WO2026026957A1 - 表面胶接性能优良的合金化热浸镀锌钢板及其制造方法 - Google Patents

表面胶接性能优良的合金化热浸镀锌钢板及其制造方法

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Publication number
WO2026026957A1
WO2026026957A1 PCT/CN2025/112156 CN2025112156W WO2026026957A1 WO 2026026957 A1 WO2026026957 A1 WO 2026026957A1 CN 2025112156 W CN2025112156 W CN 2025112156W WO 2026026957 A1 WO2026026957 A1 WO 2026026957A1
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WIPO (PCT)
Prior art keywords
dip galvanized
alloyed hot
acid
substance
sulfate
Prior art date
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Pending
Application number
PCT/CN2025/112156
Other languages
English (en)
French (fr)
Inventor
赵艳亮
孙敏
郑凯隆
戴毅刚
朱敏
毕文珍
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Baoshan Iron and Steel Co Ltd
Original Assignee
Baoshan Iron and Steel Co Ltd
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Publication date
Application filed by Baoshan Iron and Steel Co Ltd filed Critical Baoshan Iron and Steel Co Ltd
Publication of WO2026026957A1 publication Critical patent/WO2026026957A1/zh
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • 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
    • 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
    • C23C2/265—After-treatment by applying solid particles to the molten coating
    • 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

Definitions

  • This invention relates to a steel plate and a method for manufacturing the same, and more particularly to a galvanized steel plate and a method for manufacturing the same.
  • the bonding performance of vehicle body materials directly affects their structural stability and collision safety; therefore, it is necessary to ensure the adhesive performance of the body steel panels.
  • the factors influencing the surface adhesive performance of body materials mainly include two aspects: physical properties and chemical properties. Physical properties are primarily affected by the adhesive bonding along the surface physical contours and the adhesion force of the surface substances, while chemical properties are mainly affected by surface tension and the chemical reactivity of the extreme surface layers.
  • One of the objectives of this invention is to provide an alloyed hot-dip galvanized steel sheet with excellent surface bonding performance.
  • This galvanized steel sheet has good bonding performance, which can improve the overall strength of the bonded structure during service and optimize the stability of the adhesive performance.
  • the present invention provides an alloyed hot-dip galvanized steel sheet with excellent surface bonding performance, comprising a substrate having an alloyed hot-dip galvanized layer on its surface.
  • the surface of the alloyed hot-dip galvanized layer is covered with a composite nanostructure treatment layer; the composite nanostructure treatment layer includes nanoparticles and irregular nanostructures.
  • the nanoparticles are randomly distributed on the surface of the alloyed hot-dip galvanized layer in at least a needle-like morphology.
  • the irregular nanostructure has active groups that optimize the chemical bonding properties of the alloyed hot-dip galvanized layer surface.
  • nanoparticles are randomly distributed on the surface of the alloyed hot-dip galvanized layer, mainly in the form of needle-like and short rod-like shapes.
  • the needle-like nanoparticles enhance adhesion by increasing the contact area and physical anchoring effect between the adhesive and the alloyed hot-dip galvanized layer, thereby promoting uniform stress distribution after adhesive curing and improving bonding performance.
  • the active groups can increase the effective contact area of the adhesive and form good adhesion, as well as a stronger bond, thereby improving the chemical resistance of the adhesive.
  • the substrate can be selected from conventional steel sheets in the art, preferably conventional steel sheets suitable for galvanizing. There are no particular limitations on the shape and thickness of the substrate herein; an appropriate thickness can be selected according to the application field of the substrate.
  • the substrate comprises, by weight percentage: 0.01–0.20 wt% C, 0.10–0.50% Si, 0.10–0.50% Mn, P ⁇ 0.020%, S ⁇ 0.0150%, and 0.01–0.05% Ti, with the balance being Fe and unavoidable impurities.
  • the substrate is a DC53 steel sheet.
  • an exemplary alloyed hot-dip galvanized steel sheet is a DC53D+ZF cold-rolled hot-dip galvanized iron alloy steel sheet with a tensile strength of 340-420 MPa, a yield strength of 180-260 MPa, an elongation after fracture ⁇ 30%, and a hardness (HB) of 100-150.
  • the surface of the alloyed hot-dip galvanized steel sheet is covered with the composite nanostructure treatment layer described herein.
  • the thickness of the alloyed hot-dip galvanized layer there is no particular limitation on the thickness of the alloyed hot-dip galvanized layer.
  • the alloyed hot-dip galvanized layer may have a thickness conventional in the art (e.g., 30–150 g/ m2 ), as long as it does not adversely affect the use and bonding performance of the galvanized steel sheet.
  • the mass percentage content of Fe element in the Zn-Fe alloy phase of the alloyed hot-dip galvanized layer is 8%-10%.
  • the mass percentage of Fe in the Zn-Fe alloy phase of the alloyed hot-dip galvanized layer when the mass percentage of Fe in the Zn-Fe alloy phase of the alloyed hot-dip galvanized layer is too low, defects of poor alloying are prone to appear on the surface of the alloyed steel plate, resulting in a significant increase in the surface roughness of the coating and increasing the coefficient of friction of the coating surface.
  • the mass percentage of Fe in the Zn-Fe alloy phase of the alloyed hot-dip galvanized layer is too high, a phase with excessively high hardness and brittleness is easily formed in the coating. This brittle microstructure can lead to a phenomenon where the coating adhesion is lower than the adhesion at the adhesive interface during the adhesive peeling process, resulting in coating peeling.
  • the mass percentage of Fe in the Zn-Fe alloy phase of the alloyed hot-dip galvanized layer can preferably be controlled at 9%-10%.
  • the alloyed hot-dip galvanized layer also contains Al element and at least one element selected from Bi, Cd, Co, Ni and Sn.
  • the mass percentage content of Al element in the alloyed hot-dip galvanized layer is 0.03%-0.2%.
  • the main function of Al in the alloyed hot-dip galvanized layer is to improve the uniformity of the coating, thereby ensuring the product's appearance quality.
  • the mass percentage of Al in the alloyed hot-dip galvanized layer is too low, the layer is prone to unevenness, directly affecting the uniformity of surface bonding strength during adhesive bonding.
  • the mass percentage of Al in the alloyed hot-dip galvanized layer is too high, the surface brittleness increases, and zinc powder is prone to peeling off during the adhesive bonding process.
  • the mass percentage of Al in the alloyed hot-dip galvanized layer can be further controlled to 0.08%-0.15%.
  • the total mass percentage content of Bi, Cd, Co, Ni and Sn elements in the alloyed hot-dip galvanized layer does not exceed 0.1%.
  • the Bi, Cd, Co, Ni, and Sn elements in the alloyed hot-dip galvanized layer can be combined with manufacturing process requirements to further optimize the coating hardness and uniformity.
  • the surface of the alloyed hot-dip galvanized layer has zinc-iron alloy crystalline regions and randomly distributed plateau regions, with the area ratio of zinc-iron alloy crystalline regions per unit area being 15%-85%.
  • the surface of the alloyed hot-dip galvanized layer consists only of zinc-iron alloy crystalline regions and plateau regions. The area ratio of zinc-iron alloy crystalline regions per unit area can be obtained by identifying the plateau regions and calculating their area ratio.
  • the platform area is formed during the manufacturing method of alloyed hot-dip galvanized steel sheet by treating the surface of the sheet with a leveling roller in the leveling step.
  • the leveling rate in the leveling step is 0.4-1.8%.
  • the surface roughness of the zinc-iron alloy coating decreases and the surface bonding performance decreases; when the area ratio of the zinc-iron alloy crystalline region is greater than 85%, the surface roughness of the zinc-iron alloy coating is too high and it is difficult to achieve stable control, which affects the appearance quality of subsequent coating.
  • the equivalent sphere radius of the nanoparticles is 30-200 nm.
  • the equivalent sphere radius of the nanoparticles when the equivalent sphere radius of the nanoparticles is less than 30 nm, the microstructure they form on the metal surface is insufficient to provide effective mechanical anchoring, thereby reducing adhesive properties.
  • the equivalent sphere radius of the nanoparticles when the equivalent sphere radius of the nanoparticles is greater than 200 nm, it easily leads to local stress concentration on the metal surface, thereby reducing the stability of the adhesive properties on the metal surface.
  • the equivalent sphere radius of the nanoparticles can be further controlled to 50-150 nm.
  • the needle-like nanoparticles contain a metal-based compound, wherein the metal in the metal-based compound is selected from at least one of Na, Al, Ca, Zn, Ag, Mg and Zr.
