WO2019218949A1 - 一种金属防腐涂层、其制备方法和用途 - Google Patents

一种金属防腐涂层、其制备方法和用途 Download PDF

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Publication number
WO2019218949A1
WO2019218949A1 PCT/CN2019/086505 CN2019086505W WO2019218949A1 WO 2019218949 A1 WO2019218949 A1 WO 2019218949A1 CN 2019086505 W CN2019086505 W CN 2019086505W WO 2019218949 A1 WO2019218949 A1 WO 2019218949A1
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Prior art keywords
parts
coating
metal
oxide
thermal expansion
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English (en)
French (fr)
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闫东明
刘毅
黄之昊
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Zhejiang University
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Zhejiang University
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Priority to JP2020563974A priority Critical patent/JP7067754B2/ja
Priority to US17/054,177 priority patent/US20210188699A1/en
Publication of WO2019218949A1 publication Critical patent/WO2019218949A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
    • C23D5/00—Coating with enamels or vitreous layers
    • C23D5/04—Coating with enamels or vitreous layers by dry methods
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
    • E04C5/01—Reinforcing elements of metal, e.g. with non-structural coatings
    • E04C5/015—Anti-corrosion coatings or treating compositions, e.g. containing waterglass or based on another metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2207/00—Compositions specially applicable for the manufacture of vitreous enamels
    • C03C2207/04—Compositions specially applicable for the manufacture of vitreous enamels for steel

Definitions

  • the invention belongs to the field of metal anticorrosive materials, in particular to a metal anticorrosive coating, a preparation method thereof and use thereof.
  • the inorganic coating includes a phosphate coating, a silicate coating, an enamel coating, and the like.
  • the enamel coating must undergo the sintering process in the production process, and the sintering will produce two inherent defects: 1) the thermal expansion coefficient of the coating and the base metal cannot be coordinated, which makes the deformation of the coating and the base metal inconsistent, resulting in The coating produces cracks; 2) through holes caused by evaporation of water vapor during sintering.
  • the base metal refers to a metal that requires corrosion protection, such as steel, aluminum, copper, or the like.
  • the uniformity means that the thermal expansion coefficient of the coating is equal to or more than the thermal expansion coefficient of the base metal, which varies with the thermal expansion coefficient of the base metal to ensure that the coating does not crack at high temperatures and improve the corrosion resistance of the coating. .
  • the universality problem refers to how to make a metal anti-corrosion coating adapt to the thermal expansion coefficient of different types or types of metals. It is well known that the coefficients of thermal expansion of different metals vary widely. For example, the coefficient of thermal expansion of magnesium is 24 ⁇ 10 -6 /°C, while the thermal expansion of iron is only 12 ⁇ 10 -6 /°C. The prior art metal anti-corrosion coatings are not applicable. Various metals with large differences in thermal expansion coefficients.
  • Chinese patent CN106116438A discloses a magnesium phosphate based steel protective coating material and a preparation method thereof, which is a cementing material which forms a chemical bond based on an acid-base neutralization reaction to produce a strength.
  • the cost is high and the corrosion resistance is not superior.
  • Chinese patent CN105131660B discloses a steel anticorrosive coating and a coating method thereof, wherein the introduction of the fiber causes the anticorrosive coating to absorb energy during the fracture process to achieve the purpose of delaying cracking.
  • Chinese patent CN105238105B discloses a ductile coating for reinforcing steel and its coating method, wherein the coating has outstanding corrosion resistance, high toughness and high by adding feldspar powder, clay, fluorite and the like. Durability.
  • Chinese patent CN105819691A discloses a small pore size inorganic coating for corrosion protection of steel bars and a coating method thereof, which reduces the internal pore size of the anticorrosive coating to improve corrosion resistance.
  • Chinese patent CN105585883B discloses a low-temperature sintering coating for corrosion protection of steel bars and a coating method thereof, which allows the coating to be sintered at a temperature of 400 to 550 degrees.
  • Chinese patent CN 105670366 discloses a low through-porosity coating for corrosion protection of steel bars and a coating method thereof, which reduces the through-hole ratio of the coating, thereby enhancing the anti-corrosion performance.
  • U.S. Patent US7901769B2 and US8679389B2 discloses anti-corrosion coating for a glass enamel steel, the thermal expansion coefficient in the range of 12.5 ⁇ 10 -6 /°C ⁇ 13.5 ⁇ 10 -6 /°C(12.5ppm/°C ⁇ 13.5ppm/°C)
  • the coating has a thermal expansion coefficient span that is too small, spanning only 1.0 ⁇ 10 -6 /°C, and cannot fundamentally solve the adverse effect of the difference in thermal expansion coefficient between the steel and the coating on the corrosion resistance of the coating. problem.
  • the thermal expansion coefficient of the coating needs to be consistent with the thermal expansion coefficient of the base metal, that is, the thermal expansion coefficient of the coating is equal to or more than the thermal expansion coefficient of the base metal, which varies with the thermal expansion coefficient of the base metal to ensure the coating is Does not produce any small cracks at high temperatures, improving the corrosion resistance of the coating.
  • the prior art has two problems for metal anti-corrosion coatings: the first problem is that the coefficients of thermal expansion of different metals are very different, such as the thermal expansion coefficient of magnesium is 24 ⁇ 10 -6 /°C.
  • the thermal expansion of iron is only 12 x 10 -6 / °C. This results in the thermal expansion coefficient of the same metal anti-corrosion coating being inconsistent with that of magnesium and iron, and it is impossible to adapt to the corrosion protection of different base metals by the same metal anti-corrosion coating, that is, the prior art coating does not have a general Fitness.
  • the second problem is the same metal manufacturing process or the like because of their thermal expansion coefficients such that there will be some differences, such as the thermal expansion coefficient of steel will range between 11.5 ⁇ 10 -6 /°C ⁇ 14.5 ⁇ 10 -6 / °C change to U.S. Patent US7901769B2 and US8679389B2, for example, only coating the thermal expansion coefficient range of 12.5 ⁇ 10 -6 /°C ⁇ 13.5 ⁇ 10 -6 / °C , a thermal expansion coefficient of the coating is too small to span the range of thermal expansion coefficient range of the steel, Therefore, it is not applicable to all steel bars. Therefore, the prior art cannot provide a metal anticorrosive coating that is universal and can be applied to different types of metals and metals in different types and environments.
  • the technical problem to be solved by the present invention is to provide a metal anticorrosive coating having a double-layer structure with excellent corrosion resistance, the coating having a large thermal expansion coefficient range and thermal expansion.
  • the coefficient varies according to the change of the base metal, and is universal and can be applied to different types of metals and metals.
  • the metal anticorrosive coating prepared by the invention may be a dense structure, and the dense structure is a structure without through holes and a closed cell ratio of less than 5%, so that the corrosion resistance of the coating is further improved, and the coating is A small amount of closed cells will give the coating a certain degree of stretchability.
  • the corrosion resistance of the existing metal anticorrosive coatings is generally no more than 10 times that of the uncoated metal, because the problem of affecting the metal anticorrosive coating is not substantially solved.
  • the invention solves the problem in essence, thereby greatly improving the corrosion resistance of the coating, and the corrosion resistance of the metal anticorrosive coating of the invention is 14 times higher than that of the uncoated metal. Can be used in harsher corrosive environments.
  • a metal anticorrosive coating which is a two-layer structural coating composed of an enamel coating and a base oxide coating;
  • the enamel coating is an outer layer
  • the base oxide coating is an inner layer
  • the composition of the enamel coating comprises 1 to 40 parts by weight of silicon, 1 to 30 parts of sodium, and 1 to 20 parts of potassium. Parts, calcium 2 to 20 parts, fluorine 0.5 to 15 parts, cobalt 0.3 to 10 parts, nickel 0.2 to 10 parts, boron 1 to 18 parts, phosphorus 0.5 to 10 parts, magnesium 0.1 to 8 parts, and the rest is oxygen
  • the composition of the base oxide coating includes a base metal and oxygen;
  • the base metal refers to a metal that requires corrosion protection, such as steel, aluminum, copper, etc., and the base oxide coating is adjacent to the base metal (see Fig. 2).
  • thermal expansion coefficient of the two-layer structural coating is coordinated with the thermal expansion coefficient of the base metal.
  • the coordination means that the thermal expansion coefficient of the two-layer structural coating is equal to or more than the thermal expansion coefficient of the base metal, which varies with the thermal expansion coefficient of the base metal to ensure that the coating does not generate cracks at high temperatures. Improve the corrosion resistance of the coating.
  • the coating of the present invention has two advantages in the coefficient of thermal expansion.
  • the range of thermal expansion coefficient of the coating in the present invention is large. For example, when the base metal is iron or steel, the thermal expansion coefficient of the coating ranges from 10 ⁇ .
  • the thermal expansion coefficient range of 11.5 ⁇ 10 -6 /°C ⁇ 14.5 ⁇ 10 -6 / °C , of the coating of the present invention may comprise all of the iron or The type of steel can be well adapted even if the thermal expansion coefficient of a certain batch of steel bars is deviated.
  • the coefficient of thermal expansion of the coating of the present invention varies with the change of the base metal to accommodate the coefficient of thermal expansion of the base metal.
  • the base oxide coating in the double layer coating contains the base metal oxide, so that the thermal expansion coefficient of the overall coating can be changed with the change of the base metal, Adapt to different metals.
  • the two-layer structure coating has a thermal expansion coefficient from the base oxide coating to the enamel coating due to a decrease in the concentration of the base metal oxide from the base oxide coating to the enamel coating gradient.
  • the change in gradient increases.
  • the thermal expansion coefficient gradient coating can effectively promote the migration of metal elements, and the matrix metal elements react with oxygen to form corresponding matrix metal oxides, thereby forming a matrix oxide coating. This can ensure the adhesion of the two-layer structure coating to the base metal, and also the thermal expansion coefficient of the two-layer structure coating will change with the change of the base metal.
  • Specific elemental composition of the two-layer structure coating (1 to 40 parts of silicon, 1 to 30 parts of sodium, 1 to 20 parts of potassium, 2 to 20 parts of calcium, 0.5 to 15 parts of fluorine, 1 to 18 parts of boron, 0.3 to 10 parts of cobalt, 0.2-10 parts of nickel, 0.5-10 parts of phosphorus, 0.1-8 parts of magnesium, and the remaining oxygen element) firstly form the skeleton and foundation of the entire coating, and can adjust the thermal expansion coefficient of the double-layer structure coating.
  • the range of thermal expansion coefficient can be guaranteed to be around 6 ⁇ 10 -6 /°C (if the base metal is iron, the thermal expansion coefficient of the coating ranges from 10 ⁇ 10 -6 /°C to 16 ⁇ 10 -6 /°C, At this time, the thermal expansion coefficient of the coating spans 6 ⁇ 10 -6 /°C; when the base metal is copper, the thermal expansion coefficient of the coating ranges from 13 ⁇ 10 -6 /°C to 20 ⁇ 10 -6 /°C, coating The coefficient of thermal expansion spans from 7 ⁇ 10 -6 / ° C).
  • the above-mentioned fractions of silicon, sodium, potassium, calcium, fluorine, boron, cobalt, nickel, phosphorus, magnesium, and oxygen can also effectively lower the melting point of the reaction system, increase the diffusion rate of the substance, and promote the interface between various raw materials. Contact and reaction. And these elements can react with the base metal oxide in the base oxide coating to form oxides. These oxides have strong chemical bonds, which promotes the migration of the metal elements, thereby enabling the enamel coating and the matrix oxide. The bond strength of the coating is increased. At the same time, due to the presence of the enamel coating and the base oxide coating, the thermal expansion coefficient of the two-layer structural coating changes correspondingly with the change of the base metal.
