WO2024056109A1 - 一种"砖-泥"层状结构耐腐蚀磷酸盐复合涂层及其制备方法与应用 - Google Patents

一种"砖-泥"层状结构耐腐蚀磷酸盐复合涂层及其制备方法与应用 Download PDF

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WO2024056109A1
WO2024056109A1 PCT/CN2023/132227 CN2023132227W WO2024056109A1 WO 2024056109 A1 WO2024056109 A1 WO 2024056109A1 CN 2023132227 W CN2023132227 W CN 2023132227W WO 2024056109 A1 WO2024056109 A1 WO 2024056109A1
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boron nitride
hexagonal boron
composite coating
layered structure
brick
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English (en)
French (fr)
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刘雅玄
朱光晨
陈从平
戴国洪
邱枫
郭浦山
郭昶
张屹
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常州大学
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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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds

Definitions

  • the invention relates to the technical field of metal coatings, and in particular to a "brick-mud" layered structure corrosion-resistant phosphate composite coating and its preparation method and application.
  • metal materials have become indispensable and important resources. As metal parts are used for a long time and work in exposed environments, they are usually affected by various corrosions. , thereby hindering the normal operation of the device and causing significant economic losses. Therefore, how to improve the corrosion resistance of metal materials has become one of the current popular scientific research directions.
  • Phosphate composite coating is an inorganic coating. Coating it on the surface of metal parts can slow down the penetration of corrosive media and significantly reduce the corrosion rate of metal materials. Compared with organic coatings, inorganic phosphate composite coatings not only have a simpler preparation process, but also do not contain volatile organic solvents, making the protection of metal materials more stable.
  • the binder used in the preparation of the phosphate composite coating is a phosphate binder, which is prone to pores during high-temperature curing, the corrosion resistance of the coating needs to be further improved. Therefore, in order to improve the hydrophobicity and corrosion resistance of the coating, developing a "brick-mud" layered structure corrosion-resistant phosphate composite coating has become one of the effective methods. Introducing the "brick-mud" layered structure into the coating can not only significantly enhance the mechanical properties of the coating, but its special layered structure can provide ultra-high physical isolation effect and effectively reduce the penetration of water, Cl- , etc. Improve coating adhesion and corrosion resistance.
  • Hexagonal boron nitride is similar to graphene. They have similar structural characteristics and physical properties. Hexagonal boron nitride also has unique chemical stability and corrosion resistance, so it has attracted widespread attention and is often used in environmental treatment, chemical industry, and catalysis. In other fields, anti-friction and wear-resistant materials prepared from hexagonal boron nitride as raw materials, as well as anti-oxidation, High temperature resistant and corrosion resistant coatings are also favored by researchers from various countries.
  • the Chinese patent application with the publication number CN113004736A discloses a preparation method of modified boron nitride nanosheets and its application in improving the corrosion resistance of water-based organic protective coatings. It uses 3-aminopropyltriethoxysilane (APTES) modified boron nitride to prepare modified boron nitride nanosheets, which were dispersed in the water-based epoxy resin coating, thereby enhancing the corrosion resistance of the water-based epoxy resin coating.
  • APTES 3-aminopropyltriethoxysilane
  • the Chinese patent application with publication number CN108384448A discloses a composite nano-anti-corrosion coating with a shell-like structure and its preparation method.
  • This patent uses a small amount of MXene to replace part of the zinc powder in the epoxy zinc-rich primer, and combines MXene nano-sheet materials and Zn nano-coatings.
  • the sheet materials are assembled into a conductive mesh structure, using acrylic resin as the base and environmentally friendly glycol ester as the solvent to prepare a new anti-corrosion coating that is efficient, environmentally friendly, strong, and water-proof.
  • the patent enhances the corrosion resistance of the coating by constructing a shell-like layered structure, the conductive network structure composed of MXene nanosheet materials and Zn nanosheet materials lacks sufficient mechanical strength due to weak connections between materials. After long-term use, the coating may have problems such as surface peeling and delamination.
  • boron nitride hybrid materials can improve the corrosion resistance of the coating, and build a layered structure in the coating, which not only enhances the insulation effect of the coating, but also effectively improves the resistance to physical and chemical damage. , to achieve long-term protection effect, but how to modify the boron nitride material and what kind of layered structure to construct to make the coating have the best corrosion resistance and practicality requires further research.
  • the present invention provides a "brick-mud” layered structure corrosion-resistant phosphate composite coating and its preparation method and application.
  • the method adopts Construct a "brick-mud” layered structure to improve the corrosion resistance and service life of the phosphate composite coating, thereby further increasing the service life of metal materials.
  • the invention provides a method for preparing a "brick-mud" layered structure corrosion-resistant phosphate composite coating, which includes the following steps:
  • the particle size of hexagonal boron nitride is 5 ⁇ m to 15 ⁇ m.
