WO2013022118A1 - 溶融Zn－Al系合金めっき鋼板およびその製造方法 - Google Patents

溶融Zn－Al系合金めっき鋼板およびその製造方法 Download PDF

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WO2013022118A1
WO2013022118A1 PCT/JP2012/070719 JP2012070719W WO2013022118A1 WO 2013022118 A1 WO2013022118 A1 WO 2013022118A1 JP 2012070719 W JP2012070719 W JP 2012070719W WO 2013022118 A1 WO2013022118 A1 WO 2013022118A1
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molten
steel sheet
plating layer
chemical conversion
based alloy
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PCT/JP2012/070719
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English (en)
French (fr)
Japanese (ja)
Inventor
英嗣 藤沢
大居　利彦
古田　彰彦
佐藤　進
妹川　透
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Ｊｆｅ鋼板株式会社
Ｊｆｅスチール株式会社
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Application filed by Ｊｆｅ鋼板株式会社, Ｊｆｅスチール株式会社 filed Critical Ｊｆｅ鋼板株式会社
Priority to CN201280038542.7A priority Critical patent/CN103732780B/zh
Priority to AU2012293118A priority patent/AU2012293118B2/en
Priority to SG2014007579A priority patent/SG2014007579A/en
Priority to KR1020147002993A priority patent/KR101615459B1/ko
Publication of WO2013022118A1 publication Critical patent/WO2013022118A1/ja

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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
    • 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
    • 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
    • C23C22/42—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 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
    • 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
    • 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
    • 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
    • C23C28/3455—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 with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer

Definitions

  • the present invention relates to a molten Zn-Al alloy-plated steel sheet excellent in corrosion resistance and suitable for use in members of buildings, civil engineering, home appliances and the like, and a method for producing the same, and more particularly, molten Zn- with improved workability and corrosion resistance of a plating layer
  • the present invention relates to an Al-based alloy plated steel sheet.
  • hot-dip Zn-based plated steel sheets used in fields such as architecture, civil engineering, and home appliances are required to have excellent corrosion resistance.
  • a hot dip Zn-based plated steel sheet is formed into a predetermined shape and used as a structural member such as a roof, wall, or other structure.
  • it is required to be excellent in workability, and further in the corrosion resistance of the processed part, and the corrosion resistance of the material including the processed part enhances the durability of the structural member. It is an important factor to decide. For this reason, from the viewpoint of improving the durability of structural members, there is a strong demand for improving the corrosion resistance of hot-dip Zn-based plated steel sheets used as raw materials.
  • blackening refers to a phenomenon in which a dark gray discoloration occurs on a part or the whole of the plating surface.
  • the hot-dip Zn-based plated steel sheet is often used without coating in the construction field because it is excellent in corrosion resistance even in a severe environment with a lot of incoming salt such as a coastal area.
  • Patent Document 1 describes a continuous molten Zn—Al—Mg plated steel sheet.
  • the technique described in Patent Document 1 is a continuous molten Zn in which a plating layer comprising Al: 4.0 to 10%, Mg: 1.0 to 4.0%, the balance being Zn and unavoidable impurities is formed on the steel sheet surface.
  • a plating layer comprising Al: 4.0 to 10%, Mg: 1.0 to 4.0%, the balance being Zn and unavoidable impurities is formed on the steel sheet surface.
  • the cooling rate after plating is controlled to 0.5 ° C / s or more, and the plated layer is primary Al in the substrate of the ternary eutectic structure of Al / Zn / Zn 2 Mg.
  • Patent Document 2 describes a hot-dip Zn-Al alloy-plated steel sheet having a beautiful plating appearance with metallic luster and excellent blackening resistance.
  • a steel sheet is immersed in a molten Zn-Al alloy plating bath, then pulled up from the plating bath, and cooled at a cooling rate of up to 250 ° C in a range of 1 to 15 ° C / s.
  • the concentration of Ni in the plating outermost layer portion is promoted by the synergistic action of Mg and Ni. It is said.
