WO2019218950A1 - 一种低温烧结形成的双层致密金属防腐涂层、其制备方法和用途 - Google Patents

一种低温烧结形成的双层致密金属防腐涂层、其制备方法和用途 Download PDF

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WO2019218950A1
WO2019218950A1 PCT/CN2019/086508 CN2019086508W WO2019218950A1 WO 2019218950 A1 WO2019218950 A1 WO 2019218950A1 CN 2019086508 W CN2019086508 W CN 2019086508W WO 2019218950 A1 WO2019218950 A1 WO 2019218950A1
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low
temperature sintering
coating
anticorrosive coating
double
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PCT/CN2019/086508
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English (en)
French (fr)
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闫东明
刘毅
黄之昊
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浙江大学
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Priority to US17/054,773 priority Critical patent/US20210371672A1/en
Priority to JP2020563965A priority patent/JP7248990B2/ja
Publication of WO2019218950A1 publication Critical patent/WO2019218950A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • C23C24/085—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer

Definitions

  • the invention belongs to the technology of metal materials, in particular to a double-layer dense metal anticorrosive coating formed by low-temperature sintering, a preparation method thereof and use thereof.
  • the metal is in contact with the medium in the surrounding environment and undergoes a chemical reaction, which is the most common phenomenon of electrochemical corrosion of metals. Since the metal surface is in contact with the surrounding medium (such as humid air, electrolyte solution, etc.), a metal anode dissolution process occurs at the contact interface, and a corresponding cathode process exists to constitute a spontaneously corroded battery, so that the metal anode is dissolved continuously. This causes corrosion of the metal. According to the survey, the annual economic losses caused by global metal corrosion account for about 4% of the total GDP. The annual loss of metal corrosion far exceeds the sum of floods, fires, windstorms and earthquake losses. Corrosion not only causes economic losses, but also often poses a threat to safety.
  • adhesion is also an important indicator for the coating.
  • Adhesion is the ability of the coating to bond with the base metal. The greater the adhesion, the closer the bond of the coating to the base metal, and the better the integrity of the coating, so that the coating has the best protection against the base metal.
  • the existing inorganic anticorrosive coating generally has an adhesion of 5 MPa and an inorganic anticorrosive coating having an adhesion of more than 12 MPa.
  • the object of the present invention is to provide a double-layer dense metal anticorrosive coating formed by low-temperature sintering, in particular to provide a metal anticorrosive coating with adhesion exceeding 12 MPa, which is suitable for corrosion.
  • Metal anti-corrosion areas in the environment such as saline-alkali land, underground pipelines, offshore platforms, etc.
  • a first object of the present invention is to provide a two-layer dense metal anticorrosive coating formed by low-temperature sintering, which is characterized by:
  • the double-layer dense metal anticorrosive coating formed by the low-temperature sintering is a two-layer structural coating composed of an inorganic ceramic coating and a base oxide coating;
  • the inorganic ceramic coating is an outer layer, and the base oxide coating is an inner layer, and the composition of the inorganic ceramic coating comprises, by weight, 50-60 parts of a silicon oxide compound; a thermal expansion coefficient adjusting agent 20 -35 parts; 3-7 parts of binder; 5-10 parts of adhesion regulator; 1-4 parts of catalyst;
  • the adhesion modifier is selected from any one or more of methyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), and sodium silicate.
  • TMOS methyl orthosilicate
  • TEOS tetraethyl orthosilicate
  • sodium silicate sodium silicate
  • the base oxide coating is automatically formed on the surface of the base metal after sintering, and the composition of the base oxide coating is 100 parts by weight of the base metal oxide, and the composition of the base metal oxide is composed of The base metal and oxygen are composed.
  • the inner layer is in contact with the base metal, and the ratio of the thickness of the inorganic ceramic coating to the base oxide coating is (4-6):1.
  • the silicon oxy compound is selected from any one or more of quartz sand, diatomaceous earth, quartz, tridymite, cristobalite, and powder quartz.
  • the silicon oxy compound is an ultrafine powder having a powder particle size of from 1,000 to 2,000 mesh, preferably from 1,100 to 1,400 mesh.
  • the thermal expansion coefficient adjusting agent is selected from any one or more selected from the group consisting of potassium tetraborate, sodium tetraborate, lithium tetraborate, barium tetraborate, zinc oxide, cadmium oxide, and copper oxide.
  • the binder is selected from any one or more of manganese oxide, manganese dioxide, nickel monoxide, nickel oxynitride, cobalt monoxide, and cobalt sulphate.
  • the catalyst is selected from any one or both of an acidic catalyst and a basic catalyst.
  • the acidic catalyst is selected from any one or more of hydrochloric acid, acetic acid, and oxalic acid.
  • the basic catalyst is selected from any one or more of ammonia water, sodium hydroxide, and potassium hydroxide.
  • the sintering temperature is 500-540 °C.
  • the base metal is a steel material
  • the double-layer dense metal anti-corrosion coating has a ultimate tensile strain of 1400-2200 micro strain.
  • the adhesion of the double-layered dense metal anticorrosive coating may reach 13 MPa to 17 MPa.
  • a second object of the present invention is to provide a two-layer dense metal anticorrosive coating formed by low temperature sintering and a metal article with the metal anticorrosive coating, comprising the following steps:
  • step 4) second grinding: the mixture obtained in step 3) is ground again into a powder;
  • step 5) coating: coating the powder obtained in step 4) on the base metal;
  • Sintering sintering the powder-coated base metal obtained in the step 5) to obtain a double-layer dense metal anticorrosive coating formed by low-temperature sintering, wherein the double-layer dense metal anticorrosive coating formed by low-temperature sintering comprises an inorganic ceramic coating and The base oxide coating also provides a metal article with a two-layer dense metal anticorrosive coating formed by low temperature sintering comprising an inorganic ceramic coating and a base oxide coating.
