WO2026026905A1 - 涂装锆化前处理性能优良的合金化热浸镀锌钢板及其制造方法 - Google Patents

涂装锆化前处理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
WO2026026905A1
WO2026026905A1 PCT/CN2025/111780 CN2025111780W WO2026026905A1 WO 2026026905 A1 WO2026026905 A1 WO 2026026905A1 CN 2025111780 W CN2025111780 W CN 2025111780W WO 2026026905 A1 WO2026026905 A1 WO 2026026905A1
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WIPO (PCT)
Prior art keywords
dip galvanized
alloyed hot
layer
galvanized steel
steel sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2025/111780
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English (en)
French (fr)
Inventor
赵艳亮
李耀民
郑凯隆
孙敏
戴毅刚
朱敏
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Application filed by Baoshan Iron and Steel Co Ltd filed Critical Baoshan Iron and Steel Co Ltd
Publication of WO2026026905A1 publication Critical patent/WO2026026905A1/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
    • C23C2/26—After-treatment
    • 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
    • C23C2/26—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates

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.
  • zirconium treatment process achieves phosphorus-free wastewater discharge, reduced energy consumption, and significantly improved environmental performance compared to conventional phosphating pretreatment processes.
  • film thickness of the zirconium treatment process is generally around 20-200nm, which is nearly two orders of magnitude different from the film thickness of the conventional phosphating process (3-5 ⁇ m), it poses new requirements for the surface properties of the vehicle body materials.
  • pretreatment processes such as phosphating or zirconium treatment are used, which can easily lead to problems such as insufficient film thickness, uneven crystallization, poor adhesion, and appearance defects. These problems can have a significant adverse impact on the appearance of the car body coating and its anti-corrosion performance.
  • the above scheme mainly controls the structure and surface composition of the alloyed coating to optimize the performance of phosphate chemical conversion treatment, but does not mention the impact on the performance of environmentally friendly zirconium thin film pretreatment.
  • One of the objectives of this invention is to provide an alloyed hot-dip galvanized steel sheet with excellent pre-treatment performance before coating zirconization.
  • This galvanized steel sheet has good electrochemical reactivity and high efficiency in surface zirconization film formation, thereby optimizing the pre-treatment performance before coating.
  • the present invention provides an alloyed hot-dip galvanized steel sheet with excellent pre-treatment performance for zirconium coating, 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 potential difference between the nanoparticles and the alloyed hot-dip galvanized layer in the micro-region is 30-500mV.
  • the irregular nanostructure has film-forming active groups, which are selected from at least one of the following: silane groups, carboxyl groups, amino groups, allyl groups, and thiol groups.
  • the alloyed hot-dip galvanized steel sheet of the present invention which has excellent stamping and lubrication processing performance, includes a substrate and an alloyed hot-dip galvanized layer located on the surface of the substrate.
  • the initial nucleation efficiency of the zirconium annealing reaction is promoted by constructing electrochemical active sites through the micro-region potential difference formed between nanoparticles and the coating surface, thereby improving the zirconium annealing film performance.
  • the micro-region potential difference formed between nanoparticles and the alloyed hot-dip galvanized layer is too low, it cannot promote the formation of nucleation active sites during the pretreatment process before coating phosphating or zirconium annealing, thus failing to achieve a significant optimization of the phosphating or zirconium annealing performance before coating.
  • the micro-region potential difference formed between nanoparticles and the alloyed hot-dip galvanized layer is too high, uneven film formation is prone to occur during the pretreatment process before coating phosphating or zirconium annealing.
  • the active groups deposited for film formation are mainly used for growth after nucleation.
  • the chemical composition of the substrate is as follows by mass percentage: C: ⁇ 0.12%, Si: ⁇ 0.25%, Mn: ⁇ 0.8%, P: ⁇ 0.045%, S: ⁇ 0.045%, Ti: ⁇ 0.3%, with the balance being Fe and unavoidable impurities.
  • the chemical composition of the substrate by mass percentage satisfies at least one of the following:
  • the alloyed hot-dip galvanized layer comprises a Zn-Fe alloy phase.
  • the mass percentage content of Fe element in the Zn-Fe alloy phase of the alloyed hot-dip galvanized layer is 7%-12.5%.
  • the presence of Fe on the coating surface promotes phosphating or zirconization reactions, resulting in a more uniform and dense surface treatment effect. Changes in the iron content of the coating affect the nucleation and growth rate of the phosphating or zirconization reactions.