  • the molten Zn—Al-based alloy plating layer preferably contains 10 to 30 area% of a ternary eutectic of an Al—Zn—Mg intermetallic compound in a cross section of the plating layer. It is preferable.
  • a chemical conversion treatment layer, a primer layer, and a resin layer may be formed as an upper layer of the plating layer, and the chemical conversion treatment layer may be a titanium-based or zirconium-based treatment that does not contain chromium. It is said that a chromium-free treatment with a liquid may be applied.
  • Patent Document 3 discloses a molten Zn-Al alloy formed by forming a molten Zn-Al-based alloy plating layer on at least one surface of a steel sheet and further forming a surface treatment film on the surface of the plating layer.
  • a plated steel sheet is described.
  • a molten Zn—Al-based alloy plating layer is formed by mass%, Al: 1.0 to 10%, Mg: 0.2 to 1.0%, Ni: 0.005.
  • a surface treatment film formed on the surface of the plating layer containing a Zn-Al alloy plating layer containing Zn and unavoidable impurities, including a specific titanium-containing aqueous liquid and nickel By forming a surface treatment film with a surface treatment composition containing a compound and / or a cobalt compound and a fluorine-containing compound at a predetermined ratio, excellent blackening resistance can be obtained in combination with optimization of the plating composition.
  • the reactivity is increased by the action of the fluorine-containing compound, a dense reaction layer is formed on the plating surface, and a high barrier property is imparted by the surface treatment film itself, thereby obtaining excellent corrosion resistance.
  • the plated steel sheet manufactured by the technique described in Patent Document 1 contains a large amount of Al or Mg, which has higher oxidizing power than Zn, in the plating layer.
  • a dark gray discoloration black discoloration phenomenon
  • the technique described in Patent Document 1 contains a large amount of Mg in the plating layer, the plating layer is hardened, cracks are generated in the portions subjected to the forming process, and corrosion of the plating layer base ( There is a problem that red rust) progresses.
  • the blackening resistance is mainly improved by adopting a Zn—Al—Mg-based composition containing Ni in the plating layer, but Al—Mg—Ni—Zn.
  • the chemical conversion treatment film is formed on the surface of the plating layer, the chemical conversion treatment reaction may become insufficient, and the effect of suppressing blackening becomes unstable. There was a problem.
  • the object of the present invention is to solve the problems of the prior art and to provide a hot-dip Zn-Al alloy-plated steel sheet excellent in blackening resistance and corrosion resistance and a method for producing the same.
  • the present inventors diligently studied various factors affecting blackening resistance and corrosion resistance of a hot-dip Zn-Al alloy-plated steel sheet.
  • the plating layer formed on the surface of the steel sheet has a Zn—Al—Mg-based composition containing an appropriate amount of Ni, and the surface structure of the plating layer is the area of the Zn—Al—Mg-based ternary eutectic.
  • the present inventors form a chemical conversion film containing molybdate as an upper layer of the plating layer after forming the Zn—Al—Mg alloy plating layer having the composition as described above.
  • the present invention has been completed based on such findings and further studies. That is, the gist of the present invention is as follows.
  • a molten Zn-Al alloy obtained by forming a molten Zn-Al alloy plating layer on at least one surface of a steel plate and further forming a chemical conversion coating as an upper layer of the molten Zn-Al alloy plating layer A plated steel sheet,
  • the molten Zn—Al-based alloy plating layer is in mass%, Al: 3.0 to 6.0%, Mg: 0.2-1.0% and Ni: 0.01-0.10%
  • the surface structure of the plating layer contains Zn—Al—Mg ternary eutectic in an area ratio of 1 to 50%, and the chemical conversion coating film has a composition comprising the balance Zn and inevitable impurities.
  • a molten Zn-Al alloy-plated steel sheet excellent in blackening resistance and corrosion resistance characterized by containing molybdate.
  • the temperature of the steel sheet immersed in the molten Zn—Al based alloy plating bath is 420 to 600 ° C., and the temperature of the steel plate is melted. Adjust the temperature above the temperature of the Zn-Al based plating bath, immerse in the molten Zn-Al based alloy plating bath, Furthermore, after pulling up the steel sheet from the molten Zn-Al plating bath, the steel sheet is subjected to cooling at an average cooling rate of 1 to 100 ° C./s up to 350 ° C.