  • the double-layer dense metal anticorrosive coating formed by the low-temperature sintering is a two-layer structural coating composed of an inorganic ceramic coating and a base oxide coating;
  • the inorganic ceramic coating is an outer layer, and the base oxide coating is an inner layer, and the composition of the inorganic ceramic coating comprises, by weight, 50-60 parts of a silicon oxide compound; a thermal expansion coefficient adjusting agent 20 -35 parts; 3-7 parts of binder; 5-10 parts of adhesion regulator; 1-4 parts of catalyst;
  • the adhesion regulator and the catalyst undergo hydrolysis and polycondensation reactions, and complex physical and chemical reactions with the silicon oxide compound, the thermal expansion coefficient modifier, and the binder, thereby forming an inorganic ceramic coating and a matrix oxide.
  • Double-layered dense metal anti-corrosion coating for coating Because of the existence of the two-layer structure, the thickness ratio of the inorganic ceramic coating and the base oxide coating is (4-6):1, so that the adhesion of the double-layer dense metal anticorrosive coating formed by the low-temperature sintering of the present invention can be achieved. 13-17MPa, which improves the corrosion resistance of the coating by more than 10 times, and can co-deform with the building steel under high strain.
  • the adhesion modifier is selected from any one or more of methyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), and sodium silicate.
  • TMOS methyl orthosilicate
  • TEOS tetraethyl orthosilicate
  • the adhesion modifier is catalyzed by a two-step process under the action of an acidic catalyst and a basic catalyst. First, the adhesion modifier hydrolyzes to form a sol, and then the sol undergoes polycondensation to form a hydrogel containing a siliconoxy functional group. The hydrogel is adsorbed on the surface of the silicon oxide compound before the coating is sintered, wherein the silicon oxide functional group is a nucleating material of the coating matrix, and is closely connected with the silicon-oxygen bond in the silicon oxide during the sintering process to form a closed joint.
  • TMOS methyl orthosilicate
  • TEOS tetraethyl orthosilicate
  • sodium silicate sodium
  • the three-dimensional network structure can reduce the sintering temperature of the coating so that the sintering temperature is between 500 ° C and 540 ° C.
  • the silica gel also has excellent thermal insulation function, which can ensure the uniformity of the coating temperature during the high-temperature sintering process, so that the performance of the whole coated steel bar is uniform.
  • the silicon element in the silica gel and the silicon element of the silicon oxide in the main raw material can mutually diffuse and fuse, so that the silica gel can function better as a binder, making the coating more Uniform and dense to improve corrosion resistance.
  • a variety of acidic catalysts and basic catalysts can promote the hydrolysis reaction and polycondensation reaction of the adhesion regulator, respectively.
  • the formed silica gel can be more closely adsorbed on the surface of the silicon oxide compound, and the density and corrosion resistance of the coating layer are promoted.
  • the base oxide coating is automatically formed on the surface of the base metal after sintering, and the composition of the base oxide coating is 100 parts by weight of the base metal oxide, and the composition of the base metal oxide is composed of The base metal and oxygen composition; for example, when the base metal is iron plate, steel bar, steel bar, the base metal oxide is iron oxide; when the base metal is copper plate, the base metal oxide is copper oxide; when the base metal oxide When it is an aluminum plate, the base metal oxide is aluminum oxide.
  • the inner layer is in contact with the base metal, and the ratio of the thickness of the inorganic ceramic coating to the base oxide coating is (4-6):1.
  • the coating method of the step 5) may adopt an electrostatic spraying method, wherein the electrostatic voltage is 30-40 kV, the current is 20-25 microamperes, the gas output is 5-8 liters per minute, and the spraying distance is 20-50. cm.
  • the sintering parameters of the step 6) are: a temperature of 500-540 ° C, a sintering time of 10-20 minutes, and a heating rate of 5-10 ° C per minute.
  • the silicon oxy compound is selected from any one or more of quartz sand, diatomaceous earth, quartz, tridymite, cristobalite, and powder quartz.
  • the surface of the silicon oxide compound is closely adsorbed by the catalyzed silica gel, and after the reaction and sintering, a three-dimensional network structure is formed, which greatly improves the density and corrosion resistance of the coating.
  • the silicon oxy compound is an ultrafine powder having a powder particle size of from 1,000 to 2,000 mesh, preferably from 1,100 to 1,400 mesh.
  • the thermal expansion coefficient adjusting agent is selected from any one or more selected from the group consisting of potassium tetraborate, sodium tetraborate, lithium tetraborate, barium tetraborate, zinc oxide, cadmium oxide, and copper oxide.
  • Potassium tetraborate, sodium tetraborate, lithium tetraborate, and barium tetraborate are soluble in water and are alkaline.
  • Potassium tetraborate, sodium tetraborate, lithium tetraborate, and barium tetraborate increase the CTE (coefficient of thermal expansion) of the coating during sintering to avoid expansion cracking due to uneven stress during heating of the coating.
  • Zinc oxide, cadmium oxide, and copper oxide reduce the CTE (thermal expansion coefficient) of the coating during sintering, and avoid shrinkage cracking caused by the coating cooling. When combined, the coating will ensure the integrity of the coating during heating or cooling.
  • the binder is selected from any one or more of manganese oxide, manganese dioxide, nickel monoxide, nickel oxynitride, cobalt monoxide, and cobalt sulphate.
  • the coating is sintered at a high temperature, for example, when the binder is a manganese oxide, the oxygen element is linked with the silicon element in the coating to form a silicon-oxygen bond, and the manganese element is linked with the oxide layer on the surface of the metal to form a manganese-oxygen bond. This creates a strong chemical bond between the coating and the steel to ensure a tight bond between the coating and the steel.
