WO2022041594A1 - 一种耐磨防腐涂料及其制备方法与应用 - Google Patents

一种耐磨防腐涂料及其制备方法与应用 Download PDF

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WO2022041594A1
WO2022041594A1 PCT/CN2020/137942 CN2020137942W WO2022041594A1 WO 2022041594 A1 WO2022041594 A1 WO 2022041594A1 CN 2020137942 W CN2020137942 W CN 2020137942W WO 2022041594 A1 WO2022041594 A1 WO 2022041594A1
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wear
resistant
component
coating
corrosion
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French (fr)
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吕旺燕
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广东电网有限责任公司电力科学研究院
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Priority to US17/907,982 priority Critical patent/US20230078879A1/en
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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
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/086—Organic or non-macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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    • 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
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/61—Additives non-macromolecular inorganic
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/67—Particle size smaller than 100 nm
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
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    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • B05D2202/25—Metallic substrate based on light metals based on Al
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    • B05D2202/00—Metallic substrate
    • B05D2202/30—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W)
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
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    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • the invention relates to the technical field of coatings, in particular to a wear-resistant and anti-corrosion coating and a preparation method and application thereof.
  • Magnesium and its alloys are the lightest engineering metal materials, with the advantages of high specific strength, easy casting and recycling, low toxicity, non-magnetic, good plastic deformation energy absorption, etc. It has potential application prospects in industrial fields such as high thermal conductivity, low heat capacity and electrical shielding properties. But in most environments, such as humid atmospheres, seawater, simulated body fluids, engine coolants, and other corrosive environments, its application is severely limited by severe corrosion susceptibility. The high corrosion susceptibility of magnesium and its alloys is attributed to its very negative standard potential, as well as the porosity and porosity of the surface film, which provides little protection for magnesium alloys. Therefore, the poor corrosion resistance of magnesium alloys has always been a key problem restricting the wide application of magnesium alloys.
  • Magnesium alloys have low hardness, which makes magnesium alloys prone to scratches and other surface damage during use, which further accelerates the corrosion of magnesium alloys. Therefore, another factor restricting the large-area application of magnesium alloys is poor wear resistance.
  • the commonly used treatment processes include chemical conversion coatings, Ni, Cr, NiP and other coatings, but chemical conversion coatings can only be used as the bottom layer of coatings, and cannot improve the wear resistance of magnesium alloys;
  • the coating technology improves the wear resistance of magnesium alloys to a certain extent, there is a huge potential difference between the coating material and the base magnesium alloy, and defects in the coating can easily cause and accelerate the corrosion of magnesium alloys. Therefore, none of these processes can effectively improve the wear resistance and corrosion resistance of magnesium alloys.
  • the present invention provides a wear-resistant and anti-corrosion coating, a preparation method and application thereof, and the wear-resistant and anti-corrosion coating can effectively improve the wear resistance and corrosion resistance of magnesium alloys.
  • the invention provides a wear-resistant and anti-corrosion coating, which is made of A component and B component;
  • the A component includes:
  • the component B includes: a curing agent
  • the mass ratio of the A component to the component B is 1:(1-2).
  • the polyurethane resin in component A is used as a coating film-forming substance, and is matched with a corrosion inhibitor, a wear-resistant filler and a physical filler.
  • a corrosion inhibitor On the basis of the wear resistance of the polyurethane resin, through the corrosion inhibitor
  • the anti-corrosion effect of the anti-corrosion filler and the high wear-resistant performance of the wear-resistant filler improve the wear-resistant performance of the coating
  • the use of the physical filler reduces the cost of the coating
  • the thixotropic agent makes the coating have good storage stability.
  • the coating composition does not contain metal components, which avoids the problem of electrochemical potential difference with the alloy, so that the corrosion of the alloy can be effectively controlled.
  • the components of the coating of the present invention cooperate with each other and act synergistically, so that the coating has excellent comprehensive performance.
  • the wear-resistant filler is silicon nitride and/or boron nitride
  • the thixotropic agent is oily fumed silica
  • the body filler is mica and/or heavy calcium carbonate
  • the corrosion inhibitor is N-nitrosophenylhydramine and/or hexamethylenetetramine
  • the solvent is X-10, xylene or ethylene glycol ether acetate.
  • the polyurethane coating has excellent abrasion resistance, weather resistance, flexibility and water resistance.