  • the chemical conversion solution has a pH of 2 to 6.
  • the present invention it is possible to easily and inexpensively manufacture a hot-dip Zn-Al alloy-plated steel sheet having stable blackening resistance, and achieve a remarkable industrial effect.
  • the present invention as a result of improving the workability of the plating layer, cracking of the plating layer during molding processing is suppressed, and corrosion of the plating base is effectively suppressed. It is possible to provide a hot-dip Zn—Al-based alloy-plated steel sheet having excellent corrosion resistance.
  • the hot-dip Zn—Al-based alloy-plated steel sheet (hereinafter, also referred to as “the present invention-coated steel sheet”) of the present invention is formed on at least one surface of the steel sheet by mass%, Al: 3.0 to 6.0%, Mg: It has 0.2 to 1.0%, Ni: 0.01 to 0.1%, and has a molten Zn-Al alloy plating layer composed of the balance Zn and unavoidable impurities, and further has molybdic acid as an upper layer. It has a chemical conversion treatment film containing salt.
  • the mass% in the composition is simply expressed as%.
  • Al 3.0 to 6.0% If the Al contained in the plating layer is less than 3.0%, the Fe—Al-based alloy layer is formed thick at the interface between the plating layer and the underlying steel plate, and therefore the workability is lowered. On the other hand, when Al is contained in a large amount exceeding 6.0%, the sacrificial anticorrosive action of Zn is reduced, the corrosion resistance is lowered, and the blackening resistance is lowered.
  • Al in the plating layer is limited to a range of 3.0 to 6.0%. Further, it is preferably in the range of 4.0 to 5.5%.
  • Mg 0.2 to 1.0% Mg is contained in the plating layer to improve corrosion resistance. However, if Mg contained in the plating layer is less than 0.2%, the effect of improving corrosion resistance is small, while Mg exceeds 1.0% and a large amount. When contained in Zn, the formation of Zn—Al—Mg ternary eutectic increases, and the workability of the plating layer decreases. Therefore, Mg in the plating layer is limited to the range of 0.2 to 1.0%. Furthermore, it is preferably in the range of 0.3 to 0.8%.
  • Ni 0.01 to 0.10% Ni is included in the plating layer to improve corrosion resistance and blackening resistance. However, if Ni contained in the plating layer is less than 0.01%, the effect of improving corrosion resistance and blackening resistance is small. If it is contained in a large amount exceeding 0.10%, the surface of the plating layer is excessively activated and easily corroded, and white rust is likely to appear at the initial stage. For this reason, Ni in the plating layer is limited to a range of 0.01 to 0.10%.
  • the balance other than the above consists of Zn and unavoidable impurities. Examples of impurities include Si, Ca, Ti, V, Cr, Mn, Fe, Co, Cu, Sr, Zr, Nb, and Mo, and each may be included with an upper limit of 0.01%.
  • the plating layer formed on the surface of the plated steel sheet of the present invention has the above-described composition, and further has a structure containing 1 to 50% of Zn—Al—Mg ternary eutectic by area ratio on the surface of the plating layer.
  • the plated layer of the plated steel sheet of the present invention has a surface structure in which Zn—Al—Mg ternary eutectic is exposed on the surface in an area ratio of 1 to 50%.
  • the Zn—Al—Mg ternary eutectic on the surface of the plating layer is less than 1% in terms of the area ratio on the same surface, the effect of improving the corrosion resistance is small, while the Zn—Al—Mg ternary eutectic has an area on the surface. If the rate exceeds 50%, the reactivity with the plating layer surface of the chemical conversion treatment decreases, it becomes difficult to obtain a good chemical conversion coating film, the blackening resistance becomes unstable, and the surface of the plating layer becomes hard. Thus, cracks are likely to occur during the molding process. Therefore, the Zn—Al—Mg ternary eutectic in the surface structure of the plating layer is limited to the range of 1 to 50% in terms of area ratio. Note that the content is preferably 5 to 40%.