  • the metal-based compound is at least one of aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum acetate, sodium aluminate, calcium nitrate, calcium acetate, calcium sulfate, zirconium acetate, zinc acetate, zinc sulfate, zinc nitrate, magnesium sulfate, magnesium citrate, magnesium lactate, zirconium borate, silver nitrate, silver sulfate, ammonium fluorozirconate, potassium fluorozirconate, and ammonium zirconium carbonate.
  • the metal-based compound is selected from one or more of aluminum nitrate, zirconium borate, magnesium sulfate, calcium nitrate, sodium aluminate, magnesium citrate, zinc acetate, silver nitrate, potassium fluorozirconate, aluminum sulfate, and silver sulfate.
  • the nanoparticles in this invention also contain non-metallic elements, which may include two or more elements selected from Si, O, C, N and H. Their main function is to combine with metallic elements through coordinate bonds to form the nanoparticle structure.
  • the proportion of needle-like nanoparticles to all nanoparticles per unit area of the surface is 20%-70%.
  • the proportion of needle-shaped nanoparticles to all nanoparticles is less than 20%, the contact area between the adhesive and the metal surface is not sufficiently increased, resulting in an insignificant adhesive optimization effect.
  • the proportion of needle-shaped nanoparticles to all nanoparticles is greater than 70%, the needle-shaped crystalline particles are prone to local aggregation and have excessively small gaps, thereby limiting the penetration of the adhesive on the material surface and making it difficult to fully wet the crystals, leading to a decrease in adhesive performance.
  • the proportion of needle-shaped nanoparticles to all nanoparticles per unit area of the surface is 30%-60%.
  • the active groups account for 6%-70% of the mass of the irregular nanostructure.
  • the mass percentage of active groups in the irregular nanostructure when the mass percentage of active groups in the irregular nanostructure is greater than 70%, the excessive number of active groups leads to over-polymerization of the adhesive during coating, resulting in an uneven bonding surface, reduced adhesive coverage, and consequently poor bonding performance.
  • the mass percentage of active groups in the irregular nanostructure is less than 6%, the insufficient number of active groups cannot achieve a significant effect in optimizing bonding performance.
  • the mass percentage of active groups in the irregular nanostructure can be further controlled to 20-50%.
  • the active groups include amino groups and carboxyl groups.
  • the main function of the amino group is to increase the wettability of the surface with the adhesive, making the adhesive easier to penetrate and diffuse, increasing the effective contact area of the adhesive and forming good adhesion;
  • the main function of the carboxyl group is to enhance the chemical bond, directly forming chemical bonds with functional groups such as hydroxyl and amino groups in the adhesive to form a stronger bond, thereby improving the chemical resistance of the adhesive and making its performance more stable in harsh environments.
  • the molar percentage of amino groups and carboxyl groups is 10%-150%.
  • the molar percentage of amino groups to carboxyl groups when the molar percentage of amino groups to carboxyl groups is less than 10%, the low proportion of amino groups prevents the adhesive from effectively optimizing surface penetration and diffusion, resulting in insignificant optimization of adhesive performance.
  • the molar percentage of amino groups to carboxyl groups is greater than 150%, the proportion of carboxyl groups is too low, chemical bonding is insufficient, and the adhesive structure lacks performance stability in typical chemically resistant environments.
  • the molar percentage of amino groups to carboxyl groups is preferably controlled between 17% and 120%. In some embodiments, the molar percentage of amino groups to carboxyl groups is preferably controlled between 40% and 150%. In some embodiments, the molar percentage of amino groups to carboxyl groups is preferably controlled between 40% and 120%.
  • the active group is provided by at least one selected from 3,4,5-trihydroxybenzoic acid, ethylenediaminetetraacetic acid, citric acid, oxalic acid, salicylic acid, tartaric acid, tannic acid, cysteine, mercaptoacetic acid, mercaptoethanol, mercaptoethanol, polyethyleneimine, glycine, aspartic acid, ammonia, ethanolamine, propanolamine, isopropanolamine, ethylsilanol, and propylenesilanol.
  • the active group is provided by one or more selected from 3,4,5-trihydroxybenzoic acid, ammonia, tartaric acid, isopropanolamine, ethylsilanol, aspartic acid, oxalic acid, ethylsilanol, ethanolamine, polyethyleneimine, citric acid, and ethylenediaminetetraacetic acid.
  • the nanoparticles account for 20%-60% of the mass percentage in the composite nanostructure treatment layer.
  • the mass percentage of nanoparticles in the composite nanostructure treatment layer when the mass percentage of nanoparticles in the composite nanostructure treatment layer is less than 20%, the microstructure is insufficient to provide adequate and effective mechanical anchoring, thereby reducing the adhesive performance optimization effect.
  • the mass percentage of nanoparticles in the composite nanostructure treatment layer is greater than 60%, the proportion of active groups that enhance chemical bonds decreases, and an excessively high proportion of nanoparticle structure leads to instability in adhesive performance optimization, especially under service aging conditions, which may result in a decline in adhesive layer performance.
  • the mass percentage of nanoparticles in the composite nanostructure treatment layer can be further controlled to 30%-50%.
  • the composite nanostructure treatment layer is composed of nanoparticles and irregular nanostructures.
  • the irregular nanostructures account for 40%-80% by mass in the composite nanostructure treatment layer, such as 50%-70% or 40%-60%.
  • the composite nanostructure treatment layer contains at least one of: aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum acetate, sodium aluminate, calcium nitrate, calcium acetate, calcium sulfate, zirconium acetate, zinc acetate, zinc sulfate, zinc nitrate, magnesium sulfate, magnesium citrate, magnesium lactate, zirconium borate, silver nitrate, silver sulfate, ammonium fluorozirconate, potassium fluorozirconate, and ammonium zirconium carbonate, preferably containing one or more of aluminum nitrate, zirconium borate, magnesium sulfate, calcium nitrate, sodium aluminate, magnesium citrate, zinc acetate, silver nitrate, potassium fluorozirconate, aluminum sulfate, and silver sulfate; and ( 2) At least one of 3,4,5-trihydroxybenzoic acid, ethylene
  • the composite nanostructure treatment layer is prepared by a water-based treatment agent comprising the first and second substances described in any embodiment herein, through a coating and drying method.
  • coating is selected from roll coating, spraying, and dipping.
  • drying is selected from purging and baking.
  • the thickness of the composite nanostructure treatment layer in the alloyed hot-dip galvanized steel sheet can be 10-100 g/ m2 .
  • Another objective of this invention is to provide a method for manufacturing alloyed hot-dip galvanized steel sheet.
  • This method involves hot-dip galvanizing, alloying heat treatment, and flattening of a substrate, followed by surface treatment, thereby conveniently and economically obtaining an alloyed hot-dip galvanized steel sheet with excellent surface bonding performance.
  • the present invention provides a method for manufacturing alloyed hot-dip galvanized steel sheet, comprising the following steps:
  • the substrate is subjected to hot-dip galvanizing, alloying heat treatment and flattening to form the alloyed hot-dip zinc plating layer on the substrate surface;
  • the alloyed hot-dip galvanized layer is surface-treated with a water-based treatment agent to obtain the composite nanostructure treatment layer.
  • the water-based treatment agent contains a first substance providing a metal-based compound and a second substance providing active groups, wherein the mass ratio of the first substance and the second substance is 1:1 to 1:15.
  • the concentration of the first substance in the water-based treatment agent is 0.5wt% to 6wt%
  • the concentration of the second substance is 1wt% to 8wt%, preferably 0.5wt% to 1.5wt% or 1.5wt% to 6wt%, and preferably 1wt% to 3.2wt% or 3.2wt% to 8wt%.
  • the first substance is selected from at least one of: aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum acetate, sodium aluminate, calcium nitrate, calcium acetate, calcium sulfate, zirconium acetate, zinc acetate, zinc sulfate, zinc nitrate, magnesium sulfate, magnesium citrate, magnesium lactate, zirconium borate, silver nitrate, silver sulfate, ammonium fluorozirconate, potassium fluorozirconate, and ammonium zirconium carbonate.
  • the first substance is selected from one or more of aluminum nitrate, zirconium borate, magnesium sulfate, calcium nitrate, sodium aluminate, magnesium citrate, zinc acetate, silver nitrate, potassium fluorozirconate, aluminum sulfate, and silver sulfate.
  • the second substance is selected from at least one of the following: 3,4,5-trihydroxybenzoic acid, ethylenediaminetetraacetic acid, citric acid, oxalic acid, salicylic acid, tartaric acid, tannic acid, cysteine, mercaptoacetic acid, mercaptoethanol, mercaptoethanol, polyethyleneimine, glycine, aspartic acid, ammonia, ethanolamine, propanolamine, isopropanolamine, ethylsilanol, and propylenesilanol.