  • High hardness fillers can greatly improve the wear resistance of the coating; N-nitrosophenylhydramine and/or hexamethylenetetramine are used as corrosion inhibitors, which can significantly improve the corrosion resistance of the coating.
  • Mica and/or heavy calcium carbonate are used as bulk fillers to improve the compactness of the coating on the one hand, and reduce the cost of the coating on the other hand; the oil-based fumed silica thixotropic agent makes the coating have good storage stability.
  • the curing agent is a modified alkyd resin.
  • the particle size of the silicon nitride and the boron nitride is 1-20 ⁇ m, preferably 1 ⁇ m, 10 ⁇ m, 15 ⁇ m or 20 ⁇ m;
  • the particle size of the oily fumed silica is 20-100 nm, preferably 20 nm, 30 nm, 50 nm or 100 nm;
  • the particle size of the mica or ground calcium carbonate is 2-30 ⁇ m, preferably 2 ⁇ m, 5 ⁇ m, 10 ⁇ m, 12 ⁇ m, 15 ⁇ m, 25 ⁇ m or 20 ⁇ m.
  • the present invention also provides a preparation method of the above-mentioned wear-resistant and anti-corrosion coating, comprising the following steps:
  • component A Preparation of component A: after mixing polyurethane resin, wear-resistant filler, thixotropic agent, physical filler, corrosion inhibitor and solvent uniformly, grinding and dispersing to obtain component A;
  • the preparation method of the wear-resistant and anti-corrosion coating provided by the invention is simple, easy to operate, and suitable for industrial production.
  • step 1 of the present invention the polyurethane resin, the wear-resistant filler, the thixotropic agent, the physical filler, the corrosion inhibitor and the solvent are mixed uniformly and wetted, and then ground and dispersed; Put them into a stirring and dispersing mill together for grinding and dispersing; the rotating speed of the grinding and dispersing is 1500-3000 rpm, and the time is 30-60 min;
  • the component A is preferably passed through a 120-300 mesh screen, and the fineness of component A is 10-30 microns, preferably 20-30 microns, and more preferably 20 microns.
  • the component A is mixed with the B component.
  • the present invention also provides the application of the above-mentioned wear-resistant and anti-corrosion coating in the preparation of steel material, aluminum alloy, titanium alloy and/or magnesium alloy component coating, preferably in the application of magnesium alloy component coating.
  • steel materials, aluminum alloys, titanium alloys and magnesium alloys are used in the fields of automobiles, electronics, electric power, aviation and the like.
  • a coating is prepared on the surface of the magnesium alloy component that has undergone sandblasting or grinding treatment.
  • the thickness of the first anti-corrosion coating is 10-50 ⁇ m. More than two coats of coating, each coating interval 10 ⁇ 20min. After curing for more than 24 hours in a clean room temperature environment, a wear-resistant and anti-corrosion coating is obtained.
  • the present invention has the following advantages:
  • the invention provides a wear-resistant and anti-corrosion coating.
  • the polyurethane resin in the coating component A is used as a coating film-forming substance, and is equipped with a corrosion inhibitor, a wear-resistant filler and a physical filler.
  • a corrosion inhibitor On the basis of the wear resistance of the polyurethane resin, through The corrosion inhibition effect of the corrosion inhibitor and the high wear resistance of the wear-resistant filler improve the wear-resistant performance of the coating, the use of the body filler reduces the cost of the coating, and the thixotropic agent makes the coating have good storage stability.
  • the coating composition does not contain metal components, which avoids the problem of electrochemical potential difference with the alloy, so that the corrosion of the alloy can be effectively controlled.
  • the components of the coating of the present invention cooperate with each other and act synergistically, so that the coating has excellent comprehensive performance.
  • Fig. 1 is the EIS spectrum of the AZ91D magnesium alloy coated with a wear-resistant and anti-corrosion coating in Example 1 of the present invention after being immersed in a 3.5% NaCl solution for 3000 hours;
  • Fig. 2 is the abrasion loss weight of AZ91D magnesium alloy coated with wear-resistant and anti-corrosion coating in Example 1 of the present invention
  • Figure 3 shows the macroscopic morphology of the AZ31 magnesium alloy coated with a wear-resistant and anti-corrosion coating in Example 2 of the present invention after 1000h wet heat corrosion, wherein the left picture shows the sample after friction and wear test after 1000h wet heat test (GJB 150.9A-2009 ), the picture on the right is the original appearance of the coating, Abrasived coatings is the coating after wear test, humid heat exposed is the wet-hot corrosion test, and Pristine coatings is the original coating;
  • Figure 4 is the macroscopic morphology of ME20M magnesium alloy coated with a wear-resistant and anti-corrosion coating in Example 4 of the present invention after 2000h of neutral salt spray corrosion (GJB 150.11A-2009);
  • Fig. 5 EIS spectrum of the AZ91D magnesium alloy coated with a wear-resistant and anti-corrosion coating in Example 5 of the present invention during immersion in a 10% HCl solution.