  • the ratio of tris(hydroxymethyl)aminomethane solution to deionized water is (1 ⁇ 2)g:(800 ⁇ 1500)mL
  • the mass ratio of dopamine hydrochloride to hexagonal boron nitride powder is (20 ⁇ 40) :(60 ⁇ 80).
  • Step 2 Dissolve ferric chloride hexahydrate in ethylene glycol.
  • the ratio of ferric chloride hexahydrate to ethylene glycol is (1-3) g: (200-400) mL.
  • Use an ultrasonic bath to dissolve the polyethylene glycol.
  • Diol and dopamine-modified hexagonal boron nitride are added to the above solution, then sodium acetate is slowly added, and stirred vigorously at 60 to 80°C for 2 to 3 hours.
  • the resulting mixture is sealed in a polytetrafluoroethylene reactor and kept at 80 to After heating at 100°C for 2 hours, the temperature rises to 160-240°C and continues heating for 15-20 hours, then cools to room temperature, rinses with deionized water 3-5 times, and dries at 80-100°C for 15-20 hours to obtain the tetroxide.
  • Tri-iron modified hexagonal boron nitride powder Tri-iron modified hexagonal boron nitride powder.
  • the weight percentage of each raw material is: 2-4% ferric chloride hexahydrate, 18-23% polyethylene glycol, 3-7% dopamine-modified hexagonal boron nitride powder, and 66-77% sodium acetate. .
  • Step 3 Add the ferric oxide-modified hexagonal boron nitride powder to deionized water and stir evenly.
  • the dosage of boron powder and tetraethyl silicate The ratio is (1 to 2) g: (5 to 10) mL. After stirring, rinse with deionized water 3 to 5 times, and dry at 80 to 100°C for 15 to 20 hours to obtain a hexagonal boron nitride hybrid material.
  • Step 4 Weigh the hexagonal boron nitride hybrid material, curing agent and binder, mix the hexagonal boron nitride hybrid material, curing agent, powder and binder after ball milling, stir evenly, and apply by brushing or spraying
  • the method is coated on the pretreated metal substrate, and then cured at room temperature for 4 hours in a weak magnetic field environment, and then step curing is performed to obtain a "brick-mud" layered structure corrosion-resistant phosphate composite with a thickness of 0.08 ⁇ 0.25mm. coating.
  • the weight percentage of each raw material in step 4 is: 18% to 30% of hexagonal boron nitride hybrid material, 1% to 10% of curing agent, and 70% to 80% of phosphate binder.
  • the curing agent is at least one of magnesium oxide and zinc oxide.
  • the binder is aluminum dihydrogen phosphate.
  • the rotation speed during ball milling is 250r ⁇ min -1
  • the total ball milling time is 1 hour
  • the mass ratio of balls to materials is 1.2:1
  • agate balls are used as balls.
  • the pretreatment in step 4 includes roughening and cleaning pretreatment on the surface of the metal substrate.
  • the specific process is as follows: first, use coarse sandpaper to remove rust spots and surface oxide layers on the metal surface; then use running water to initially wash away the surface wear debris; Then it is ultrasonic cleaned with an ultrasonic cleaning machine.
  • the cleaning solution is alcohol and the cleaning time is 30 minutes. Finally, a hair dryer is used to dry the surface of the metal substrate.
  • the magnetic field intensity of the weak magnetic field environment is 0.5-1.0T.
  • the gradient solidification treatment process is as follows: solidify at 100°C, 150°C, 200°C, 270°C to 800°C for 1 hour each, and then cool in the furnace.
  • the gradient curing treatment process is as follows: 100°C, 150°C, 200°C, and 400°C.
  • the "brick-mud" layered structure corrosion-resistant phosphate composite coating prepared by the above method is used in the maintenance of mechanical equipment in the aerospace, mining, marine, natural gas and new energy industries.
  • hexagonal boron nitride is sequentially coated with dopamine, ferric oxide, and silicon dioxide to prepare a hexagonal boron nitride hybrid material; hexagonal boron nitride has good corrosion resistance and oxidation resistance and can be used in To a certain extent, it can overcome the shortcoming of graphene "promoting corrosion" in the current research on graphene anti-corrosion coatings. Its powder is modified with dopamine, which enhances the surface adhesion of hexagonal boron nitride and effectively improves the bonding strength between the coating and the metal matrix.
  • ferroferric oxide is evenly coated on the surface of hexagonal boron nitride to form a protective layer, which limits the penetration of external electrolytes, thereby effectively preventing the electrochemical corrosion and attenuation of the coating, and improving the coating corrosion resistance.