  • the catalyst is selected from any one or both of an acidic catalyst and a basic catalyst.
  • a variety of acidic catalysts and basic catalysts respectively promote the hydrolysis reaction and polycondensation reaction of the silicon aerogel precursor.
  • the hydrolysis and polycondensation reaction can be promoted to make the formed silicon aerogel more closely adsorbed on the surface of the silicon oxide compound, thereby promoting the density and corrosion resistance of the coating.
  • the acidic catalyst is selected from any one or more of hydrochloric acid, acetic acid, and oxalic acid.
  • the basic catalyst is selected from any one or more of ammonia water, sodium hydroxide, and potassium hydroxide.
  • a third object of the present invention is to provide a metal article comprising a two-layer dense metal anticorrosive coating formed by low-temperature sintering in any form as described above.
  • the base metal of the metal product is selected from the group consisting of an iron plate, a steel plate, a steel bar, a copper plate, and an aluminum plate.
  • a fourth object of the present invention is to provide a double-layer dense metal anticorrosive coating formed by low-temperature sintering of any of the forms described above, and the use of the metal article, which can be applied to civil construction, pipelines, underground pipe corridors, Marine oil production platform, saline-alkali foundation construction, new energy power generation and other fields.
  • the invention has the following beneficial effects:
  • the invention incorporates a silicon oxide compound, a thermal expansion coefficient regulator, a binder, an adhesion regulator, and a catalyst to make the coating of the present invention have a two-layer structure, including an outer layer of an inorganic ceramic coating and an inner layer of a base oxide coating.
  • the layer and the thickness ratio of the inorganic ceramic coating to the base oxide coating are (4-6):1.
  • the ductility of the coating is improved.
  • the ultimate tensile strain of the coating of the present invention is 1400-2200 microstrain, which can be synergistically deformed with the building steel.
  • Figure 1 is a partial electron micrograph of Example 1 (scale is 200 ⁇ m)
  • a double-layer dense metal anticorrosive coating formed by low-temperature sintering characterized in that the raw material comprises the following components: 60 parts of quartz sand, 24 parts of potassium tetraborate, 3 parts of zinc oxide, 7 parts of nickel monoxide, and ethyl orthosilicate ( TEOS) 5 parts, 1 part hydrochloric acid.
  • the raw material comprises the following components: 60 parts of quartz sand, 24 parts of potassium tetraborate, 3 parts of zinc oxide, 7 parts of nickel monoxide, and ethyl orthosilicate ( TEOS) 5 parts, 1 part hydrochloric acid.
  • the first grinding grinding 60 parts of quartz sand, 24 parts of potassium tetraborate, 3 parts of zinc oxide, and 7 parts of nickel oxide into a powder;
  • step 4) second grinding: the mixture obtained in step 3) is ground again into a powder;
  • the powder obtained in the step 4) is coated on the base metal, wherein the electrostatic voltage is 35 kV, the current is 23 microamperes, the gas output is 6 liters per minute, and the spraying distance is 30 cm;
  • Example 1 The specific steps of Examples 1-3 and Comparative Examples 1-3 are as in Example 1, and the specific ratio (weight ratio) is shown in Table 1.
  • the thickness ratio of the inorganic ceramic coating to the base oxide coating in the coating of the present invention can be calculated by SEM scanning electron microscopy.
  • the double-layer dense metal anticorrosion of the present invention can be obtained only by satisfying the specific material silicon oxide compound, the thermal expansion coefficient regulator, the binder, the adhesion regulator, the material ratio of the catalyst, and the corresponding preparation process parameters.
  • the coating, and the ratio of the thickness of the inorganic ceramic coating to the base oxide coating satisfies (4-6):1.
  • Example 1-3 Four sets of coated steel bars of Examples 1-3 and Comparative Examples 1-3 were selected, three replicate samples per set, and three resistive strain gauges were attached to each of the coated steel bars. At the beginning of the experiment, the steel bars were placed on a tensile test machine, and the strain was measured as a function of load. The strain gauges were connected to strain gauges to measure the strain changes on the coated steel bars.
  • the average strain values of the coated steel bars of Examples 1-3 when the steel bars were subjected to tensile cracking were 1600-1900 micro strain.
  • the average strain values of the coated steel bars of Comparative Example 1-3 ranged from 750 to 1000 microstrains. Therefore, the coatings of Examples 1-3 can be cooperatively stretched with the reinforcing steel bars of the building, and the coatings of Comparative Examples 1-3 cannot be accompanied.
  • the reinforcing steel bars of the building were synergistically deformed, so Examples 1-3 had extremely high ductility compared to Comparative Examples 1-3.
  • Example 1-3 Four sets of coated steel bars of Examples 1-3 and Comparative Examples 1-3 were selected, and the control group was uncoated steel bars, and the total number of experimental steel bars was 21. It was placed in a 3.5% sodium chloride solution and subjected to an accelerated corrosion test after being energized.
  • the coated steel bars of Examples 1, 2, and 3 were kept from corrosion for 9-10 times of the time of the uncoated steel bars, and the coated steel bars of Comparative Examples 1, 2, and 3 were not retained.
  • the time of corrosion is five times that of uncoated steel bars, which is only one-half of that of Examples 1, 2, and 3.
  • Example 1-3 and Comparative Example 1-3 the control group was an uncoated steel plate, and the number of steel plates per group was 3, and the total number of experimental steel plates was 21. It was placed in a 3.5% sodium chloride solution and subjected to an accelerated corrosion test after being energized.
  • the coated steel sheets of Examples 1, 2, and 3 were kept from corrosion for 10-11 times of the uncoated steel sheets, and the coated steel sheets of Comparative Examples 1, 2, and 3 were kept from corrosion.
  • the time is six times that of the uncoated steel sheet, but only one-half of the coated steel sheets of Examples 1, 2, and 3.