  • the polyurethane resin and curing agent are purchased from TS01-3 two-component polyurethane coating of Tianjin Light Tower Paint Co., Ltd.;
  • X-10 solvent is purchased from Tianjin Light Tower Paint Co., Ltd., wherein, X-10 solvent is anhydrous toluene A mixed solvent consisting of 60 parts, 25 parts of butyl acetate and 15 parts of cyclohexanone.
  • a wear-resistant and anti-corrosion coating was prepared on the surface of the sandblasted AZ91D magnesium alloy by spraying. One spray was applied, and the second layer was sprayed after the surface was dry for 15 minutes. The sample was cured in a dry room temperature environment for 24 hours, and the thickness was obtained. Wear-resistant and anti-corrosion coating of 65 ⁇ m.
  • the performance parameters of the wear-resistant and anti-corrosion coating are as follows:
  • the AZ91D magnesium alloy coated with the above-mentioned wear-resistant and anti-corrosion coating was soaked in a 3.5% NaCl solution for 3000 h. As shown in FIG. 1 , the coating resistance is maintained at 10 9 ⁇ cm 2 , indicating that the coating of this embodiment has excellent corrosion resistance.
  • the weight loss of the coating after being worn for 30 minutes at a load of 1000 g is 47 times lower than that of the AZ91D magnesium alloy, indicating that the coating of this example has excellent wear resistance.
  • This comparative example adopts the same preparation process as in Example 1, except that the coating is prepared by using zinc powder as a corrosion inhibitor and alumina powder as a wear-resistant filler.
  • the coating is prepared by using zinc powder as a corrosion inhibitor and alumina powder as a wear-resistant filler.
  • the coating was applied on the surface of AZ91D magnesium alloy, the potential of zinc was higher than that of AZ91D magnesium alloy, which promoted the corrosion of magnesium alloy. loss of protection. Under the same friction and wear conditions, the wear loss of the coating is only 15 times higher than that of the AZ91D magnesium alloy.
  • a wear-resistant and anti-corrosion coating was prepared on the surface of the sandblasted AZ31 magnesium alloy by spraying. One layer was sprayed, and the second layer was sprayed after the surface was dry for 10 minutes. The sample was cured in a dry room temperature environment for 24 hours to obtain the thickness. 70 ⁇ m wear-resistant and anti-corrosion coating.
  • the performance parameters of the anti-corrosion coating are as follows:
  • the AZ31 magnesium alloy coated with the above-mentioned wear-resistant and anti-corrosion coating was subjected to a hot and humid corrosion test for 1000 hours. As shown in Figure 3, the coating was intact after 1000 hours, and no damage such as blistering and peeling occurred.
  • Example 2 the same preparation method as in Example 2 is adopted, except that the coating is prepared when polyamide powder with a molecular weight of 19000 is used as the thixotropic agent.
  • the coating was applied on the surface of AZ31 magnesium alloy, due to the poor compatibility of polyamide with the coating, the coating had more pores. After 830h of hot and humid corrosion, the coating appeared bubbling and the protective performance was reduced.
  • the performance parameters of the wear-resistant and anti-corrosion coating are as follows:
  • This comparative example adopts the same preparation process as in Example 3, except that the coating is prepared when kaolin is used as the body filler.
  • the coating was applied on the surface of ME20M magnesium alloy, the magnesium alloy was easily corroded due to the high content of kaolin and iron. After 560h of salt spray corrosion, the magnesium alloy substrate was corroded.
  • component B curing agent weigh 40 parts of component B curing agent, and fully mix it with component A (the mass ratio of component A and component B is 1:1-2) to obtain a wear-resistant and anti-corrosion coating.
  • the wear-resistant and anti-corrosion coating was prepared on the surface of the sandblasted AZ91D magnesium alloy by spraying. One spray was applied, and the second layer was sprayed after the surface was dry for 12 minutes. The sample was cured in a dry room temperature environment for 24 hours, and the thickness was obtained. 60 ⁇ m wear-resistant and anti-corrosion coating.