  • the mass percentage of Fe in the Zn-Fe alloy phase of the alloyed hot-dip galvanized layer is too low, it will be detrimental to the film-forming efficiency of the phosphating and zirconization reactions; when the mass percentage of Fe in the Zn-Fe alloy phase of the alloyed hot-dip galvanized layer is too high, the brittle microstructure of the coating increases, the hardness rises, and there is a risk of poor coating adhesion and insufficient corrosion resistance.
  • the mass percentage of Fe in the Zn-Fe alloy phase of the alloyed hot-dip galvanized layer can be further controlled to 8%-11%.
  • the alloyed hot-dip galvanized layer also contains Al element and at least one of Bi, Cd, Co, Ni, and Sn elements.
  • the alloyed hot-dip galvanized layer further contains Al element and at least one of Bi, Co, Ni, and Sn elements.
  • the mass percentage content of Al element in the alloyed hot-dip galvanized layer is 0.03%-0.2%.
  • the Al element in the alloyed hot-dip galvanized layer can improve the uniformity of the coating and ensure the appearance quality of the product.
  • the mass percentage of Al element in the alloyed hot-dip galvanized layer is too low, unevenness is likely to occur, directly affecting the consistency of surface activity during the pre-coating treatment process.
  • the mass percentage of Al element in the alloyed hot-dip galvanized layer is too high, the surface brittleness of the alloyed hot-dip galvanized layer will increase, making it prone to zinc powder peeling, which in turn leads to poor coating adhesion and insufficient corrosion resistance.
  • the mass percentage of Al element in the alloyed hot-dip galvanized layer can be further controlled to 0.08%-0.15%.
  • the total mass percentage of Bi, Cd, Co, Ni, and Sn elements in the alloyed hot-dip galvanized layer does not exceed 0.1% (i.e., ⁇ 0.1%).
  • the total mass percentage of Bi, Co, Ni, and Sn elements in the alloyed hot-dip galvanized layer does not exceed 0.1% (i.e., ⁇ 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 platform regions, and the area ratio of zinc-iron alloy crystalline regions per unit area is 15%-85%.
  • the platform area is formed in the manufacturing method of alloyed hot-dip galvanized steel sheet by treating the surface of the alloyed hot-dip galvanized steel sheet with a leveling roller in the leveling step.
  • the zinc-iron alloy crystalline region possesses a certain degree of crystallinity and grain size, exhibiting good corrosion resistance and providing more active sites through its physical structure, which facilitates the adsorption and reaction of the zirconium oxidizing agent.
  • the area ratio of the zinc-iron alloy crystalline region is too low, it is detrimental to the adhesion and stability of the zirconium oxidizing film, and there is a risk of decreased anti-corrosion performance of the coating.
  • the area ratio of the zinc-iron alloy crystalline region is too high, exceeding 85%, the surface roughness of the zinc-iron alloy coating is too high, thus affecting the appearance quality of the coating.
  • the equivalent sphere radius of the nanoparticles is 10-150 nm.
  • the equivalent sphere radius of the nanoparticles when the equivalent sphere radius of the nanoparticles is too low, it easily leads to uneven distribution and local aggregation of particles on the surface, resulting in over-zirconization or lack of zirconization in some local areas, thereby reducing the uniformity of the zirconization layer.
  • the equivalent sphere radius of the nanoparticles is too high, the zirconizing agent cannot penetrate into the deep layers or micro-depressions of the metal surface, causing local areas of the metal surface to fail to form a zirconization layer, thus reducing the zirconization effect of the metal.
  • the equivalent sphere radius of the nanoparticles can be further controlled between 30-100 nm.
  • the nanoparticles are randomly distributed on the surface of the alloyed hot-dip galvanized layer in at least a spherical morphology.
  • nanoparticles are distributed on the surface of the alloyed hot-dip galvanized layer. In some embodiments, the nanoparticles are randomly distributed on the surface of the alloyed hot-dip galvanized layer.
  • At least a portion of the nanoparticles are spherical in shape.
  • Spherical nanoparticles can provide more effective reaction surface, thereby further increasing the contact area between the metal surface and the zirconitizing agent, which is more conducive to the zirconization reaction.
  • the spherical nanoparticles contain a metal-based compound, wherein the metal in the metal-based compound is selected from at least one of Fe, Cu, Sr, Ba, Mn, V, Ti, and Sn.
  • Cu, Sr, Ba, Mn, V, Ti, and Sn are mainly derived from water-based treatment agents, while Fe is mainly derived from steel plates.
  • the nanoparticles also contain non-metallic elements, which include one or more of the elements Si, O, C, N, and H.
  • spherical nanoparticles account for 30%-80% of the total number of nanoparticles per unit area of the surface.
