WO2015083325A1 - 溶融Ｚｎ合金めっき鋼板 - Google Patents

溶融Ｚｎ合金めっき鋼板 Download PDF

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Publication number
WO2015083325A1
WO2015083325A1 PCT/JP2014/005701 JP2014005701W WO2015083325A1 WO 2015083325 A1 WO2015083325 A1 WO 2015083325A1 JP 2014005701 W JP2014005701 W JP 2014005701W WO 2015083325 A1 WO2015083325 A1 WO 2015083325A1
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Prior art keywords
alloy
hot
dip
steel sheet
plated steel
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PCT/JP2014/005701
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English (en)
French (fr)
Japanese (ja)
Inventor
厚雄 清水
雅典 松野
山本　雅也
博文 武津
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日新製鋼株式会社
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Application filed by 日新製鋼株式会社 filed Critical 日新製鋼株式会社
Priority to RU2016121849A priority Critical patent/RU2647416C2/ru
Priority to CA2931988A priority patent/CA2931988C/en
Priority to US15/037,068 priority patent/US20160305003A1/en
Priority to KR1020167013546A priority patent/KR101770342B1/ko
Priority to EP14867197.7A priority patent/EP3078765A4/en
Priority to AU2014358646A priority patent/AU2014358646C1/en
Priority to MX2016006897A priority patent/MX2016006897A/es
Priority to CN201480065804.8A priority patent/CN105793469B/zh
Publication of WO2015083325A1 publication Critical patent/WO2015083325A1/ja
Priority to US16/152,455 priority patent/US20190040512A1/en

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    • 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
    • C22C18/00—Alloys based on zinc
    • C22C18/04—Alloys based on zinc with aluminium 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
    • 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
    • C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
    • C23C2/18—Removing excess of molten coatings from elongated material
    • C23C2/20—Strips; Plates
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips
    • 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

Definitions

  • the present invention relates to a hot-dip Zn alloy-plated steel sheet excellent in blackening resistance.
  • a hot-dip Zn alloy plated steel sheet in which a hot-dip Zn alloy plated layer containing Al and Mg is formed on the surface of a base steel sheet is known.
  • the composition of the plated layer of the hot-dip Zn alloy-plated steel sheet is, for example, Al: 4.0 to 15.0 mass%, Mg: 1.0 to 4.0 mass%, Ti: 0.002 to 0.1 mass%, B: 0.001 to 0.045% by mass, balance: Zn and some containing inevitable impurities
  • This hot-dip Zn alloy-plated steel sheet has a plating layer composed of a metal structure in which [primary Al] and [Zn single phase] are mixed in a base of [Al / Zn / Zn 2 Mg ternary eutectic structure]. It has sufficient corrosion resistance and surface appearance as an industrial product.
  • the aforementioned hot-dip Zn alloy-plated steel sheet can be continuously manufactured by the following steps. First, after immersing the base steel plate (steel strip) passed through the furnace in a molten Zn alloy plating bath, for example, by passing it through a gas wiping device, the molten metal adhering to the surface of the base steel plate becomes a predetermined amount. Adjust to. Next, the molten metal is cooled by passing the steel strip to which a predetermined amount of molten metal is attached through an air jet cooler and an air-water cooling region, and a molten Zn alloy plating layer is formed. Furthermore, the hot-dip Zn alloy-plated steel sheet is obtained by passing the steel strip on which the hot-dip Zn alloy plating layer is formed through the water quench zone and bringing cooling water into contact therewith.
  • the surface of the plating layer may change black over time. Since the hot-dip Zn alloy-plated steel sheet, in which the black change has progressed, has a black-gray appearance that has lost its metallic luster and impairs the aesthetic appearance, a method for suppressing the black change has been demanded.
  • Patent Document 1 a method of adjusting the temperature of the plating layer surface in the water quench zone has been proposed (see, for example, Patent Document 1).
  • the black change of the plating layer surface is prevented by making the temperature of the plating layer surface at the time of making it contact with cooling water in a water quench zone below 105 degreeC.
  • an easily oxidizable element (rare earth element, Y, Zr or Si) is added to the plating bath and the temperature of the plating layer surface is set to 105 to 300 ° C. , Preventing the black change of the plating layer surface.