  • the performance parameters of the anti-corrosion coating are as follows:
  • the coating impedance remained at 10 9 ⁇ cm 2 , the coating has excellent acid corrosion resistance.
  • This comparative example adopts the same preparation process as in Example 4, the only difference is: the coating prepared by using ferrophosphorus powder as the corrosion inhibitor. After the coating was coated on the surface of AZ91D magnesium alloy and soaked in 10% HCl solution for 843 hours, the magnesium alloy substrate was corroded.
  • the mass ratio of component A to component B is 1:1 ⁇ 2)
  • the wear-resistant and anti-corrosion coating can be obtained.
  • the wear-resistant and anti-corrosion coating was prepared on the surface of the sandblasted AZ31 magnesium alloy by spraying. One spray was applied, and the second layer was sprayed after the surface was dry for 13 minutes. The sample was cured in a dry room temperature environment for 24 hours, and the thickness was obtained. 80 ⁇ m wear-resistant and anti-corrosion coating.
  • the performance parameters of the anti-corrosion coating are as follows:
  • the AZ31 magnesium alloy coated with the above-mentioned wear-resistant and anti-corrosion coating after the friction and wear test under a load of 1000g for 30 minutes, the weight loss is 52 times lower than that of the AZ31 magnesium alloy. , cracking and other damage, the magnesium alloy under the coating does not corrode, and the coating plays a good protective role.
  • This comparative example adopts the same preparation process as in Example 5, the only difference is that: 90 parts of the coating prepared by polyurethane resin are used in the A component. After the coating was applied to the AZ31 magnesium alloy surface friction and wear test, the wear loss was only reduced by 13 times, and the magnesium alloy substrate was corroded after being immersed in artificial seawater for 796 hours.