  • a suitable ratio of needle-like and spherical particles can more fully utilize their physical bonding function.
  • the proportion of spherical nanoparticles to all nanoparticles is too low, the excessive number of needle-like particles can easily lead to uneven coverage and decreased density of the zirconium annealing layer, thus affecting the adhesion of the electrophoretic coating and the corrosion resistance of the coating.
  • the proportion of spherical nanoparticles to all nanoparticles is too high, the relatively small surface area and high volume of the spherical particles may result in an insignificant effect on promoting the zirconium annealing reaction rate.
  • the potential difference between the nanoparticles and the alloyed hot-dip galvanized layer in the micro-region is 80-400mV.
  • the nanoparticles account for 30%-70% of the mass percentage in the composite nanostructure treatment layer.
  • the optimization of electrochemical reaction activity is not significant, affecting the efficiency of phosphating or zirconium coating before coating; when the mass percentage of nanoparticles in the composite nanostructure treatment layer is too high, the electrochemical reaction activity is too high, which increases the risk of uneven phosphating or zirconium coating before coating.
  • the mass percentage of the deposited film-forming active groups (hereinafter referred to as active groups) in the irregular nanostructure is 10%-75%.
  • the mass proportion of active groups in the irregular nanostructure when the mass proportion of active groups in the irregular nanostructure is too high, the excessive number of active groups can easily lead to an excessively fast or uneven film formation rate during the pretreatment of phosphating or zirconium leaching before coating, thereby affecting the quality and stability of the zirconium leaching film.
  • the mass proportion of active groups in the irregular nanostructure is too low, the insufficient number of active groups cannot promote the film formation reaction rate, resulting in insufficient film formation efficiency and incomplete film formation, which in turn affects the adhesion and anti-corrosion performance of the coating film.
  • 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 leveling of a substrate, followed by surface treatment, thereby conveniently and economically obtaining an alloyed hot-dip galvanized steel sheet with excellent pre-treatment performance before coating zirconium coating.
  • 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 comprises a first substance providing a metal-based compound and a second substance providing active groups for film deposition, wherein the mass ratio of the first substance and the second substance is 2:1 to 1:8.
  • the mass content of the first substance in the water-based treatment agent can be 0.5%-10%, and the mass content of the second substance in the water-based treatment agent can be 2%-10%.
  • the first substance is selected from at least one of: manganese nitrate, silver nitrate, sodium fluorotitanate, ammonium fluorotitanate, potassium fluorotitanate, copper nitrate, strontium nitrate, barium nitrate, vanadium oxalate, ammonium vanadate, vanadium acetate, stannous chloride, tin nitrate, tin citrate, and tin acetate.
  • 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 chemical composition of the zinc bath used for hot-dip galvanizing is as follows (mass percentage): Al: 0.02-0.3%; Bi: 0-0.03%; Co: 0-0.03%; Ni: 0-0.08%; Sn: 0-0.08%; with the balance being Zn and unavoidable impurities.
  • the temperature of the alloying heat treatment is 470-570°C.
  • 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 pre-treatment performance for coating zirconium treatment described in this invention has good electrochemical reactivity and high efficiency in surface zirconium treatment film formation, thereby optimizing the pre-treatment performance for coating.
  • the surface treatment layer of the alloyed hot-dip galvanized steel sheet with excellent pretreatment performance before coating zirconium coating described in this invention is environmentally friendly and phosphorus-free, avoiding the negative environmental impact of phosphorus-containing surface chemical treatments and exhibiting higher environmental friendliness.
  • the manufacturing method of the alloyed hot-dip galvanized steel sheet with excellent pretreatment performance for coating zirconium coating described in this invention is convenient and economical, and can reduce production costs.
  • 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 Examples 1-3 of this invention is DC53D+ZF (Baosteel) with a thickness of 0.7 ⁇ m.
  • Table 1 lists the chemical composition ratios of the substrates used in Examples 1-7 and Comparative Examples 1-3 of the present 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.
  • Cold-rolled strip steel is 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 470-570°C in a vertical heat treatment furnace for alloying heat treatment, and then held at that temperature for 2-8 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. Finally, a leveling process is performed using leveling rollers.
  • Table 2-1 lists the chemical composition of the zinc solutions in Examples 1-7 and Comparative Examples 1-3 of the present invention.
  • Table 2-2 lists the chemical composition content and process parameters of the alloyed hot-dip galvanized layer in the alloyed hot-dip galvanized steel sheets of Examples 1-7 and Comparative Examples 1-3 of the present invention.