  • Further coating with silica prevents ferric tetroxide from reacting with the aluminum dihydrogen phosphate binder to lose its magnetism, thereby affecting the construction of the "brick-mud" layered structure. At the same time, it prevents the growth of microorganisms and chemical corrosion media. The erosion leads to the weakening of the corrosion resistance of the coating and increases the service life of the coating.
  • silica coating can also enhance the mechanical properties such as strength and hardness of hexagonal boron nitride hybrid materials.
  • the present invention uses the hexagonal boron nitride hybrid material as a "brick” structure and the phosphate binder as a "mud" structure. Under the assistance of a weak magnetic field, a coating with a "brick-mud” layered structure is constructed.
  • a coating with a "brick-mud” layered structure is constructed.
  • the phosphate composite coating with a "brick-mud" layered structure prepared by the present invention requires safe and environmentally friendly materials, a simple operation process, greatly reduces processing energy consumption, is easy to promote and apply in practice, and has good market potential. .
  • Figure 1 (a) is a microscopic morphology of hexagonal boron nitride powder, (b) is a tetroxide prepared in Example 1 Microscopic morphology of tri-iron modified hexagonal boron nitride powder.
  • Figure 2 shows the hexagonal boron nitride hybrid material prepared in Example 1 and the hexagonal boron nitride powder modified with ferroferric oxide respectively dispersed in aluminum dihydrogen phosphate binder and left to stand for 0 hours (a) and 12h ( b) Comparison chart.
  • Figure 3 (a) is a microscopic morphology of the phosphate composite coating prepared in Comparative Example 1, and (b) is a microscopic morphology of the "brick-mud" layered structure phosphate composite coating prepared in Example 1.
  • Figure 4 is a schematic diagram of the magnetic field application direction of the corrosion-resistant phosphate composite coating with a "brick-mud" layered structure.
  • Figure 5 is an electrochemical polarization curve diagram of the phosphate composite coating prepared in Examples 1-5, Comparative Examples 1-4, and Comparative Example 6.
  • Electrochemical performance test Use the CHI660-E model electrochemical workstation to conduct electrochemical tests. Platinum electrode and Ag/AgCl electrode (3M) in saturated KCl solution were used as comparison electrode and reference electrode respectively. Before the test, the phosphate composite coating surface was taken as the working surface, and the remaining surfaces were encapsulated and insulated with silicone rubber. During the test, the area of the sample immersed in 3.5wt% sodium chloride solution was approximately 1cm 2 . The voltammetry polarization scan rate is 2mV ⁇ s -1 . To ensure the reliability of the results, three repeated parallel measurements were performed for each experiment.
  • the metal matrix used in the following examples and comparative examples is titanium alloy.
  • the mass ratio is as follows: 22% hexagonal boron nitride hybrid material, 2% zinc oxide, and 76% aluminum dihydrogen phosphate.
  • the curing process is: first curing at room temperature for 4 hours, then curing at room temperature.
  • a weak magnetic field with a magnetic field strength of 0.8T is used to assist in controlling the arrangement direction of the hexagonal boron nitride hybrid material. See Figure 4 for a schematic diagram of the magnetic field application direction, and then cured at 100°C, 150°C, 200°C, and 270°C for 1 hour each.
  • a "brick-mud" layered structure corrosion-resistant phosphate composite coating with a thickness of 0.2mm was obtained.
  • the micromorphology of the coating is shown in Figure 3(b).
  • the obtained polarization curve and the polarization curve are shown in Figure 3(b).
  • the corresponding electrochemical parameters are shown in Figure 5 and Table 1.
  • the curing process is as follows: first curing at room temperature for 4 hours. During the room temperature curing process, a weak magnetic field with a magnetic field strength of 0.8T is used to assist in controlling the arrangement direction of the hexagonal boron nitride hybrid material and the direction of magnetic field application. See Figure 4 for the schematic diagram. Then, it is cured at 100°C, 150°C, 200°C, and 270°C for 1 hour each. After cooling in the furnace, a "brick-mud" layered structure corrosion-resistant phosphate composite coating with a thickness of 0.2mm is obtained. layer, the resulting polarization curve and the electrochemical parameters corresponding to the polarization curve are shown in Figure 5 and Table 1.
  • the curing process is as follows: first curing at room temperature for 4 hours. During the room temperature curing process, a weak magnetic field with a magnetic field strength of 0.8T is used to assist in controlling the arrangement direction of the hexagonal boron nitride hybrid material and the direction of magnetic field application. See Figure 4 for the schematic diagram. Then, it is cured at 100°C, 150°C, 200°C, and 270°C for 1 hour each. After cooling in the furnace, a "brick-mud" layered structure corrosion-resistant phosphate composite coating with a thickness of 0.2mm is obtained. The result is extremely The electrochemical parameters corresponding to the polarization curve and polarization curve are shown in Figure 5 and Table 1.