  • the second substance is selected from one or more of the following: 3,4,5-trihydroxybenzoic acid, ammonia, tartaric acid, isopropanolamine, ethylsilanol, aspartic acid, oxalic acid, ethylsilanol, ethanolamine, polyethyleneimine, citric acid, and ethylenediaminetetraacetic acid.
  • a water-based treatment agent contains two or more primary substances
  • the proportion of each primary substance there is no particular limitation on the proportion of each primary substance, as long as the total mass concentration of all primary substances in the water-based treatment agent is between 0.5 wt% and 6 wt%.
  • a water-based treatment agent contains two or more secondary substances
  • the proportion of each secondary substance there is also no particular limitation on the proportion of each secondary substance, as long as the total mass concentration of all secondary substances in the water-based treatment agent is between 1 wt% and 8 wt%.
  • the zinc plating bath includes Zn and Al; preferably, the Al content is 0.03–0.20 wt%.
  • the zinc plating bath may also contain trace amounts of one or more of Bi, Cd, Co, Ni, and Sn elements, the total amount of which preferably does not exceed 0.1 wt%.
  • the temperature of the alloying heat treatment is 470-500°C.
  • the holding time for the alloying heat treatment is 2-6 seconds.
  • the flatness rate of the flattening is 0.4%-1.8%, preferably 0.4%-1%.
  • the water-based treatment agent is coated onto the alloyed hot-dip galvanized layer by roller coating, spraying or immersion coating for surface treatment, and then dried into a film by blowing or drying.
  • the alloyed hot-dip galvanized steel sheet with excellent surface bonding performance described in this invention has good bonding properties, which can improve the overall strength of the bonded structure during service and optimize the stability of the adhesive performance.
  • the surface treatment layer of the alloyed hot-dip galvanized steel sheet with excellent surface bonding performance described in this invention is environmentally friendly and phosphorus-free, avoiding the negative environmental impact of phosphorus-containing surface chemical treatments and thus exhibiting higher environmental friendliness.
  • the manufacturing method of the alloyed hot-dip galvanized steel sheet with excellent surface bonding performance described in this invention is convenient and economical, with low manufacturing costs, and the product has broad market application prospects.
  • Figure 1 shows a schematic diagram comparing the adhesive properties of alloyed hot-dip galvanized steel sheets of Example 1 and Comparative Example 1 of the present invention.
  • Figure 2 shows that the surface of the alloyed hot-dip galvanized layer of the present invention has zinc-iron alloy crystalline regions and randomly distributed plateau regions; the plateau regions can be identified and their area proportions calculated using the ImageJ image processing software.
  • the black parts represent the plateau regions.
  • the alloyed hot-dip galvanized steel sheets of Examples 1-7 of this invention were all prepared by the following method:
  • the substrate used in Examples 1-7 and Comparative Example 1 of this invention is DC53 with a thickness of 1.2 mm.
  • Table 1 lists the chemical composition ratios of the substrates used in Examples 1-7 and Comparative Example 1 of this invention.
  • the substrate is subjected to hot-dip galvanizing, alloying heat treatment and flattening to form an alloyed hot-dip zinc plating layer on the substrate surface.
  • the substrate can be immersed in molten zinc in a hot-dip galvanizing pot for hot-dip galvanizing, with a coating thickness of 45 g/ m2 . Then, it is heated to 470-500°C in a vertical heat treatment furnace for alloying heat treatment, and then held at that temperature for a certain time (specifically 4 seconds) to allow the steel substrate to react and diffuse with the liquid zinc, transforming into Fe-Zn intermetallic compounds, thereby forming an alloyed hot-dip galvanized layer on the substrate surface. Then, a leveling roller is used for a leveling process, with the leveling rate controlled within the range of 0.4-1.8%.
  • Table 2 lists the chemical composition content and process parameters of the alloyed hot-dip galvanized layer of the alloyed hot-dip galvanized steel sheets of Examples 1-7 and Comparative Example 1 of the present invention.
  • the "area ratio of zinc-iron alloy crystallization region" in Table 2 is obtained by randomly selecting a 1cm2 area from the photograph, and then using the ImageJ image processing software to identify the platform area and calculate the area ratio.
  • a water-based treatment agent is used to treat the surface of the alloyed hot-dip galvanized layer to obtain a composite nanostructure treatment layer.
  • the water-based treatment agent includes a first substance that provides a metallic element and a second substance that provides an active group.
  • the first substance providing the metallic element is selected from at least one of the following: aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum acetate, sodium aluminate, calcium nitrate, calcium acetate, calcium sulfate, zirconium acetate, zinc acetate, zinc sulfate, zinc nitrate, magnesium sulfate, magnesium citrate, magnesium lactate, zirconium borate, silver nitrate, silver sulfate, ammonium fluorozirconate, potassium fluorozirconate, and ammonium zirconium carbonate.
  • the second substance providing the active group is selected from at least one of the following: 3,4,5-trihydroxybenzoic acid, ethylenediaminetetraacetic acid, citric acid, oxalic acid, salicylic acid, tartaric acid, tannic acid, cysteine, mercaptoacetic acid, mercaptoethanol, mercaptoethanol, polyethyleneimine, glycine, aspartic acid, ammonia, ethanolamine, propanolamine, isopropanolamine, ethylsilanol, and propylenesilanol.
  • water-based treatment agents are applied by roller coating, spraying, or immersion, and then dried to form a film by sweeping or baking to prepare coiled steel.
  • Comparative Example 1 used the same substrate as the embodiment of the present invention and performed steps (1) and (2), but did not perform step (3).
  • the concentration of the first substance is 1.5 wt%.
  • the concentration of the second substance is 3.2 wt%.
  • Table 3 lists the composition and coating process of the water-based treatment agent for alloyed hot-dip galvanized steel sheets of Examples 1-7 and Comparative Example 1 of the present invention.
  • the first substance was not used in Examples 1-7 above, it may also be selected from at least one of aluminum chloride, aluminum acetate, calcium acetate, calcium sulfate, zirconium acetate, zinc nitrate, magnesium lactate, ammonium fluorozirconate and ammonium zirconium carbonate; the second substance may also be selected from at least one of salicylic acid, tannic acid, cysteine, mercaptoacetic acid, mercaptoethanol, mercaptoethanol, glycine, propanolamine and propylenesilanol.
  • Table 4 lists the characteristics of the composite nanostructure treatment layer of the alloyed hot-dip galvanized steel sheets of Examples 1-7 and Comparative Example 1 of the present invention.
  • the equivalent sphere radius of the nanoparticles was observed and its size measured using a high-resolution scanning electron microscope (measurement plane of the largest scale orientation observed).
  • the proportion of needle-shaped nanoparticles to all nanoparticles is evaluated using the proportion of particles per unit area.
  • the weight of the surface composite nanostructure treatment layer was obtained by weighing before and after coating. The mass of the first substance was then subtracted to obtain the mass of the irregular nanostructure.
  • the content of the two active groups was tested by detecting the nitrogen element in the amino group and the characteristic chemical bonds in the carboxyl group using X-ray photoelectron spectroscopy (XPS). The mass of the two active groups was calculated using the following formula: (mass of amino groups + mass of carboxyl groups) / mass of irregular nanostructure * 100%.
  • X-ray photoelectron spectroscopy was used to detect the nitrogen element in amino groups and the characteristic chemical bonds in carboxyl groups to determine the content of the two active groups. The content was then converted to molar content and converted as a percentage.
  • the mass percentage of nanoparticles in the composite nanostructure treatment layer was determined by transmission electron microscopy (TEM), X-ray diffraction (XRD), and atomic absorption spectrometry (AAS), respectively, to identify the composition and volume percentage of the nanoparticles and the thin film. The mass percentage was then calculated by combining the composition density and volume percentage.
  • TEM transmission electron microscopy
  • XRD X-ray diffraction
  • AAS atomic absorption spectrometry
  • the alloyed hot-dip galvanized steel sheets obtained in Examples 1-7 and Comparative Example 1 were processed to a size of 100*25.4mm, and edge burrs were effectively removed.
  • a typical automotive structural adhesive TEROSON EP 5089
  • the bonding sample preparation followed standard SAE J1523, with the bonding area controlled at 3.2 cm2 , the bonding thickness controlled at 0.2mm, and the adhesive curing temperature (harsh curing conditions) at 160°C for 15 minutes. After the adhesive cured, the bonding performance was evaluated, and the evaluation results are listed in Table 5.