  • Fig. 1 is an electron micrograph of Comparative Example 1, which is similar to Embodiments 2 and 3, and is represented by 1.
  • the coating is very dense with only a few closed cells.
  • the coating is a two-layer structure, which is divided into a base oxide coating and an inorganic ceramic coating.
  • the base oxide coating makes the bond between the coating and the steel bar tighter, and can effectively improve the corrosion resistance of the coating.
  • the thickness of the base oxide coating is 35.6 ⁇ m
  • the thickness of the inorganic ceramic coating is 160.5 ⁇ m
  • the thickness ratio of the inorganic ceramic coating to the base oxide coating is 4.5:1.

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Abstract

一种低温烧结形成的双层致密金属防腐涂层，由外层的无机陶瓷涂层和内层的基体氧化物涂层构成。原料包括以下组份：硅氧化合物50‑60份；热膨胀系数调节剂20‑35份；粘结剂3‑7份；附着力调节剂5‑10份；催化剂1‑4份。一种低温烧结形成的双层致密金属防腐涂层的制备工艺，包括以下步骤：1）研磨；2）制备混料；3）干燥；4）研磨；5）涂覆；6）烧结。

Description

一种低温烧结形成的双层致密金属防腐涂层、其制备方法和用途 技术领域
本发明属于金属材料技术，尤其涉及一种低温烧结形成的双层致密金属防腐涂层、其制备方法和用途。
背景技术
金属与周围环境中的介质接触并发生化学反应，这是最常见的金属电化学腐蚀现象。由于金属表面与周围的介质(如湿空气、电解质溶液等)接触，在接触界面上会发生金属阳极溶解过程，同时还存在相应的阴极过程，构成自发的腐蚀电池，使金属阳极溶解持续进行，从而引起金属的腐蚀。据调查，每年全球金属腐蚀造成的经济损失约占GDP总量的4％左右，金属腐蚀的年损失远远超过水灾、火灾、风灾和地震损失的总和。腐蚀不仅造成经济损失，也常对安全构成威胁，国内外都曾发生过许多灾难性腐蚀事故。尤其值得指出，在海洋环境下，金属的腐蚀尤为严重。由于船舶、钻井平台等金属结构的海洋设施常年运行在海洋环境中，会受到各种腐蚀介质的侵蚀，从而发生不同程度的腐蚀。
同时对于涂层，附着力(adhesion)也是一项重要的指标，附着力是涂层与基体金属之间相互结合的能力。附着力越大，涂层与基体金属的粘结就更加紧密，于是涂层拥有更好的完整性，从而涂层对于基体金属的保护效果最好。现有的无机防腐涂层的附着力一般为5MPa，还没有附着力超过12MPa的无机防腐涂层。
发明内容
为了克服现有技术的缺点与不足，本发明的目的在于提供一种具有一种采用低温烧结形成的双层致密金属防腐涂层，尤其提供一种附着力超过12MPa金属防腐涂层，适用于腐蚀环境下的金属防腐领域，例如盐碱地，地下管道，海洋平台等方面。
本发明是通过以下技术方案实现的：
本发明的第一个目的是提供一种低温烧结形成的双层致密金属防腐涂层，其 特征在于：
所述低温烧结形成的双层致密金属防腐涂层为双层结构涂层，由无机陶瓷涂层和基体氧化物涂层构成；
所述双层结构中，无机陶瓷涂层是外层，基体氧化物涂层是内层，所述无机陶瓷涂层的成分按重量计包括：硅氧化合物50-60份；热膨胀系数调节剂20-35份；粘结剂3-7份；附着力调节剂5-10份；催化剂1-4份；
所述的附着力调节剂选自正硅酸甲酯(TMOS)、正硅酸乙酯(TEOS)、硅酸钠中的任意一种或多种。
所述基体氧化物涂层是在烧结之后自动在基体金属表面生成的，所述的基体氧化物涂层的成分按重量计为100份基体金属氧化物，所述的基体金属氧化物的成分由基体金属和氧组成。
所述的内层与基体金属接触，无机陶瓷涂层和基体氧化物涂层的厚度之比为(4-6)∶1。
进一步地，所述硅氧化合物选自石英砂、硅藻土、石英、鳞石英、方石英、粉石英的任意一种或多种。
进一步地，所述硅氧化合物为超细粉末，粉末粒径为1000-2000目，优选为1100-1400目。
进一步地，所述热膨胀系数调节剂选自四硼酸钾、四硼酸钠、四硼酸锂、四硼酸铷、氧化锌、氧化镉、氧化铜中的任意一种或多种。
进一步地，所述粘结剂选自一氧化锰、二氧化锰、一氧化镍、三氧化二镍、一氧化钴、三氧化二钴中的任意一种或多种。
进一步地，所述催化剂选自酸性催化剂、碱性催化剂的任意一种或任意两种。
进一步地，所述酸性催化剂选自盐酸、醋酸、草酸中的任意一种或多种。
进一步地，所述碱性催化剂选自氨水、氢氧化钠、氢氧化钾中的任意一种或多种。
进一步地，所述烧结的温度为500-540℃。