  • Patent Document 1 since it was necessary to cool the surface of the plating layer to a predetermined temperature before passing through the water quench zone, the production of the hot-dip Zn alloy-plated steel sheet may be limited. For example, in the case of a plated steel plate having a large plate thickness, it is necessary to slow down the feed rate of the plated steel plate to cool the plated steel plate to a predetermined temperature, and thus productivity has been reduced. Moreover, when an easily oxidizable element is blended in the plating bath, the easily oxidizable element is liable to become dross, and the concentration control of the easily oxidizable element is complicated, so that the manufacturing process becomes complicated.
  • An object of the present invention is to provide a hot-dip Zn alloy-plated steel sheet excellent in blackening resistance, which can be manufactured without reducing productivity and without performing complicated management of plating bath components.
  • the present inventors solve the above-mentioned problems by forming a composite oxide film containing the constituent components of the plating layer and vanadium on the surface of the plating layer, and further reducing the ratio of Zn hydroxide contained in the composite oxide film. As a result, the present invention was completed.
  • the present invention relates to the following hot-dip Zn alloy-plated steel sheets.
  • S [Oxide] is the area which the peak centering on about 1022 eV derived from the oxide of Zn shows in the intensity profile of the XPS analysis of the surface of the said composite oxide film.
  • S [Hydroxide] is an area indicated by a peak centered at about 1023 eV derived from a hydroxide of Zn in the XPS analysis intensity profile of the surface of the composite oxide film.
  • the molten Zn alloy plating layer includes Al: 1.0 to 22.0% by mass, Mg: 0.1 to 10.0% by mass, and the balance: Zn and inevitable impurities.
  • the hot-dip Zn alloy plating layer is formed of the group consisting of Si: 0.001 to 2.0 mass%, Ti: 0.001 to 0.1 mass%, and B: 0.001 to 0.045 mass%.
  • a hot-dip Zn alloy-plated steel sheet excellent in blackening resistance can be easily produced with high productivity.
  • FIG. 1A to 1D are intensity profiles of chemical bond energies corresponding to 2p orbitals of Zn on the surface of the composite oxide film.
  • FIG. 2A is a diagram illustrating an example of a method in which a cooling aqueous solution is brought into contact with the surface of a molten Zn alloy plating layer by a spray method.
  • FIG. 2B is a diagram showing an example of a method in which a cooling aqueous solution is brought into contact with the surface of the molten Zn alloy plating layer by an immersion method. It is a schematic diagram which shows the structure of a part of manufacturing line of a hot-dip Zn alloy plating steel plate.
  • the hot-dip Zn alloy plated steel sheet according to the present invention includes a base steel plate, a hot-dip Zn alloy plating layer, and a composite oxide film. Since the hot-dip Zn alloy-plated steel sheet according to the present invention has a predetermined composite oxide film, it is excellent in resistance to blackening.
  • the type of the base steel plate is not particularly limited.
  • a steel plate made of low carbon steel, medium carbon steel, high carbon steel, alloy steel, or the like can be used as the base steel plate.
  • a steel sheet for deep drawing made of low carbon Ti-added steel, low carbon Nb-added steel, or the like is preferable as the base steel sheet.
  • the molten Zn alloy plating layer is disposed on the surface of the base steel plate.
  • the composition of the hot-dip Zn alloy plating layer is appropriately selected according to the purpose.
  • the plating layer contains Al: 1.0 to 22.0% by mass, Mg: 0.1 to 10.0% by mass, the balance: Zn and inevitable impurities.
  • the plating layer is one or more selected from the group consisting of Si: 0.001 to 2.0 mass%, Ti: 0.001 to 0.1 mass%, and B: 0.001 to 0.045 mass%. May further be included.
