图5或图6中所示的镀覆钢板1中也可以包含镀层6或预镀层5上的无铬酸盐皮膜8。无铬酸盐皮膜8优选与无铬酸盐皮膜7同样地构成。
实施例
接着，对本发明的实施例进行说明，但实施例中的条件是为了确认本发明的可实施性及效果而采用的一条件例，本发明并不限定于该一条件例。只要不脱离本发明的主旨，且达成本发明的目的，则本发明可以采用各种条件。
首先，通过普通的转炉中的精炼及真空脱气处理来熔炼钢，得到钢坯。接着，对钢坯在通常的条件下进行热轧、冷轧及连续退火，制造板厚为0.8mm的极低碳钢板。
之后，在极低碳钢板的两面，利用电镀，形成Zn、Sb、Sn、In、Cu、Zn-Sb合金、Sn-Cu合金、Sn-Sb-In合金、Co、Mn、Cr或Ni的预镀层。在电镀时，使用以硫酸盐、氯化物盐、硝酸盐、甲酸盐或醋酸盐的形式含有预镀层中包含的金属的溶液。预镀层的附着量在0g/m2～6g/m2的范围内变化。将预镀层的组成及附着量示于表4中。
接着，在预镀层上形成Zn-Ni合金的镀层。用于形成镀层的镀覆液通过准备含有硫酸锌：180g/L、硫酸钠：100g/L及硫酸钠的水溶液，并将其pH用硫酸调整为1.2而制作。此时，使硫酸镍的量在0g/L～300g/L的范围内变化。Zn-Ni合金的Ni含有率在0质量％～20质量％的范围内变化，附着量在3g/m2～50g/m2的范围内变化。将镀层的Ni含有率及附着量示于表4中。
接着，在镀层上通过无铬酸盐处理形成无铬酸盐皮膜。将无铬酸盐处理中使用的处理液的主要成分及无铬酸盐皮膜的附着量示于表4中。
这样操作而制造了各种镀覆钢板。
之后，调查镀覆钢板的加工性、相对于劣化汽油的耐受性以及相对于汽油及醇的混合燃料的耐受性。
(加工性)
在加工性的调查中，通过液压成形试验机，使用直径为50mm的圆筒冲头，将拉深比设定为2.3进行成形试验。此时的防皱压力设定为500kg/cm2。并且，按照下面的基准来评价加工性。
〇：能够成形，无镀层的剥离
×：能够成形，有镀层剥离
(相对于劣化汽油的耐受性)
在相对于劣化汽油的耐受性的调查中，将镀覆钢板成形为直径为100mm的圆筒杯的形状，在其内部封入下面那样操作而制作的腐蚀液。在腐蚀液的制作中，通过依据JIS K2287的方法准备劣化汽油，相对于该劣化汽油添加10体积％的水。腐蚀液是按照二相分离成汽油相和水相，且作为下相侧的水相中的甲酸浓度成为100mg/L、醋酸浓度成为200mg/L的方式使用甲酸试剂、醋酸试剂而调制的。之后，将封入了腐蚀液的圆筒杯在45℃下静置，经过1000小时后测定圆筒杯的侵蚀深度。并且，按照下面的基准评价加工性。
○：无侵蚀
△：有深度为20μm以下的侵蚀
×：有深度超过20μm的侵蚀
(相对于混合燃料的耐受性)
在相对于混合燃料的耐受性的调查中，将镀覆钢板成形为直径为100mm的圆筒杯的形状，在其内部封入下面那样操作而制作的腐蚀液。在腐蚀液的制作中，准备以体积比计汽油：乙醇：水＝69：29：2的混合燃料，相对于该混合燃料整体添加醋酸：100mg/L及NaCl：100mg/L。之后，将封入了腐蚀液的圆筒杯在45℃下静置，经过1000小时后测定圆筒杯的侵蚀深度。进而，按照下面的基准评价加工性。
◎：无侵蚀
○：有深度低于5μm的侵蚀
△：有深度为5μm以上且20μm以下的侵蚀
×：有深度超过20μm的侵蚀
在表4中示出它们的评价结果。
如表4中所示的那样，在本发明的范围内的实施例No.1～No.12中，加工性、相对于劣化汽油的耐受性以及相对于混合燃料的耐受性中的任一者均得到良好的结果。在实施例No.1～No.10中，由于包含优选的无铬酸盐皮膜，所以相对于混合燃料的耐受性特别优异。
另一方面，在比较例No.13～No.15中，由于没有形成预镀层、或者预镀层的附着量少，所以没有得到相对于混合燃料的充分的耐受性。在比较例No.16～No.18、No.23及No.24中，由于预镀层中包含的金属不适合，所以没有得到相对于混合燃料的充分的耐受性。在比较例No.19及No.20中，由于构成镀层的Zn-Ni合金的Ni含有率低，所以没有得到相对于劣化汽油的充分的耐受性及相对于混合燃料的充分的耐受性。在比较例No.21中，由于构成镀层的Zn-Ni合金的Ni含有率高，所以得不到充分的加工性，产生镀层的剥离。与此相伴，也没有得到相对于劣化汽油的充分的耐受性及相对于混合燃料的充分的耐受性。在比较例No.22中，由于镀层的附着量少，所以没有得到相对于劣化汽油的充分的耐受性及相对于混合燃料的充分的耐受性。
产业上的可利用性
本发明例如可以利用于与汽车、双轮车等的燃料罐有关的产业。

Claims (5)

1.一种镀覆钢板，其特征在于，其具有：
钢板、
所述钢板的至少一个表面上的包含Al、Cu、In、Zn、Sn或Sb或它们的任意的组合的预镀层、和
所述预镀层上的由Ni含有率为5质量％～15质量％的Zn-Ni合金构成的镀层，
所述预镀层的附着量为0.5g/m2以上，
所述镀层的附着量为5g/m2以上。
2.根据权利要求1所述的镀覆钢板，其特征在于，其具有所述镀层上的10mg/m2以上的无铬酸盐皮膜。
3.根据权利要求2所述的镀覆钢板，其特征在于，所述无铬酸盐皮膜含有氟化合物、磷酸及钒化合物，所述氟化合物为氟钛酸或氟锆酸或它们两者。
4.根据权利要求2所述的镀覆钢板，其特征在于，所述无铬酸盐皮膜使用包含Zr或Ti或它们两者的盐的处理液、或包含硅烷偶联剂的处理液而形成。
5.根据权利要求4所述的镀覆钢板，其特征在于，所述包含硅烷偶联剂的处理液包含分子中含有1个氨基的第1硅烷偶联剂、和分子中含有1个缩水甘油基的第2硅烷偶联剂。
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