  • the area ratio of the Zn—Al—Mg ternary eutectic on the surface of the plating layer can be determined by, for example, observing the surface of the plating layer with a scanning electron microscope (magnification: about 1000 times) and randomizing the surface structure of the plating layer. It is preferable to obtain several fields of view and obtain the field of view (photograph) using image processing software. In the present invention, the area ratio obtained in each field of view is arithmetically averaged to obtain the area ratio of the Zn—Al—Mg ternary eutectic in the plating layer. In FIG. 1, an example of the plating layer surface structure of this invention plated steel plate is shown.
  • FIG. 2 is an image analysis diagram showing the result of analyzing the result of analyzing Mg on the surface of the plating layer shown in FIG. 1 by EPMA and showing the surface distribution of the Zn—Al—Mg ternary eutectic.
  • the surface area ratio of the Zn—Al—Mg ternary eutectic may be obtained by a method of making two gradations in black and white and calculating from a histogram.
  • a black part is a Zn-Al-Mg ternary eutectic.
  • the adhesion amount of the hot-dip Zn—Al—Mg alloy plating layer in the plated steel sheet of the present invention may be set according to the usage as usual, and is not particularly limited, but is about 30 to 300 g / m 2 per side. It is preferable to do.
  • the adhesion amount of the plating layer is 30 g / m 2 or more, the plating layer thickness is not insufficient, and desired corrosion resistance can be maintained. On the other hand, if it is 300 g / m 2 or less, the plating layer thickness will not be too thick and the plating layer will not peel off.
  • the plated steel sheet of the present invention has a chemical conversion treatment film containing molybdate as an upper layer of the molten Zn—Al—Mg alloy plating layer.
  • the chemical conversion film formed as the upper layer of the plating layer contains molybdate, and the combination of this molybdate and Zn-Al-Mg ternary eutectic improves blackening resistance and corrosion resistance.
  • the molybdate is not particularly limited as long as it dissolves during the chemical conversion treatment. Examples of the molybdate include salts such as ammonium and sodium.
  • the content of molybdate in the chemical conversion coating is not particularly limited, but from the viewpoint of blackening resistance and corrosion resistance, it is advantageous to contain it in the range of 0.3 to 3% by mass in terms of molybdenum. It is.
  • the chemical conversion film includes chromic acid, phosphate, fluoride or salt such as Ti, Zr, V, Mn, Ni, Co, silane compound, metal chelating agent, aqueous You may contain oxide sols, such as resin and a silica sol.
  • the adhesion amount per one side of the chemical conversion coating may be appropriately determined according to the use and is not particularly limited. However, if it is 0.05 g / m 2 or more, the blackening resistance and the corrosion resistance are not lowered. On the other hand, if it is 1.5 g / m 2 or less, the amount of film formation will not increase, and the production cost will not increase. For this reason, the amount of adhesion per one side of the chemical conversion film is preferably 0.05 to 1.5 g / m 2 . Below, the preferable manufacturing method of this invention plated steel plate is demonstrated.
  • the steel plate used as a substrate is immersed in a molten Zn-Al alloy plating bath using, for example, a continuous hot-dip Zn plating production facility, and then pulled up and cooled, and a molten Zn-Al alloy on the steel plate surface. A plating layer is formed.
  • the type and composition of the steel plate used as the substrate are not particularly limited, and can be appropriately selected from known hot-rolled steel plates and cold-rolled steel plates according to the application.
  • a steel plate as a substrate is heated to a desired heating temperature using, for example, a continuous hot-dip Zn plating manufacturing facility.
  • the heating temperature may be appropriately determined according to the steel plate to be used, and is not particularly limited.
  • the steel plate temperature (plate temperature) is adjusted to a desired temperature when immersed in the plating bath. It is necessary to set the heating temperature to ensure a desired steel plate temperature (plate temperature) when immersed in the plating bath.
  • the steel sheet heated to a predetermined temperature is immersed in a molten Zn—Al alloy plating bath maintained at a predetermined composition and bath temperature.