进一步地，所述的基体金属为钢材，所述双层致密金属防腐涂层的极限拉应变为1400-2200微应变。
进一步地，所述双层致密金属防腐涂层的附着力可以达到13MPa-17MPa。
本发明的第二个目的是提供一种低温烧结形成的双层致密金属防腐涂层和带有所述金属防腐涂层的金属制品，包括如下步骤：
1)第一次研磨：将原料50-60份硅氧化合物、20-35份热膨胀系数调节剂、3-7份粘结剂研磨成粉末；
2)制备混料：将上述原料加入5-10份附着力调节剂、1-4份催化剂和水混合搅拌得到混料；
3)干燥：在将步骤2)得到的混料干燥；
4)第二次研磨：将步骤3)得到的混料再次研磨成粉末；
5)涂覆：将步骤4)得到的粉末涂覆在基体金属上；
6)烧结：将步骤5)得到的涂覆有粉末的基体金属烧结，得到低温烧结形成的双层致密金属防腐涂层，其中低温烧结形成的双层致密金属防腐涂层包括无机陶瓷涂层和基体氧化物涂层，同时也得到带有包括无机陶瓷涂层和基体氧化物涂层的低温烧结形成的双层致密金属防腐涂层的金属制品。
所述低温烧结形成的双层致密金属防腐涂层为双层结构涂层，由无机陶瓷涂层和基体氧化物涂层构成；
所述双层结构中，无机陶瓷涂层是外层，基体氧化物涂层是内层，所述无机陶瓷涂层的成分按重量计包括：硅氧化合物50-60份；热膨胀系数调节剂20-35份；粘结剂3-7份；附着力调节剂5-10份；催化剂1-4份；
本发明中，附着力调节剂与催化剂发生水解和缩聚反应，并且与硅氧化合物，热膨胀系数调节剂，粘结剂发生复杂的物理变化和化学反应，从而形成包括无机陶瓷涂层和基体氧化物涂层的双层致密金属防腐涂层。因为双层结构的存在同时无机陶瓷涂层和基体氧化物涂层的厚度比为(4-6)：1，所以使得本发明的低温烧结形成的双层致密金属防腐涂层的附着力可以达到13-17MPa，从而使得涂层的耐腐蚀性能提升了10倍以上，并且可以与建筑钢筋在高应变的情况下协同变形。
所述的附着力调节剂选自正硅酸甲酯(TMOS)、正硅酸乙酯(TEOS)、硅酸钠中的任意一种或多种。附着力调节剂在酸性催化剂和碱性催化剂的作用下被两步催化，首先是附着力调节剂水解形成溶胶，然后溶胶进行缩聚，从而形成含有硅氧官能团的水凝胶。水凝胶在涂层烧结前吸附在硅氧化合物的表面，其中的 硅氧官能团是涂层基体的成核材料，在烧结过程中，与硅氧化合物中的硅氧键紧密连接，共同形成封闭的三维网状结构，从而可以降低涂层的烧结温度，使得烧结温度在500℃-540℃左右。同时氧化硅凝胶也拥有极好的保温隔热功能，可以使涂层在高温烧结过程中，保证涂层温度的均匀性，使得整根涂层钢筋的性能均匀一致。此外，氧化硅凝胶中的硅元素与主要原料中的硅氧化合物的硅元素可以相互扩散和融合，从而使得氧化硅凝胶可以更好地起到粘结剂的作用，使得涂层更为均匀致密，以提高耐腐蚀能力。多种酸性催化剂和碱性催化剂可以分别促进附着力调节剂的水解反应和缩聚反应。同时，在促进水解和缩聚反应之后，可以使得形成的氧化硅凝胶更加紧密地吸附在硅氧化合物的表面，促进涂层的致密度和耐腐蚀能力。
所述基体氧化物涂层是在烧结之后自动在基体金属表面生成的，所述的基体氧化物涂层的成分按重量计为100份基体金属氧化物，所述的基体金属氧化物的成分由基体金属和氧组成；例如，当基体金属为铁板、钢筋、钢筋时，基体金属氧化物为铁氧化物；当基体金属为铜板时，基体金属氧化物为铜氧化物；当基体金属氧化物为铝板时，基体金属氧化物为铝氧化物。
所述的内层与基体金属接触，无机陶瓷涂层和基体氧化物涂层的厚度之比为(4-6)∶1。
进一步地，步骤5)的涂覆方法可以采用静电喷涂方法，其中静电电压为30-40千伏，电流为20-25微安，出气量为5-8升每分钟，喷涂距离为20-50厘米。
进一步地，步骤6)的烧结参数为：温度为500-540℃，烧结时间为10-20分钟，升温速度为每分钟5-10℃。
进一步地，所述硅氧化合物选自石英砂、硅藻土、石英、鳞石英、方石英、粉石英的任意一种或多种。硅氧化合物表面将被催化后的氧化硅凝胶紧紧吸附，经过反应和烧结后形成三维网状结构，大大提高了涂层致密度和耐腐蚀性能。
进一步地，所述硅氧化合物为超细粉末，粉末粒径为1000-2000目，优选为1100-1400目。
进一步地，所述热膨胀系数调节剂选自四硼酸钾、四硼酸钠、四硼酸锂、四硼酸铷、氧化锌、氧化镉、氧化铜中的任意一种或多种。四硼酸钾、四硼酸钠、四硼酸锂、四硼酸铷溶于水，呈现碱性。四硼酸钾、四硼酸钠、四硼酸锂、四硼 酸铷在烧结时增大涂层的CTE(热膨胀系数)，避免涂层升温时由于应力不均导致膨胀开裂。氧化锌、氧化镉、氧化铜在烧结时降低涂层的CTE(热膨胀系数)，避免涂层降温后导致的收缩开裂。两者配合后，会使得涂层在升温或是降温过程中都能够保证涂层的完整性。
进一步地，所述粘结剂选自一氧化锰、二氧化锰、一氧化镍、三氧化二镍、一氧化钴、三氧化二钴中的任意一种或多种。在涂层高温烧结时，举例当粘结剂为锰氧化物时，其中的氧元素与涂层中的硅元素链接组成硅氧键，锰元素与金属表面的氧化层链接组成锰氧键。这样在涂层和钢筋中形成较强的化学键，可以保证涂层与钢筋之间紧密的粘结。
进一步地，所述催化剂选自酸性催化剂、碱性催化剂的任意一种或任意两种。多种的酸性催化剂以及碱性催化剂分别促进硅气凝胶前驱体的水解反应和缩聚反应。同时促进水解和缩聚反应之后可以使得形成的硅气凝胶更加紧密地吸附在硅氧化合物的表面，促进涂层的致密度和耐腐蚀能力。
进一步地，所述酸性催化剂选自盐酸、醋酸、草酸中的任意一种或多种。
进一步地，所述碱性催化剂选自氨水、氢氧化钠、氢氧化钾中的任意一种或多种。