  • Adhesive peel strength decline rate (Initial adhesive peel strength - Adhesive peel strength under aging conditions) / Initial adhesive peel strength under aging conditions * 100%.
  • Table 5 lists the adhesive performance evaluation results of Examples 1-7 and Comparative Example 1 of the present invention.
  • Examples 1-7 of the present invention all exhibit good performance in terms of initial adhesive peel strength and adhesive peel strength attenuation under aging conditions. Furthermore, Examples 1, 3, and 7 demonstrate that the effective composite nanostructures imparted to the surface through typical coating methods such as spraying, dipping, and roller coating all achieve good surface adhesive properties, indicating that the preparation of composite nanostructures has broader process adaptability.
  • Comparative Example 1 without the composite nanostructure treatment layer, there will be a phenomenon of poor initial adhesive peel performance and a deterioration in the rate of decrease in adhesive peel strength under aging conditions.
  • Figure 1 shows a schematic diagram comparing the adhesive properties of the alloyed hot-dip galvanized steel sheets of Example 1 and Comparative Example 1 according to the present invention. Fifty sets of experiments were conducted on the alloyed hot-dip galvanized steel sheets of Example 1 and Comparative Example 1 according to the method described in the initial adhesive peel strength evaluation. The obtained adhesive peel strength data were statistically analyzed to obtain Figure 1.
  • the coating of Example 1 contains 10% Fe, exhibiting good structural toughness and resistance to brittleness under shear force, thus improving coating adhesion.
  • the composite nanostructure treatment layer covering its surface strengthens the physical bonding between the adhesive and the coating interface and increases chemical bonding sites, significantly enhancing the adhesion strength of the adhesive interface.
  • the bonding strength between the coating and the interface exceeds the cohesive strength of the adhesive, the weak points during the tensile shear process are concentrated within the adhesive, significantly improving peel strength and stability.
  • the surface and adhesive of Comparative Example 1 are mainly physically adsorbed, with fewer chemical bonding points, resulting in lower bonding strength. The tensile shear fracture process is affected by three factors, reducing the adhesive peel strength and stability.

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Abstract

本发明公开了一种表面胶接性能优良的合金化热浸镀锌钢板，其包括基板，所述基板表面具有合金化热浸镀锌层；所述合金化热浸镀锌层表面覆盖有复合纳米结构处理层；所述复合纳米结构处理层包括纳米颗粒以及不规则纳米结构；其中所述纳米颗粒至少以针叶状的形态随机分布在所述合金化热浸镀锌层表面；所述不规则纳米结构具有优化合金化热浸镀锌层表面化学键合性能的活性基团。本发明还公开了一种合金化热浸镀锌钢板的制造方法，其包括步骤：对基板进行热浸镀、合金化热处理和平整，以在基板表面形成所述合金化热浸镀锌层；采用水基处理剂对合金化热浸镀锌层进行表面处理，以获得所述复合纳米结构处理层。

Description

表面胶接性能优良的合金化热浸镀锌钢板及其制造方法 技术领域
本发明涉及一种钢板及其制造方法，尤其涉及一种镀锌钢板及其制造方法。
背景技术
车身材料的连接性能直接影响其结构稳定性和碰撞安全性，因此需要保证车身钢板的胶粘性能。车身用材表面胶粘性能的影响因素主要包括物理特性和化学特性两个方面，其中物理特性主要受表面物理轮廓的胶粘剂铆着和表层物质结合力影响，而化学特性主要受表面张力和极表层化学活性反应影响。
上世纪末，汽车行业为解决汽车镀锌板表面成型性能不足的问题，促使了单功能磷酸盐润滑皮膜技术的广泛应用。但镀层表面磷酸盐化合物直接改变了表面的化学成分，在胶接过程磷酸盐与胶接剂发生相互作用，形成障碍层，阻碍胶接剂与金属表面的有效结合，同时磷酸盐与胶粘剂的粘结性能较差易出现胶粘性能不足的问题。
近年来，随着汽车行业对胶接性能的关注度进一步提升，粘结强度要求逐步提高。单功能磷酸盐润滑皮膜产品在应用实践中表面胶接性能下降问题显现。现有技术中，例如：
公开号为CN101910466A，公开日为2010年12月8日，名称为“具有良好的密封剂粘合性和耐腐蚀性的锌合金涂层钢板及其制备方法”的中国专利文献公开了一种具有良好密封剂粘合性和耐蚀性的锌合金镀层钢板，其主要是通过真空沉积的方式在合金化镀锌钢板表面沉积一层0.1-1微米厚度的金属层的方法来改善汽车合金化镀层钢板耐蚀性和密封胶粘合性能。
又例如：公开号为CN102666903A，公开日为2012年9月12日，名称为“成形性及粘接后的耐剥离性优异的合金化熔融镀锌钢板及其制造方法”的中国专利文献公开了一种成型性及胶粘后耐剥离性优异的合金化热浸镀锌钢板极其制造方法，主要通过在镀层表面形成包含Mn，Zn，P的复合氧化物和水溶性P化合物的混合层，主要通过构成比例控制来实现兼顾合金化镀层钢板表面润滑和粘接性能优化。但是该项技术含P化合物，环保性能不足。
发明内容
本发明的目的之一在于提供一种表面胶接性能优良的合金化热浸镀锌钢板，该镀锌钢板具有良好的胶接性能，可以提升胶接结构服役过程整体强度，优化胶粘性能稳定性。
为了实现上述目的，本发明提供了一种表面胶接性能优良的合金化热浸镀锌钢板，其包括基板，所述基板表面具有合金化热浸镀锌层；
所述合金化热浸镀锌层表面覆盖有复合纳米结构处理层；所述复合纳米结构处理层包括纳米颗粒以及不规则纳米结构；