  • the two-layer structure coating is a dense structure.
  • the dense structure is a structure having no through holes and a closed cell ratio of less than 5%.
  • No through hole refers to a through hole from the surface of the enamel coating to the surface of the base metal.
  • the closed cell ratio of less than 5% means that the ratio of the cross-sectional area of the closed hole (non-through hole) to the total cross-sectional area of the coating is not more than 5%.
  • sintering is an essential step in the preparation of enamel coatings. In the sintering process, because the water evaporates, the impurities in the metal product react with high temperature to generate gas and other factors, which may lead to the occurrence of through holes in the coating.
  • the double-layered structural coating of the present invention is added with silicon, sodium, potassium, calcium, fluorine, cobalt, nickel, boron, phosphorus, magnesium, and oxygen in a specific ratio (1 to 40 parts by weight, sodium 1 to 30 by weight).
  • the rest is oxygen
  • the coating has a double-layer thermal expansion coefficient gradient structure, so that there is no through hole, and at the same time, the coating has a closed cell ratio of less than 5%.
  • the two points of no through hole and low closed porosity can further improve the corrosion resistance of the coating structure, and a small number of closed cells in the coating will make the coating have a certain extension and deformation ability.
  • the base metal oxide has a base metal content of 40 to 85 parts, and the balance is oxygen.
  • the composition of the enamel coating layer comprises 2 to 30 parts, preferably 3 to 15 parts, 2 to 20 parts, preferably 7 to 16 parts, and 2 to 15 parts, preferably 3 to 10 parts, of potassium; 4 to 16 parts, preferably 5 to 11 parts, 2 to 10 parts, preferably 3 to 7 parts, 0.5 to 7 parts, preferably 1 to 4 parts, and 0.3 to 8 parts, preferably 0.5 to 4 parts.
  • the base metal is selected from the group consisting of iron, steel, copper, copper alloy, aluminum, aluminum alloy, magnesium, magnesium alloy; when the base metal is iron or steel, the thermal expansion coefficient of the double-layer structural coating ranges from 10 ⁇ 10 -6 / ° C ⁇ 16 ⁇ 10 -6 / ° C; when the base metal is copper or copper alloy, the thermal expansion coefficient of the double-layer structural coating ranges from 13 ⁇ 10 -6 / ° C to 20 ⁇ 10 -6 / °C; when the base metal is aluminum or aluminum alloy, the thermal expansion coefficient of the double-layer structure coating ranges from 20 ⁇ 10 -6 /°C to 26 ⁇ 10 -6 /°C; when the base metal is magnesium or magnesium alloy,
  • the double layer structural coating has a coefficient of thermal expansion ranging from 23 x 10 -6 / ° C to 29 x 10 -6 / ° C.
  • the silicon, sodium, potassium, calcium, fluorine, cobalt, nickel, boron, phosphorus, magnesium, and oxygen elements are determined by an energy spectrometer (EDS), and the specific method is: the EDS test is performed by using a spectrometer.
  • EDS energy spectrometer
  • the surface of the sample is ground and polished, and the gold film is sprayed on the surface to make it conductive and paste the conductive tape.
  • the acceleration voltage is adjusted to 10 ⁇ 40kV, the dead time is 15 ⁇ 45%, the measurement time is set to 50 ⁇ 400s, and the sample is placed.
  • vacuum is applied to make the focus clear, select the area where element analysis is needed and maintain the position, and perform elemental analysis using point scan, surface scan, and line scan.
  • the source of the enamel coating component is selected from the group consisting of enamel powder, thermal expansion regulator, flux, and binder, and the enamel powder is contained in an amount of 40 to 90 parts, preferably 60 to 75 parts; and a thermal expansion regulator
  • the content is 5 to 40 parts, preferably 10 to 25 parts;
  • the content of the flux is 1 to 20 parts, preferably 5 to 12 parts;
  • the content of the binder is 0.5 to 12 parts, preferably 2 to 6 parts.
  • the content stated is by weight.
  • the enamel coating 40 to 90 parts of enamel powder is the basis of the entire enamel coating, and the addition of a thermal expansion regulator, a binder and a flux allows the enamel coating to adhere to the base oxide coating during sintering. Tightly, a double-layer thermal expansion coefficient gradient structure is formed, and the overall structure of the coating is dense. Further, the addition of 5 to 40 parts of the thermal expansion regulator, 1 to 20 parts of the flux, and 0.5 to 12 parts of the binder can effectively control the thermal expansion coefficient of the enamel powder, the binder and the flux, thereby allowing the enamel coating to be removed from the inside.
  • the addition of thermal expansion modifier allows the range of thermal expansion coefficient of the two-layer structure coating to be guaranteed to be around 6 ⁇ 10 -6 /°C (if the base metal is iron, the thermal expansion coefficient of the coating is 10 ⁇ 10 -6 /°C) ⁇ 16 ⁇ 10 -6 /°C, the thermal expansion coefficient of the coating spans 6 ⁇ 10 -6 /°C; when the base metal is copper, the thermal expansion coefficient of the coating is 13 ⁇ 10 -6 /°C ⁇ 20 ⁇ 10 -6 / ° C, the thermal expansion coefficient of the coating spans 7 ⁇ 10 -6 / ° C).
  • the addition of 5 to 40 parts of thermal expansion regulator, 1 to 20 parts of flux, and 0.5 to 12 parts of binder can effectively lower the melting point of the reaction system, increase the diffusion rate of the substance, and promote the contact and reaction between various raw material interfaces.
  • the sintering temperature of the enamel coating is lowered and the adhesion to the base oxide layer is increased.
  • the enamel coating and the base oxide coating can be reacted during the sintering process to form a strong chemical bond, which effectively promotes the migration of the metal element, thereby bonding the enamel coating to the base oxide coating.
  • the bond is tight and the base oxide coating is tightly bonded to the base metal.
  • the synergistic action of the enamel powder, the thermal expansion regulator, the flux and the binder as a whole of the invention results in the formation of an enamel coating and a base oxide coating, and the presence of the two layers allows the thermal expansion coefficient of the double-layered coating to follow The change in the base metal changes accordingly.
  • the binder consumes part of the base metal oxide, this also causes the concentration of the base metal oxide of the overall coating to decrease from the base oxide coating to the enamel coating gradient, resulting in coating.
  • the coefficient of thermal expansion of the layer increases as a result of the gradient of the base oxide coating to the enamel coating. Thereby solving the universality problem of the coating.
  • the enamel powder has an element content of 1 to 40 parts, preferably 2 to 15 parts, 1 to 20 parts, preferably 3 to 12 parts, and 1 to 23 parts, preferably 4 to 13 parts, of potassium.
  • the enamel powder does not contain toxic substances such as mercury and lead, and has a low melting point, which can greatly reduce the sintering temperature of the coating, thereby reducing the performance degradation of the metal due to high temperature.
  • the content of silicon oxide accounts for 3 to 39 parts
  • the content of sodium oxide accounts for 3 to 28 parts
  • the content of potassium oxide accounts for 1 to 25 parts
  • the content of boron oxide accounts for 0 to 15 parts
  • phosphorus oxidation The content is from 0.5 to 10 parts by weight, and the content is by weight.
  • the silicon oxide is selected from one or more of silicon oxide, silicon dioxide, and silicon oxide.
  • the sodium oxide is selected from one or more of sodium oxide, sodium peroxide, and sodium hydroxide.
  • the potassium oxide is selected from one or more of potassium oxide, potassium carbonate, and potassium hydroxide.
  • the phosphorus oxide is one or more selected from the group consisting of phosphorus trioxide and phosphorus pentoxide.
  • the thermal expansion regulator is selected from one or more of sodium silicate, potassium silicate, calcium silicate, magnesium silicate, sodium tetraborate, potassium tetraborate, calcium borate, barium borate, lithium borate.
  • the fluxing agent is selected from one or more of sodium carbonate, potassium carbonate, magnesium carbonate, barium carbonate, lithium carbonate, calcium carbonate, barium carbonate, calcium fluoride, magnesium fluoride, and potassium fluoride.
  • the binder is selected from one or more of cobalt monoxide, cobalt oxychloride, nickel monoxide, and nickel oxynitride.
  • the thickness of the two-layer structure coating layer is not less than 40 ⁇ m; preferably, the thickness of the two-layer structure coating layer is not less than 50 ⁇ m.
  • the enamel coating has a thickness of 40 to 320 ⁇ m
  • the base oxide coating layer has a thickness of 10 to 50 ⁇ m. If the thickness is less than 40 ⁇ m, the corrosion resistance of the coating is significantly impaired. If the thickness exceeds 400 ⁇ m, the internal stress of the coating will be too large, resulting in the formation of internal cracks in the coating, which will also reduce the corrosion resistance of the coating.
  • the base metal is steel
  • the thermal expansion coefficient of the double-layer structural coating ranges from 10 ⁇ 10 -6 /°C to 16 ⁇ 10 ⁇ 6 / ° C
  • the ultimate tensile strain of the two-layer structure coating is 1200 ⁇ 2300 micro strain ( ⁇ ⁇ ), preferably 1400 ⁇ 2200 micro strain ( ⁇ ⁇ ).
  • the two-layer structure coating of the present invention is composed of a specific proportion of silicon, sodium, potassium, calcium, fluorine, cobalt, nickel, boron, phosphorus, magnesium, oxygen (1 to 40 parts by weight of silicon).
  • the ultimate tensile strain value of the present invention is 1200 to 2300 microstrain ( ⁇ ), which includes the range of the maximum strain value of all the steel bars for construction, so theoretically it can be considered that the coating can be co-deformed with the steel bar, which means that it is normal. Under working conditions, the coating will not crack and can have excellent corrosion resistance.
  • the double-layer structure coating is sintered on the metal, so that the corrosion resistance of the metal is compared with that of the uncoated metal. Increase by 14 times or more.
  • the corrosion resistance of the existing metal anticorrosive coatings is generally no more than 10 times that of the uncoated metal, because the problem of affecting the metal anticorrosive coating is not substantially solved.
  • the invention solves the problem in essence, thereby greatly improving the corrosion resistance of the coating, and the corrosion resistance of the metal anticorrosive coating of the invention is 14 times higher than that of the uncoated metal. Can be used in harsher corrosive environments.
  • a second object of the present invention is to provide a metal anticorrosive coating and a method for preparing a metal article with a metal anticorrosive coating, comprising the steps of:
  • First grinding weigh enamel powder, thermal expansion regulator, flux, binder, the enamel powder content is 40-90 parts, preferably 60-75 parts; the thermal expansion regulator content is 5 ⁇ 40 parts, preferably 10 to 25 parts; flux content of 1 to 20 parts, preferably 5 to 12 parts; binder content of 0.5 to 12 parts, preferably 2 to 6 parts, said content being Weight meter. And ground into a powder.
  • step 3 second grinding: the mixture obtained in step 2) is dried and ground to a powder;
  • step 4) high temperature reaction: the mixture obtained in step 3) is reacted in a high temperature furnace at 520 to 720 ° C for 10 to 20 minutes;
  • the powder-coated base metal obtained in the step 6) is sintered at a high temperature to obtain a metal anticorrosive coating and a metal product with a metal anticorrosive coating.
  • the coating method of the step 6) may be an electrostatic spraying method, wherein the electrostatic voltage is 30 to 90 kV, the current is 20 to 80 microamperes, the powder output is 200 to 700 g per minute, and the spraying distance is 10 to 30 cm;
  • the sintering parameters of the step 7) are: a temperature of 500 to 620 ° C, a sintering time of 10 to 20 minutes, and a heating rate of 5 to 15 ° C per minute.