本发明的第三个目的是提供一种金属制品，所述金属制品包含如前所述任何一种形式的低温烧结形成的双层致密金属防腐涂层。
进一步地，所述的金属制品的基体金属选自铁板、钢板，钢筋，铜板，铝板。
本发明的第四个目的是提供如前所述任何一种形式的低温烧结形成的双层致密金属防腐涂层、所述的金属制品的用途，可应用于民用建，管道，地下管廊，海洋采油平台，盐碱地基建，新能源发电等多个领域。
本发明与现有技术相比，具有如下的有益效果：
本发明加入了硅氧化合物，热膨胀系数调节剂，粘结剂，附着力调节剂，催化剂使得本发明的涂层为双层结构，包括外层的无机陶瓷涂层和内层的基体氧化物涂层，且无机陶瓷涂层和基体氧化物涂层的厚度比为(4-6)：1。从而使得涂层的附着力得到显著的提升，达到13MPa-17Mpa，是一般涂层的2-4倍。2)因为附着力的提升，使得涂层的耐腐蚀性能提升，本发明的涂层在模拟海水的浸泡环境中能提高钢筋的耐腐蚀性能达10倍以上。3)因为附着力的提升，涂层的延 性提升，在应用于钢筋时，本发明的涂层的极限拉应变在1400-2200微应变，可以与建筑钢筋发生协同变形。
附图说明
图1是实施例1的局部电镜图片(标尺为200μm)
具体实施方式
以下实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本发明所附权利要求书所限定的范围。
实施例1：
一种低温烧结形成的双层致密金属防腐涂层，其特征在于原料包括以下组成：石英砂60份、四硼酸钾24份、氧化锌3份、一氧化镍7份、正硅酸乙酯(TEOS)5份、盐酸1份。
1)第一次研磨：将石英砂60份、四硼酸钾24份、氧化锌3份、一氧化镍7份研磨成粉末；
2)制备混料：将上述原料加入正硅酸乙酯(TEOS)5份、盐酸1份和水混合搅拌得到混料；
3)干燥：在将步骤2)得到的混料干燥；
4)第二次研磨：将步骤3)得到的混料再次研磨成粉末；
5)涂覆：将步骤4)得到的粉末涂覆在基体金属上，其中静电电压为35千伏，电流为23微安，出气量为6升每分钟，喷涂距离为30厘米；；
6)烧结：将步骤5)得到的涂覆有粉末的基体金属在520℃烧结，烧结时间为15分钟，升温速率为7.5℃每分钟。得到低温烧结形成的双层致密金属防腐涂层，其中低温烧结形成的双层致密金属防腐涂层包括无机陶瓷涂层和基体氧化物涂层，同时也得到带有包括无机陶瓷涂层和基体氧化物涂层的低温烧结形成的双层致密金属防腐涂层的金属制品。
实施例1-3和对比实施例1-3的具体步骤如实施例1，具体配比(重量比)参见表1
表1 实施例1-3和对比实施例1-3的具体成分配比(重量比)与制作工艺参数设置
Figure PCTCN2019086508-appb-000001
Figure PCTCN2019086508-appb-000002
通过SEM扫描电镜可以计算出本发明的涂层中无机陶瓷涂层和基体氧化物涂层的厚度比值。
可见，只有满足特定的材硅氧化合物、热膨胀系数调节剂、粘结剂、附着力调节剂、催化剂的材料配比、相应的制备工艺参数，才能制得本发明所述的双层致密金属防腐涂层，并且无机陶瓷涂层和基体氧化物涂层的厚度之比满足(4-6)∶1。
为了验证本发明的用于钢筋防腐的涂层和涂覆方法的效果，进行了如下试验：
1)附着力实验
选择实施例1-3以及对比实施例1-3的四组涂层钢板，每组3个重复试样。根据GB/T5210规范要求，用附着力测试仪进行附着力测试，读出仪器上的数值。
表2 涂层附着力试验
Figure PCTCN2019086508-appb-000003
从附着力实验的结果来看，实施例1-3的附着力范围为13-17MPa，可以看出明显优于一般的有机涂层，对比实施例1-3的附着力范围在5-6MPa左右，仅为实施例1-3的三分之一。
2)拉伸实验
选择实施例1-3以及对比实施例1-3的四组涂层钢筋，每组3个重复试样，每根涂层钢筋上贴上3个电阻应变片。开始实验时，钢筋置于拉伸实验机上，测量应变随荷载变化情况，电阻应变片连接应变仪测量涂层钢筋上的应变变化。
表3 钢筋拉伸试验
Figure PCTCN2019086508-appb-000004
Figure PCTCN2019086508-appb-000005
根据上述表3实验结果，实施例1-3的涂层钢筋随钢筋拉伸开裂时的平均应变值范围为1600-1900微应变。对比实施例1-3涂层钢筋的平均应变值范围为750-1000微应变，因此，实施例1-3涂层可以随同建筑钢筋发生协同拉伸，对比实施例1-3的涂层不能随同建筑钢筋发生协同变形，所以实施例1-3相比于对比实施例1-3具有极高的延性。
3)钢筋耐腐蚀实验
分别取选择实施例1-3以及对比实施例1-3的四组涂层钢筋，对照组为无涂层钢筋，总计实验钢筋个数为21个。将其置于3.5％的氯化钠溶液中，通电后进行加速腐蚀试验。
表4 钢筋加速腐蚀试验
Figure PCTCN2019086508-appb-000006
Figure PCTCN2019086508-appb-000007
从表4可得，实施例1，2，3的涂层钢筋保持不被腐蚀的时间是无涂层钢筋的的9-10倍，对比实施例1，2，3的涂层钢筋保持不被腐蚀的时间是无涂层钢筋的5倍，仅为实施例1，2，3的二分之一。
4)钢板耐腐蚀实验
分别取实施例1-3以及对比实施例1-3，对照组为无涂层钢板，每组钢板数为3块，总计实验钢板个数为21个。将其置于3.5％的氯化钠溶液中，通电后进行加速腐蚀试验。
表5 钢板加速腐蚀试验