其中所述纳米颗粒至少以针叶状的形态随机分布在所述合金化热浸镀锌层表面；
所述不规则纳米结构具有优化合金化热浸镀锌层表面化学键合性能的活性基团。
在本发明中，纳米颗粒主要以针叶状和短棒状的形态随机分布在所述合金化热浸镀锌层表面，其中针叶状的纳米颗粒通过提高胶粘剂与合金化热浸镀锌层之间的接触面积和物理铆着作用，来增强黏附力促进胶粘剂固化后的应力均匀分布，进而提高胶接性能。
在本发明中，活性基团可以增加胶接的有效接触面积并形成良好的黏附，以及形成更牢固的接合，从而提高胶接的耐化学性。
进一步地，所述基板可选自本领域常规钢板，优选为本领域常规的可用于镀锌的钢板。本文对基板的形状和厚度没有特别的限定，可根据基板的应用领域选择适当的厚度。在一些实施方案中，以质量百分含量计，所述基板包括：0.01～0.20wt％的C、0.10～0.50％的Si、0.10～0.50％的Mn、P≤0.020％、S≤0.0150％和0.01～0.05％的Ti，余量为Fe和不可避免的杂质。在一些实施方案中，所述基板为DC53钢板。在一些实施方案中，示例性的合金化热浸镀锌钢板是DC53D+ZF冷轧热镀锌铁合金钢板，其抗拉强度为340～420MPa、屈服强度为180～260MPa，断后伸长率≥30％，硬度(HB)为100～150，在该合金化热浸镀锌钢板表面覆盖有本文所述的复合纳米结构处理层。
进一步地，在本发明所述的合金化热浸镀锌钢板中，对合金化热浸镀锌层的厚度无特殊限定。合金化热浸镀锌层可具有本领域常规的厚度(如30～150g/m2)，只要对镀锌钢板的使用和胶接性能无不利影响即可。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述合金化热浸镀锌层中的Zn-Fe合金相中的Fe元素质量百分含量为8％-10％。
在本发明中，当合金化热浸镀锌层中的Zn-Fe合金相中的Fe元素质量百分含量过低时，合金化钢板表面容易出现合金化不良的缺陷，造成镀层表面粗糙度上升明显，增大了镀层表面的摩擦系数；当合金化热浸镀锌层中的Zn-Fe合金相中的Fe元素质量百分含量过高时，镀层中容易形成硬度过高且脆性大的相，该脆性组织结构会导致在胶接剥离过程中易出现镀层结合力低于胶接界面结合力的现象，从而出现镀层剥落的问题。在一些实施方式中，可以将合金化热浸镀锌层中的Zn-Fe合金相中的Fe元素质量百分含量优选地控制为9％-10％。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述合金化热浸镀锌层还含有Al元素以及选自Bi、Cd、Co、Ni和Sn元素中的至少其中一种。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述合金化热浸镀锌层中的Al元素质量百分含量为0.03％-0.2％。
在本发明中，合金化热浸镀锌层中Al元素的主要作用是提升镀层的均匀性，从而保障产品外观质量。当合金化热浸镀锌层中的Al元素质量百分含量过低时，合金化热浸镀锌层易出现不均匀现象，直接影响胶粘过程中表面粘结强度的均一性能；当合金化热浸镀锌层中的Al元素质量百分含量过高时，合金化热浸镀锌层的表面脆性增加，胶接剥离过程易出现锌粉剥落现象。在一些实施方式中，可以将合金化热浸镀锌层中的Al元素质量百分含量进一步控制为0.08％-0.15％。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述合金化热浸镀锌层中的Bi、Cd、Co、Ni和Sn元素的总质量百分含量不超过0.1％。
在本发明中，合金化热浸镀锌层中的Bi，Cd，Co，Ni，Sn元素可以结合制造工艺需求，进一步优化镀层硬度和均匀性。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述合金化热浸镀锌层表面具有锌铁合金结晶区域和随机分布的平台区域，在表面单位面积内，锌铁合金结晶区域的面积占比为15％-85％。在一些实施方案中，在本发明所述的合金化热浸镀锌钢板中，所述合金化热浸镀锌层表面仅由锌铁合金结晶区域和平台区域组成。可通过识别平台区域并测算其面积占比来获得单位面积内锌铁合金结晶区域的面积占比。
在本发明中，平台区域是在合金化热浸镀锌钢板的制造方法中，在平整步骤中采用平整辊对合金化热浸镀锌钢板的表面进行处理形成的。在一些实施方案中，平整步骤中平整率是0.4-1.8％。
在本发明中，当锌铁合金结晶区域的面积占比小于15％时，锌铁合金镀层表面粗糙度下降，表面胶接性能下降；当锌铁合金结晶区域的面积占比大于85％时，锌铁合金镀层表面粗糙度偏高且难以实现稳定控制，影响后续涂装外观质量。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述纳米颗粒的等效球半径为30-200nm。
在本发明中，当纳米颗粒的等效球半径小于30nm时，其在金属表面形成的微观结构不足以提供有效的机械锚固作用，从而降低了胶粘性能。当纳米颗粒的等效球半径高于200nm时，其在金属表面易导致局部应力集中，从而降低了金属表面的胶粘性能的稳定效果。在一些实施方式中，可以将纳米颗粒的等效球半径进一步地控制为50-150nm。
进一步地，在本发明所述的合金化热浸镀锌钢板中，针叶状的纳米颗粒含有金属基化合物，所述金属基化合物中的金属选自Na、Al、Ca、Zn、Ag、Mg和Zr中的至少其中之一。
进一步地，所述金属基化合物为硫酸铝，氯化铝，硝酸铝，乙酸铝，偏铝酸钠，硝酸钙，乙酸钙，硫酸钙，醋酸锆，乙酸锌，硫酸锌，硝酸锌，硫酸镁，柠檬酸镁，乳酸镁，硼酸锆，硝酸银，硫酸银，氟锆酸铵，氟锆酸钾和碳酸锆铵中的至少其中之一。优选地，所述金属基化合物选自硝酸铝，硼酸锆，硫酸镁，硝酸钙，偏铝酸钠，柠檬酸镁，乙酸锌，硝酸银，氟锆酸钾，硫酸铝和硫酸银中的一种或多种。
本发明中的纳米颗粒还具有非金属元素，非金属元素可以包含选自Si、O、C、N和H元素中的两种或多种，其作用主要是与金属元素通过配位键结合共同构成纳米颗粒结构。
进一步地，在本发明所述的合金化热浸镀锌钢板中，在表面单位面积内，针叶状的纳米颗粒占全部纳米颗粒的数量比例为20％-70％。
在本发明中，通过合理控制针叶状的纳米颗粒占全部纳米颗粒的数量比例，可以更为充分的发挥其物理铆着功能。当针叶状的纳米颗粒占全部纳米颗粒的数量比例低于20％时，胶粘剂与金属表面之间的接触面积增加不充分，导致胶粘优化效果不明显；当针叶状的纳米颗粒占全部纳米颗粒的数量比例高于70％时，针叶状结晶颗粒易出现局部聚集且间隙过小，从而限制胶粘剂在材料表面的渗透，使其在结晶之间难以充分润湿，导致胶粘性能下降。在一些实施方案中，在表面单位面积内，针叶状的纳米颗粒占全部纳米颗粒的数量比例为30％-60％。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述活性基团在不规则纳米结构中的质量占比为6％-70％。
在本发明中，当活性基团在不规则纳米结构中的质量占比大于70％时，过多的活性基团会导致胶粘剂在涂覆过程中发生过度聚合，使得胶接表面变得不均匀，降低了胶粘剂的覆盖面积，进而出现胶接性能不良的现象；当活性基团在不规则纳米结构中的质量占比小于6％时，过少的活性基团无法实现胶接性能优化的显著效果。在一些实施方式中，可以将活性基团在不规则纳米结构中的质量占比进一步地控制为20-50％。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述活性基团包括氨基基团与羧基基团。
在本发明中，氨基基团的主要作用是增加表面与胶粘剂的润湿性，使胶粘剂更容易渗透和扩散，增加胶接的有效接触面积并形成良好的黏附；羧基基团的主要作用是增强化学键结合，直接与胶粘剂中的羟基、胺基等官能团发生化学键结合，形成更牢固的接合，从而提高胶接的耐化学性，使其在恶劣环境下的性能更为稳定。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述氨基基团与羧基基团的摩尔百分比为10％-150％。
在本发明中，当氨基基团与羧基基团的摩尔百分比低于10％时，氨基占比过低无法发挥有效的胶粘剂在表面渗透和扩散优化的作用，导致胶粘性能优化不显著。当氨基基团与羧基基团的摩尔百分比高于150％时，羧基基团占比过低，化学键结合不够充分，胶接结构在典型的耐化学介质环境下性能稳定性不足。在一些实施方式中，可以将氨基基团与羧基基团的摩尔百分比优选地控制在17％-120％之间。在一些实施方式中，将氨基基团与羧基基团的摩尔百分比优选地控制在40％-150％之间。在一些实施方式中，将氨基基团与羧基基团的摩尔百分比优选地控制在40％-120％之间。
在一些实施方案中，所述活性基团由选自3,4,5-三羟基苯甲酸，乙二胺四乙酸，柠檬酸，草酸，水杨酸，酒石酸，丹宁酸，半胱氨酸，巯基乙酸，巯基甲醇，巯基乙醇，聚乙烯亚胺，甘氨酸，天冬氨酸，氨水，乙醇胺，丙醇胺，异丙醇胺，乙基硅醇和丙烯基硅醇中的至少一种提供。在一些实施方案中，所述活性基团由选自3,4,5-三羟基苯甲酸，氨水，酒石酸，异丙醇胺，乙基硅醇，天冬氨酸，草酸，乙基硅醇，乙醇胺，聚乙烯亚胺，柠檬酸和乙二胺四乙酸中的一种或多种提供。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述纳米颗粒在复合纳米结构处理层中所占的质量百分比为20％-60％。