  • the results of the examples show that the magnesium alloy wear-resisting and anti-corrosion coating obtained by this process significantly improves the wear-resisting and corrosion-resisting properties of the magnesium alloy, is easy to control, and is suitable for industrial production.

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Abstract

一种耐磨防腐涂料及其制备方法和应用，由A组分和B组分制成。其中组分A中的聚氨酯树脂作为涂料成膜物，配以缓蚀剂、耐磨填料和体质填料，在聚氨酯树脂耐磨性的基础上，通过缓蚀剂的缓蚀作用，以及耐磨填料的高耐磨性提高了涂层的耐磨损性能，体质填料的使用降低了涂料的成本，触变剂使得涂料具有良好的贮存稳定性。B组分包括固化剂。该涂料中不含金属成分。

Description

一种耐磨防腐涂料及其制备方法与应用
本申请要求于2020年08月26日提交中国专利局、申请号为202010870983.X、发明名称为“一种耐磨防腐涂料及其制备方法与应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及涂料技术领域，尤其涉及一种耐磨防腐涂料及其制备方法与应用。
背景技术
镁及其合金是最轻的工程金属材料，具有比强度高、易于铸造和回收、低毒、无磁性、良好的塑性变形吸能等优点，在汽车、电子、航空、航天、能源、生物医学等工业领域具有潜在的应用前景，高导热、低热容量和电屏蔽性能。但在大多数环境中，如潮湿大气、海水、模拟体液、发动机冷却液和其他腐蚀性环境中，其应用受到严重的腐蚀敏感性的严格限制。镁及其合金的高腐蚀敏感性归因于其非常负的标准电位，以及表面膜的疏松和多孔性，这几乎对镁合金没有保护作用。因此，镁合金的耐蚀性能差一直是制约镁合金获得广泛应用的关键性问题。
镁合金具有较低的硬度，导致镁合金在使用过程中容易发刮伤等表面破坏，进一步加速了镁合金的腐蚀，因此，制约镁合金大面积应用的另一个因素是耐磨性差。
为提高镁合金的耐腐蚀性能，常用的处理工艺包括化学转化膜、Ni、Cr、NiP等镀层等技术，但化学转化膜只能作为涂料底层使用，并且不能提高镁合金的耐磨损性能；虽然镀层技术在一定程度上提高了镁合金的耐磨损性能，但镀层材料与基体镁合金之间存在巨大的电位差，镀层中的缺陷容易引起并加速镁合金的腐蚀。因此，这些工艺均不能有效提高镁合金的耐磨损和防腐蚀性能。
发明内容
有鉴于此，本发明提供了一种耐磨防腐涂料及其制备方法与应用，耐磨防腐涂料可以有效提高镁合金的耐磨损和防腐蚀性能。
其具体技术方案如下：
本发明提供了一种耐磨防腐涂料，由A组分和B组分制成；
按重量分计，所述A组分包括：
聚氨酯树脂10～60份；
耐磨填料1～60份；
触变剂0.5～1份；
体质填料5～15份；
缓蚀剂0.5～2份；
溶剂20～80份；
所述组分B包括：固化剂；
所述A组分与所述组分B的质量比为1:(1～2)。
本发明提供的耐磨防腐涂料中，组分A中的聚氨酯树脂作为涂料成膜物，配以缓蚀剂、耐磨填料和体质填料，在聚氨酯树脂耐磨性的基础上，通过缓蚀剂的缓蚀作用，以及耐磨填料的高耐磨性能提高了涂层的耐磨损性能，体质填料的使用降低了涂料的成本，触变剂使得涂料具有良好的贮存稳定性。该涂料成分中不含金属成分，避免了与合金之间的电化学电位差问题，使得合金的腐蚀得到有效控制。本发明涂料各组分相互配合，协同作用，使得该涂料综合性能优异。
本发明中，所述耐磨填料为氮化硅和/或氮化硼；
所述触变剂为油性气相二氧化硅；
所述体质填料为云母和/重质碳酸钙；
所述缓蚀剂为N-亚硝基苯胲胺和/或六次甲基四胺；
所述溶剂为X-10、二甲苯或乙二醇乙醚乙酸酯。
本发明中，聚氨酯涂料具有优异的耐磨性、耐候性、柔韧性和耐水性。高硬度填料，极大提高涂层的耐磨性能；N-亚硝基苯胲胺和/或六次甲基四胺作为缓蚀剂，可以显著提高涂层的防腐蚀性能。云母和/或重质碳酸钙作为体质填料一方面提高涂料致密性，另一方面降低了涂料成本；油性气相二氧化硅触变剂使得涂料具有良好的贮存稳定性。