  • the base metal is selected from the group consisting of iron, steel, copper, copper alloy, aluminum, aluminum alloy, magnesium, and magnesium alloy.
  • the base metal oxide has a base metal content of 40 to 85 parts, and the balance is oxygen.
  • the enamel coating is composed of an added enamel powder, a thermal expansion regulator, a flux, and a binder, the enamel powder is 40 to 90 parts, and the thermal expansion regulator is 5 to 40 parts.
  • the content of the flux is 1 to 20 parts, and the content of the binder is 0.5 to 12 parts.
  • Corresponding element content 2 to 30 parts of silicon, 2 to 20 parts of sodium, 2 to 15 parts of potassium, 4 to 16 parts of calcium, 2 to 10 parts of fluorine, 0.5 to 7 parts of cobalt, 0.3 to 8 parts of nickel, and boron 2 ⁇ 10 parts, 0.8 to 6 parts of phosphorus, 0.2 to 5 parts of magnesium, and the rest is oxygen.
  • the content is by weight.
  • the enamel powder is composed of silicon oxide, sodium oxide, potassium oxide, boron oxide and phosphorus oxide added, the silicon oxide content is 3 to 39 parts, and the sodium oxide content is 3 to 28 parts.
  • the potassium oxide content is 1 to 25 parts
  • the boron oxide content is 0 to 15 parts
  • the phosphorus oxide content is 0.5 to 10 parts.
  • Corresponding element content 1 to 40 parts of silicon, 1 to 20 parts of sodium, 1 to 23 parts of potassium, 1 to 18 parts of calcium, 0 to 10 parts of boron, and 0.8 to 10 parts of phosphorus, and the content is by weight.
  • the enamel powder has a particle diameter of from 1,000 to 2,000 mesh, preferably from 1200 to 1800 mesh.
  • the silicon oxide is selected from one or more of silicon oxide, silicon dioxide, and silicon oxide.
  • the sodium oxide is selected from one or more of sodium oxide, sodium peroxide, and sodium hydroxide.
  • the potassium oxide is selected from one or more of potassium oxide, potassium carbonate, and potassium hydroxide.
  • the phosphorus oxide is one or more selected from the group consisting of phosphorus trioxide and phosphorus pentoxide.
  • the thermal expansion regulator is selected from one or more of sodium silicate, potassium silicate, calcium silicate, magnesium silicate, sodium tetraborate, potassium tetraborate, calcium borate, barium borate, lithium borate.
  • the fluxing agent is selected from one or more of sodium carbonate, potassium carbonate, magnesium carbonate, barium carbonate, lithium carbonate, calcium carbonate, barium carbonate, calcium fluoride, magnesium fluoride, and potassium fluoride.
  • the binder is selected from one or more of cobalt monoxide, cobalt oxychloride, nickel monoxide, and nickel oxynitride.
  • the thickness of the two-layer structure coating layer is not less than 40 ⁇ m; preferably, the thickness of the two-layer structure coating layer is not less than 50 ⁇ m.
  • the enamel coating has a thickness of 40 to 320 ⁇ m
  • the base oxide coating layer has a thickness of 10 to 50 ⁇ m.
  • a third object of the present invention is to provide a metal article comprising any of the metal anticorrosive coatings as described above.
  • the metal product is selected from the group consisting of iron products, steel products, steel products, copper products, and aluminum products.
  • the metal article may be in various shapes, for example, the shape of the iron article includes, but is not limited to, a plate shape, a stick shape, a rod shape, or the like.
  • a fourth object of the present invention is to provide the metal anticorrosive coating and the use of the metal product in anticorrosion, which can be applied to civil buildings, pipelines, underground pipe corridors, marine oil production platforms, saline-alkali foundation construction, and new energy generation. And so on.
  • the invention has the following beneficial effects:
  • the present invention not only focuses on optimizing the properties of the coating itself from the optimization of the material itself, but also optimizes performance by introducing a two-layer coating structure.
  • the invention not only makes the coating adapt to the thermal expansion coefficient of different metals from the perspective of the thermal expansion coefficient of the coating, but also makes the coating dense without through holes from the viewpoint of the coating structure, and the closed cell ratio is less than 5%.
  • the coating is changed in volume by mass change.
  • the corrosion resistance is 5 times of the CN105131660B patent, 2.5 times of the CN105238105B patent, 2 times of the CN105585883B patent, 1.5 times of the CN105670366B patent, 1.4 times of the CN105819691A patent, and 14 times of the ordinary bare steel. .
  • the coating of the invention has a double-layer thermal expansion coefficient gradient structure, and the thermal expansion coefficient increases as the metal oxide concentration decreases, thereby reducing the internal stress in the coating and making the coating tightly bonded to the base metal. It is not easy to crack, which can improve the corrosion resistance of the coating.
  • the coefficient of thermal expansion and various base metals can be coordinated with each other. For metals such as iron, steel, copper, copper alloy, aluminum, aluminum alloy, magnesium, magnesium alloy, etc., the base metal oxide penetrates into the coating. This serves to adjust the thermal expansion coefficient of the coating. This also means that the coating can be applied to a variety of metals and is universal.
  • the coating has a wide range of thermal expansion coefficients and can be applied to the same metal of different models and environments.
  • the problem that the enamel coating is sintered with through holes is solved, and the coating of the present invention has no through holes and the closed cell ratio is less than 5%.
  • the crack caused by the difference in thermal expansion coefficient is also solved.
  • the coating of the present invention requires a sintering temperature of between 500 and 620 °C. At this temperature range, the metal yield strength decreased by 2%, the ultimate strength decreased by 1.4%, and the elongation decreased by 3%.
  • the wear resistance of the present invention is good. In practical applications, metal inevitably encounters friction and touch of various objects, improves the wear resistance of the coating, and can ensure the integrity of the coating to a certain extent.
  • Figure 1a is a macroscopic picture of an electrostatically sprayed round steel
  • Figure 1b is a macroscopic picture of an electrostatically sprayed rebar.
  • Fig. 2 is a partial electron micrograph of the first embodiment (the scale is 250 ⁇ m).
  • Fig. 3 is a partial electron micrograph of the first embodiment (the scale is 100 ⁇ m).
  • Example 1 Preparation of a double layer thermal expansion coefficient gradient structure coating
  • First grinding weigh enamel powder, thermal expansion regulator, flux, binder, the enamel powder content is 40-90 parts, preferably 60-75 parts; the thermal expansion regulator content is 5 ⁇ 40 parts, preferably 10 to 25 parts; flux content of 1 to 20 parts, preferably 5 to 12 parts; binder content of 0.5 to 12 parts, preferably 2 to 6 parts, said content being Weight meter. And ground into a powder.
  • step 3 second grinding: the mixture obtained in step 2) is dried and ground to a powder;
  • step 4) high temperature reaction: the mixture obtained in step 3) is reacted in a high temperature furnace at 600 ° C for 15 minutes;
  • Coating powder obtained in the step 5) is applied to the base metal by electrostatic spraying, wherein the electrostatic voltage is 80 kV, the current is 20 microamps, and the powder output is 500 g per minute. The distance is 15 cm;
  • Example 1 The specific steps of Examples 1-8 and Comparative Examples 1-3 are as in Example 1, and the specific ratio (weight ratio) is shown in Table 1.
  • Example 1 According to the coating process of Example 1 and Comparative Example 1, the coating of the present invention was separately fabricated on a steel sheet, and each experimental group was repeated for 2 samples, for a total of 4 samples.
  • the contents of the elements of silicon, sodium, potassium, calcium, fluorine, cobalt, nickel, boron, phosphorus, magnesium and oxygen in Comparative Example 1 are not within the scope of the claims.
  • the abrasion resistance of the coating was tested in accordance with the falling sand scouring test method of ASTM D968-93, and the sand was used as the Chinese ISO standard sand. After the surface of the coating was flushed out of a 2 mm diameter area, the falling sand was stopped and the volume of falling sand consumed was recorded. The larger the falling sand volume, the better the wear resistance of the coating.
  • Example 1 Six experimental groups (Examples 1, 2, and 3, and Comparative Examples 1, 2, and 3) were selected, and three replicate samples were placed in each group, and three strain gauges were attached to each of the coated steel bars. At the beginning of the experiment, the steel bar was placed on a tensile test machine, and the strain was measured with the load. The strain gauge was connected to the strain gauge to measure the strain change on the coated steel bar.
  • the average strain values of the three sets of coated steel bars of Examples 1-3 with tensile cracking of the steel bars ranged from 1200 to 2300 microstrain, and the average of the coated steel bars of Comparative Examples 1, 2, and 3 was compared.
  • the strain values range from 650 to 850 microstrain. Therefore, the steel bar coated with the ductile coating for reinforcing steel for corrosion prevention of the present invention can be cooperatively stretched along with the reinforcing steel bars of the building, and if the specific material ratio and the specific preparation process parameters are not followed, the performance of the coating layer may not satisfy the demand.
  • Control group 1 is the coating data of group 2 in the accelerated corrosion test of steel bars in Table 1 of CN105670366B
  • control group 2 is the data of group 1 coating in the accelerated corrosion test of steel bars in CN105819691A patent
  • control group 3 is the patent of CN105585883B.
  • Table 1 the data of the coated steel bar in the accelerated corrosion test of the steel bar is coated.
  • the control group 4 is the coated data of the group 3 in the accelerated corrosion test of the steel plate in the CN105238105B patent, and the control group 5 is the steel plate accelerated in the CN105131660B patent.
  • the data for the fiber-free coating in the corrosion test, the control group 6 was the uncoated bare steel. It was placed in a 3.5% sodium chloride solution and subjected to an accelerated corrosion test after being energized.
  • the experimental group was coated metal plates (Examples 1, 6, 7, and 8), and the control group was uncoated steel plate, uncoated copper plate, uncoated aluminum plate, and Uncoated magnesium plate, the total number of test steel plates is 15. It was placed in a 3.5% sodium chloride solution and subjected to an accelerated corrosion test after being energized.
  • the coated metal sheet of the present invention is kept from corrosion for about 14 times of the uncoated metal sheet, and has excellent corrosion resistance for steel sheets, aluminum sheets, magnesium sheets, and copper sheets.
  • the thermal expansion coefficient of each of the eight examples and the three comparative examples was tested.
  • the base metals of Examples 1 to 5 and Comparative Examples 1, 2, and 3 were steel plates, and the base metal of Example 6 was a copper plate.
  • the base metal was an aluminum plate, and the base metal of Example 8 was a magnesium plate.
  • three sets of plates with different thermal expansion coefficients were taken, and a total of 33 test pieces were tested for coating thermal expansion coefficient.
  • the enamel coating is C1
  • the base oxide coating is C2
  • the enamel coating and the base oxide coating are collectively referred to as a two-layer structural coating of C1+C2.
  • the thermal expansion coefficients were determined for the enamel coating, the base oxide coating, and the double-layer structural coating, respectively.
  • the thermal expansion coefficient of the double-layer structure coating ranges from 10 ⁇ 10 -6 /°C to 16 ⁇ 10 -6 /°C; when the base metal is copper or copper alloy The thermal expansion coefficient of the two-layer structural coating ranges from 13 ⁇ 10 -6 /°C to 20 ⁇ 10 -6 /°C; when the base metal is aluminum or aluminum alloy, the thermal expansion coefficient of the double-layer structural coating The range is 20 ⁇ 10 -6 /°C ⁇ 26 ⁇ 10 -6 /°C; when the base metal is magnesium or magnesium alloy, the thermal expansion coefficient of the double-layer structural coating ranges from 23 ⁇ 10 -6 /°C to 29 ⁇ 10 -6 /°C.