  • Table 2-2 Note: (1) In Table 2, the mass percentage of Fe in the Zn-Fe alloy phase was determined by X-ray fluorescence spectroscopy; (2) In Table 2, The mass percentage of Al, Bi, Co, Ni and Sn elements in the alloyed hot-dip galvanized layer was measured by inductively coupled plasma atomic emission spectrometry/mass spectrometry (ICP-OES/MS); (3) The “area ratio of zinc-iron alloy crystallization region” in Table 2 was obtained by randomly selecting a 1 cm 2 area from the photograph, identifying the platform area and calculating the area ratio through the image processing program.
  • ICP-OES/MS inductively coupled plasma atomic emission spectrometry/mass spectrometry
  • 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.
  • Water-based treatment agents include a first substance that provides a metal-based compound and a second substance that provides active groups for film deposition.
  • the first substance providing the metallic element is selected from at least one of the following: manganese nitrate, silver nitrate, sodium fluorotitanate, ammonium fluorotitanate, potassium fluorotitanate, copper nitrate, strontium nitrate, barium nitrate, vanadium oxalate, ammonium vanadate, vanadium acetate, stannous chloride, tin nitrate, tin citrate, and tin acetate.
  • the second substance providing the active group for film deposition 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 water-based treatment agent consists of a first substance, a second substance, and water.
  • Water-based treatment agents are applied by roller coating, spraying, or immersion, and then dried into a film by blowing or drying to prepare coiled steel.
  • Comparative Examples 1 and 2 also employed the above steps, but their specific parameters did not meet the requirements of this invention.
  • Comparative Example 3 used the same substrate as the embodiments of this invention and performed steps (1) and (2), but did not perform step (3).
  • Table 3 lists the composition and coating process of the water-based treatment agent for alloyed hot-dip galvanized steel sheets in Examples 1-7 and Comparative Examples 1-3 of the present invention.
  • the values in parentheses after the components are the mass percentages of the components in the water-based treatment agent.
  • 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 Examples 1-3 of the present invention.
  • the potential difference of the micro-area formed by nanoparticles and alloyed hot-dip coating is evaluated by scanning electrochemical microscopy (SECM); (5) The mass percentage of nanoparticles in the composite nanostructure treatment layer is determined by transmission electron microscopy (TEM), X-ray diffraction (XRD), and atomic absorption spectrometry (AAS) to clarify the composition and volume percentage of nanoparticles and film respectively, and then the mass percentage is calculated by combining the composition density and volume percentage; (6)
  • the measurement method of the types of active groups and the mass percentage of active groups in the irregular nanostructure is as follows: the weight of the composite nanostructure film on the surface is obtained by weighing before and after coating with water-based treatment agent, and the content of the two active groups is tested by detecting the N element in amino groups and the characteristic chemical bonds in carboxyl groups by X-ray photoelectron spectroscopy (XPS).
  • the mass percentage of active groups is calculated by the following formula: (mass of amino groups + mass of carboxyl groups) /
  • the alloyed hot-dip galvanized steel sheets obtained in Examples 1-7 and Comparative Examples 1-3 were processed into a size of 75*150mm.
  • the alloyed hot-dip galvanized steel sheets of Examples 1-7 and Comparative Examples 1-3 were subjected to degreasing, washing, zirconization, washing, and electrophoresis processes according to the pretreatment process flow for zirconization of the coating film.
  • the degreasing agent used was Pacrose FC2011
  • the zirconization agent was Pacrose 2000 series products
  • the electrophoretic paint was BASF electrophoretic paint. Product series.
  • Table 5 lists the specific process parameters for the pretreatment steps of zirconification of the coating film in Examples 1-7 and Comparative Examples 1-3 of the present invention.
  • Zirconium film thickness assessment The film thickness was tested using X-ray fluorescence spectrometry (XRF) to detect surface elements. A curve showing the relationship between the peak intensity of characteristic elements and the film weight was established by physical weighing method. The test results were converted into the weight data of the zirconium film per square meter (unit: mg/ m2 ).
  • XRF X-ray fluorescence spectrometry
  • the specific method refers to the standard ISO 2409, and the coating adhesion (percentage) is evaluated by cross-cut adhesion test.
  • Table 6 lists the performance evaluation results of Examples 1-7 and Comparative Examples 1-3 of the present invention.
  • the zirconization film-forming properties of the alloyed hot-dip galvanized steel sheets of Examples 1-7 are good in terms of zirconization film thickness and surface paint film adhesion performance after electrophoresis.