在本发明中，当纳米颗粒在复合纳米结构处理层中所占的质量百分比小于20％时，微观结构不足以提供充分有效的机械锚固作用，从而降低了胶粘性能优化效果。当纳米颗粒在复合纳米结构处理层中所占的质量百分比大于60％时，增强化学键的活性基团占比减少，过高的纳米颗粒结构占比会导致胶粘性能优化不稳定性，特别是在服役老化条件下，可能会出现胶粘层性能下降的现象。在一些实施方式中，可以将纳米颗粒在复合纳米结构处理层中所占的质量百分比进一步地控制为30％-50％。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述复合纳米结构处理层由纳米颗粒和不规则纳米结构组成。进一步地，在本发明所述的合金化热浸镀锌钢板中，所述不规则纳米结构在复合纳米结构处理层中所占的质量百分比为40％-80％，如50％-70％或40％-60％。
在一些实施方案中，所述复合纳米结构处理层含有：(1)硫酸铝，氯化铝，硝酸铝，乙酸铝，偏铝酸钠，硝酸钙，乙酸钙，硫酸钙，醋酸锆，乙酸锌，硫酸锌，硝酸锌，硫酸镁，柠檬酸镁，乳酸镁，硼酸锆，硝酸银，硫酸银，氟锆酸铵，氟锆酸钾和碳酸锆铵中的至少其中之一，优选含有硝酸铝，硼酸锆，硫酸镁，硝酸钙，偏铝酸钠，柠檬酸镁，乙酸锌，硝酸银，氟锆酸钾，硫酸铝和硫酸银中的一种或多种；和(2)3,4,5-三羟基苯甲酸，乙二胺四乙酸，柠檬酸，草酸，水杨酸，酒石酸，丹宁酸，半胱氨酸，巯基乙酸，巯基甲醇，巯基乙醇，聚乙烯亚胺，甘氨酸，天冬氨酸，氨水，乙醇胺，丙醇胺，异丙醇胺，乙基硅醇和丙烯基硅醇中的至少一种，优选含有3,4,5-三羟基苯甲酸，氨水，酒石酸，异丙醇胺，乙基硅醇，天冬氨酸，草酸，乙基硅醇，乙醇胺，聚乙烯亚胺，柠檬酸和乙二胺四乙酸中的一种或多种。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述复合纳米结构处理层由包括本文任一实施方案所述的第一物质和第二物质的水基处理剂通过涂敷、干燥的方法制得。在一些实施方案中，涂敷选自辊涂、喷淋和浸渍。在一些实施方案中，干燥选自吹扫和烘干。
在本发明中，在本发明所述的合金化热浸镀锌钢板中，所述复合纳米结构处理层的厚度可为10-100g/m2。
本发明的另一目的在于提供一种合金化热浸镀锌钢板的制造方法，该方法通过对基板进行热浸镀、合金化热处理和平整，并进行表面处理，从而便捷且经济的获得一种表面胶接性能优良的合金化热浸镀锌钢板。
为了实现上述目的，本发明提供一种合金化热浸镀锌钢板的制造方法，其包括步骤：
对基板进行热浸镀、合金化热处理和平整，以在基板表面形成所述合金化热浸镀锌层；
采用水基处理剂对合金化热浸镀锌层进行表面处理，以获得所述复合纳米结构处理层。
进一步地，在本发明所述的制造方法中，所述水基处理剂含有提供金属基化合物的第一物质和提供活性基团的第二物质，其中第一物质和第二物质的质量比为1:1至1:15。在一些实施方案中，所述水基处理剂中，第一物质的浓度为0.5wt％～6wt％，第二物质的浓度为1wt％～8wt％，第一物质的浓度优选为0.5wt％～1.5wt％或1.5wt％～6wt％，第二物质的浓度优选为1wt％～3.2wt％或3.2wt％～8wt％。
进一步地，在本发明所述的制造方法中，所述第一物质选自：硫酸铝，氯化铝，硝酸铝，乙酸铝，偏铝酸钠，硝酸钙，乙酸钙，硫酸钙，醋酸锆，乙酸锌，硫酸锌，硝酸锌，硫酸镁，柠檬酸镁，乳酸镁，硼酸锆，硝酸银，硫酸银，氟锆酸铵，氟锆酸钾和碳酸锆铵中的至少其中之一。优选地，第一物质选自硝酸铝，硼酸锆，硫酸镁，硝酸钙，偏铝酸钠，柠檬酸镁，乙酸锌，硝酸银，氟锆酸钾，硫酸铝和硫酸银中的一种或多种。
进一步地，在本发明所述的制造方法中，所述第二物质选自：3,4,5-三羟基苯甲酸，乙二胺四乙酸，柠檬酸，草酸，水杨酸，酒石酸，丹宁酸，半胱氨酸，巯基乙酸，巯基甲醇，巯基乙醇，聚乙烯亚胺，甘氨酸，天冬氨酸，氨水，乙醇胺，丙醇胺，异丙醇胺，乙基硅醇和丙烯基硅醇中的至少其中之一。优选地，所述第二物质选自3,4,5-三羟基苯甲酸，氨水，酒石酸，异丙醇胺，乙基硅醇，天冬氨酸，草酸，乙基硅醇，乙醇胺，聚乙烯亚胺，柠檬酸和乙二胺四乙酸中的一种或多种。
当水基处理剂含有两种以上第一物质时，对各第一物质之间的用量比例无特殊限定，只要所有第一物质的总质量在水基处理剂中的浓度满足0.5wt％～6wt％即可。类似地，当水基处理剂含有两种以上第二物质时，对各第二物质之间的用量比例也无特殊限定，只要所有第二物质的总质量在水基处理剂中的浓度满足1wt％～8wt％即可。
进一步地，在本发明所述的制造方法中，可采用本领域常规工艺对基板镀锌，例如将基板浸入镀锌液中热镀锌。在一些实施方案中，镀锌液包括Zn和Al；优选地，Al的含量为0.03～0.20wt％。在一些实施方案中，镀锌液中还可含有微量的Bi，Cd，Co，Ni，Sn元素中的一种或多种，其总量优选不超过0.1wt％。
进一步地，在本发明所述的制造方法中，所述合金化热处理的温度为470-500℃。
进一步地，在本发明所述的制造方法中，所述合金化热处理的保温时间为2-6s。
进一步地，在本发明所述的制造方法中，所述平整的平整率为0.4％-1.8％，优选为0.4％-1％。
进一步地，在本发明所述的制造方法中，将水基处理剂以辊涂、喷淋或浸渍涂敷的方式涂覆在合金化热浸镀锌层，以进行表面处理，然后采用吹扫或烘干的方式进行干燥成膜。
本发明所述的表面胶接性能优良的合金化热浸镀锌钢板及其制造方法具有以下特点和有益效果：
本发明所述的表面胶接性能优良的合金化热浸镀锌钢板具有良好的胶接性能，可以提升胶接结构服役过程整体强度，优化胶粘性能稳定性。
本发明所述的表面胶接性能优良的合金化热浸镀锌钢板的表面处理层环保无磷，避免了含磷表面化学处理对环境造成的负面影响，具有更高的环保性。
本发明所述的表面胶接性能优良的合金化热浸镀锌钢板的制造方法便捷且经济，制造生产成本低，该产品具有广泛的市场应用前景。
附图说明
图1显示了本发明所述的实施例1和对比例1的合金化热浸镀锌钢板的胶粘性能对比示意图。
图2显示本发明的合金化热浸镀锌层表面具有锌铁合金结晶区域和随机分布的平台区域；可通过图像处理程序ImageJ软件计算对平台区域进行识别并测算得出其面积占比。图中，黑色部分为平台区域。
具体实施方式
下面将结合具体的实施例对本发明所述的表面胶接性能优良的合金化热浸镀锌钢板及其制造方法做进一步的解释和说明，然而该解释和说明并不对本发明的技术方案构成不当限定。
实施例1-7和对比例1
本发明所述的实施例1-7的合金化热浸镀锌钢板均采用下述方法制得：
(1)获得基板：本发明实施例1-7和对比例1中所选用的基板牌号为DC53，厚度规格1.2mm。
表1列出了本发明实施例1-7和对比例1中所选用的基板的化学成分配比。
表1(余量为Fe和其他不可避免的杂质)
(2)对基板进行热浸镀、合金化热处理和平整，以在基板表面形成合金化热浸镀锌层。
在一些具体的实施方式中，可以通过热浸镀锌锅将基板浸入锌液进行热浸镀，镀层厚度可以为45g/m2；然后在立式热处理炉加热至470-500℃以进行合金化热处理，然后保温一定时间(具体为4s)，使钢板基体与液态锌发生反应和扩散，转变为Fe-Zn金属间化合物，从而在基板表面形成合金化热浸镀锌层；然后采用平整辊进行平整工序，平整率控制在0.4-1.8％的范围内。
表2列出了本发明实施例1-7和对比例1的合金化热浸镀锌钢板的合金化热浸镀锌层中的化学成分含量和工艺参数。
表2.
注：表2中的“锌铁合金结晶区域的面积占比”采用拍摄照片随机选取1cm2区域，通过图像处理程序ImageJ软件，对平台区域进行识别并进行面积占比测算得出。
(3)采用水基处理剂对合金化热浸镀锌层进行表面处理，以获得复合纳米结构处理层。
在一些具体的实施方式中，水基处理剂包括提供金属元素的第一物质和提供活性基团的第二物质。
其中，提供金属元素的第一物质选自：硫酸铝，氯化铝，硝酸铝，乙酸铝，偏铝酸钠，硝酸钙，乙酸钙，硫酸钙，醋酸锆，乙酸锌，硫酸锌，硝酸锌，硫酸镁，柠檬酸镁，乳酸镁，硼酸锆，硝酸银，硫酸银，氟锆酸铵，氟锆酸钾和碳酸锆铵中的至少其中之一。
提供活性基团的第二物质选自：3,4,5-三羟基苯甲酸，乙二胺四乙酸，柠檬酸，草酸，水杨酸，酒石酸，丹宁酸，半胱氨酸，巯基乙酸，巯基甲醇，巯基乙醇，聚乙烯亚胺，甘氨酸，天冬氨酸，氨水，乙醇胺，丙醇胺，异丙醇胺，乙基硅醇和丙烯基硅醇中的至少其中之一。
在一些实施方式中，水基处理剂通过辊涂、喷淋或浸渍涂敷，然后可以采用吹扫或烘干的方式进行干燥成膜的方式进行卷钢的制备。
对比例1采用了与本发明实施例相同的基板也进行了步骤(1)和(2)，但未进行步骤(3)。
水基处理剂中，第一物质的浓度为1.5wt％。
水基处理剂中，第二物质的浓度为3.2wt％。
表3列出了本发明实施例1-7和对比例1的合金化热浸镀锌钢板的水基处理剂的成分组成和涂覆工艺。
表3.