  • a metal coating of a particular two-layer structure of the present invention is produced in which a matrix metal oxide having a reduced concentration gradient is present from the inner layer to the outer layer.
  • Fig. 1a is a macroscopic picture of an electrostatically sprayed round steel using the raw material formulation of Example 1. It can be seen from both macroscopic and microscopic that the coating is very shiny. This enamel gloss indicates that the coating has a high density, there is no crack on the coating due to the low coefficient of thermal expansion, and there is no coefficient of thermal expansion. Large peeling, which means that the coating agrees well with the thermal expansion coefficient of the base metal. This dense structure also means that the coating has good corrosion resistance.
  • the detection method of the energy spectrometer is as follows: the EDS test is carried out by using an energy spectrometer. First, the surface of the sample is polished and polished, and a gold film is sprayed on the surface to make it conductive and paste the conductive tape to adjust the acceleration voltage value of 10 to 40 kV. The dead time is 15 ⁇ 45%, the measurement time is set to 50 ⁇ 400s, the sample is placed in the sample cavity, the parameters are set and then hollowed out to make the focus clear, select the area where element analysis is needed and maintain the position, use point scan, surface scan, Line scan for elemental analysis.
  • the silicon content is 7%, the sodium content is 12%, the potassium content is 7%, the calcium content is 8%, the fluorine content is 5%, the cobalt content is 2%, the nickel content is 2%, the boron content is 5%, and phosphorus is obtained.
  • the content is 2%, the magnesium content is 1%, and the oxygen content is 49%.
  • Figure 1b is a macroscopic view of an electrostatically sprayed rebar using the raw material formulation of Example 1. It can also be seen that the coating has a dense structure and has an enamel finish. It can be seen that there is no cracking at the interface between the convex surface and the plane, indicating that the coating does not crack during the high-temperature sintering process, and further demonstrates that the double-layer coating of the thermal expansion coefficient gradient of the present invention can cooperate with the base metal at a high temperature. Deformation.
  • Embodiment 2 is an electron micrograph of Embodiment 1, which is similar to Embodiments 2 and 3, and is represented by Embodiment 1. It can be seen that the thickness of the coating is about 200 ⁇ m, the density is very high, there is no through hole, and only a small number of closed cells, wherein the area of the closed cells is calculated, and the closed cell ratio is 4.3%. The presence of a small amount of closed cells allows the coating to have some ductility.
  • the coating has two parts, which are composed of an enamel coating (C1) and a base oxide coating (C2). The thickness of C1 is about 180 ⁇ m, and the thickness of C2 is about 20 ⁇ m. C1, C2 and steel form a sandwich structure.
  • C2 Due to the sintering in an oxidizing atmosphere, there is the presence of C2, in which not only iron oxides but also Fe-Co, Fe-Ni mixed crystals are present, so that the coating can be more closely bonded to the steel bars. And the thickness of C2 is controllable, and its thickness will become larger as the sintering temperature increases. At the same time, due to the presence of the outer coating C1, the contact between the external oxygen and the C2 layer is suppressed, so the thickness of the coating is controlled. About 20 ⁇ m. In addition, the presence of the C2 transition layer can both increase the adhesion and effectively improve the corrosion resistance of the coating.
  • Fig. 3 is a partial enlarged view of Fig. 2; It can be clearly seen in Figure 3 that the coating near the steel portion is significantly different from the coating away from the steel.
  • the area of white spots in the coating closer to the steel bar is getting larger and larger, and EDS elemental analysis tests show that the white spots are iron oxide components.
  • the iron content of the entire coating (C1+C2) changes from the inside to the outside in a gradient, so the iron oxide also changes from the inside to the outside in a gradient. This change also causes a gradient change in the thermal expansion coefficient of the coating. As the iron oxide decreases, the thermal expansion coefficient of the coating gradually increases.
  • the double-layer thermal expansion coefficient gradient structure of the sandwich structure has a strong adhesion between the coating and the steel bar and a corrosion resistance of 14 times that of the ordinary bare steel.

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Abstract

一种金属防腐涂层，其具有双层结构，包括外层的搪瓷涂层和内层的基体氧化物涂层，其中，基体氧化物涂层的金属氧化物含量由内层向外层递减。外层的搪瓷涂层的成分按重量计包括硅1～40份，钠1～30份，钾1～20份，钙2～20份，氟0.5～15份，钴0.3～10份，镍0.2～10份，硼1～18份，磷0.5～10份，镁0.1～8份，其余为氧；内层的基体氧化物涂层的成分包括基体金属和氧。

Description