  • the phosphate composite coating was prepared according to the method of Example 1. The difference is that the gradient curing process of the coating is 1 hour at 100°C, 150°C, 200°C, and 400°C. The other conditions are the same as in Example 1.
  • the obtained polarization curve The electrochemical parameters corresponding to the line diagrams and polarization curves are shown in Figure 5 and Table 1.
  • the phosphate composite coating was prepared according to the method of Example 1. The difference is that the gradient curing process of the coating is 1 hour each at 100°C, 150°C, 200°C, and 800°C. The other conditions are the same as in Example 1. The obtained polarization curve and The electrochemical parameters corresponding to the polarization curves are shown in Figure 5 and Table 1.
  • the phosphate composite coating was prepared according to the method of Example 1. The difference was that no magnetic field was added. Other conditions were the same as Example 1.
  • the obtained coating micromorphology diagram, polarization curve diagram and the electrochemical parameters corresponding to the polarization curve are as shown in the figure. 3(a), Figure 5 and Table 1.
  • the phosphate composite coating was prepared according to the method of Example 2, except that no magnetic field was added, and other conditions were the same as Example 2.
  • the obtained polarization curve and the electrochemical parameters corresponding to the polarization curve are shown in Figure 5 and Table 1.
  • the phosphate composite coating was prepared according to the method of Example 3, except that no magnetic field was added, and other conditions were the same as Example 3.
  • the obtained polarization curve and the electrochemical parameters corresponding to the polarization curve are shown in Figure 5 and Table 1.
  • the metal substrate without phosphate composite coating was used as a blank control example.
  • the metal substrate used was titanium alloy.
  • the obtained polarization curve and the electrochemical parameters corresponding to the polarization curve are shown in Figure 5 and Table 1.
  • the phosphate composite coating was prepared according to the method of Example 3, except that the content of hexagonal boron nitride was 32%, zinc oxide was 1%, and aluminum dihydrogen phosphate was 67%. Other conditions were the same as Example 3.
  • the curing process is: first curing at room temperature for 4 hours, then curing at room temperature.
  • a weak magnetic field with a magnetic field strength of 0.8T is used to assist in controlling the arrangement direction of hexagonal boron nitride powder modified with ferroferric oxide. See Figure 4 for a schematic diagram of the magnetic field application direction, and then 100°C, 150°C, 200°C, and 270°C.
  • Each was cured for 1 hour, and after cooling in the furnace, a "brick-mud" layered structure corrosion-resistant phosphate composite coating with a thickness of 0.2mm was obtained.
  • the obtained polarization curve and the electrochemical parameters corresponding to the polarization curve are shown in Figure 5 and shown in Table 1.
  • Table 1 shows the electrochemical performance test results of Examples 1-5, Comparative Examples 1-4, and Comparative Example 6.
  • the metal substrate coated with the "brick-mud" layered structure phosphate composite coating prepared by the present invention has superior High physical isolation effect and better corrosion resistance can protect the matrix from damage and extend the service life of the metal matrix.
  • the corrosion current density decreases and the resistance value increases.
  • the inside of the paint will have an obvious graininess, making it difficult to stir evenly, and the viscosity will be too high and difficult to coat.
  • the corrosion resistance of the layered structure phosphate composite coating applied to a magnetic field is higher. This is mainly due to the introduction of the layered structure, which will give full play to the enhancement of the mechanical properties and isolation effect of the flake fillers. function, thereby significantly improving the corrosion resistance of the coating.
  • Figure 2 shows a hybrid material of hexagonal boron nitride without silicon dioxide and hexagonal boron nitride with silicon dioxide. Photos of boron hybrid materials dispersed in aluminum dihydrogen phosphate binder and left to stand for 0h and 12h. As can be seen from Figure 2 and Table 1, the hexagonal boron nitride material that is not coated with silica will react with aluminum dihydrogen phosphate. Since the hexagonal boron nitride is modified with ferric tetroxide, it is placed in aluminum dihydrogen phosphate.
  • the coating of silica can prevent the reaction between iron ferric oxide and aluminum dihydrogen phosphate binder, which is beneficial to the construction of "brick-mud" layered structure.
  • the difference in curing temperature will also affect the corrosion resistance of the coating.
  • the corrosion resistance of the coating is significantly improved.
  • the curing temperature reaches 800°C the coating-substrate corrosion current density decreases. As the resistance increases, the resistance value decreases, and the corrosion resistance of the coating-substrate system also decreases.