  • hot dip Zn alloy plating examples include hot dip Zn-0.18 wt% Al-0.09 wt% Sb alloy plating, hot dip Zn-0.18 wt% Al-0.06 wt% Sb alloy plating, hot dip Zn- 0.18% by mass Al alloy plating, molten Zn-1% by mass Al-1% by mass Mg alloy plating, molten Zn-1.5% by mass Al-1.5% by mass Mg alloy plating, molten Zn-2.5% % Al-3 mass% Mg alloy plating, hot-dip Zn-2.5 mass% Al-3 mass% Mg-0.4 mass% Si alloy plating, hot-melt Zn-3.5 mass% Al-3 mass% Mg alloy plating , Molten Zn-4 mass% Al-0.75 mass% Mg alloy plating, molten Zn-6 mass% Al-3 mass% Mg-0.05 mass% Ti-0.003 mass% B alloy plating, molten Zn- 6 mass% Al-3 mass% Mg-0.02 mass% Si-0.05 mass%
  • the black change of the plating layer can be suppressed by adding Si.
  • the hot-dip Zn alloy plated steel sheet according to the present invention does not need to add Si to the plating layer. Also, the black change of the plating layer can be suppressed.
  • the adhesion amount of the molten Zn alloy plating layer is not particularly limited.
  • the adhesion amount of the plating layer is about 60 to 500 g / m 2 .
  • the composite oxide film is disposed on the surface of the molten Zn alloy plating layer, and preferably disposed on the entire surface.
  • the composite oxide film is mainly composed of constituent components (for example, Zn, Al, Mg, etc.) of the molten Zn alloy plating layer and vanadium.
  • the composite oxide film satisfies the following formula (2) over the entire surface.
  • S [Oxide] is an area indicated by a peak centered at about 1022 eV derived from the oxide of Zn in the XPS analysis intensity profile of the surface of the composite oxide film.
  • S [Hydroxide] is an area indicated by a peak centered at about 1023 eV derived from Zn hydroxide in the XPS analysis intensity profile of the surface of the composite oxide film.
  • the above formula (2) shows the peak area centered at about 1022 eV derived from Zn oxide and the peak centered at about 1023 eV derived from Zn hydroxide in the intensity profile measured by XPS analysis.
  • the ratio of the area of the peak centered at about 1023 eV derived from Zn hydroxide to the total area (hereinafter referred to as “hydroxide ratio”) is 40% or less.
  • FIG. 1 is an intensity profile of chemical bond energy corresponding to 2p orbital of Zn on the surface of a composite oxide film of a hot-dip Zn alloy plated steel sheet.
  • FIG. 1A is an intensity profile with a Zn hydroxide ratio of about 80%
  • FIG. 1B is an intensity profile with a Zn hydroxide ratio of about 40%
  • FIG. 1C is a Zn hydroxide.
  • FIG. 1D is an intensity profile in which the ratio of Zn hydroxide is about 10%.
  • the dotted line is the baseline, the broken line is the intensity profile derived from Zn oxide (peak centered at about 1022 eV), and the alternate long and short dash line is the intensity profile derived from Zn hydroxide (peak centered at about 1023 eV) It is.
  • the ratio of Zn hydroxide is 40% or less as shown in FIGS. 1B to 1D on the entire surface of the plating layer.
  • the XPS analysis of the composite oxide film surface of the hot-dip Zn alloy plated steel sheet according to the present invention is performed using an XPS analyzer (AXISAXNova; Kratos GroupratPLC.).
  • AXISAXNova XPS analyzer
  • the peak position derived from the Zn oxide is exactly 1021.6 eV, and the peak position derived from the Zn hydroxide is exactly 1023.3 eV. Changes may occur due to characteristics, sample contamination, sample charging, and the like. However, those skilled in the art are able to distinguish between peaks derived from Zn oxide and peaks derived from Zn hydroxide.
  • the adhesion amount of vanadium contained in the composite oxide film is not particularly limited, but is preferably in the range of 0.01 to 10.0 mg / m 2 .
  • the adhesion amount of vanadium is 0.01 mg / m 2 or more, blackening resistance can be further improved.
  • the amount of vanadium deposited is 10.0 mg / m 2 or less, the reactivity with the chemical conversion treatment liquid can be improved when chemical conversion treatment is performed.
  • the amount of vanadium attached to the composite oxide film can be measured using an ICP emission spectrometer.
  • the manufacturing method of the hot-dip Zn alloy plated steel sheet according to the present invention is not particularly limited.