一种金属防腐涂层、其制备方法和用途 技术领域
本发明属于金属防腐材料领域，尤其涉及一种金属防腐涂层、其制备方法和用途。
背景技术
进入21世纪，中国已经迈入沿海经济大发展的时代，将会有大批海港码头、跨海桥梁、隧道等会使用钢筋混凝土结构。其中，钢筋被锈蚀的问题是影响钢筋混凝土耐久性的一项主要因素。不仅在海边，在盐碱地区的电线杆、潮湿环境下的管桩、桥墩等钢混结构也都会遭受到锈蚀的影响。因此，对恶劣环境中(如酸雨、海洋环境、除冰盐、高低温环境、潮湿环境等)的钢筋混凝土建筑结构，必须采取有效的防腐措施，以保证建筑达到设计使用的寿命。
无机涂层包括磷酸盐涂层、硅酸盐涂层、搪瓷涂层等。其中搪瓷涂层在制作过程中必然要经过烧结的过程，而烧结会产生两个先天缺点：1)涂层与基体金属热膨胀系数无法实现协调一致，使得涂层与基体金属的变形不一致，进而造成涂层产生裂缝；2)烧结中水汽蒸发造成的通孔。所述的基体金属的指需要防腐的金属，例如，钢筋、铝板、铜板等。所述的协调一致是指涂层的热膨胀系数等于或适当大于基体金属的热膨胀系数，随基体金属热膨胀系数的变化而变化，才能确保涂层在高温下不产生裂缝，提高涂层的耐腐蚀性能。
现有技术中，有的技术仅针对热膨胀系数问题，有的技术仅针对通孔问题，但是，到目前为止热膨胀问题和通孔问题都还没有很好地解决，更没有能够同时解决这两个问题的技术方案被报道。此外，金属防腐涂层的普适性问题也未见相关研究报道，所述的普适性问题是指如何使得一种金属防腐涂层能够适应不同种类或不同型号的金属的热膨胀系数。众所周知，不同金属的热膨胀系数差别很大，例如镁的热膨胀系数是24×10 -6/℃，而铁的热膨胀系仅有12×10 -6/℃，现有技术的金属防腐涂层无法适用于热膨胀系数差别较大的各种金属。
中国专利CN106116438A公开了一种磷酸镁基钢筋防护涂层材料及其制备方法，此涂层是以酸碱中和反应为基础形成化学键而产生强度的胶凝材料。但是成本高昂并且耐腐蚀的性能也并不优越。中国专利CN105131660B公开了一种钢筋防腐涂料及其涂覆方法,其中通过引入纤维使得防腐涂层在断裂过程中吸收能量从而达成延缓开裂的目的。中国专利CN105238105B公开了一种用于钢筋防腐的韧性涂料及其涂覆方法，其中通过加入长石粉，粘土，氟石等原料使得涂层有突出的抗腐蚀能力，极高的韧性以及较高的耐久性。中国专利CN105819691A公开了一种用于钢筋防腐的小孔径无机涂层及其涂覆方法，这使得防腐涂层的内部孔径减小从而提升防腐性能。中国专利CN105585883B公开了一种用于钢筋防腐的低温烧结涂料及其涂覆方法，这使得涂层在400-550度的温度中可以烧结。中国专利CN 105670366公开了一种用于钢筋防腐的低通孔率涂层及其涂覆方法，这使得涂层的通孔率得到降低，从而起到提升防腐性能的作用。2014年阳东方在其硕士论文《钢筋表面防腐蚀与增强钢筋/水泥结合力的玻璃涂层研究》中提及了一种耐腐蚀的玻璃涂层，其具有良好 的耐腐蚀性以及与混凝土的粘结力。但是以上的专利主要关注涂层配方的改进，并没有对涂层的结构进行优化改进，而涂层结构对材料的耐腐蚀性能起着决定性作用，因此，上述专利中对于耐腐蚀性能没有革命性的提升。
美国专利US7901769B2和US8679389B2公开了一种用于钢筋瓷釉的防腐玻璃涂层，其热膨胀系数范围为12.5×10 -6/℃～13.5×10 -6/℃(12.5ppm/℃～13.5ppm/℃)，但是这种涂层的热膨胀系数跨度范围过小，其跨度范围仅为1.0×10 -6/℃，不能从根本上解决钢筋和涂层的热膨胀系数的差异对涂层耐腐蚀性能不利影响的问题。市场上的钢筋因为制造工艺、批次、烧结温度的不同，而使得钢筋的热膨胀系数会在11.5×10 -6/℃～14.5×10 -6/℃之间变化，以上的涂层的热膨胀系数范围过小，不能适用于热膨胀系数大于13.5×10 -6/℃的钢筋，因此不具有普适性，不能适用于不同型号的钢筋。如果涂层的热膨胀系数小于钢筋的热膨胀系数，那么在烧结的过程中涂层会发生和钢筋不协调的变形(钢筋的变形大于涂层的变形)，进而在涂层上就会产生小裂缝。众所周知，对于防腐涂层而言，涂层上的任何小裂缝都会造成耐腐蚀性能的下降，甚至会加速腐蚀的进行，所以涂层的热膨胀系数一定不能小于基体金属的热膨胀系数，否则就会导致涂层上产生裂缝；同时涂层的热膨胀系数也不能比基体金属的热膨胀系数大很多，这是因为当涂层的热膨胀系数过大时，涂层内会产生较大的面内压应力，从而导致涂层翘曲失稳从而剥落。涂层的剥落也必然会导致涂层的耐腐蚀能力极速下降。以上述美国的为例具体说明，当使用的基体钢筋的热膨胀系数在11.5×10 -6/℃～12.5×10 -6/℃以及13.5×10 -6/℃～14.5×10 -6/℃的范围时，此时美国专利中的涂层的热膨胀系数仅在12.5×10 -6/℃～13.5×10 -6/℃，所以涂层没有与钢筋达到协调一致，从而会发生涂层开裂的不良后果。
因此，涂层的热膨胀系数与基体金属的热膨胀系数需要达到协调一致，也就是涂层的热膨胀系数等于或适当大于基体金属的热膨胀系数，随基体金属热膨胀系数的变化而变化，才能确保涂层在高温下不产生任何小裂缝，提高涂层的耐腐蚀性能。
综上所述，现有技术对于金属防腐涂层有两个问题尚未解决：第一个问题是不同的金属热膨胀系数的差别很大，如镁的热膨胀系数是24×10 -6/℃，而铁的热膨胀系仅有12×10 -6/℃。这导致同一种金属防腐涂层的热膨胀系数无法实现与镁和铁的协调一致，也就无法通过同一种金属防腐涂层来适应不同基体金属的防腐，也就是现有技术的涂层不具有普适性。第二个问题是同一种金属因为生产制造工艺等原因使得自身热膨胀系数也会有一些差异，比如钢筋的热膨胀系数范围会在11.5×10 -6/℃～14.5×10 -6/℃之间变化，以美国专利US7901769B2和US8679389B2为例，涂层热膨胀系数范围仅为12.5×10 -6/℃～13.5×10 -6/℃，涂层的热膨胀系数跨度范围太小无法包括钢筋的热膨胀系数范围，从而无法适用于所有的钢筋。因此，现有技术无法提供具有普适性、能够适用于各种不同的金属以及金属的不同型号、不同环境下的金属防腐涂层。
发明内容
为了克服现有技术的缺点与不足，本发明所要解决的技术问题是提供一种具有优良耐腐蚀性能的具有双层结构的金属防腐涂层，所述的涂层热膨胀系数范围较大，并且热膨胀系数会根据基体金属的变化而变化，具有普适性、能够适用于各种不同的金属以及金属的不同型号。进一步地，本发明制得的金属防腐涂层可以是致密结构，所述的致密结构为无通孔、闭孔率低于5％的结构，使得涂层的耐腐蚀性能进一步提高，涂层中的少许闭孔会使得涂层拥有一定的延展变形能力。现有的金属防腐涂层的耐腐蚀能力相比与没有涂层的金属的耐腐蚀能力一般不超过10倍，其原因是没有从本质上解决影响金属防腐涂层的问题。本发明从本质上解决了该问题，从而大幅度提高了涂层的耐腐蚀能力，本发明的金属防腐涂层的耐腐蚀能力相比与没有涂层的金属的耐腐蚀能力提高14倍以上，可以用于更严苛的腐蚀环境。
本发明是通过以下技术方案实现的：
一种金属防腐涂层，所述金属防腐涂层为双层结构涂层，由搪瓷涂层与基体氧化物涂层构成；
所述双层结构中，搪瓷涂层是外层，基体氧化物涂层是内层，所述搪瓷涂层的成分按重量计包括硅1～40份，钠1～30份，钾1～20份，钙2～20份，氟0.5～15份，钴0.3～10份，镍0.2～10份，硼1～18份，磷0.5～10份，镁0.1～8份，其余为氧，所述的基体氧化物涂层的成分包括基体金属和氧；
所述双层结构涂层中由内层向外层存在浓度梯度减小的基体金属氧化物。
所述的基体金属是指需要防腐的金属，例如，钢筋、铝板、铜板等，所述的基体氧化物涂层靠近所述的基体金属(参见图2)。
进一步地，所述双层结构涂层的热膨胀系数与所述基体金属的热膨胀系数协调一致。
所述的协调一致是指所述双层结构涂层的热膨胀系数等于或适当大于所述基体金属的热膨胀系数，随基体金属热膨胀系数的变化而变化，以确保涂层在高温下不产生裂缝，提高涂层的耐腐蚀性能。
众所周知，当涂层的热膨胀系数小于基体金属的热膨胀系数时，涂层上会产生小裂缝，从而导致涂层的耐腐蚀性能急速下降；当涂层的热膨胀系数过大时，又会在涂层中产生面内压应力导致涂层翘曲失稳剥落，也会降低涂层的耐腐蚀性能。所以本发明中的涂层在热膨胀系数上有两个优点：一是本发明中的涂层热膨胀系数的跨度范围大，例如基体金属为铁或钢时，涂层的热膨胀系数的范围为10×10 -6/℃～16×10 -6/℃，铁或钢的热膨胀系数范围为11.5×10 -6/℃～14.5×10 -6/℃，本发明涂层的范围可以包含所有的铁或钢的种类，即使某批钢筋热膨胀系数有所偏差，也能够很好的适应。二是本发明中的涂层的热膨胀系数会随着基体金属的变化而变化，以适应基体金属的热膨胀系数。当基体金属为铁、铜、镁、铝时，双层涂层中的基体氧化物涂层因为含有基体金属氧化物，所以使得整体涂层的热膨胀系数可以随着基体金属的变化而变化，以适应不同的金属。
所述双层结构涂层因为基体金属氧化物浓度从基体氧化物涂层向搪瓷涂层梯度减小的变化，使得所述双层结构涂层具有热膨胀系数从基体氧化物涂层向搪瓷涂层梯度增大的变化。此外，热膨胀系数梯度涂层可以有效促进金属元素的迁移，是基体金属元素与氧元素反应，形成相应的基体金属氧化物，从而形成基体氧化物涂层。这样可以保证双层结构涂层与基体金属的粘结性能，也可以使得双层结构涂层的热膨胀系数会随着基体金属的变化而变化。双层结构涂层的特定元素组成(1～40份硅元素、1～30份钠、1～20份钾、2～20份钙、0.5～15份氟、1～18份硼元素、0.3～10份钴、0.2～10份镍、0.5～10份磷、0.1～8份镁元素、其余的氧元素)首先是形成整个涂层的骨架和基础，同时可以调节双层结构涂层的热膨胀系数，使热膨胀系数的范围跨度可以保证在6×10 -6/℃左右(如基体金属为铁时，涂层的热膨胀系数的范围为10×10 -6/℃～16×10 -6/℃，此时涂层的热膨胀系数范围跨度为6×10 -6/℃；基体金属为铜时，涂层的热膨胀系数的范围为13×10 -6/℃～20×10 -6/℃，涂层的热膨胀系数范围跨度为7×10 -6/℃)。进一步的按上述份数的硅、钠、钾、钙、氟、硼、钴、镍、磷、镁、氧元素也可以有效降低反应体系的熔点，提高物质扩散速度，促进多种原料界面之间的接触与反应。并且这些元素可以与基体氧化物涂层中的基体金属氧化物反应，形成氧化物，这些氧化物的化学键都很强，这就有效促进金属元素的迁移，从而可以使得搪瓷涂层与基体氧化物涂层的粘结强度增加。同时因为搪瓷涂层以及基体氧化物涂层的存在，使得双层结构涂层的热膨胀系数会随着基体金属的变化而相应变化。同时由于以上的元素消耗了部分氧元素，这也导致了整体涂层的基体金属氧化物的浓度会呈现从基体氧化物涂层向搪瓷涂层梯度减少的结果，也就导致了涂层的热膨胀系数会从基体氧化物涂层向搪瓷涂层梯度增大的结果，从而解决了金属防腐涂层的普适性问题。
进一步地，所述的双层结构涂层为致密结构。所述的致密结构为无通孔，闭孔率低于5％的结构。无通孔是指没有从搪瓷涂层表面到基体金属表面的贯通孔，闭孔率低于5％是指闭孔(非贯通孔)的横截面积与涂层总横截面积的比例不大于5％。众所周知，在搪瓷涂层的制备过程中，烧结是必需的步骤。而在烧结过程中，因为水分蒸发，金属制品中的杂质高温反应生成气体等因素的影响，会导致涂层中极易出现通孔。本发明的双层结构涂层因为按特定比例加入硅、钠、钾、钙、氟、钴、镍、硼、磷、镁、氧元素(按重量计，硅1～40份，钠1～30份，钾1～20份，钙2～20份，氟0.5～15份，钴0.3～10份，镍0.2～10份，硼1～18份，磷0.5～10份，镁0.1～8份，其余为氧)，使涂层具有双层热膨胀系数梯度结构，所以不会出现通孔，也同时使得涂层的闭孔率低于5％。无通孔和低闭孔率这两点可以使得涂层结构的耐腐蚀性能进一步提高，涂层中的少许闭孔会使得涂层拥有一定的延展变形能力。