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  • Organic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Coating With Molten Metal (AREA)
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  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

本发明公开了一种涂装锆化前处理性能优良的合金化热浸镀锌钢板，其包括基板，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；复合纳米结构处理层包括：纳米颗粒以及不规则纳米结构；其中所述纳米颗粒与合金化热浸镀锌层形成的微区电势差为30-500mV；其中不规则纳米结构具有沉积成膜活性基团，所述沉积成膜活性基团选自：硅烷基团，羧基基团，氨基基团，烯丙基基团，巯基基团中至少其中之一。本发明还公开了上述钢板的制造方法，其包括：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，以获得复合纳米结构处理层。

Description

涂装锆化前处理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
无磷薄膜锆化工艺(简称“锆化工艺”)相对于常规磷化前处理工艺实现了废水排放无磷，能耗下降，环保性能显著提升。但由于锆化工艺成膜厚度一般20-200nm左右，与常规磷化工艺处理膜厚(3-5μm)相差近两个数量级，因此对车身材料表面特性提出了全新要求。
车身用镀层材料在应用过程中涂装前处理磷化或锆化易发生成膜厚度不足、结晶不均、附着力不良、外观缺陷的问题，上述问题的出现会对车身涂装外观和涂装防腐性能产生显著不良影响。
为了解决上述问题，现有技术主要是通过对合金化镀层成分和热处理工艺进行调整，例如：
公开号为CN103814148A，公开日为2014年5月21日，名称为“涂装后耐腐蚀性优良的合金化热镀锌钢板”的中国专利文献中公开了一种涂装后耐蚀性能优良的合金化热镀锌钢板，其显著特征是在钢板的表面，具有含Fe：7～15％、Al：0.02～0.30％，且余量由Zn和不可避免的杂质构成的镀锌层，并且该镀锌层表面的金属Zn露出率为20％以上。
公开号为CN101583734，公开日为2009年11月18日，名称为“磷酸盐处理性优异的高强度合金化熔融镀锌钢板”的中国专利文献中公开了一种稳定显示出良好的磷酸盐处理性的合金化熔融镀锌钢板，其主要是针对高强基板合金化热镀锌，通过镀层中元素的优化控制来提升磷化性能。
但是，上述方案主要是控制合金化镀层结构和表面组成，以达到磷酸盐化学转化处理性能的优化，但未提及对环保锆化薄膜锆化前处理性能方面影响。
发明内容
本发明的目的之一在于提供一种涂装锆化前处理性能优良的合金化热浸镀锌钢板，该镀锌钢板具有良好的电化学反应活性、表面锆化处理成膜效率，从而能够优化涂装前处理性能。
为了实现上述目的，本发明提供了一种涂装锆化前处理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；
其中所述纳米颗粒与合金化热浸镀锌层形成的微区电势差为30-500mV；
其中不规则纳米结构具有沉积成膜活性基团，所述沉积成膜活性基团选自：硅烷基团，羧基基团，氨基基团，烯丙基基团，巯基基团中的至少其中之一。
本发明的冲压润滑加工性能优良的合金化热浸镀锌钢板包括基板和位于基板表面的合金化热浸镀锌层。
在本发明中，主要通过纳米颗粒和镀层表面形成的微区电位差的构建电化学活性位点的方式，来促进锆化反应的初始形核效率，进而提升锆化成膜性能。当纳米颗粒与合金化热浸镀锌层形成的微区电势差过低时，无法在涂装磷化或锆化前的处理过程中起到促进形核活性位点的作用，从而实现涂装前处理磷化或锆化性能显著优化的效果；当纳米颗粒与合金化热浸镀锌层形成的微区电势差过高时，在涂装磷化或锆化前处理过程中易出现成膜不均现象。
在本发明中沉积成膜活性基团主要用于形核后的长大。
在一些实施方案中，基板的化学成分质量百分比为：C：≤0.12％，Si：≤0.25％，Mn：≤0.8％，P：≤0.045％，S：≤0.045％，Ti：≤0.3％，余量为Fe和不可避免的杂质。
在一些实施方案中，基板的化学成分质量百分比满足以下至少一项：
C：0.01％～0.12％；
Si：0.05％～0.25％；
Mn：0.05％～0.8％；
P：0.005％～0.045％；
S：0.005％～0.045％；
Ti：0.01％～0.3％。
在本发明中，合金化热浸镀锌层包括Zn-Fe合金相。
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7％-12.5％。
在本发明中，镀层表面Fe的存在可以促进磷化或锆化反应，从而形成更均匀、致密的表面处理效果。镀层中的铁含量的改变会对磷化或锆化反应形核和生长速率产生影响。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，将不利于磷化和锆化反应的成膜效率；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，镀层中的脆性组织结构增加、硬度上升，易出现涂装附着不良和防腐性能不足的风险。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元素质量百分含量进一步地控制为8％-11％。
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Bi，Cd，Co，Ni，Sn元素中的至少其中一种。