  • the hot-dip Zn alloy-plated steel sheet according to the present invention includes (1) a first step of forming a hot-dip Zn alloy plating layer (hereinafter also referred to as “plating layer”) on the surface of a base steel sheet, and (2) a predetermined aqueous solution. Is brought into contact with the surface of the plating layer, the base steel plate and the plating layer heated by the formation of the plating layer are cooled, and the second step of forming a composite oxide film.
  • plating layer a hot-dip Zn alloy plating layer
  • the base steel plate is immersed in a hot-dip Zn alloy plating bath to form a hot-dip Zn alloy plating layer on the surface of the base steel plate.
  • the base steel plate is immersed in a molten Zn alloy plating bath, and a predetermined amount of molten metal is adhered to the surface of the base steel plate by using gas wiping or the like.
  • the type of the base steel plate is not particularly limited.
  • the composition of the plating bath is appropriately selected according to the composition of the molten Zn alloy plating layer to be formed.
  • the molten metal adhering to the surface of the base steel sheet is cooled to 100 ° C. or more and below the freezing point of the plating layer, and the molten metal is solidified, so that the composition almost the same as the component composition of the plating bath on the surface of the base steel sheet A plated steel sheet on which a plating layer is formed is obtained.
  • prescribed aqueous solution is made to contact the surface of a hot-dip Zn alloy plating layer, and the base-material steel plate and plating layer which were heated up by formation of the hot-dip Zn alloy plating layer are cooled.
  • the second step is preferably performed as a water quench (water cooling) step.
  • the temperature of the surface of the molten Zn alloy plating layer is about 100 ° C. or more and below the freezing point of the plating layer.
  • the cooling aqueous solution is an aqueous solution containing a vanadium compound.
  • the concentration of the vanadium compound in the cooling aqueous solution is preferably 0.01 g / L or more in terms of V element. When the concentration of the vanadium compound is less than 0.01 g / L in terms of V element, the black change on the surface of the composite oxide film may not be sufficiently suppressed.
  • the method for preparing the aqueous solution (cooling aqueous solution) containing the vanadium compound is not particularly limited.
  • a vanadium compound and, if necessary, a dissolution accelerator may be dissolved in water (solvent).
  • suitable vanadium compounds include acetylacetone vanadyl, vanadium acetylacetonate, vanadium oxysulfate, vanadium pentoxide, ammonium vanadate. These vanadium compounds may be used alone or in combination of two or more.
  • the addition amount of the dissolution accelerator is not particularly limited. For example, 90 to 130 parts by mass of a dissolution accelerator may be added to 100 parts by mass of the vanadium compound. When the addition amount of the dissolution accelerator is too small, the vanadium compound may not be sufficiently dissolved. On the other hand, when the addition amount of the dissolution accelerator is excessive, the effect is saturated, which is disadvantageous in terms of cost.
  • dissolution accelerator examples include 2-aminoethanol, tetraethylammonium hydroxide, ethylenediamine, 2,2'-iminodiethanol, and 1-amino-2-propanol.
  • the method for bringing the cooling aqueous solution into contact with the surface of the molten Zn alloy plating layer is not particularly limited.
  • Examples of the method of bringing the cooling aqueous solution into contact with the surface of the molten Zn alloy plating layer include a spray method and an immersion method.
  • FIG. 2 is a diagram showing an example of a method for bringing a cooling aqueous solution into contact with the surface of the molten Zn alloy plating layer.
  • FIG. 2A is a diagram illustrating an example of a method in which a cooling aqueous solution is brought into contact with the surface of a molten Zn alloy plating layer by a spray method.
  • FIG. 2B is a diagram showing an example of a method in which a cooling aqueous solution is brought into contact with the surface of the molten Zn alloy plating layer by an immersion method.
  • the spray-type cooling device 100 includes a plurality of spray nozzles 110, a squeezing roll 120 disposed on the downstream side in the feed direction of the steel strip S from the spray nozzle 110, and a casing 130 that covers these. And have.
  • the spray nozzle 110 is arranged on both surfaces of the steel strip S.