  • the composition of the hot-dip Zn-Al alloy plating bath in which the steel sheet is immersed is as follows: mass: Al: 3-6%, Mg: 0.2-1.0%, Ni: 0.01-0.10% And a composition comprising the balance Zn and inevitable impurities.
  • the bath temperature of the plating bath is 420 ° C. to 520 ° C. When the bath temperature of the plating bath is lower than 420 ° C., the bath temperature is too low and the plating bath may partially solidify, and the predetermined plating treatment cannot be performed.
  • the bath temperature of the plating bath is limited to a temperature in the range of 420 ° C. to 520 ° C. Furthermore, the bath temperature of the plating bath is preferably in the range of 450 to 500 ° C.
  • the temperature (plate temperature) of the steel sheet immersed in the plating bath is adjusted to a temperature in the range of 420 to 600 ° C. and higher than the bath temperature of the plating bath.
  • the bath temperature gradually decreases, so that the viscosity of the plating bath increases and the operation is hindered.
  • the temperature exceeds 600 ° C. the bath temperature gradually increases and the plating fixability decreases. For this reason, the temperature (plate temperature) of the steel sheet immersed in the plating bath is limited to a temperature in the range of 420 to 600 ° C. and higher than the bath temperature of the plating bath.
  • the temperature of the steel sheet immersed in the plating bath (plate temperature) is adjusted to a temperature in the range of 420 to 600 ° C., and further immersed in the plating bath.
  • the temperature (plate temperature) of the steel sheet to be adjusted is adjusted to be equal to or higher than the bath temperature of the plating bath.
  • the steel plate immersed in the plating bath is then lifted from the plating bath and cooled.
  • the cooling after the pulling is performed at a surface temperature of the steel sheet at an average cooling rate of up to 350 ° C. at 1 to 100 ° C./s.
  • the average cooling rate up to 350 ° C. is less than 1 ° C./s, the time required for cooling becomes long, so that productivity is lowered.
  • the Zn—Al—Mg ternary crystal exceeds 50% in terms of the surface area ratio, and the reactivity of the chemical conversion treatment and the workability of the plating layer are lowered.
  • the cooling rate after pulling the steel plate up from the plating bath was limited to 1 to 100 ° C./s on average up to 350 ° C. It is preferably 2 to 70 ° C./s.
  • chemical conversion treatment solution used in the chemical conversion treatment according to the present invention a solution prepared by adding molybdate to a solvent such as water and preferably adjusted to pH: 2 to 6 is used.
  • chemical conversion treatment liquid includes fluoride such as chromic acid, phosphate, Ti, Zr, V, Mn, Ni, Co, Ti, Zr, V, Mn, Ni, Co, etc. It goes without saying that any one or more of sols, silane compounds, metal chelating agents, aqueous resins and oxide sols such as silica sol may be contained.
  • the pH of a chemical conversion liquid is 2 or more, the solubility to a plating layer surface is moderate, a chemical conversion treatment film will be formed normally, and fixability and corrosion resistance will not fall.
  • the pH is 6 or less, the stability of the chemical conversion solution does not deteriorate, and adhesion and corrosion resistance do not deteriorate.
  • it is preferable to adjust the pH of the chemical conversion solution to a range of 2-6. More preferably, it is 4-5.
  • the coating method is not particularly limited, but any of the generally known coating methods such as roll coating, shower ringer, dip gas squeezing, etc. can be applied.
  • any one of conventionally known methods such as a hot air furnace, an electric heating furnace, induction heating and the like can be applied.
  • Cold-rolled steel plate (plate thickness: 0.8 mm, unannealed) was used as a substrate, and the substrate was heated to the steel plate temperature (plate temperature) during immersion shown in Table 1, and then various compositions shown in Table 1 were obtained. It was immersed in a molten Zn—Al based alloy plating bath having a bath temperature, pulled up and cooled to form a molten Zn—Al based alloy plating layer having the composition and adhesion amount shown in Table 2 on the substrate surface. In addition, it cooled at the cooling rate shown in Table 1 by the average after the raising shown in Table 1 to 350 degreeC after raising.