Figure PCTCN2019086508-appb-000008
从表5可得，实施例1，2，3的涂层钢板保持不被腐蚀的时间是无涂层钢板的10-11倍，对比实施例1，2，3的涂层钢板保持不被腐蚀的时间是无涂层钢板的6倍，但仅为实施例1，2，3的涂层钢板的二分之一。
5)涂层横截面电镜图
图1为对比实施例1的电镜图片，与实施例2，3相似，所以以1作为代表。从图中可以看出，涂层十分致密，其中只有极少数的闭孔。同时也可以看到涂层 为双层结构，分别分为基体氧化物涂层和无机陶瓷涂层。其中基体氧化物涂层使得涂层与钢筋之间粘结更加紧密，同时可以有效提高涂层的耐腐蚀能力。其中基体氧化物涂层厚度为35.6μm，无机陶瓷涂层厚度为160.5μm，无机陶瓷涂层和基体氧化物涂层的厚度比为4.5∶1。

Claims (24)

  1. 一种低温烧结形成的双层致密金属防腐涂层，其特征在于：
    所述低温烧结形成的双层致密金属防腐涂层为双层结构涂层，由无机陶瓷涂层和基体氧化物涂层构成；
    所述双层结构中，无机陶瓷涂层是外层，基体氧化物涂层是内层，所述无机陶瓷涂层的成分按重量计包括：硅氧化合物50-60份；热膨胀系数调节剂20-35份；粘结剂3-7份；附着力调节剂5-10份；催化剂1-4份；所述的附着力调节剂选自正硅酸甲酯(TMOS)、正硅酸乙酯(TEOS)、硅酸钠中的任意一种或多种；
    所述基体氧化物涂层是在烧结之后自动在基体金属表面生成的，所述的基体氧化物涂层的成分按重量计为100份基体金属氧化物，所述的基体金属氧化物的成分由基体金属和氧组成；
    所述的内层与基体金属接触，无机陶瓷涂层和基体氧化物涂层的厚度之比为(4-6)∶1。
  2. 根据权利要求1所述的一种低温烧结形成的双层致密金属防腐涂层，其特征在于，所述硅氧化合物选自石英砂、硅藻土、石英、鳞石英、方石英、粉石英的任意一种或多种。
  3. 根据权利要求2所述的一种低温烧结形成的双层致密金属防腐涂层，其特征在于，所述硅氧化合物为超细粉末，粉末粒径为1000-2000目，优选为1100-1400目。
  4. 根据权利要求1所述的一种低温烧结形成的双层致密金属防腐涂层，其特征在于，所述热膨胀系数调节剂选自四硼酸钾、四硼酸钠、四硼酸锂、四硼酸铷、氧化锌、氧化镉、氧化铜中的任意一种或多种。
  5. 根据权利要求1所述的一种低温烧结形成的双层致密金属防腐涂层，其特征在于，所述粘结剂选自一氧化锰、二氧化锰、一氧化镍、三氧化二镍、一氧化钴、三氧化二钴中的任意一种或多种。
  6. 根据权利要求1所述的一种低温烧结形成的双层致密金属防腐涂层，其特征在于，所述催化剂选自酸性催化剂、碱性催化剂的任意一种或任意两种。
  7. 根据权利要求6所述的一种低温烧结形成的双层致密金属防腐涂层，其特征在于，所述酸性催化剂选自盐酸、醋酸、草酸中的任意一种或多种。
  8. 根据权利要求6所述的一种低温烧结形成的双层致密金属防腐涂层，其特征在于，所述碱性催化剂选自氨水、氢氧化钠、氢氧化钾中的任意一种或多种。
  9. 根据权利要求1-8任一项所述的一种低温烧结形成的双层致密金属防腐涂层，其特征在于，所述烧结的温度为500-540℃。
  10. 根据权利要求1-9任一项所述的一种低温烧结形成的双层致密金属防腐涂层，其特征在于，所述的基体金属为钢材，所述低温烧结形成的双层致密金属防腐涂层的极限拉应变为1400-2200微应变。
  11. 根据权利要求1-9任一项所述的一种低温烧结形成的双层致密金属防腐涂层，其特征在于，所述低温烧结形成的双层致密金属防腐涂层的附着力可以达到13MPa-17MPa。
  12. 一种低温烧结形成的双层致密金属防腐涂层和带有所述金属防腐涂层的金属制品，包括如下步骤：
    1)第一次研磨：将原料50-60份硅氧化合物、20-35份热膨胀系数调节剂、3-7份粘结剂研磨成粉末；
    2)制备混料：将上述原料加入5-10份附着力调节剂、1-4份催化剂和水混合搅拌得到混料；
    3)干燥：在将步骤2)得到的混料干燥；
    4)第二次研磨：将步骤3)得到的混料再次研磨成粉末；
    5)涂覆：将步骤4)得到的粉末涂覆在基体金属上；
    6)烧结：将步骤5)得到的涂覆有粉末的基体金属烧结，得到低温烧结形成的双层致密金属防腐涂层，其中低温烧结形成的双层致密金属防腐涂层包括无机陶瓷涂层和基体氧化物涂层，同时也得到带有包括无机陶瓷涂层和基体氧化物涂层的低温烧结形成的双层致密金属防腐涂层的金属制品。
  13. 根据权利要求12所述的制备方法，其特征在于，步骤5)的涂覆方法可以采用静电喷涂方法，其中静电电压为30-40千伏，电流为20-25微安，出气量为5-8升每分钟，喷涂距离为20-50厘米。
  14. 根据权利要求13所述的制备方法，其特征在于，步骤6)的烧结参数为：温度为500-540℃，烧结时间为10-20分钟，升温速度为每分钟5-10℃。
  15. 根据权利要求12-14任一项所述的制备方法，其特征在于，所述硅氧化合物 选自石英砂、硅藻土、石英、鳞石英、方石英、粉石英的任意一种或多种。
  16. 根据权利要求12-14任一项所述的制备方法，其特征在于，所述硅氧化合物为超细粉末，粉末粒径为1000-2000目，优选为1100-1400目。
  17. 根据权利要求12-14任一项所述的制备方法，其特征在于，所述热膨胀系数调节剂选自四硼酸钾、四硼酸钠、四硼酸锂、四硼酸铷、氧化锌、氧化镉、氧化铜中的任意一种或多种。