  • the steel strip S is cooled by supplying a cooling aqueous solution from the spray nozzle 110 inside the housing 130 so that a water film is temporarily formed on the surface of the plating layer. Then, the cooling aqueous solution is removed by the squeeze roll 120. At this time, the adhesion amount of vanadium contained in the composite oxide film can be adjusted by controlling the opening degree of the squeeze roll 120.
  • the immersion type cooling device 200 includes an immersion rod 210 in which a cooling aqueous solution is stored, an immersion roll 220 disposed inside the immersion rod 210, and a steel strip S from the immersion roll 220. And a squeeze roll 230 for removing excess cooling aqueous solution adhering to the steel strip S.
  • the steel strip S is cooled by contacting with the cooling aqueous solution after being put into the immersion trough 210. Thereafter, the steel strip S is turned up by the rotating dipping roll 220 and pulled upward. Then, the cooling aqueous solution is removed by the squeeze roll 230. At this time, the amount of vanadium contained in the composite oxide film can be adjusted by controlling the opening degree of the squeeze roll 230.
  • the hot-dip Zn alloy plated steel sheet according to the present invention can be manufactured.
  • the composite oxide film was formed by contacting the aqueous solution containing the vanadium compound in the water quench step.
  • the aqueous solution containing the vanadium compound is applied and dried.
  • Post-treatment method can also be considered to be able to form a composite oxide film. Therefore, the present inventors cooled the molten Zn alloy-plated steel sheet to room temperature with general industrial water, and then applied an aqueous solution containing the vanadium compound (the same aqueous solution used in the above production method) and dried. To form a composite oxide film.
  • the hot-dip Zn alloy-plated steel sheet produced in this way showed no significant difference in blackening resistance even when compared with a hot-dip Zn alloy-plated steel sheet that did not have a composite oxide film.
  • the hot-dip Zn alloy-plated steel sheet according to the present invention is superior in blackening resistance compared to hot-dip Zn alloy-plated steel sheet that does not have a composite oxide film.
  • the Zn hydroxide ratio in the composite oxide film exceeds 40%.
  • the hot-dip Zn alloy-plated steel sheet according to the present invention is considered to be excellent in blackening resistance. It is done.
  • the hot-dip Zn alloy-plated steel sheet according to the present invention can be manufactured, for example, in the following manufacturing line.
  • FIG. 3 is a schematic diagram of a part of a production line 300 for a hot-dip Zn alloy-plated steel sheet.
  • the production line 300 can continuously produce the hot-dip Zn alloy plated steel sheet according to the present invention by forming a plating layer and a composite oxide film on the surface of the base steel sheet (steel strip).
  • the manufacturing line 300 can also form a chemical conversion treatment film in the surface of a composite oxide film as needed, and can manufacture a chemical conversion treatment plated steel plate continuously.
  • the production line 300 includes a furnace 310, a plating bath 320, an air jet cooler 340, an air-water cooling zone 350, a water quench zone 360, a skin pass mill 370, and a tension leveler 380.
  • the steel strip S fed out from a feeding reel (not shown) is heated in the furnace 310 through a predetermined process.
  • the molten steel adheres to both surfaces of the steel strip S by immersing the heated steel strip S in the plating bath 320.
  • excess molten metal is removed by a wiping device having the wiping nozzle 330, and a predetermined amount of molten metal is adhered to the surface of the steel strip S.
  • the steel strip S to which a predetermined amount of molten metal adheres is cooled to below the freezing point of the molten metal by the air jet cooler 340 and the air / water cooling zone 350.
  • the air jet cooler 340 is a facility for cooling the steel strip S by gas blowing.
  • the air-water cooling zone 350 is a facility intended to cool the steel strip S by spraying a mist-like fluid (for example, cooling water) and gas. Thereby, the molten metal is solidified and a molten Zn alloy plating layer is formed on the surface of the steel strip S.
  • a mist-like fluid for example, cooling water
  • the hot-dip Zn alloy plated steel sheet cooled to a predetermined temperature is further cooled in the water quench zone 360.
  • the water quench zone 360 is equipment for the purpose of cooling the steel strip S by contact with a large amount of cooling water compared to the air-water cooling zone 350, and the amount by which a water film is temporarily formed on the surface of the plating layer. Supply water.