进一步地，所述的基体氧化物涂层中的基体金属的含量为40～85份，其余为氧。
进一步地，所述搪瓷涂层的成分包括硅2～30份，优选为3～15份；钠2～20份，优选为7～16份；钾2～15份，优选为3～10份；钙4～16份，优选为5～11份；氟2～10份， 优选为3～7份；钴0.5～7份，优选为1～4份；镍0.3～8份，优选为0.5～4份；硼2～10份，优选为2.5～8份；磷0.8～6份，优选为1～4份；镁0.2～5份，优选为0.5～2份；其余为氧。
所述的基体金属选自铁、钢、铜、铜合金、铝、铝合金、镁、镁合金；当基体金属为铁或钢时，所述双层结构涂层的热膨胀系数的范围为10×10 -6/℃～16×10 -6/℃；当基体金属为铜或铜合金时，所述双层结构涂层的热膨胀系数范围为13×10 -6/℃～20×10 -6/℃；当基体金属为铝或铝合金时，所述双层结构涂层的热膨胀系数范围为20×10 -6/℃～26×10 -6/℃；当基体金属为镁或镁合金时，所述双层结构涂层的热膨胀系数范围为23×10 -6/℃～29×10 -6/℃。
进一步地，所述硅、钠、钾、钙、氟、钴、镍、硼、磷、镁、氧元素采用能谱仪(EDS)来测定，具体方法为：EDS测试采用能谱仪进行测试，首先将样品表面磨平抛光，并在表面喷镀金膜使其导电并粘贴导电胶带，调节加速电压值10～40kV，死时间为15～45％，测量时间定为50～400s，将样品放入样品腔中，设置参数后抽真空使得聚焦清晰，选择需要元素分析的区域并维持位置，使用点扫描、面扫描、线扫描进行元素分析。
进一步地，所述搪瓷涂层成分的来源选自瓷釉粉末、热膨胀调节剂、助熔剂、粘合剂，所述瓷釉粉末的含量为40～90份，优选为60～75份；热膨胀调节剂的含量为5～40份，优选为10～25份；助熔剂的含量为1～20份，优选为5～12份；粘合剂的含量为0.5～12份，优选为2～6份，所述的含量以重量计。
所述搪瓷涂层中，40～90份瓷釉粉末是整个搪瓷涂层的基础，热膨胀调节剂，粘合剂和助熔剂的加入使得搪瓷涂层在烧结过程中可以与基体氧化物涂层粘结紧密，形成双层热膨胀系数梯度结构，并且涂层整体结构致密。进一步的，5～40份热膨胀调节剂、1～20份助熔剂、0.5～12份粘合剂的加入可以有效调控瓷釉粉末，粘结剂以及助熔剂的热膨胀系数，从而使搪瓷涂层从内到外具有热膨胀系数梯度，以达到协同均匀膨胀和收缩的目的，从而有效避免搪瓷涂层升温和降温过程中由于应力不均导致膨胀或收缩开裂以及脱落。正是由于热膨胀系数从内到外梯度的变化，也就使得涂层不会因为内外部应力不均匀而造成膨胀或收缩开裂。同时热膨胀调节剂的加入使得双层结构涂层的热膨胀系数的范围跨度可以保证在6×10 -6/℃左右(如基体金属为铁时，涂层的热膨胀系数为10×10 -6/℃～16×10 -6/℃，此时涂层的热膨胀系数范围跨度为6×10 -6/℃；基体金属为铜时，涂层的热膨胀系数为13×10 -6/℃～20×10 -6/℃，涂层的热膨胀系数范围跨度为7×10 -6/℃)。同时，5～40份热膨胀调节剂、1～20份助熔剂、0.5～12份粘合剂的加入可以有效降低反应体系的熔点，提高物质扩散速度，促进多种原料界面之间的接触与反应，使得搪瓷涂层的烧结温度降低并且与基体氧化层的粘结力增加。进一步的，可以使得搪瓷涂层与基体氧化物涂层在烧结过程中发生反应，形成较强的化学键，这就有效促进金属元素的迁移，从而使得搪瓷涂层与基体氧化物涂层的粘结紧密并且基体氧化物涂层与基体金属的粘结紧密。本发明的瓷釉粉末、热膨胀调节剂、助熔剂、粘合剂作为一个整体的协同作用使得生成搪瓷涂层以及基体氧化物涂层，这两层的存在使得 双层结构涂层的热膨胀系数会随着基体金属的变化而相应变化。同时由于粘合剂会消耗了部分基体金属氧化物，这也导致了整体涂层的基体金属氧化物的浓度会呈现从基体氧化物涂层向搪瓷涂层梯度减少的结果，也就导致了涂层的热膨胀系数会从基体氧化物涂层向搪瓷涂层梯度增大的结果。从而解决了涂层的普适性问题。
进一步地，所述瓷釉粉末的元素含量为：硅1～40份，优选为2～15份；钠1～20份，优选为3～12份；钾1～23份，优选为4～13份；钙1～18份，优选为3～11份；硼0～10份，优选为0～5份；磷0.8～10份，优选为1～5份；优选的，所述瓷釉粉末的粒径为1000～2000目，优选目数为1200～1800目。这种瓷釉粉末中不含汞、铅等有毒物质，并且熔点较低，可以大大降低涂层的烧结温度，从而减少金属因高温而造成的性能下降。
进一步地，所述瓷釉粉末中，硅氧化物含量占3～39份，钠氧化物含量占3～28份，钾氧化物含量占1～25份，氧化硼含量占0～15份，磷氧化物含量占0.5～10份，所述的含量以重量计。
进一步地，所述的硅氧化物选自氧化硅、二氧化硅、过氧化硅的一种或多种。
进一步地，所述的钠氧化物选自氧化钠，过氧化钠，氢氧化钠的一种或多种。
进一步地，所述的钾氧化物选自氧化钾、碳酸钾、氢氧化钾的一种或多种。
进一步地，所述的磷氧化物选自三氧化二磷、五氧化二磷的一种或多种。
进一步地，所述热膨胀调节剂选自硅酸钠、硅酸钾、硅酸钙、硅酸镁、四硼酸钠、四硼酸钾、硼酸钙、硼酸钡、硼酸锂中的一种或几种。
进一步地，所述助熔剂选自碳酸钠、碳酸钾、碳酸镁、碳酸锶、碳酸锂、碳酸钙、碳酸钡、氟化钙、氟化镁、氟化钾中的一种或几种。
进一步地，所述粘合剂选自一氧化钴、三氧化二钴、一氧化镍、三氧化二镍中的一种或几种。
进一步地，所述双层结构涂层的厚度不小于40μm；优选的，所述双层结构涂层的厚度不小于50μm。
进一步地，所述搪瓷涂层的厚度为40～320μm，基体氧化物涂层的厚度为10～50μm。如果厚度小于40μm，那么涂层的耐腐蚀能力会有明显的削弱。如果厚度超过400μm，那么涂层的内应力会过大导致涂层内部裂缝的生成，也会降低涂层的耐腐蚀能力。
进一步地，当所述双层结构涂层应用于钢筋防腐时，所述的基体金属为钢，所述双层结构涂层的热膨胀系数的范围为10×10 -6/℃～16×10 -6/℃，所述双层结构涂层的极限拉应变(ultimate tensile strain)为1200～2300微应变(με)，优选为1400～2200微应变(με)。这是因为本发明的双层结构涂层是由特定比例的硅、钠、钾、钙、氟、钴、镍、硼、磷、镁、氧元素组成的(按重量计，硅1～40份，钠1～30份，钾1～20份，钙2～20份，氟0.5～15份，钴0.3～10份，镍0.2～10份，硼1～18份，磷0.5～10份，镁0.1～8份，其余为氧)，这些元素在烧结过程中会形成双层结构涂层，正是因为双层的结构，能够扩大了极限拉应变 的范围，并且适应于钢筋。同时涂层中存在的少量闭孔(闭孔率低于5％)也能够使得涂层具有更好的延展性能，同时也就提升了涂层的极限拉应变。从中国专利CN105238105B中可以得知，建筑钢筋设计时规定的最大应变值范围是：1286-2175微应变(με)，其中HPB300级钢筋的最大应变值最小，HRB500级钢筋最大。众所周知建筑设计强度值往往会比建筑实际使用时的强度值有所提高，即所谓的设计富余值，所以建筑钢筋实际使用时的应变值往往不会达到设计的最大值。而本发明的极限拉应变值为1200～2300微应变(με)，包括了所有建筑用钢筋的最大应变值的范围，所以理论上可以认为涂层能够与钢筋协同变形，也就意味着在正常工作状态下，涂层都不会开裂，能够拥有极优的耐腐蚀能力。
进一步地，当所述双层结构涂层应用于金属防腐时，所述双层结构涂层烧结在金属上之后，使得所述金属的耐腐蚀能力相比与没有涂层的金属的耐腐蚀能力提高14倍以上。现有的金属防腐涂层的耐腐蚀能力相比与没有涂层的金属的耐腐蚀能力一般不超过10倍，其原因是没有从本质上解决影响金属防腐涂层的问题。本发明从本质上解决了该问题，从而大幅度提高了涂层的耐腐蚀能力，本发明的金属防腐涂层的耐腐蚀能力相比与没有涂层的金属的耐腐蚀能力提高14倍以上，可以用于更严苛的腐蚀环境。
本发明的第二个目的是提供一种金属防腐涂层和带有金属防腐涂层的金属制品的制备方法，包括如下步骤：
1)第一次研磨：称量瓷釉粉末、热膨胀调节剂、助熔剂、粘合剂，所述瓷釉粉末的含量为40～90份，优选为60～75份；热膨胀调节剂的含量为5～40份，优选为10～25份；助熔剂的含量为1～20份，优选为5～12份；粘合剂的含量为0.5～12份，优选为2～6份，所述的含量以重量计。并研磨成粉末。
2)制备混料：将上述4种原料与水混合搅拌得到混料；
3)第二次研磨：将步骤2)得到的混料干燥后研磨成粉末；
4)高温反应：将步骤3)得到的混料在520～720℃的高温炉中反应10～20分钟；
5)第三次研磨：将高温反应后的混料研磨，得到涂层粉末；
6)涂覆：将步骤5)得到的涂层粉末涂覆在基体金属上；
7)烧结：将步骤6)得到的涂覆有粉末的基体金属高温烧结，得到金属防腐涂层和带有金属防腐涂层的金属制品。
进一步地，步骤6)的涂覆方法可以采用静电喷涂方法，其中静电电压为30～90千伏，电流为20～80微安，出粉量为200～700克每分钟，喷涂距离为10～30厘米；
进一步地，步骤7)的烧结参数为：温度为500～620℃，烧结时间为10～20分钟，升温速率为每分钟5～15℃。
进一步地，所述的基体金属选自铁、钢、铜、铜合金、铝、铝合金、镁、镁合金。
进一步地，所述基体氧化物涂层中的基体金属的含量为40～85份，其余为氧。
进一步地，所述的搪瓷涂层是由加入的瓷釉粉末、热膨胀调节剂、助熔剂、粘合剂组成，所述瓷釉粉末的含量为40～90份，热膨胀调节剂的含量为5～40份，助熔剂的含量为1～20份，粘合剂的含量为0.5～12份。对应的元素含量：硅为2～30份，钠2～20份，钾2～15份，钙4～16份，氟2～10份，钴0.5～7份，镍0.3～8份，硼2～10份，磷0.8～6份，镁0.2～5份，其余为氧。所述含量以重量计。
进一步地，所述的瓷釉粉末是由加入的硅氧化物，钠氧化物，钾氧化物，氧化硼，磷氧化物组成，硅氧化物含量占3～39份，钠氧化物含量占3～28份，钾氧化物含量占1～25份，氧化硼含量占0～15份，磷氧化物含量占0.5～10份。对应的元素含量：硅1～40份，钠1～20份，钾1～23份，钙1～18份，硼0～10份，磷0.8～10份，所述的含量以重量计。优选的，所述瓷釉粉末的粒径为1000～2000目，优选目数为1200～1800目。
进一步地，所述的硅氧化物选自氧化硅、二氧化硅、过氧化硅的一种或多种。
进一步地，所述的钠氧化物选自氧化钠、过氧化钠、氢氧化钠的一种或多种。
进一步地，所述的钾氧化物选自氧化钾、碳酸钾、氢氧化钾的一种或多种。
进一步地，所述的磷氧化物选自三氧化二磷、五氧化二磷的一种或多种。
进一步地，所述热膨胀调节剂选自硅酸钠、硅酸钾、硅酸钙、硅酸镁、四硼酸钠、四硼酸钾、硼酸钙、硼酸钡、硼酸锂中的一种或几种。
进一步地，所述助熔剂选自碳酸钠、碳酸钾、碳酸镁、碳酸锶、碳酸锂、碳酸钙、碳酸钡、氟化钙、氟化镁、氟化钾中的一种或几种。
进一步地，所述粘合剂选自一氧化钴、三氧化二钴、一氧化镍、三氧化二镍中的一种或几种。
进一步地，所述双层结构涂层的厚度不小于40μm；优选的，所述双层结构涂层的厚度不小于50μm。
进一步地，所述搪瓷涂层的厚度为40～320μm，基体氧化物涂层的厚度为10～50μm。
本发明的第三个目的是提供一种金属制品，所述的金属制品包括如前所述任意一种金属防腐涂层。
进一步地，所述的金属制品选自铁制品、钢制品、钢制品、铜制品、铝制品。所述的金属制品可以是各种形状，例如铁制品的形状包括但不限于板状、棍状、棒状等。
本发明的第四个目的是提供所述的金属防腐涂层、所述的金属制品在防腐中的用途，可应用于民用建筑、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：