  18. 根据权利要求12-14任一项所述的制备方法，其特征在于，所述粘结剂选自一氧化锰、二氧化锰、一氧化镍、三氧化二镍、一氧化钴、三氧化二钴中的任意一种或多种。
  19. 根据权利要求12-14任一项所述的制备方法，其特征在于，所述催化剂选自酸性催化剂、碱性催化剂的任意一种或任意两种。
  20. 根据权利要求19所述的制备方法，其特征在于，所述酸性催化剂选自盐酸、醋酸、草酸中的任意一种或多种。
  21. 根据权利要求19所述制备方法，其特征在于，所述碱性催化剂选自氨水、氢氧化钠、氢氧化钾中的任意一种或多种。
  22. 一种金属制品，其特征在于，所述金属制品包含权利要求1-11任一项所述的低温烧结形成的双层致密金属防腐涂层。
  23. 根据权利要求22所述的金属制品，其特征在于，所述的基体金属选自铁板、钢板，钢筋，铜板，铝板。
  24. 权利要求1-11任一项所述的低温烧结形成的双层致密金属防腐涂层、权利要求22-23任一项所述的金属制品可应用于民用建，管道，地下管廊，海洋采油平台，盐碱地基建，新能源发电等多个领域。
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CN110218084B (zh) * 2019-05-29 2021-06-11 浙江大学 一种除甲醛金属防腐涂层及其涂覆方法
CN110317477B (zh) * 2019-05-29 2020-08-07 浙江大学 一种减少电磁波干扰的高表面粗糙度金属防腐涂层及其涂覆方法
CN110342919A (zh) * 2019-05-29 2019-10-18 浙江大学 一种光催化杀菌防霉的金属防腐涂层及其涂覆方法
CN116078637B (zh) * 2023-03-14 2024-05-28 王梦欣 一种用于水龙头输水管材内表面的防腐涂层及其制备方法
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1269384A (zh) * 2000-02-22 2000-10-11 曾庆衿 金属高温绝缘膜
CN1730570A (zh) * 2005-08-02 2006-02-08 陈国军 一种高温节能耐腐蚀涂料及其制备和使用方法
CN105585883A (zh) * 2016-03-04 2016-05-18 浙江大学 用于钢筋防腐的低温烧结涂料及其涂覆方法
CN108795128A (zh) * 2018-05-12 2018-11-13 浙江大学 一种低温烧结形成的双层致密金属防腐涂层、其制备方法和用途

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2206801A1 (en) * 2008-12-24 2010-07-14 Seb Sa Composite cookware comprising a vitreous protective coating
JP5565816B2 (ja) 2010-11-17 2014-08-06 株式会社トレードサービス 耐熱・耐酸化被覆材水溶液及び被覆処理方法
DE102012022731A1 (de) * 2012-11-21 2014-05-22 Epg (Engineered Nanoproducts Germany) Ag Hochabriebfeste Antikalkschichten mit hoher chemischer Beständigkeit
JP6088294B2 (ja) * 2013-03-07 2017-03-01 東海高熱工業株式会社 炭化珪素複合材およびその製造方法
CN104879067A (zh) * 2014-02-28 2015-09-02 北京赛亿科技股份有限公司 石油管道用抗螺纹粘扣陶瓷涂层油套管及其制备方法
JP6540695B2 (ja) 2014-06-02 2019-07-10 Ａｇｃ株式会社 防眩膜付き基材、その製造方法、および物品
CN104193288B (zh) * 2014-07-01 2016-08-24 浙江大学自贡创新中心 一种水性陶瓷防腐涂料的制备及涂覆方法
CN106519941B (zh) * 2016-11-04 2018-08-03 中国航空工业集团公司北京航空材料研究院 一种疏水耐蚀杂化防护涂料及其制备方法
CN108531908B (zh) * 2018-05-12 2020-08-14 浙江大学 一种金属防腐涂层、其制备方法和用途

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1269384A (zh) * 2000-02-22 2000-10-11 曾庆衿 金属高温绝缘膜
CN1730570A (zh) * 2005-08-02 2006-02-08 陈国军 一种高温节能耐腐蚀涂料及其制备和使用方法
CN105585883A (zh) * 2016-03-04 2016-05-18 浙江大学 用于钢筋防腐的低温烧结涂料及其涂覆方法
CN108795128A (zh) * 2018-05-12 2018-11-13 浙江大学 一种低温烧结形成的双层致密金属防腐涂层、其制备方法和用途

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