本发明中，所述固化剂为改性醇酸树脂。
本发明中，所述氮化硅和所述氮化硼的粒径为1～20μm，优选为1μm、10μm、15μm或20μm、；
所述油性气相二氧化硅的粒径为20～100nm，优选为20nm、30nm、50nm或100nm；
所述云母或重质碳酸钙的粒径为2～30μm，优选为2μm、5μm、10μm、12μm、15μm、25μm或20μm。
本发明还提供了上述耐磨防腐涂料的制备方法，包括以下步骤：
1)A组分的制备：将聚氨酯树脂、耐磨填料、触变剂、体质填料、缓蚀剂和溶剂混均匀后，研磨分散，得到A组分；
2)将A组分与B组分混合搅拌，得到耐磨防腐涂料。
本发明提供的耐磨防腐涂料的制备方法简单，易于操作，适用于工业化生产。
本发明步骤1中，聚氨酯树脂、耐磨填料、触变剂、体质填料、缓蚀剂和溶剂混均匀并润湿后，进行研磨分散；所述研磨分散具体为：将0.5～2mm的研磨珠一并放入搅拌分散研磨机中进行研磨分散；所述研磨分散的转速为1500～3000rpm，时间为30min～60min；
所述组分A优选过120～300目的网筛，A组分的细度为10～30微米，优选为20～30微米，更优选为20微米的组分A再与B组分混合。
本发明还提供了上述耐磨防腐涂料在制备钢铁材料、铝合金、钛合金和/或镁合金构件涂层中的应用，优选在镁合金构件涂层中的应用。
本发明中，钢铁材料、铝合金、钛合金和镁合金用于汽车、电子、电力、航空等领域。
本发明中，优选采用喷涂、刷涂或浸涂的方式，在经过喷砂或者打磨处理的镁合金构件表面制备涂层，第一道防腐蚀涂层厚度为10～50μm，根据需要进行一道或两道以上多道涂装，每道涂装间隔10～20min。在洁净的室温环境下固化24h以上，即得到耐磨防腐蚀涂层。
从以上技术方案可以看出，本发明具有以下优点：
本发明提供了一种耐磨防腐涂料，该涂料组分A中的聚氨酯树脂作为涂料成膜物，配以缓蚀剂、耐磨填料和体质填料，在聚氨酯树脂耐磨性的基础上，通过缓蚀剂的缓蚀作用，以及耐磨填料的高耐磨性能提高了涂层的耐磨损性能，体质填料的使用降低了涂料的成本，触变剂使得涂料具有良好的贮存稳定 性。该涂料成分中不含金属成分，避免了与合金之间的电化学电位差问题，使得合金的腐蚀得到有效控制。本发明涂料各组分相互配合，协同作用，使得该涂料综合性能优异。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其它的附图。
图1为本发明实施例1中涂装耐磨防腐蚀涂层的AZ91D镁合金在3.5％NaCl溶液中浸泡3000h后的EIS谱；
图2为本发明实施例1中涂装耐磨防腐蚀涂层的AZ91D镁合金磨损失重；
图3为本发明实施例2中涂装耐磨防腐蚀涂层的AZ31镁合金湿热腐蚀1000h后的宏观形貌，其中，左图为摩擦磨损测试后样品经1000h湿热试验(GJB 150.9A-2009)后宏观形貌，右图为涂层原始形貌，Abrasived coatings为磨损测试后涂层，humid heat exposed为湿热腐蚀测试，Pristine coatings为原始涂层；
图4为本发明实施例4中涂装耐磨防腐蚀涂层的ME20M镁合金中性盐雾腐蚀(GJB 150.11A-2009)2000h后的宏观形貌；
图5本发明实施例5中涂装耐磨防腐蚀涂层的AZ91D镁合金在10％HCl溶液中浸泡过程中EIS谱。
具体实施方式
为使得本发明的发明目的、特征、优点能够更加的明显和易懂，下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，下面所描述的实施例仅仅是本发明一部分实施例，而非全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
本发明实施例中，聚氨酯树脂和固化剂购于天津灯塔涂料有限公司的TS01-3双组分聚氨酯涂料；X-10溶剂购于天津灯塔涂料有限公司，其中，X-10 溶剂为无水甲苯60份、乙酸丁酯25份和环己酮15份组成的混合溶剂。
实施例1
本实施例中，按质量份数计，称取20份粒径为10μm份氮化硅粉，0.8份粒径为20nm气相二氧化硅，10份粒径为12μm白云母粉，0.9份N-亚硝基苯胲胺，依次放入30份聚氨酯树脂中，再称取并放入30份X-10溶剂，搅拌均匀后连同50份粒径为1mm的研磨珠放入涂料搅拌分散研磨机中以2000rpm转速研磨分散40min后取出，用120目不锈钢网过滤即获得10～30微米的组分A，称取15份B组分改性醇酸树脂固化剂，与组分A(组分A与组分B的质量比为1:1～2)充分混合均匀后即获得耐磨防腐蚀涂料。