  • a chemical conversion treatment liquid (liquid temperature: 25 ° C.) is applied to the surface of the plated layer of the obtained plated steel sheet by roll coating, followed by drying in a hot air oven at 220 ° C. for 3 seconds, and 0.6 g / m 2.
  • a chemical conversion treatment was performed to form a chemical conversion treatment film.
  • the used chemical conversion liquid has 10 mass% of any one of molybdate, a zirconate, and a titanate by mass ratio to a solvent (water), and has pH shown in Table 1. A liquid was used.
  • the test method was as follows. (1) Structure observation on the surface of the plating layer A specimen for structure observation was collected from the obtained molten Zn-Al alloy-plated steel sheet, and the structure on the surface of the plating layer was obtained using a scanning electron microscope (magnification: 1000 times). Observed. In addition, Mg is analyzed on the surface of the plating layer using EPMA, and the analysis result is image-analyzed to be converted into black and white, and the area ratio of the Zn—Al—Mg ternary eutectic is calculated from the histogram. did. Next, the obtained hot-dip Zn-Al alloy-plated steel sheet was subjected to a blackening resistance test to evaluate blackening resistance. The test method is as follows.
  • Score 3 ⁇ L: 8 or less (a state in which blackening hardly occurs)
  • Evaluation 2 ⁇ L: More than 8 to less than 15 (a state where slight blackening occurs)
  • Score 1 ⁇ L: 15 or more (a state in which significant blackening has occurred)
  • the test method was as follows.
  • the examples of the present invention are all hot-dip Zn-Al alloy-plated steel sheets that are excellent in blackening resistance and excellent in corrosion resistance of processed parts.
  • the blackening resistance is reduced, the corrosion resistance of the processed part is reduced, or both are reduced.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Coating With Molten Metal (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
PCT/JP2012/070719 2011-08-09 2012-08-08 溶融Zn－Al系合金めっき鋼板およびその製造方法 WO2013022118A1 (ja)

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CN201280038542.7A CN103732780B (zh) 2011-08-09 2012-08-08 熔融Zn-Al合金镀覆钢板及其制造方法
AU2012293118A AU2012293118B2 (en) 2011-08-09 2012-08-08 Molten Zn-Al alloy-plated steel sheet and manufacturing method thereof
SG2014007579A SG2014007579A (en) 2011-08-09 2012-08-08 Molten zn-al alloy-plated steel sheet and manufacturing method thereof
KR1020147002993A KR101615459B1 (ko) 2011-08-09 2012-08-08 용융 Zn―Al계 합금 도금 강판 및 그 제조 방법

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018070350A1 (ja) * 2016-10-11 2018-04-19 Ｊｆｅスチール株式会社 亜鉛系めっき鋼板用表面処理液、表面処理皮膜付き亜鉛系めっき鋼板の製造方法、及び表面処理皮膜付き亜鉛系めっき鋼板
JP2018062710A (ja) * 2016-10-11 2018-04-19 Ｊｆｅスチール株式会社 亜鉛系めっき鋼板用表面処理液、表面処理皮膜付き亜鉛系めっき鋼板の製造方法、及び表面処理皮膜付き亜鉛系めっき鋼板
WO2021038102A1 (en) * 2019-08-30 2021-03-04 Rijksuniversiteit Groningen Characterization method of formability properties of zinc alloy coating on a metal substrate