  • the water quench zone 360 seven rows of 10 flat spray nozzles arranged at intervals of 150 mm in the width direction of the steel strip S are arranged in the feed direction of the base steel plate S.
  • an aqueous solution of a vanadium compound is used as a cooling aqueous solution.
  • the steel strip S is cooled in the water quench zone 360 while being supplied with a cooling aqueous solution in such an amount that a water film is temporarily formed on the surface of the plating layer.
  • a cooling aqueous solution for example, the water temperature of the cooling aqueous solution is about 20 ° C.
  • the water pressure is about 2.5 kgf / cm 2
  • the amount of water is about 150 m 3 / h.
  • “Temporarily forming a water film” refers to a state in which a water film in contact with the hot-dip Zn alloy-plated steel sheet is observed for about 1 second or more visually.
  • a composite oxide film containing a component of the plating layer and vanadium and having a Zn hydroxide ratio of 40% or more is formed on the surface of the plating layer. Is done.
  • the water-cooled hot-dip Zn alloy-plated steel sheet is temper-rolled by a skin pass mill 370, straightened by a tension leveler 380, and wound around a tension reel 390.
  • a predetermined chemical conversion treatment solution is applied by the roll coater 400 to the surface of the hot dip Zn alloy plated steel plate corrected by the tension leveler 380.
  • the hot-dip Zn alloy plated steel sheet that has been subjected to the chemical conversion treatment is dried and cooled in the drying zone 410 and the air cooling zone 420 and then wound around the tension reel 390.
  • the hot-dip Zn alloy-plated steel sheet according to the present invention is excellent in blackening resistance and can be easily manufactured with high productivity.
  • Hot-dip Zn alloy-plated steel sheet A hot-dip Zn alloy-plated steel sheet was manufactured using the production line 300 shown in FIG.
  • As the base steel plate (steel strip) S a hot-rolled steel strip having a thickness of 2.3 mm was prepared.
  • the base steel plate was plated with the plating bath composition and plating conditions shown in Table 1 to produce 14 types of hot-dip Zn alloy plated steel plates having different plating layer compositions.
  • the composition of the plating bath and the composition of the plating layer are almost the same.
  • the cooling conditions in the air jet cooler 340 were changed, and the temperature of the steel sheet (plated layer surface) immediately before passing through the water quench zone 360 was adjusted to 200 ° C.
  • any of the aqueous solutions shown in Table 2 was used as a cooling aqueous solution in order to form a composite oxide film.
  • Each cooling aqueous solution was prepared by dissolving the metal compound shown in Table 2 in water at pH 7.6 and a dissolution accelerator at a predetermined ratio as required, and then adjusting the water temperature to 20 ° C.
  • the concentration of the metal compound in each cooling aqueous solution is 250 mg / L in terms of metal element.
  • each cooling aqueous solution supplied from the water quench zone 360 were water pressure: 2.5 kgf / cm 2 and water amount: 150 m 3 / h.
  • water quench zone 360 instead of using any of the aqueous solutions shown in Table 2, water that does not contain a metal compound is used, and thereafter, it is shown in Table 2 by a roll coat method or a spray ringer method. Any aqueous solution was applied and dried to form a composite oxide film (post-treatment method).
  • Optical conditions d / 8 ° method (double beam optical system) Field of view: 2 degree field of view Measurement method: Reflected light measurement Standard light: C Color system: CIELAB Measurement wavelength: 380 to 780 nm Measurement wavelength interval: 5 nm Spectrometer: Diffraction grating 1200 / mm Lighting: Halogen lamp (voltage 12V, power 50W, rated life 2000 hours) Measurement area: 7.25mm ⁇ Detection element: Photomultiplier tube (R928; Hamamatsu Photonics Co., Ltd.) Reflectance: 0-150% Measurement temperature: 23 ° C Standard plate: white
  • the blackening resistance of the test pieces of Nos. 1 to 6, 52 to 57 and the blackening resistance of the test pieces of Nos. 7 to 36 and 58 to 87 were compared, the adhesion of vanadium contained in the composite oxide film It can be seen that the blackening resistance is particularly excellent when the amount is 0.01 mg / m 2 or more.