优选地，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Bi，Co，Ni，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的Al元素可以提升镀层的均匀性，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，易出现不均匀现象，直接影响涂装前处理过程中表面的活性的一致性；当合金化热浸镀锌层中的Al元素质量百分含量过高时，合金化热浸镀锌层表面脆性会增加，易出现锌粉剥落现象，进而出现涂装附着不良和防腐性能不足的风险。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地控制为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，Sn元素总质量百分含量不超过0.1％(即≤0.1％)。
优选地，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，Co，Ni，Sn元素总质量百分含量不超过0.1％(即≤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，在单位面积内，锌铁合金结晶区域的面积占比为15％-85％。
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。
在本发明中，锌铁合金结晶区域具有一定的结晶度和晶粒尺寸，其耐蚀性能较好，且存在通过物理结构提供更多的活性位点，有助于锆化剂的吸附和反应。当锌铁合金结晶区域的面积占比过低时，不利于锆化膜的附着和稳定性，同时会出现涂装防腐性能下降的风险；当锌铁合金结晶区域的面积占比过高时，当锌铁合金结晶区域面积占比过高大于85％时，锌铁合金镀层表面粗糙度偏高，进而对涂装外观质量产生影响。
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10-150nm。
在本发明中，当纳米颗粒的等效球半径过低时，易导致颗粒在表面局部聚集分布不均匀现象，产生一些局部区域的过度锆化或未锆化现象，从而降低了锆化层的均匀性。当纳米颗粒的等效球半径过高时，会导致锆化剂无法渗透到金属表面的深层或者微小凹陷中，致使金属表面的局部区域无法形成锆化层，从而降低了金属的锆化效果。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在30-100nm之间。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述纳米颗粒至少以球状的形态随机分布在所述合金化热浸镀锌层表面。
在本发明中，纳米颗粒分布在合金化热浸镀锌层表面。在一些实施方案中，纳米颗粒随机分布在合金化热浸镀锌层表面。
在本发明中，至少一部分纳米颗粒的形态为球状。
球状的纳米颗粒能够提供更多的有效反应表面，从而进一步增加金属表面与锆化剂之间的接触面积，更有利于锆化反应的进行。
进一步地，在本发明所述的合金化热浸镀锌钢板中，球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Fe，Cu，Sr，Ba，Mn，V，Ti，Sn中的至少其中之一。
在本发明中，Cu，Sr，Ba，Mn，V，Ti，Sn主要来自水基处理剂，而Fe主要来自钢板。
在本发明中，构成纳米颗粒的还有非金属元素，该非金属元素包含Si，O，C，N，H元素中的一种或多种。
进一步地，在本发明所述的合金化热浸镀锌钢板中，在表面单位面积内，球状的纳米颗粒占全部纳米颗粒的数量比例为30％-80％。
在本发明中，针叶状颗粒和球状颗粒形成合适的数量比例可以更为充分的发挥其物理铆着功能。当球状的纳米颗粒占全部纳米颗粒的数量比例过低时，针叶状颗粒过多，易出现锆化层的覆盖率不均匀致密性下降，进而影响电泳漆膜附着力和涂装耐腐蚀性能；当球状的纳米颗粒占全部纳米颗粒的数量比例过高时，由于球状颗粒相对较小的表面积和较高的体积，会导致在锆化反应中可能表现锆化反应速率促进效果不明显的现象。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述纳米颗粒与合金化热浸镀锌层形成的微区电势差为80-400mV。
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30％-70％。
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过低时，电化学反应活性优化不显著，影响涂装前处理磷化或锆化成膜效率；当纳米颗粒在复合纳米结构处理层中所占的质量百分比过高时，电化学反应活性过高，会增加涂装前处理磷化或锆化成膜不均匀的风险。
进一步地，在本发明所述的合金化热浸镀锌钢板中，所述沉积成膜活性基团(简称活性基团)在不规则纳米结构中的质量占比为10％-75％。
在本发明中，当活性基团在不规则纳米结构中的质量占比过高时，过多的活性基团易导致膜的涂装前处理磷化或锆化成膜速率过快或不均匀，从而影响锆化膜的质量和稳定性；当活性基团在不规则纳米结构中的质量占比过低时，过少的活性基团无法达到促进成膜反应速率的作用，导致成膜效率不足，出现成膜的不完全的现象，进而影响涂装漆膜附着和防腐性能。
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涂装锆化前处理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。
进一步地，在本发明所述的制造方法中，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沉积成膜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2:1至1:8。