需要说明的是，虽然上述实施例1-7中没有采用，但是第一物质还可以选自氯化铝，乙酸铝，乙酸钙，硫酸钙，醋酸锆，硝酸锌，乳酸镁，氟锆酸铵和碳酸锆铵中的至少其中之一；第二物质还可以选自水杨酸，丹宁酸，半胱氨酸，巯基乙酸，巯基甲醇，巯基乙醇，甘氨酸，丙醇胺和丙烯基硅醇中的至少其中之一。
表4列出了本发明实施例1-7和对比例1的合金化热浸镀锌钢板的复合纳米结构处理层的特征。
纳米颗粒的等效球半径采用高分辨扫描电镜进行观察和尺寸测量(测量平面观测到的最大尺度取向)。
针叶状的纳米颗粒占全部纳米颗粒的数量比例采用单位面积颗粒数量占比进行评估。
通过涂敷前后称重法获得表面复合纳米结构处理层的重量，减去第一物质的质量，可获得不规则纳米结构的质量；利用X射线光电子谱(XPS)分别检测氨基中的N元素和羧基中的特征化学键对两种活性基团进行含量测试，通过下述公式进行计算获得：(氨基基团质量+羧基基团质量)/不规则纳米结构质量*100％。
利用X射线光电子谱(XPS)分别检测氨基中的N元素和羧基中的特征化学键对两种活性基团进行含量测试，换算为摩尔含量后进行百分比换算。
纳米颗粒在复合纳米结构处理层中所占的质量百分比，通过透射电镜(TEM)、X射线衍射(XRD)、原子吸收光谱(AAS)方法分别明确纳米颗粒和薄膜的成分构成及体积占比，然后结合成分组织密度和体积占比计算出质量占比。
表4.

对制得的实施例1-7和对比例1的合金化热浸镀锌钢板加工为100*25.4mm尺寸，并有效去除边部毛刺。为了验证本发明实施例的实施效果，选取典型汽车用结构胶粘剂：TEROSON EP 5089作为胶粘剂，胶接制样参照标准SAE J1523，胶接面积控制为3.2cm2，粘接厚度控制为0.2mm，胶粘剂固化(苛刻固化条件)温度为160℃，固化时间为15min。胶粘剂固化后，进行胶接性能评估，并将胶接性能评估结果列于表5中。其中：
初始胶粘剥离性能评估：制样胶粘剂固化后室温条件放置24h，进行拉伸剥离试验(参照ASTM D 1002，拉伸速度为13mm/min)，记录剥离强度。通过剥离方式评估胶粘效果的优劣：对完成拉伸剥离后的两片式样进行剥离方式分析(剥离方式分为两种：内聚剥离，即胶粘剂内部断裂；界面剥离，即胶粘剂和金属表面脱离)，通过内聚剥离的面积百分比进行胶粘性能评判。
老化条件胶粘剥离强度衰减比例评估：制样胶粘剂固化后室温条件放置24h，进行长周期循环腐蚀条件(参照PV1210)。测试90个周期后进行拉伸剥离试验(参照ASTM D 1002，拉伸速度为13mm/min)，记录剥离强度。计算剥离强度衰减比例如下：胶粘剥离强度衰减比例＝(初始胶粘剥离强度-老化条件胶粘剥离强度)/初始条件胶粘剥离强度*100％。
表5列出了本发明所述的实施例1-7和对比例1的胶接性能评估结果。
表5.

表5中的胶接性能评估的初始条件中各符号释义如下：
◎：内聚剥离面积＝100％
○：85％≤内聚剥离面积＜100％
Δ：65％≤内聚剥离面积＜85％
×：内聚剥离面积＜65％
表5中的胶接性能评估的老化条件中各符号释义如下：
◎：胶粘剥离强度衰减比例≤20％
○：20％＜胶粘剥离强度衰减比例≤30％
Δ：30％＜胶粘剥离强度衰减比例≤40％
×：40％＜胶粘剥离强度衰减比例
从上述表5中可以看出，本发明实施例1-7在初始胶粘剥离性能和老化条件胶粘剥离强度衰减性能方面均表现良好。同时，从实施例1、3、7可以看出通过喷淋、浸渍和辊涂典型的涂敷处理方式赋予表面的有效复合纳米结构，均实现了良好的表面胶粘性能，复合纳米结构的制备具有更广泛的工艺适配性。
从对比例1可以看出，在没有复合纳米结构处理层条件下，会出现初始胶粘剥离性能不良且老化条件胶粘剥离强度衰减比例恶化的现象。
图1显示了本发明所述的实施例1和对比例1的合金化热浸镀锌钢板的胶粘性能对比示意图。将实施例1和对比例1的合金化热浸镀锌钢板按照初始胶粘剥离性能评估中记载的方法进行50组实验，将获得的胶粘剥离强度数据进行强度分布比例统计，得到图1。
如图1所示的，实施例1的材料镀层含有10％的Fe，结构韧性好，在剪切力作用下不易脆裂，提升了镀层附着力。同时，其表面覆盖的复合纳米结构处理层强化了胶粘剂与镀层界面的物理铆着，并增加了化学键合位点，大幅提升胶粘界面的结合力。当镀层和界面结合强度高于胶粘剂的内聚强度时，胶接拉伸剪切过程中的薄弱点聚焦在胶粘剂内，显著提升了剥离强度和稳定性。相比之下，对比例1的表面与胶粘剂主要为物理吸附，化学键合点少，导致结合强度偏低，拉伸剪切断裂过程受三方面共同影响，降低了胶接剥离强度和稳定性。
需要注意的是，以上所列举实施例仅为本发明的具体实施例。显然本发明不局限于以上实施例，随之做出的类似变化或变形是本领域技术人员能从本发明公开的内容直接得出或者很容易便联想到的，均应属于本发明的保护范围。

Claims (15)

  1. 一种表面胶接性能优良的合金化热浸镀锌钢板，其包括基板，所述基板表面具有合金化热浸镀锌层；其特征在于：
    所述合金化热浸镀锌层表面覆盖有复合纳米结构处理层；所述复合纳米结构处理层包括纳米颗粒以及不规则纳米结构；
    其中所述纳米颗粒至少以针叶状的形态随机分布在所述合金化热浸镀锌层表面；
    所述不规则纳米结构具有优化合金化热浸镀锌层表面化学键合性能的活性基团。
  2. 如权利要求1所述的合金化热浸镀锌钢板，其特征在于，所述合金化热浸镀锌层中的Zn-Fe合金相中的Fe元素质量百分含量为8％-10％。
  3. 如权利要求2所述的合金化热浸镀锌钢板，其特征在于，所述合金化热浸镀锌层还含有Al元素以及选自Bi、Cd、Co、Ni和Sn元素中的至少其中一种；优选地，所述合金化热浸镀锌层中的Al元素质量百分含量为0.03％-0.2％；优选地，所述合金化热浸镀锌层中的Bi、Cd、Co、Ni和Sn元素的总质量百分含量不超过0.1％。
  4. 如权利要求1所述的合金化热浸镀锌钢板，其特征在于，所述合金化热浸镀锌层表面具有锌铁合金结晶区域和随机分布的平台区域；优选地，在表面单位面积内，锌铁合金结晶区域的面积占比为15％-85％。
  5. 如权利要求1所述的合金化热浸镀锌钢板，其特征在于：
    所述针叶状的纳米颗粒含有金属基化合物，所述金属基化合物中的金属选自Na，Al，Ca，Zn，Ag，Mg和Zr中的至少其中之一；优选地，所述针叶状的纳米颗粒为金属基化合物；优选地，所述金属基化合物为硫酸铝，氯化铝，硝酸铝，乙酸铝，偏铝酸钠，硝酸钙，乙酸钙，硫酸钙，醋酸锆，乙酸锌，硫酸锌，硝酸锌，硫酸镁，柠檬酸镁，乳酸镁，硼酸锆，硝酸银，硫酸银，氟锆酸铵，氟锆酸钾和碳酸锆铵中的至少一种；和/或
    在表面单位面积内，所述针叶状的纳米颗粒占全部纳米颗粒的数量比例为20％-70％；和/或
    所述纳米颗粒的等效球半径为30-200nm。
  6. 如权利要求1所述的合金化热浸镀锌钢板，其特征在于：
    所述活性基团在不规则纳米结构中的质量占比为6％-70％；和/或，