采用喷涂的方式在经喷砂处理的AZ91D镁合金表面制备耐磨防腐蚀涂层，喷涂一道，表干15min后喷涂第二道，将试样放在干燥的室温环境下固化24h，即获得厚度为65μm的耐磨防腐蚀涂层。
本实施例中，耐磨防腐蚀涂层的性能参数如下：
涂装上述耐磨防腐蚀涂层的AZ91D镁合金在3.5％NaCl溶液中浸泡3000h。如图1所示，涂层阻抗保持在10 9Ωcm 2，说明本实施例的涂层具有优异的防腐蚀性能。
如图2所示，涂层在载荷为1000g、磨损30min后的失重较AZ91D镁合金降低47倍，说明本实施例的涂层具有优异的耐磨性能。
对比例1
本对比例采用与实施例1相同的制备工艺，区别仅在于：采用锌粉作为缓蚀剂和采用氧化铝粉作为耐磨填料制备涂料。将该涂料涂装在AZ91D镁合金表面时，由于锌的电位高于AZ91D镁合金的电位，促进了镁合金的腐蚀，当浸泡520h后，涂层阻抗降为10 5Ωcm 2数量级，涂层已经失去防护作用。在相同摩擦磨损条件下，涂层的磨损失重较AZ91D镁合金仅提高15倍。
实施例2
本实施例中，按质量份数计，称取30份粒径为15μm份氮化硼粉，1份粒径为50nm气相二氧化硅，8份粒径为25μm重质碳酸钙粉，1.5份六次甲基四胺，依次放入50份聚氨酯树脂中，再称取并放入35份二甲苯，搅拌均匀后连同60份粒径为2mm的研磨珠放入涂料搅拌分散研磨机中以3000rpm转 速研磨分散30min后取出，用300目不锈钢网过滤即获得10～30微米的组分A，称取25份B组分固化剂，与组分A(组分A与组分B的质量比为1:1～2)充分混合均匀后即获得耐磨防腐蚀涂料。
采用喷涂的方式在经喷砂处理的AZ31镁合金表面制备耐磨防腐蚀涂层，喷涂一道，表干10min后喷涂第二道，将试样放在干燥的室温环境下固化24h，即获得厚度为70μm的耐磨防腐蚀涂层。
本实施例中，防腐蚀涂层的性能参数如下：
涂装上述耐耐磨防腐蚀涂层的AZ31镁合金经湿热腐蚀试验1000h，如图3所示，1000h后涂层完好，未发生起泡、剥落等破坏。
对比例2
本对比例采用与实施例2相同的制备方法，区别仅在于：采用分子量为19000聚酰胺粉作为触变剂时制备涂料。将该涂料涂装在AZ31镁合金表面时，由于聚酰胺与涂料的相容性较差，造成涂层较多的孔隙，当湿热腐蚀830h后，涂层出现鼓泡，保护性能降低。
实施例3
本实施例中，按质量份数计，称取10份粒径为20μm份氮化硅粉，15份粒径为15μm氮化硼粉，1.2份粒径为100nm气相二氧化硅，5份粒径为2μm白云母粉，7份粒径为20μm重质碳酸钙粉，0.8份N-亚硝基苯胲胺，1份六次甲基四胺，依次放入60份聚氨酯树脂中，再称取并放入40份X-10稀释剂和40份二甲苯，搅拌均匀后连同80份粒径为0.5mm的研磨珠放入涂料搅拌分散研磨机中以1500rpm转速研磨分散60min后取出，用120目不锈钢网过滤即获得10～30微米的组分A，称取30份B组分固化剂，与组分A(组分A与组分B的质量比为1:1～2)充分混合均匀后即获得耐磨防腐蚀涂料。采用喷涂的方式在经喷砂处理的ME20M镁合金表面制备耐磨防腐蚀涂层，喷涂一道，表干20min后喷涂第二道，将试样放在干燥的室温环境下固化24h，即获得厚度为75μm的耐磨防腐蚀涂层。
本实施例中，耐磨防腐蚀涂层的性能参数如下：
涂装上述耐磨防腐蚀涂层的ME20M镁合金经2000h中性盐雾腐蚀后，如图4所示，涂层未发生鼓泡、起皮和开裂，涂层具有优异的耐盐雾腐蚀性能。
对比例3
本对比例采用与实施例3相同制备工艺，区别仅在于：采用高岭土作为体质填料时制备涂料。将该涂料涂装在ME20M镁合金表面时，由于高岭土铁含量较高，易于对镁合金造成腐蚀，盐雾腐蚀560h后，镁合金基体发生腐蚀。
实施例4
本实施例中，按质量份数计，称取60份粒径为20μm份氮化硅粉，0.6份粒径为30nm气相二氧化硅，10份粒径为5μm白云母粉，5份粒径为10μm重质碳酸钙粉，0.1份N-亚硝基苯胲胺，0.7份六次甲基四胺，依次放入40份聚氨酯树脂中，再称取并放入40份乙二醇乙醚乙酸酯稀释剂，搅拌均匀后连同60份粒径为1mm的研磨珠放入涂料搅拌分散研磨机中以2500rpm转速研磨分散50min后取出，用220目不锈钢网过滤即获得10～30微米的组分A，称取40份B组分固化剂，与组分A(组分A与组分B的质量比为1:1～2)充分混合均匀后即获得耐磨防腐蚀涂料。采用喷涂的方式在经喷砂处理的AZ91D镁合金表面制备耐磨防腐蚀涂层，喷涂一道，表干12min后喷涂第二道，将试样放在干燥的室温环境下固化24h，即获得厚度为60μm的耐磨防腐蚀涂层。