进一步地，在本发明所述的制造方法中，所述水基处理剂中第一物质的质量含量可以为0.5％-10％，所述水基处理剂中第二物质的质量含量可以为2％-10％。
进一步地，在本发明所述的制造方法中，所述第一物质选自：硝酸锰，硝酸银，氟钛酸钠，氟钛酸铵，氟钛酸钾，硝酸铜，硝酸锶，硝酸钡，草酸氧钒，钒酸铵，乙酸钒，氯化亚锡，硝酸锡，柠檬酸锡，醋酸锡的至少其中之一。
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，丙烯基硅醇的至少其中之一。
在一些实施方案中，在本发明所述的制造方法中，热浸镀使用的锌液的化学成分质量百分比满足：Al：0.02～0.3％；Bi：0～0.03％；Co：0～0.03％；Ni：0～0.08％；Sn：0～0.08％；余量为Zn及不可避免杂质。
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470-570℃。
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。
本发明所述的涂装锆化前处理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：
本发明所述的涂装锆化前处理性能优良的合金化热浸镀锌钢板具有良好的电化学反应活性、表面锆化处理成膜效率，以优化涂装前处理性能。
本发明所述的涂装锆化前处理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。
本发明所述的涂装锆化前处理性能优良的合金化热浸镀锌钢板的制造方法便捷且经济，可以降低生产成本。
具体实施方式
下面将结合具体的实施例对本发明所述的涂装锆化前处理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1-3
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1-3中所选用的基板牌号为DC53D+ZF(宝钢)，厚度规格0.7m。
表1列出了本发明实施例1-7和对比例1-3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。
通过热浸镀锌锅将冷轧带钢浸入锌液进行热浸镀，镀层厚度为45g/m2；然后在立式热处理炉加热至470-570℃以进行合金化热处理，然后保温2-8s，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。
表2-1列出了本发明实施例1-7和对比例1-3的锌液的化学成分。
表2-1.(wt％，余量为Zn及不可避免杂质)

表2-2列出了本发明实施例1-7和对比例1-3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2-2.

注：(1)表2中，Zn-Fe合金相中的Fe元素质量百分含量采用X射线荧光光谱测得；(2)表2中，
合金化热浸镀锌层中的Al、Bi、Co、Ni、Sn元素质量百分含量采用电感耦合等离子体发射光谱/质谱(ICP-OES/MS)测得；(3)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。
水基处理剂包括提供金属基化合物的第一物质和提供沉积成膜活性基团的第二物质。
其中，提供金属元素的第一物质选自：硝酸锰，硝酸银，氟钛酸钠，氟钛酸铵，氟钛酸钾，硝酸铜，硝酸锶，硝酸钡，草酸氧钒，钒酸铵，乙酸钒，氯化亚锡，硝酸锡，柠檬酸锡，醋酸锡的至少其中之一。
提供沉积成膜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，丙烯基硅醇的至少其中之一。
水基处理剂由第一物质、第二物质和水组成。
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和2也采用了上述步骤，但是其具体的参数不满足本发明。而对比例3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)。
表3列出了本发明实施例1-7和对比例1-3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，成分后面括号内的数值为该成分占水基处理剂的质量百分含量。
表3.

表4列出了本发明实施例1-7和对比例1-3的合金化热浸镀锌钢板的复合纳米结构处理层的特征。
表4.

注：(1)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；(2)金属基化合物的金属种
类采用能谱仪(EDS)方法进行检测；(3)球状的纳米颗粒占全部纳米颗粒的数量比例采用单位面积(如1mm2)颗粒数量占比进行评估；(4)纳米颗粒与合金化热浸镀层形成的微区电势差采用扫描电化学显微镜(SECM)；(5)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；(6)活性基团的种类以及活性基团在不规则纳米结构中的质量占比的测量方法为：通过涂敷水基处理剂前后称重法获得表面复合纳米结构成膜的重量，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活性基团质量占比：(氨基基团质量+羧基基团质量)/复合纳米结构层质量*100％。
对制得的实施例1-7和对比例1-3的合金化热浸镀锌钢板加工为75*150mm尺寸。
为了验证本发明实施例的实施效果，参照涂装薄膜锆化前处理工艺流程对制得的实施例1-7和对比例1-3的合金化热浸镀锌钢板进行脱脂，水洗，锆化，水洗和电泳工序，所选用的脱脂剂为帕卡濑精FC2011，锆化处理剂为帕卡濑精2000系产品，电泳漆为电泳漆巴斯夫系产品。
表5列出了本发明所述的实施例1-7和对比例1-3的涂装薄膜锆化前处理工序的具体工艺参数。
表5.