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JP6165529B2 (ja) * 2013-07-12 2017-07-19 日新製鋼株式会社 化成処理鋼板の製造方法および製造装置
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KR101879093B1 (ko) 2016-12-22 2018-07-16 주식회사 포스코 내부식성 및 표면 품질이 우수한 합금도금강재 및 그 제조방법
JP6753369B2 (ja) * 2017-06-29 2020-09-09 Ｊｆｅスチール株式会社 溶融Ｚｎ系めっき鋼板及びその製造方法
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5735671A (en) * 1980-08-11 1982-02-26 Nippon Kokan Kk <Nkk> Continuously galvanizing method for strip
JP2001262303A (ja) * 2000-03-21 2001-09-26 Kawasaki Steel Corp 溶融めっき性に優れた溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼板の製造方法
JP2002371345A (ja) * 2001-06-13 2002-12-26 Sumitomo Metal Ind Ltd 溶融Ｚｎ−Ａｌ−Ｍｇ合金めっき鋼板の製造方法
JP2005146340A (ja) * 2003-11-14 2005-06-09 Nisshin Steel Co Ltd 耐食性，耐黒変性に優れた溶融Ｍｇ含有亜鉛合金めっき鋼板
JP2005146339A (ja) * 2003-11-14 2005-06-09 Nisshin Steel Co Ltd 耐黒変性に優れた溶融Ａｌ含有亜鉛合金めっき鋼板
JP2010255084A (ja) * 2009-04-28 2010-11-11 Jfe Galvanizing & Coating Co Ltd 溶融Ｚｎ系めっき鋼板

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3179401B2 (ja) * 1996-12-13 2001-06-25 日新製鋼株式会社 耐食性および表面外観の良好な溶融Ｚｎ−Ａｌ−Ｍｇめっき鋼板およびその製造法
JP5101249B2 (ja) * 2006-11-10 2012-12-19 Ｊｆｅ鋼板株式会社 溶融Ｚｎ−Ａｌ系合金めっき鋼板およびその製造方法
JP5317516B2 (ja) * 2007-04-27 2013-10-16 Ｊｆｅスチール株式会社 表面処理溶融Ｚｎ−Ａｌ系合金めっき鋼板

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5735671A (en) * 1980-08-11 1982-02-26 Nippon Kokan Kk <Nkk> Continuously galvanizing method for strip
JP2001262303A (ja) * 2000-03-21 2001-09-26 Kawasaki Steel Corp 溶融めっき性に優れた溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼板の製造方法
JP2002371345A (ja) * 2001-06-13 2002-12-26 Sumitomo Metal Ind Ltd 溶融Ｚｎ−Ａｌ−Ｍｇ合金めっき鋼板の製造方法
JP2005146340A (ja) * 2003-11-14 2005-06-09 Nisshin Steel Co Ltd 耐食性，耐黒変性に優れた溶融Ｍｇ含有亜鉛合金めっき鋼板
JP2005146339A (ja) * 2003-11-14 2005-06-09 Nisshin Steel Co Ltd 耐黒変性に優れた溶融Ａｌ含有亜鉛合金めっき鋼板
JP2010255084A (ja) * 2009-04-28 2010-11-11 Jfe Galvanizing & Coating Co Ltd 溶融Ｚｎ系めっき鋼板

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018070350A1 (ja) * 2016-10-11 2018-04-19 Ｊｆｅスチール株式会社 亜鉛系めっき鋼板用表面処理液、表面処理皮膜付き亜鉛系めっき鋼板の製造方法、及び表面処理皮膜付き亜鉛系めっき鋼板
JP2018062710A (ja) * 2016-10-11 2018-04-19 Ｊｆｅスチール株式会社 亜鉛系めっき鋼板用表面処理液、表面処理皮膜付き亜鉛系めっき鋼板の製造方法、及び表面処理皮膜付き亜鉛系めっき鋼板
JP6341342B1 (ja) * 2016-10-11 2018-06-13 Ｊｆｅスチール株式会社 亜鉛系めっき鋼板用表面処理液、表面処理皮膜付き亜鉛系めっき鋼板の製造方法、及び表面処理皮膜付き亜鉛系めっき鋼板
US11174556B2 (en) 2016-10-11 2021-11-16 Jfe Steel Corporation Surface-treatment solution for zinc or zinc alloy coated steel sheet, method of producing zinc or zinc alloy coated steel sheet with surface-coating layer, and zinc or zinc alloy coated steel sheet with surface-coating layer
WO2021038102A1 (en) * 2019-08-30 2021-03-04 Rijksuniversiteit Groningen Characterization method of formability properties of zinc alloy coating on a metal substrate

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CN103732780B (zh) 2016-01-20
SG2014007579A (en) 2014-03-28
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KR20140043471A (ko) 2014-04-09
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