  • Example 2 In Experiment 2, the 90 types of hot-dip Zn alloy-plated steel sheets produced in Experiment 1 were subjected to chemical conversion treatment under the following chemical conversion treatment conditions A to C. Subsequently, the blackening resistance when the gloss deterioration accelerating treatment was performed in the same manner as in Experiment 1 was measured. Moreover, the external appearance after chemical conversion treatment was also evaluated.
  • Zinchrome 3387N (chromium concentration 10 g / L, Nippon Parkerizing Co., Ltd.) was used as the chemical conversion treatment liquid.
  • the chemical conversion treatment liquid was applied by a spray ringer roll method so that the chromium adhesion amount was 10 mg / m 2 .
  • the chemical conversion treatment condition B an aqueous solution containing magnesium phosphate 50 g / L, potassium titanium fluoride 10 g / L, and organic acid 3 g / L was used as the chemical conversion treatment liquid.
  • the chemical conversion treatment liquid was applied by a roll coating method so that the metal component adhesion amount was 50 mg / m 2 .
  • chemical conversion treatment condition C an aqueous solution containing 20 g / L of urethane resin, 3 g / L of ammonium dihydrogen phosphate, and 1 g / L of vanadium pentoxide was used as the chemical conversion treatment liquid.
  • the chemical conversion solution was applied by a roll coating method so that the dry film thickness was 2 ⁇ m.
  • Tables 7 to 10 show the relationship between the type of chemical conversion treatment plate and the type of chemical conversion treatment, the evaluation result of the degree of black change, and the appearance of each plated steel sheet.
  • a plated steel sheet on which a composite oxide film containing vanadium and having a Zn hydroxide ratio on the surface of 40% or less is formed is resistant to the formation of a chemical conversion treatment film. Black denaturation was good.
  • the adhesion amount of vanadium contained in the composite oxide film exceeds 10.0 mg / m 2 (No. 31 to 36, 82 to 87 test pieces)
  • the chemical conversion solution and the plating layer surface As a result, the chemical conversion film became cloudy.
  • the adhesion amount of vanadium contained in the composite oxide film is 10.0 mg / m 2 or less.
  • the hot-dip Zn alloy-plated steel sheet obtained by the production method of the present invention is excellent in blackening resistance, it is useful as a plated steel sheet used for, for example, building roofing materials, exterior materials, home appliances, and automobiles.

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RU2016121849A RU2647416C2 (ru) 2013-12-03 2014-11-13 Покрытый погружением в расплав цинкового сплава стальной лист
CA2931988A CA2931988C (en) 2013-12-03 2014-11-13 Hot-dip zn-alloy-plated steel sheet
US15/037,068 US20160305003A1 (en) 2013-12-03 2014-11-13 Hot-dip zn-alloy-plated steel sheet
KR1020167013546A KR101770342B1 (ko) 2013-12-03 2014-11-13 용융 Zn 합금 도금 강판
EP14867197.7A EP3078765A4 (en) 2013-12-03 2014-11-13 Hot-dip zn-alloy-plated steel sheet
AU2014358646A AU2014358646C1 (en) 2013-12-03 2014-11-13 Hot-dip Zn-alloy-plated steel sheet
MX2016006897A MX2016006897A (es) 2013-12-03 2014-11-13 Lamina de acero enchapada en aleacion de zinc (zn) por inmersion en caliente.
CN201480065804.8A CN105793469B (zh) 2013-12-03 2014-11-13 热浸镀Zn合金钢板的制造方法
US16/152,455 US20190040512A1 (en) 2013-12-03 2018-10-05 Method of producing hot-dip zn-alloy-plated steel sheet

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JP6973017B2 (ja) * 2017-12-15 2021-11-24 日本製鉄株式会社 塗装金属板の製造方法
US11384419B2 (en) * 2019-08-30 2022-07-12 Micromaierials Llc Apparatus and methods for depositing molten metal onto a foil substrate
CN113621852B (zh) * 2021-07-13 2023-02-17 株洲冶炼集团股份有限公司 一种锌铝镁涂镀材料及其制备方法

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