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Abstract

一种"砖-泥"层状结构耐腐蚀磷酸盐复合涂层及其制备方法与应用，通过盐酸多巴胺、四氧化三铁以及二氧化硅对六方氮化硼进行改性处理，然后加入磷酸盐粘结剂、固化剂得到磷酸盐复合涂料，最后将磷酸盐复合涂料涂覆在基材表面后得到磷酸盐复合涂层，涂层固化过程中利用磁场辅助作用控制六方氮化硼的排列方向，进而得到"砖-泥"层状结构耐腐蚀磷酸盐复合涂层。该涂层具有独特的层状结构可以有效抵抗电解质的渗透，提供超高的物理隔绝效果，增强金属基体的抗腐蚀能力并一定程度上延长其使用寿命，适用于各种严苛的腐蚀环境，在金属基体表面防护领域具有广泛的应用前景。

Description

一种“砖-泥”层状结构耐腐蚀磷酸盐复合涂层及其制备方法与应用 技术领域
本发明涉及金属涂层技术领域，尤其涉及一种“砖-泥”层状结构耐腐蚀磷酸盐复合涂层及其制备方法与应用。
背景技术
在工业化水平急速发展的时代背景下，金属材料成了不可或缺的重要资源，而随着金属零部件的长时间使用，加之工作在暴露的环境中，通常会致使其受到各种腐蚀的影响，进而妨碍器件的正常运行，造成重大经济损失。因此如何提高金属材料抗腐蚀性能成了当下热门的科研方向之一。
磷酸盐复合涂层属于无机涂层，将其涂敷在金属零部件表面，可以减缓腐蚀介质的渗透，显著降低金属材料的腐蚀速率。相较于有机涂层而言，无机磷酸盐复合涂层不仅制备工艺更为简单，而且不含易挥发的有机溶剂，对金属材料的防护更为稳定。
由于磷酸盐复合涂层制备所用的粘结剂为磷酸盐粘结剂，在高温固化时易产生气孔，涂层耐腐蚀性能需进一步改善。因此，为了提高涂层的疏水性以及耐腐蚀性能，开发一种“砖-泥”层状结构耐腐蚀磷酸盐复合涂层成为行之有效的方法之一。在涂层中引入“砖-泥”层状结构，不仅能显著增强涂层的力学性能，并且其特殊的层状结构可以提供超高的物理隔绝效果，有效降低水、Cl-等的渗透，提高涂层的附着力和抗腐蚀性能。
六方氮化硼与石墨烯类似，二者具有相近的结构特征和物理特性，且六方氮化硼还具备独特的化学稳定性和耐腐蚀性，因而被广泛关注，常用于环境处理、化工、催化等领域，以六方氮化硼为原料制备的减摩耐磨材料以及抗氧化、 耐高温、耐腐蚀涂层也备受各国研究者青睐。通过加入六方氮化硼粉末，与磷酸盐粘结剂制成磷酸盐复合涂层，可在提高涂层疏水性能以及抗腐蚀能力的同时，有效延长其使用寿命，提高对物理及化学破坏的抵抗，实现长效防护效果。
公开号为CN113004736A的中国专利申请公开了一种改性氮化硼纳米片的制备方法及其在提高水性有机防护涂料耐腐蚀性能中的应用，其通过3-氨丙基三乙氧基硅烷(APTES)对氮化硼进行改性制备得到改性氮化硼纳米片，并分散在水性环氧树脂涂层中，增强了水性环氧树脂涂层的耐腐蚀性能。公开号为CN108384448A的中国专利申请公开了仿贝壳结构的复合纳米防腐涂层及其制备方法，此专利以少量MXene替代环氧富锌底漆中部分锌粉，将MXene纳米片层材料和Zn纳米片层材料组装成导电网状结构，以丙烯酸类树脂为基底、环境友好型二元醇酯为溶剂，制备出一种高效、环保、强韧、隔水的新型防腐涂料。虽然专利中通过构建仿贝壳层状结构增强了涂层的耐腐蚀性能，但是由于材料之间连接薄弱，MXene纳米片层材料和Zn纳米片层材料组成的导电网状结构缺乏足够的机械强度，长期使用后涂层可能会出现表面剥落、脱层等问题。可以看出，氮化硼杂化材料的添加可以提高涂层的耐腐蚀性能，并且在涂层中构建层状结构，增强涂层隔绝效果的同时，还能有效提高对物理及化学破坏的抵抗，实现长效防护效果，但是如何对氮化硼材料进行改性、构建何种层状结构，才能使得涂层耐腐蚀性能最佳、实用性最好，还需进一步开展研究。
发明内容
为了克服现有磷酸盐复合涂层在使用过程中易发生腐蚀等问题，本发明提供了一种“砖-泥”层状结构耐腐蚀磷酸盐复合涂层及其制备方法与应用，该方法通过构造“砖-泥”层状结构，提升磷酸盐复合涂层的耐腐蚀性能以及使用寿命，从而进一步提高金属材料的服役周期。