    所述活性基团包括氨基基团与羧基基团；优选地，所述活性基团由选自3,4,5-三羟基苯甲酸，乙二胺四乙酸，柠檬酸，草酸，水杨酸，酒石酸，丹宁酸，半胱氨酸，巯基乙酸，巯基甲醇，巯基乙醇，聚乙烯亚胺，甘氨酸，天冬氨酸，氨水，乙醇胺，丙醇胺，异丙醇胺，乙基硅醇和丙烯基硅醇中的至少一种提供。
  7. 如权利要求6所述的合金化热浸镀锌钢板，其特征在于，所述氨基基团与羧基基团的摩尔百分比为10％-150％。
  8. 如权利要求1所述的合金化热浸镀锌钢板，其特征在于：
    所述纳米颗粒在复合纳米结构处理层中所占的质量百分比为20％-60％；和/或，
    所述不规则纳米结构在复合纳米结构处理层中所占的质量百分比为40％-80％；和/或，
    所述复合纳米结构处理层的厚度为10-100g/m2。
  9. 如权利要求1所述的合金化热浸镀锌钢板，其特征在于：所述复合纳米结构处理层含有：(1)硫酸铝，氯化铝，硝酸铝，乙酸铝，偏铝酸钠，硝酸钙，乙酸钙，硫酸钙，醋酸锆，乙酸锌，硫酸锌，硝酸锌，硫酸镁，柠檬酸镁，乳酸镁，硼酸锆，硝酸银，硫酸银，氟锆酸铵，氟锆酸钾和碳酸锆铵中的至少其中之一，优选含有硝酸铝，硼酸锆，硫酸镁，硝酸钙，偏铝酸钠，柠檬酸镁，乙酸锌，硝酸银，氟锆酸钾，硫酸铝和硫酸银中的一种或多种；和(2)3,4,5-三羟基苯甲酸，乙二胺四乙酸，柠檬酸，草酸，水杨酸，酒石酸，丹宁酸，半胱氨酸，巯基乙酸，巯基甲醇，巯基乙醇，聚乙烯亚胺，甘氨酸，天冬氨酸，氨水，乙醇胺，丙醇胺，异丙醇胺，乙基硅醇和丙烯基硅醇中的至少一种，优选含有3,4,5-三羟基苯甲酸，氨水，酒石酸，异丙醇胺，乙基硅醇，天冬氨酸，草酸，乙基硅醇，乙醇胺，聚乙烯亚胺，柠檬酸和乙二胺四乙酸中的一种或多种。
  10. 如权利要求1所述的合金化热浸镀锌钢板，其特征在于：所述复合纳米结构处理层由包括第一物质和第二物质的水基处理剂通过涂敷、干燥的方法制得；其中，所述第一物质选自：硫酸铝，氯化铝，硝酸铝，乙酸铝，偏铝酸钠，硝酸钙，乙酸钙，硫酸钙，醋酸锆，乙酸锌，硫酸锌，硝酸锌，硫酸镁，柠檬酸镁，乳酸镁，硼酸锆，硝酸银，硫酸银，氟锆酸铵，氟锆酸钾和碳酸锆铵中的至少一种；所述第二物质选自：3,4,5-三羟基苯甲酸，乙二胺四乙酸，柠檬酸，草酸，水杨酸，酒石酸，丹宁酸，半胱氨酸，巯基乙酸，巯基甲醇，巯基乙醇，聚乙烯亚胺，甘氨酸，天冬氨酸，氨水，乙醇胺，丙醇胺，异丙醇胺，乙基硅醇和丙烯基硅醇中的至少一种；
    优选地，所述水基处理剂中，第一物质的浓度为0.5wt％～6wt％；
    优选地，所述水基处理剂中，第二物质的浓度为1wt％～8wt％；
    优选地，所述水基处理剂中，所述第一物质和第二物质的质量比为1:1至1:15。
  11. 如权利要求1-10中任意一项所述的合金化热浸镀锌钢板的制造方法，其特征在于，包括步骤：
    对基板进行热浸镀、合金化热处理和平整，以在基板表面形成所述合金化热浸镀锌层；
    采用水基处理剂对合金化热浸镀锌层进行表面处理，以获得所述复合纳米结构处理层。
  12. 如权利要求11所述的制造方法，其特征在于，所述水基处理剂包括提供金属基化合物的第一物质和提供活性基团的第二物质，其中第一物质和第二物质的质量比为1:1至1:15。
  13. 如权利要求11所述的制造方法，其特征在于，所述第一物质选自：硫酸铝，氯化铝，硝酸铝，乙酸铝，偏铝酸钠，硝酸钙，乙酸钙，硫酸钙，醋酸锆，乙酸锌，硫酸锌，硝酸锌，硫酸镁，柠檬酸镁，乳酸镁，硼酸锆，硝酸银，硫酸银，氟锆酸铵，氟锆酸钾和碳酸锆铵的至少其中之一；和/或，所述第二物质选自：3,4,5-三羟基苯甲酸，乙二胺四乙酸，柠檬酸，草酸，水杨酸，酒石酸，丹宁酸，半胱氨酸，巯基乙酸，巯基甲醇，巯基乙醇，聚乙烯亚胺，甘氨酸，天冬氨酸，氨水，乙醇胺，丙醇胺，异丙醇胺，乙基硅醇和丙烯基硅醇的至少其中之一；和/或，所述水基处理剂中，第一物质的浓度为0.5wt％～6wt％；和/或，所述水基处理剂中，第二物质的浓度为1wt％～8wt％。
  14. 如权利要求11所述的制造方法，其特征在于：
    所述合金化热处理的温度为470-500℃；和/或，
    将水基处理剂以辊涂、喷淋或浸渍涂敷的方式涂覆在合金化热浸镀锌层，以进行表面处理，然后采用吹扫或烘干的方式进行干燥成膜；和/或，
    所述平整的平整率为0.4-1.8％。
  15. 包括第一物质和第二物质的处理剂，所述第一物质和第二物质如权利要求12所述；优选地，第一物质和第二物质的质量比为1:1至1:15；优选地，所述处理剂为水基处理剂；优选地，所述水基处理剂中，第一物质的浓度为0.5wt％～6wt％；优选地，所述水基处理剂中，第二物质的浓度为1wt％～8wt％。
PCT/CN2025/112156 2024-08-01 2025-08-01 表面胶接性能优良的合金化热浸镀锌钢板及其制造方法 Pending WO2026026957A1 (zh)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005290395A (ja) * 2000-12-04 2005-10-20 Jfe Steel Kk 亜鉛系めっき鋼板及びその製造方法
CN1986754A (zh) * 2005-12-22 2007-06-27 宝山钢铁股份有限公司 镀锌钢板表面润滑处理剂及其处理方法
CN102245807A (zh) * 2008-12-16 2011-11-16 日本帕卡濑精株式会社 镀锌钢板用表面处理剂
CN108018512A (zh) * 2016-10-31 2018-05-11 宝山钢铁股份有限公司 一种具有优良加工成形性的合金化热镀锌钢板及其制造方法
CN111748758A (zh) * 2019-03-27 2020-10-09 宝山钢铁股份有限公司 一种粘胶性优良的润滑处理热镀锌钢板及其制造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005290395A (ja) * 2000-12-04 2005-10-20 Jfe Steel Kk 亜鉛系めっき鋼板及びその製造方法
CN1986754A (zh) * 2005-12-22 2007-06-27 宝山钢铁股份有限公司 镀锌钢板表面润滑处理剂及其处理方法
CN102245807A (zh) * 2008-12-16 2011-11-16 日本帕卡濑精株式会社 镀锌钢板用表面处理剂
CN108018512A (zh) * 2016-10-31 2018-05-11 宝山钢铁股份有限公司 一种具有优良加工成形性的合金化热镀锌钢板及其制造方法
CN111748758A (zh) * 2019-03-27 2020-10-09 宝山钢铁股份有限公司 一种粘胶性优良的润滑处理热镀锌钢板及其制造方法

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