而后，对实施例1-7和对比例1-3的合金化热浸镀锌钢板进行涂装薄膜锆化前处理性能评估，并将评估结果列于表6中。其中：
锆化成膜厚度评估：成膜厚度测试采用X射线荧光光谱仪(XRF)进行表面元素检测，通过物理称重法建立特征元素峰强与膜重关系曲线，将检测结果换算为每平方米锆化膜的重量数据(单位mg/m2)。
电泳后表面漆膜附着性能评估：具体方法参照标准ISO 2409，通过百格测试漆膜密着性(百分比)进行评估。
表6列出了本发明所述的实施例1-7和对比例1-3的性能评价结果。
表6.

表6中的锆化成膜厚度评估中各符号释义如下：
◎：60≤锆化处理膜重
○：40≤锆化处理膜重＜60
Δ：20≤锆化处理膜重＜40
×：锆化处理膜重＜20
表6中的电泳后表面漆膜附着性能评估中各符号释义如下：
◎：漆膜密着比例＝100％
○：90％≤漆膜密着比例＜100％
Δ：80％≤漆膜密着比例＜90％
×：漆膜密着比例＜80％
从上述表6中可以看出，实施例1-7的合金化热浸镀锌钢板的锆化成膜性能在锆化成膜厚度和电泳后表面漆膜附着性能方面均表现良好。
从对比例1可以看出，其复合纳米结构处理层中电化学反应活性纳米颗粒与镀层之间微区电势差过高，出现锆化成膜厚度不足/成膜不均现象，同时电泳漆膜附着性能劣化。
从对比例2可以看出，其复合纳米结构处理层中电化学反应活性纳米颗粒与镀层之间微区电势差过低，出现锆化成膜厚度偏薄，且电泳后表面漆膜附着性能恶化的现象。
从对比例3可以看出，由于其不具有复合纳米结构，因此锆化成膜和电泳后表面漆膜附着性能均出现不足的现象。
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. 一种涂装锆化前处理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；
    其中所述纳米颗粒与合金化热浸镀锌层形成的微区电势差为30-500mV；
    其中不规则纳米结构具有沉积成膜活性基团，所述沉积成膜活性基团选自：硅烷基团，羧基基团，氨基基团，烯丙基基团，巯基基团中的至少其中之一。
  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包括Zn-Fe合金相，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7％-12.5％。
  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Bi，Co，Ni，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，Co，Ni，Sn元素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，在单位面积内，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，所述纳米颗粒的等效球半径为10-150nm。
  6. 如权利要求1所述的合金化热浸镀锌钢板，其特征在于，所述纳米颗粒至少以球状的形态随机分布在所述合金化热浸镀锌层表面。
  7. 如权利要求6所述的合金化热浸镀锌钢板，其特征在于，球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Fe，Cu，Sr，Ba，Mn，V，Ti，Sn中的至少其中之一。
  8. 如权利要求6所述的合金化热浸镀锌钢板，其特征在于，在表面单位面积内，球状的纳米颗粒占全部纳米颗粒的数量比例为30％-80％。
  9. 如权利要求1所述的合金化热浸镀锌钢板，其特征在于，所述纳米颗粒与合金化热浸镀锌层形成的微区电势差为80-400mV。
  10. 如权利要求1所述的合金化热浸镀锌钢板，其特征在于，所述纳米颗粒在复合纳米结构处理层中所占的质量百分比为30％-70％。
  11. 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10％-75％。
  12. 如权利要求1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。
  13. 如权利要求12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沉积成膜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2:1至1:8；
    优选地，所述第一物质选自：硝酸锰，硝酸银，氟钛酸钠，氟钛酸铵，氟钛酸钾，硝酸铜，硝酸锶，硝酸钡，草酸氧钒，钒酸铵，乙酸钒，氯化亚锡，硝酸锡，柠檬酸锡，醋酸锡的至少其中之一。
    优选地，所述第二物质选自：3,4,5-三羟基苯甲酸，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，丙烯基硅醇的至少其中之一。
  14. 如权利要求12所述的制造方法，其特征在于，所述合金化热处理的温度为470-570℃。
  15. 如权利要求12所述的制造方法，其特征在于，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。
PCT/CN2025/111780 2024-08-01 2025-07-31 涂装锆化前处理性能优良的合金化热浸镀锌钢板及其制造方法 Pending WO2026026905A1 (zh)

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