本发明提供一种“砖-泥”层状结构耐腐蚀磷酸盐复合涂层的制备方法，包括如下步骤：
步骤一、将三(羟甲基)氨基甲烷溶液与去离子水混合均匀，滴加适量盐酸直到pH＝8.5，然后将六方氮化硼粉末分散在所得溶液中，六方氮化硼粉末与三(羟甲基)氨基甲烷溶液的质量比为(90～95):(5～10)，超声处理20～30min后加入盐酸多巴胺，在50～80℃下搅拌6h，反应结束后，用去离子水洗涤3～5次，在80～100℃下干燥15～20小时得到经多巴胺修饰的六方氮化硼粉末。
作为优选，六方氮化硼的粒度为5μm～15μm。
作为优选，三(羟甲基)氨基甲烷溶液与去离子水的比值为(1～2)g:(800～1500)mL，盐酸多巴胺与六方氮化硼粉末的质量比为(20～40):(60～80)。
步骤二、将六水三氯化铁溶解于乙二醇中，六水三氯化铁与乙二醇的比值为(1～3)g:(200～400)mL，通过超声波浴将聚乙二醇和经多巴胺修饰的六方氮化硼添加到上述溶液中，然后缓慢加入醋酸钠，并在60～80℃下剧烈搅拌2～3h，将所得混合物密封在聚四氟乙烯反应釜内，80～100℃保温加热2h后，温度升至160～240℃继续加热15～20h，然后冷却至室温，用去离子水冲洗3～5次，在80～100℃下干燥15～20小时得到经四氧化三铁修饰的六方氮化硼粉末。
作为优选，各原料的重量百分比为：六水三氯化铁2～4％，聚乙二醇18～23％，经多巴胺修饰的六方氮化硼粉末3～7％，醋酸钠66～77％。
步骤三、将经四氧化三铁修饰六方氮化硼粉末加入去离子水搅拌均匀，经四氧化三铁修饰六方氮化硼粉末与去离子水的用量比为(1～2)g:(100～300)mL，滴加适量氨水直到pH＝10，常温搅拌20～24h，搅拌过程中分十次滴加质量浓度为30％的硅酸四乙酯溶液，经四氧化三铁修饰六方氮化硼粉末与硅酸四乙酯的用量 比为(1～2)g:(5～10)mL，搅拌结束后，用去离子水冲洗3～5次，在80～100℃下干燥15～20小时得到六方氮化硼杂化材料。
步骤四、称取六方氮化硼杂化材料、固化剂和粘结剂，将六方氮化硼杂化材料、固化剂球磨混合后的粉体和粘结剂混合搅拌均匀，通过刷涂或者喷涂方式涂覆在预处理的金属基体上，然后先在弱磁场环境下室温固化4小时，再进行阶梯固化处理，得到厚度为0.08～0.25mm的“砖-泥”层状结构耐腐蚀磷酸盐复合涂层。
作为优选，步骤四中各原料的重量百分比为：六方氮化硼杂化材料18％～30％、固化剂1％～10％、磷酸盐粘结剂70％～80％。
作为优选，所述固化剂为氧化镁和氧化锌中的至少一种。
作为优选，所述粘结剂为磷酸二氢铝。
作为优选，球磨时转速为250r·min-1，球磨总时间为1小时，球与料的质量比例为1.2:1，球采用玛瑙小球。
作为优选，步骤四中所述预处理包括对金属基体表面进行粗糙化处理和清洗预处理，具体过程如下：首先采用粗砂纸去除金属表面锈斑和表面氧化层；接着经过流水初步冲刷表面磨屑；然后通过超声波清洗机超声清洗，清洗溶液为酒精，清洗时间为30分钟；最后利用吹风机干燥金属基体表面。
作为优选，所述弱磁场环境磁场强度为0.5～1.0T。
作为优选，所述梯度固化处理工艺如下：在100℃、150℃、200℃、270℃～800℃各固化1小时，随炉冷却即可。
作为优选，所述梯度固化处理工艺如下：100℃、150℃、200℃、400℃。
上述方法制备的“砖-泥”层状结构耐腐蚀磷酸盐复合涂层在维护航空航天、矿业、海洋、天然气和新能源行业中机械设备中的应用。
本发明的有益效果为：