本实施例中，防腐蚀涂层的性能参数如下：
涂装了上述耐磨防腐蚀涂层的AZ91D镁合金在10％HCl溶液中经2163h的浸泡后，涂层未见鼓泡、起皮和开裂，如图5所示，涂层阻抗保持在10 9Ωcm 2，涂层具有优异的耐酸腐蚀性能。
对比例4
本对比例采用与实施例4相同的制备工艺，区别仅在于：采用磷铁粉作为缓蚀剂制备的涂料。该涂料涂装在AZ91D镁合金表面并经10％HCl溶液浸泡843h后，镁合金基体发生腐蚀。
实施例5
本实施例中，按质量份数计，称取5份粒径为1μm份氮化硅粉，0.7份粒径为20nm气相二氧化硅，5份粒径为15μm白云母粉，0.2份N-亚硝基苯胲胺，1.2份六次甲基四胺，依次放入15份聚氨酯树脂中，再称取并放入35份二甲苯，搅拌均匀后连同25份粒径为0.8mm的研磨珠放入涂料搅拌分散研 磨机中以1800rpm转速研磨分散40min后取出，用150目不锈钢网过滤即获得10～30微米的组分A，称取10份B组分固化剂，与组分A(组分A与组分B的质量比为1:1～2)充分混合均匀后即获得耐磨防腐蚀涂料。采用喷涂的方式在经喷砂处理的AZ31镁合金表面制备耐磨防腐蚀涂层，喷涂一道，表干13min后喷涂第二道，将试样放在干燥的室温环境下固化24h，即获得厚度为80μm的耐磨防腐蚀涂层。
本实施例中，防腐蚀涂层的性能参数如下：
涂装上述耐磨防腐蚀涂层的AZ31镁合金，在1000g载荷下摩擦磨损测试30min后，失重较AZ31镁合金降低52倍，在人工海水中经2000h浸泡后，涂层未发生起泡、剥落、开裂等破坏，涂层下的镁合金未发生腐蚀，涂层起到很好的防护作用。
对比例5
本对比例采用与实施例5相同的制备工艺，区别仅在于：A组分中采用90份聚氨酯树脂制备的涂料。该涂料涂装在AZ31镁合金表面摩擦磨损试验后，磨损失重仅降低13倍，人工海水浸泡796h后镁合金基体腐蚀。
实施例结果表明，通过该工艺得到的镁合金耐磨防腐蚀涂层显著提高了镁合金的耐磨损和耐腐蚀性能，易于控制，适合工业化生产。
以上所述，以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims (9)

  1. 一种耐磨防腐涂料，其特征在于，由A组分和B组分制成；
    按重量分计，所述A组分包括：
    聚氨酯树脂10～60份；
    耐磨填料1～60份；
    触变剂0.5～1份；
    体质填料5～15份；
    缓蚀剂0.5～2份；
    溶剂20～80份；
    所述组分B包括：固化剂；
    所述A组分与所述组分B的质量比为1:(1～2)。
  2. 根据权利要求1所述的耐磨防腐涂料，其特征在于，所述耐磨填料为氮化硅和/或氮化硼；
    所述触变剂为油性气相二氧化硅；
    所述体质填料为云母和/重质碳酸钙；
    所述缓蚀剂为N-亚硝基苯胲胺和/或六次甲基四胺；
    所述溶剂为X-10、二甲苯或乙二醇乙醚乙酸酯。
  3. 根据权利要求1所述的耐磨防腐涂料，其特征在于，所述固化剂为改性醇酸树脂。
  4. 根据权利要求2所述的耐磨防腐涂料，其特征在于，所述氮化硅和所述氮化硼的粒径为1～20μm；
    所述油性气相二氧化硅的粒径为20～100nm；
    所述云母或重质碳酸钙的粒径为2～30μm。
  5. 权利要求1至4任意一项所述的耐磨防腐涂料的制备方法，其特征在于，包括以下步骤：
    1)A组分的制备：将聚氨酯树脂、耐磨填料、触变剂、体质填料、缓蚀剂和溶剂混均后，研磨分散，得到A组分；
    2)将A组分与组分B混合搅拌均匀，得到耐磨防腐涂料。
  6. 根据权利要求5所述的制备方法，其特征在于，所述组分A的细度为10～30微米。
  7. 根据权利要求5所述的制备方法，其特征在于，所述研磨分散的转速为1500～3000rpm，时间为30min～60min。
  8. 权利要求1至4任意一项所述的耐磨防腐涂料在制备钢铁材料、铝合金、钛合金和/或镁合金构件的耐磨防腐涂层中的应用。
  9. 根据权利要求8所述的应用，其特征在于，包括以下步骤：
    将所述耐磨防腐涂料采用喷涂、刷涂或浸涂的方法在所述构件表面涂装涂层，相邻涂层间隔10～20min涂装，室温下固化24h以上，得到耐磨防腐涂层。
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