本发明不仅关注于从材料本身的优化来提升涂层性能，同时通过引入双层涂层结构来优化性能。本发明不仅从涂层热膨胀系数角度来使得涂层能够适应不同金属的热膨胀系数，同时也从涂层结构的角度来使得涂层致密无通孔，闭孔率低于5％，这两个方面使涂层由量变产生质变，耐腐蚀性能是CN105131660B专利的5倍，CN105238105B专利的2.5倍， CN105585883B专利的2倍，CN105670366B专利的1.5倍，CN105819691A专利的1.4倍，同时是普通裸钢的14倍。耐腐蚀性能极其优越2)本发明涂层具有双层热膨胀系数梯度结构，热膨胀系数随着金属氧化物浓度的降低而增高，从而可以减少涂层中的内应力，使得涂层与基体金属结合紧密，不易开裂，从而能够提升涂层的耐腐蚀性能。3)本发明中，热膨胀系数与各种基体金属都能够相互协调，对于铁、钢、铜、铜合金、铝、铝合金、镁、镁合金等金属，都会因为基体金属氧化物渗入到涂层当中从而起到调整涂层热膨胀系数的功能。这也就意味着所述涂层可以适用于多种金属，具有普适性。4)本发明中，对于同一种金属，涂层的热膨胀系数范围跨度大，可以适用于不同型号与不同环境下的同一金属。5)本发明中，解决了搪瓷涂层烧结会有通孔的问题，本发明的涂层无通孔且闭孔率低于5％。同时也解决了由于热膨胀系数差异造成的裂缝。之前没有专利同时解决这两方面问题。6)本发明的涂层所需烧结温度在500-620℃之间。此温度范围下烧结金属，金属的屈服强度下降2％，极限强度下降1.4％，延伸率下降3％。7)本发明的耐磨性好。在实际应用中金属难免遇到各种物体的摩擦和触碰，提高涂层的耐磨性能，可以一定程度上保证涂层的完整性。
附图说明
图1a是静电喷涂圆钢的宏观图片，图1b是静电喷涂螺纹钢的宏观图片。
图2是实施例1的局部电镜图片(标尺为250μm)。
图3是实施例1的局部电镜图片(标尺为100μm)。
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：制备双层热膨胀系数梯度结构涂层
1)第一次研磨：称量瓷釉粉末、热膨胀调节剂、助熔剂、粘合剂，所述瓷釉粉末的含量为40～90份，优选为60～75份；热膨胀调节剂的含量为5～40份，优选为10～25份；助熔剂的含量为1～20份，优选为5～12份；粘合剂的含量为0.5～12份，优选为2～6份，所述的含量以重量计。并研磨成粉末。
2)制备混料：将上述4种原料与水混合搅拌得到混料；
3)第二次研磨：将步骤2)得到的混料干燥后研磨成粉末；
4)高温反应：将步骤3)得到的混料在600℃的高温炉中反应15分钟；
5)第三次研磨：将高温反应后的混料研磨，得到涂层粉末；
6)涂覆：将步骤5)得到的涂层粉末通过静电喷涂的方式涂覆在基体金属上，其中静电电压为80千伏，电流为20微安，出粉量为500克每分钟，喷涂距离为15厘米；
7)烧结：将步骤6)得到的涂覆有涂层粉末的基体金属在530℃下进行烧结，烧结时间为15分钟，升温速率为每分钟7.5℃，结束后自然降温至室温，得到金属防腐涂层和带有金属防腐涂层的金属制品。
实施例1-8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1-8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 PCTCN2019086505-appb-000001
Figure PCTCN2019086505-appb-000002
Figure PCTCN2019086505-appb-000003
表2 实施例1-8和对比实施例1-3中瓷釉粉末的成分配比(质量比)
Figure PCTCN2019086505-appb-000004
Figure PCTCN2019086505-appb-000005
表3 实施例1-8和对比实施例1-3中搪瓷涂层的元素含量(质量比)
Figure PCTCN2019086505-appb-000006
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，进行了以下试验。
1)耐磨性实验
按照实施例1与对比实施例1的涂层工艺，分别在钢板上制作本发明涂层，每个实验组2个重复试样，总共4个试样。其中对比实施例1中的硅、钠、钾、钙、氟、钴、镍、硼、磷、镁、氧元素的含量均不在权利要求书的范围内。参照ASTM D968-93的落砂冲刷试验法测试涂层的耐磨性，使用砂为中国ISO标准砂。当涂层表面冲刷出一个直径为2mm的区域后，停止落砂，并记录所消耗的落砂体积。落砂体积越大，涂层的耐磨性越好。
表4 耐磨性试验数据
Figure PCTCN2019086505-appb-000007
由表4可知：落砂体积的数值上来看，本发明实施例1落砂体积平均值为12.5L，而对比实施例1落砂体积平均值为4.1L。可以看出实施例1的涂层的耐磨性远远优于对比实施例1。
2)拉伸实验
选择6个实验组(实施例1、2、3及对比实施例1、2、3)，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5 钢筋拉伸试验
Figure PCTCN2019086505-appb-000008
根据上述表5实验结果，实施例1-3的三组涂层钢筋随钢筋拉伸开裂时的平均应变值范围为1200-2300微应变，对比实施例1、2、3的涂层钢筋的平均应变值范围为650-850微应变。因此，覆有本发明的钢筋防腐用韧性涂料的钢筋可以随同建筑钢筋发生协同拉伸，并且如果没有按照特定的材料配比和特定的制备工艺参数时，那么涂层的性能会不满足需求。
3)钢筋耐腐蚀实验
分别取6个实验组和6个对照组，实验组为有涂层钢筋(实施例1、4、5及对比实施例1、2、3)。对照组1为CN105670366B专利中表1钢筋加速腐蚀试验中组2有涂层的数据，对照组2为CN105819691A专利中表1钢筋加速腐蚀试验中组1有涂层的数据，对照组3为CN105585883B专利中表1钢筋加速腐蚀试验中光圆钢筋有涂层的数据，对照组4为CN105238105B专利中表4钢筋加速腐蚀试验中组3有涂层的数据，对照组5为CN105131660B专利中表1钢筋加速腐蚀试验中不含纤维的涂层的数据，对照组6为无涂层的裸钢。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6 钢筋加速腐蚀试验
Figure PCTCN2019086505-appb-000009
从表6可知，实施例1、4、5的涂层钢筋保持不被腐蚀的时间是无涂层钢筋的14倍左右，是CN105131660B专利钢筋耐腐蚀时间的5倍，CN105238105B专利钢筋耐腐蚀时间的2.5倍，CN105585883B专利钢筋耐腐蚀时间的2倍，CN105670366B专利钢筋耐腐蚀时间的1.5倍，CN105819691A专利钢筋耐腐蚀时间的1.4倍。同时可以看出对比实施例1、2、3的耐腐蚀性能仅为实施例1，4，5的三分之一，说明如果没有按照特定的材料配比和特定的制备工艺参数时，那么涂层的性能会不满足需求。
4)金属板耐腐蚀实验
分别取4个实验组和一个对照组，实验组为有涂层金属板(实施例1、6、7、8)，对照组分别为无涂层钢板、无涂层铜板、无涂层铝板和无涂层镁板，总计试验钢板个数为15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7 金属板加速腐蚀试验
Figure PCTCN2019086505-appb-000010
从表7可得，将本发明的涂层金属板保持不被腐蚀的时间是无涂层金属板的14倍左右，对于钢板、铝板、镁板、铜板，都有着极好的耐腐蚀性能。
5)金属板的热膨胀系数测试
对8个实施例和3个对比实施例都进行热膨胀系数测试，实施例1～5和对比实施例1、2、3的基体金属为为钢板，实施例6的基体金属为铜板，实施例7的基体金属为铝板，实施例8的基体金属为镁板。并且对于钢板、铜板、铝板和镁板分别取三组热膨胀系数不同的板块，共33个试件分别进行涂层热膨胀系数测定测试。其中搪瓷涂层为C1，基体氧化物涂层为C2，搪瓷涂层和基体氧化物涂层整体称为双层结构涂层为C1+C2。分别对搪瓷涂层，基体氧化物涂层，双层结构涂层整体测定热膨胀系数。
表8 金属板热膨胀系数测定试验
Figure PCTCN2019086505-appb-000011
由表8可以得到，本发明中的双层结构涂层(C1+C2)的热膨胀系数会随着基体金属的改变而改变，所以整体的双层结构涂层和基体金属协调一致，从而证明了这种涂层具有普适性，可以应用于各种金属。同时也得到了当基体金属为铁或钢时，所述双层结构涂层的热膨胀系数的范围为10×10 -6/℃～16×10 -6/℃；当基体金属为铜或铜合金时，所述双层结构涂层的热膨胀系数范围为13×10 -6/℃～20×10 -6/℃；当基体金属为铝或铝合金时，所述双层结构涂层的热膨胀系数范围为20×10 -6/℃～26×10 -6/℃；当基体金属为镁或镁合金时，所述双层结构涂层的热膨胀系数范围为23×10 -6/℃～29×10 -6/℃。同时可以看出基体金属，基体氧化物涂层(C2)，搪瓷涂层(C1)的热膨胀系数是逐渐增大的，所以可以看出涂层具有热膨胀系数梯度。同时可以看出对比实施例1，2，3的热膨胀系数不满于协调一致的要求，同时对比实施例1，2，3都不存在基体氧化物涂层。说明如果没有按照特定的材料配比和特定的制备工艺参数时，那么涂层的性能会不满足需求。
由表3-表8可见，涂层的组分硅，钠，钾，钙，氟，钴，镍，硼，磷，镁，氧元素满足特定的成分配比，结合特定的制备工艺参数，才能制得本发明特定双层结构的金属涂层，所述双层结构涂层中由内层向外层存在浓度梯度减小的基体金属氧化物。
6)钢筋涂层的光学图片以及扫描电镜图片
图1a是静电喷涂圆钢的宏观图片，采用实施例1的原料配方。从宏观和微观上都可以看到涂层都非常有光泽，这种瓷釉光泽表明涂层具有较高的致密度，涂层上没有因为热膨胀系数过低而引起的裂缝，也没有因为热膨胀系数过大而造成的剥落，这也就意味涂层与基体金属的热膨胀系数吻合的很好。这种致密结构也意味着涂层具有较好的耐腐蚀能力。
能谱仪(EDS)的检测方法为：EDS测试采用能谱仪进行测试，首先将样品表面磨平抛光，并在表面喷镀金膜使其导电并粘贴导电胶带，调节加速电压值10～40kV，死时间为15～45％，测量时间定为50～400s，将样品放入样品腔中，设置参数后抽中空使得聚焦清晰，选择需要元素分析的区域并维持位置，使用点扫描、面扫描、线扫描进行元素分析。同时通过EDS技术的检测，得出硅含量7％，钠含量12％，钾含量7％，钙含量8％，氟含量5％，钴含量2％，镍含量2％，硼含量5％，磷含量2％，镁含量1％，氧含量49％。
图1b是静电喷涂螺纹钢的宏观图片，采用实施例1的原料配方。同样的可以看出涂层具有致密的结构，并且拥有瓷釉光泽。可以看出凸面和平面的交界处并没有发生开裂，说明涂层在高温烧结的过程中没有发生开裂，也进一步说明了本发明的热膨胀系数梯度的双层涂层能够与基体金属在高温下协同变形。
图2为实施例1的电镜图片，与实施例2,3相似，所以以实施例1作为代表。可以看出涂层的厚度在200μm左右，致密性很高，没有通孔，只有少量的闭孔，其中将闭孔的面积进行计算，得到闭孔率为4.3％。少量闭孔的存在可以使得涂层有一定的延展性。同时涂层有两部分组成，分别为搪瓷涂层(C1)以及基体氧化物涂层(C2)组成，C1的厚度在180μm左右，C2的厚度在20μm左右。C1，C2和钢筋形成了三明治结构。由于在氧化气氛中烧结，所以有C2的存在，此层中不仅存在铁的氧化物，而且存在Fe-Co，Fe-Ni混合晶，这样使得涂层能够与钢筋粘结的更加紧密。并且C2的厚度是可控的，其厚度会随着烧结温度的升高而变大，同时由于外涂层C1的存在，会抑制外界氧气与C2层的接触，所以涂层的厚度被控制在20μm左右。另外，C2过渡层的存在，既能起到增加粘结力的作用，也可以有效提高涂层的耐腐蚀性能。