(1)本发明由六方氮化硼依次包覆多巴胺、四氧化三铁、二氧化硅制得六方氮化硼杂化材料；六方氮化硼具有良好的耐腐蚀性和抗氧化性，可以在一定程度上克服当前石墨烯防腐涂料研究中石墨烯存在“促进腐蚀”的不足。其粉末经多巴胺修饰，增强了六方氮化硼的表面粘附性，有效提高涂层与金属基体之间的结合强度。在多巴胺包覆层的作用下，四氧化三铁均匀的包覆在六方氮化硼表面形成保护层，限制外部电解质的渗透，从而有效地防止了涂层的电化学腐蚀和衰减，提高涂层的耐腐蚀性。通过二氧化硅的进一步包覆，防止四氧化三铁与磷酸二氢铝粘结剂发生反应失去磁性，进而影响“砖-泥”层状结构的构建，同时，防止微生物的滋生和化学腐蚀介质的侵蚀导致的涂层耐腐蚀性的减弱，增加涂层的使用寿命。此外，二氧化硅的包覆还可以增强六方氮化硼杂化材料的强度、硬度等力学性能。
(2)本发明以六方氮化硼杂化材料为“砖”结构，磷酸盐粘结剂为“泥”结构，在弱磁场辅助作用下，构建“砖-泥”层状结构的涂层，充分发挥六方氮化硼杂化材料对涂层力学性能和隔绝效果的增强作用，进而在提高涂层对物理和化学腐蚀破坏的抵抗的同时，增强涂层的防护性能，提高涂层的耐腐蚀性能，有效防止金属基体被环境中的腐蚀物质侵蚀，并且可以增强涂层与基体间的粘结强度，延长其使用寿命。
(3)本发明制备的具有“砖-泥”层状结构的磷酸盐复合涂层，所需材料安全环保，操作过程简单，大幅减少加工能耗，易于推广和实际应用，具有良好的市场潜力。
附图说明：
图1(a)为六方氮化硼粉末微观形貌图，(b)为实施例1中制得的四氧化 三铁修饰六方氮化硼粉末微观形貌图。
图2为实施例1制得的六方氮化硼杂化材料和经四氧化三铁修饰六方氮化硼粉末分别分散于磷酸二氢铝粘结剂中，静置0小时(a)和12h(b)对比图。
图3(a)为对比例1制得的磷酸盐复合涂层微观形貌图，(b)为实施例1制得的“砖-泥”层状结构磷酸盐复合涂层微观形貌图。
图4为“砖-泥”层状结构耐腐蚀磷酸盐复合涂层磁场施加方向示意图。
图5为实施例1-5和对比例1-4、对比例6制得的磷酸盐复合涂层电化学极化曲线图。
具体实施方式
为了对本发明作进一步的说明，以下结合附图和实施例对本发明提供的一种“砖-泥”层状结构耐腐蚀磷酸盐复合涂层及其制备方法与应用进行详细描述，但不能将其理解为对本发明保护范围的限定。
电化学性能测试：使用CHI660-E型号电化学工作站进行电化学试验。铂电极和在饱和KCl溶液中的Ag/AgCl电极(3M)分别作为对比电极和参比电极。试验前取磷酸盐复合涂层面为工作面，其余面用硅橡胶进行封装绝缘。测试过程中样品浸泡在3.5wt％氯化钠溶液中的面积约为1cm2。伏安偏振扫描速率为2mV·s-1。为确保结果的可靠性，每次试验均进行了三次重复平行测量。
以下实施例和对比例中采用的金属基体为钛合金。
实施例1
(1)将0.4g三(羟甲基)氨基甲烷溶液与300ml去离子水混合搅拌均匀，滴入3滴盐酸将pH调至8.5，加入4g粒径10μm的六方氮化硼粉末，其微观形貌图参见图1(a)，超声30分钟，然后加入1.4g盐酸多巴胺，水浴60℃下搅拌6小时，得到的产物用去离子水洗涤3次，离心干燥得到经多巴胺修饰的六 方氮化硼粉末。
(2)将1g六水三氯化铁分散到200ml乙二醇中，再加入5g聚乙二醇和1.5g经多巴胺修饰的六方氮化硼粉末，超声1小时后，加入18g醋酸钠，并在60℃搅拌2小时，之后放入聚四氟乙烯反应釜100℃保温加热2小时，调至180℃再次加热15小时，得到的产物用去离子水洗涤3次，离心干燥得到经四氧化三铁修饰的六方氮化硼粉末。经四氧化三铁修饰六方氮化硼粉末微观形貌图参见图1(b)。
(3)将1.5g经四氧化三铁修饰六方氮化硼粉末分散到200ml去离子水中，滴加3ml氨水将pH调至10，常温搅拌20小时，搅拌过程中分10次滴加7ml质量浓度为30％的硅酸四乙酯溶液，得到的产物用去离子水洗涤三次，离心干燥得到六方氮化硼杂化材料。
(4)称取六方氮化硼杂化材料、固化剂和粘结剂。质量配比如下：六方氮化硼杂化材料22％、氧化锌2％、磷酸二氢铝76％。
(5)使用球磨机对六方氮化硼杂化材料、氧化锌进行混料，球磨时转速为250r·min-1，球磨时间为1h，球与料的质量比例为1.2:1，球采用玛瑙小球。
(6)向球磨后的粉末加磷酸二氢铝粘结剂，通过磁力搅拌使其充分混合均匀，搅拌时间1小时，得复合涂料。