图3是图2的局部放大图。在图3中可以清晰的看到靠近钢筋部分的涂层和远离钢筋的涂层有着明显的不同。越靠近钢筋的部分涂层中白色斑点的区域越来越大，EDS元素分析测试表明，白色斑点是铁氧化物组分。整个涂层(C1+C2)从内到外的铁元素由多到少呈梯度变化，因此铁氧化物也从内到外由多到少呈梯度变化。而这种变化也使得涂层热膨胀系数也发生梯度变化，随着铁氧化物的减少，涂层的热膨胀系数逐渐增大。这种三明治结构的双层热膨胀系数梯度结构，使得涂层与钢筋之间有着极强的粘结力和优于普通裸钢14倍的耐腐蚀性能。

Claims (40)

  1. 一种金属防腐涂层，其特征在于：
    所述金属防腐涂层为双层结构涂层，由搪瓷涂层与基体氧化物涂层构成；
    所述双层结构中，搪瓷涂层是外层，基体氧化物涂层是内层，所述的内层与基体金属接触，所述搪瓷涂层的成分按重量计包括硅1～40份，钠1～30份，钾1～20份，钙2～20份，氟0.5～15份，钴0.3～10份，镍0.2～10份，硼1～18份，磷0.5～10份，镁0.1～8份，其余为氧，所述的基体氧化物涂层的成分包括基体金属和氧；
    所述双层结构涂层中由内层向外层存在浓度梯度减小的基体金属氧化物。
  2. 根据权利要求1所述的金属防腐涂层，其特征在于，所述双层结构涂层的热膨胀系数与所述基体金属的热膨胀系数协调一致。
  3. 根据权利要求1所述的金属防腐涂层，其特征在于，所述的双层结构涂层为致密结构。
  4. 根据权利要求1所述的金属防腐涂层，其特征在于，所述的基体氧化物涂层中的基体金属的含量为40～85份，其余为氧。
  5. 根据权利要求1所述的金属防腐涂层，其特征在于，所述搪瓷涂层的成分包括硅2～30份，优选为3～15份；钠2～20份，优选为7～16份；钾2～15份，优选为3～10份；钙4～16份，优选为5～11份；氟2～10份，优选为3～7份；钴0.5～7份，优选为1～4份；镍0.3～8份，优选为0.5～4份；硼2～10份，优选为2.5～8份；磷0.8～6份，优选为1～4份；镁0.2～5份，优选为0.5～2份；其余为氧。
  6. 根据权利要求1所述的金属防腐涂层，其特征在于，所述的基体金属选自铁、钢、铜、铜合金、铝、铝合金、镁、镁合金；当基体金属为铁或钢时，所述双层结构涂层的热膨胀系数的范围为10×10 -6/℃～16×10 -6/℃；当基体金属为铜或铜合金时，所述双层结构涂层的热膨胀系数范围为13×10 -6/℃～20×10 -6/℃；当基体金属为铝或铝合金时，所述双层结构涂层的热膨胀系数范围为20×10 -6/℃～26×10 -6/℃；当基体金属为镁或镁合金时，所述双层结构涂层的热膨胀系数范围为23×10 -6/℃～29×10 -6/℃。
  7. 根据权利要求1所述的金属防腐涂层，其特征在于，所述硅、钠、钾、钙、氟、钴、镍、硼、磷、镁、氧元素采用能谱仪(EDS)来测定，具体方法为：EDS测试采用能谱仪进行测试，首先将样品表面磨平抛光，并在表面喷镀金膜使其导电并粘贴导电胶带，调节加速电压值10～40kV，死时间为15～45％，测量时间定为50～400s，将样品放入样品腔中，设置参数后抽真空使得聚焦清晰，选择需要元素分析的区域并维持位置，使用点扫描、面扫描、线扫描进行元素分析。
  8. 根据权利要求1所述的金属防腐涂层，其特征在于，所述搪瓷涂层成分选自瓷釉粉末、热膨胀调节剂、助熔剂、粘合剂，所述瓷釉粉末的含量为40～90份，优选为60～75份；热膨胀调节剂的含量为5～40份，优选为10～25 份；助熔剂的含量为1～20份，优选为5～12份；粘合剂的含量为0.5～12份，优选为2～6份，所述的含量以重量计。
  9. 根据权利要求8所述的金属防腐涂层，其特征在于，所述瓷釉粉末的元素含量为：硅1～40份，优选为2～15份；钠1～20份，优选为3～12份；钾1～23份，优选为4～13份；钙1～18份，优选为3～11份；硼0～10份，优选为0～5份；磷0.8～10份，优选为1～5份；优选的，所述瓷釉粉末的粒径为1000～2000目，优选目数为1200～1800目。
  10. 根据权利要求8所述的金属防腐涂层，其特征在于，所述瓷釉粉末中，硅氧化物含量占3～39份，钠氧化物含量占3～28份，钾氧化物含量占1～25份，氧化硼含量占0～15份，磷氧化物含量占0.5～10份，所述的含量以重量计。
  11. 根据权利要求10所述的金属防腐涂层，其特征在于，所述的硅氧化物选自氧化硅、二氧化硅、过氧化硅的一种或多种。
  12. 根据权利要求10所述的金属防腐涂层，其特征在于，所述的钠氧化物选自氧化钠、过氧化钠、氢氧化钠的一种或多种。
  13. 根据权利要求10所述的金属防腐涂层，其特征在于，所述的钾氧化物选自氧化钾、碳酸钾、氢氧化钾的一种或多种。
  14. 根据权利要求10所述的金属防腐涂层，其特征在于，所述的磷氧化物选自三氧化二磷、五氧化二磷的一种或多种。
  15. 根据权利要求8所述的金属防腐涂层，其特征在于，所述热膨胀调节剂选自硅酸钠、硅酸钾、硅酸钙、硅酸镁、四硼酸钠、四硼酸钾、硼酸钙、硼酸钡、硼酸锂中的一种或几种。
  16. 根据权利要求8所述的金属防腐涂层，其特征在于，所述助熔剂选自碳酸钠、碳酸钾、碳酸镁、碳酸锶、碳酸锂、碳酸钙、碳酸钡、氟化钙、氟化镁、氟化钾中的一种或几种。
  17. 根据权利要求8所述的金属防腐涂层，其特征在于，所述粘合剂选自一氧化钴、三氧化二钴、一氧化镍、三氧化二镍中的一种或几种。
  18. 根据权利要求1所述的金属防腐涂层，其特征在于，所述双层结构涂层的厚度不小于40μm；优选的，所述双层结构涂层的厚度不小于50μm。
  19. 根据权利要求1所述的金属防腐涂层，其特征在于，所述搪瓷涂层的厚度为40～320μm，基体氧化物涂层的厚度为10～50μm。
  20. 根据权利要求1-19任一项所述的金属防腐涂层，其特征在于，当所述双层结构涂层应用于钢筋防腐时，所述的基体金属为钢，所述双层结构涂层的热膨胀系数的范围为10×10 -6/℃～16×10 -6/℃，所述双层结构涂层的极限拉应变(ultimate tensile strain)为1200～2300微应变，优选为1400～2200微应变。
  21. 根据权利要求1-19任一项所述的金属防腐涂层，其特征在于，当所述双层结构涂层应用于金属防腐时，所述双层结构涂层烧结在金属上之后，使得所述金属的耐腐蚀能力相比与没有涂层的金属的耐腐蚀能力提高14倍以上。
  22. 一种金属防腐涂层和带有金属防腐涂层的金属制品的制备方法，其特征在于，包括如下步骤：
    1)第一次研磨：称量瓷釉粉末、热膨胀调节剂、助熔剂、粘合剂，所述瓷釉粉末的含量为40～90份，优选为60～75份；热膨胀调节剂的含量为5～40份，优选为10～25份；助熔剂的含量为1～20份，优选为5～12份；粘合剂的含量为0.5～12份，优选为2～6份，所述的含量以重量计，并研磨成粉末；
    2)制备混料：将上述4种原料与水混合搅拌得到混料；
    3)第二次研磨：将步骤2)得到的混料干燥后研磨成粉末；
    4)高温反应：将步骤3)得到的混料在520～720℃的高温炉中反应10～20分钟；
    5)第三次研磨：将高温反应后的混料研磨，得到涂层粉末；
    6)涂覆：将步骤5)得到的金属涂层粉末涂覆在基体金属上；
    7)烧结：将步骤6)得到的涂覆有金属粉末的基体金属高温烧结，得到金属防腐涂层和带有金属防腐涂层的金属制品，所述金属防腐涂层为双层结构涂层，由搪瓷涂层与基体氧化物涂层构成，所述双层结构中，搪瓷涂层是外层，基体氧化物涂层是内层，所述的内层与基体金属接触，所述的基体氧化物涂层的成分包括基体金属和氧，所述双层结构涂层中由内层向外层存在浓度梯度减小的基体金属氧化物；
    所述搪瓷涂层的成分按重量计包括硅1～40份，钠1～30份，钾1～20份，钙2～20份，氟0.5～15份，钴0.3～10份，镍0.2～10份，硼1～18份，磷0.5～10份，镁0.1～8份，其余为氧，所述的基体氧化物涂层的成分包括基体金属和氧。
  23. 根据权利要求22所述的制备方法，其特征在于，步骤6)的涂覆方法可以采用静电喷涂方法，其中静电电压为30～90千伏，电流为20～80微安，出粉量为200～700克每分钟，喷涂距离为10～30厘米；
  24. 根据权利要求22所述的制备方法，其特征在于，步骤7)的烧结参数为：温度为500～620℃，烧结时间为10～20分钟，升温速率为每分钟5～15℃。
  25. 根据权利要求22所述的制备方法，其特征在于，所述的基体金属选自铁、钢、铜、铜合金、铝、铝合金、镁、镁合金。
  26. 根据权利要求22-24所述的制备方法，其特征在于，基体氧化物涂层中的基体金属的含量为40～85份，其余为氧。
  27. 根据权利要求22-24所述的制备方法，其特征在于，所述的搪瓷涂层是由加入的瓷釉粉末、热膨胀调节剂、助熔剂、粘合剂组成，所述瓷釉粉末的含量为40～90份，热膨胀调节剂的含量为5～40份，助熔剂的含量为1～20份，粘合剂的含量为0.5～12份；对应的元素含量为：硅2～30份，钠2～20份，钾2～15份，钙4～16份，氟2～10份，钴0.5～7份，镍0.3～8份，硼2～10份，磷0.8～6份，镁0.2～5份，其余为氧，所述含量以重量计。
  28. 根据权利要求22-24所述的制备方法，其特征在于，所述的瓷釉粉末是由加入的硅氧化物，钠氧化物，钾氧化物，氧化硼，磷氧化物组成，硅氧化物含量占3～39份，钠氧化物含量占3～28份，钾氧化物含量占1～25份，氧化硼含量占0～15份，磷氧化物含量占0.5～10份；对应的元素含量为：硅1～40份，钠1～20份，钾1～23份，钙1～18份，硼0～10份，磷0.8～10份，所述的含量以重量计；优选的，所述瓷釉粉末的粒径为1000～2000目，优选目数为1200～1800目。
  29. 根据权利要求22-24所述的制备方法，其特征在于，所述的硅氧化物选自氧化硅、二氧化硅、过氧化硅的一种或多种。
  30. 根据权利要求22-24所述的制备方法，其特征在于，所述的钠氧化物选自氧化钠、过氧化钠、氢氧化钠的一种或多种。
  31. 根据权利要求22-24所述的制备方法，其特征在于，所述的钾氧化物选自氧化钾、碳酸钾、氢氧化钾的一种或多种。
  32. 根据权利要求22-24所述的制备方法，其特征在于，所述的磷氧化物选自三氧化二磷、五氧化二磷的一种或多种。
  33. 根据权利要求22-24所述的制备方法，其特征在于，所述热膨胀调节剂选自硅酸钠、硅酸钾、硅酸钙、硅酸镁、四硼酸钠、四硼酸钾、硼酸钙、硼酸钡、硼酸锂中的一种或几种。
  34. 根据权利要求22-24所述的制备方法，其特征在于，所述助熔剂选自碳酸钠、碳酸钾、碳酸镁、碳酸锶、碳酸锂、碳酸钙、碳酸钡、氟化钙、氟化镁、氟化钾中的一种或几种。
  35. 根据权利要求22-24所述的制备方法，其特征在于，所述粘合剂选自一氧化钴、三氧化二钴、一氧化镍、三氧化二镍中的一种或几种。
  36. 根据权利要求22-24所述的制备方法，其特征在于，所述双层结构涂层的厚度不小于40μm；优选的，所述双层结构涂层的厚度不小于50μm。
  37. 根据权利要求22-24所述的制备方法，其特征在于，所述搪瓷涂层的厚度为40～320μm，基体氧化物涂层的厚度为10～50μm。
  38. 一种金属制品，其特征在于，所述的金属制品包括权利要求1-21任一项所述的金属防腐涂层。
  39. 根据权利要求38所述的金属制品，其特征在于，所述的金属制品选自铁板、钢板、钢筋、铜板、铝板。
  40. 权利要求1-21任一项所述的金属防腐涂层，权利要求22-23任一项所述的金属制品可应用于民用建筑、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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