(7)对金属基体表面进行粗糙化处理和清洗预处理。首先采用粗砂纸去除其表面锈斑和表面氧化层，接着经过流水初步冲刷表面磨屑；然后通过超声波清洗机超声清洗，清洗溶液为酒精，清洗时间为30分钟；最后利用吹风机干燥金属基体表面。
(8)通过刮涂法将复合涂料涂覆在经过处理的金属基体表面。
(9)对涂层进行固化处理，固化工艺为：先室温固化4小时，室温固化过 程中利用磁场强度为0.8T的弱磁场辅助作用控制六方氮化硼杂化材料的排列方向，磁场施加方向示意图参见图4，然后100℃、150℃、200℃、270℃各固化1小时，随炉冷却后，得到厚度为0.2mm的“砖-泥”层状结构耐腐蚀磷酸盐复合涂层，涂层微观形貌图参见图3(b)，所得极化曲线图及极化曲线所对应的电化学参数如图5和表1所示。
实施例2
(1)六方氮化硼杂化材料的制备方法同实施例1中的步骤(1)、(2)、(3)。
(2)称取六方氮化硼杂化材料、固化剂和粘结剂。质量配比如下：六方氮化硼杂化材料26％、氧化锌1％、磷酸二氢铝73％。
(3)使用球磨机对六方氮化硼杂化材料、氧化锌进行混料，球磨时转速为250r·min-1，球磨总时间为1小时，球与料的质量比例为1.2:1，球采用玛瑙小球。
(4)向球磨后的粉末加磷酸二氢铝粘结剂，通过磁力搅拌使其充分混合均匀，搅拌时间1小时，得复合涂料。
(5)对金属基体表面进行粗糙化处理和清洗预处理。首先采用粗砂纸去除其表面锈斑和表面氧化层，接着经过流水初步冲刷表面磨屑；然后通过超声波清洗机超声清洗，清洗溶液为酒精，清洗时间为30分钟；最后利用吹风机干燥金属基体表面。
(6)通过刮涂法将复合涂料涂覆在经过处理的金属基体表面。
(7)对涂层进行固化处理，固化工艺为：先室温固化4小时，室温固化过程中利用磁场强度为0.8T的弱磁场辅助作用控制六方氮化硼杂化材料的排列方向，磁场施加方向示意图参见图4，然后100℃、150℃、200℃、270℃各固化1小时，随炉冷却后得到厚度为0.2mm的“砖-泥”层状结构耐腐蚀磷酸盐复合涂 层，所得极化曲线图及极化曲线所对应的电化学参数如图5和表1所示。
实施例3
(1)六方氮化硼杂化材料的制备方法同实施例1中的步骤(1)、(2)、(3)。
(2)称取六方氮化硼杂化材料、固化剂和粘结剂。质量配比如下：六方氮化硼杂化材料30％、氧化锌2％、磷酸二氢铝68％。
(3)使用球磨机对六方氮化硼杂化材料、固化剂进行混料，球磨时转速为250r·min-1，球磨总时间为1小时，球与料的质量比例为1.2:1，球采用玛瑙小球。
(4)向球磨后的粉末加磷酸二氢铝粘结剂，通过磁力搅拌使其充分混合均匀，搅拌时间1小时，得复合涂料。
(5)对金属基体表面进行粗糙化处理和清洗预处理。首先采用粗砂纸去除其表面锈斑和表面氧化层，接着经过流水初步冲刷表面磨屑；然后通过超声波清洗机超声清洗，清洗溶液为酒精，清洗时间为30分钟；最后利用吹风机干燥金属基体表面。
(6)通过刮涂法将复合涂料涂覆在经过处理的金属基体表面。
(7)对涂层进行固化处理，固化工艺为：先室温固化4小时，室温固化过程中利用磁场强度为0.8T的弱磁场辅助作用控制六方氮化硼杂化材料的排列方向，磁场施加方向示意图参见图4，然后100℃、150℃、200℃、270℃各固化1小时，随炉冷却后得到厚度为0.2mm的“砖-泥”层状结构耐腐蚀磷酸盐复合涂层，所得极化曲线图及极化曲线所对应的电化学参数如图5和表1所示。
实施例4
按照实施例1的方法制备磷酸盐复合涂层，区别在于涂层梯度固化工艺为100℃、150℃、200℃、400℃各固化1小时，其它条件同实施例1，所得极化曲 线图及极化曲线所对应的电化学参数如图5和表1所示。
实施例5
按照实施例1的方法制备磷酸盐复合涂层，区别在于涂层梯度固化工艺为100℃、150℃、200℃、800℃各固化1小时，其它条件同实施例1，所得极化曲线图及极化曲线所对应的电化学参数如图5和表1所示。
对比例1
按照实施例1的方法制备磷酸盐复合涂层，区别在于未添加磁场，其它条件同实施例1，所得涂层微观形貌图、极化曲线图及极化曲线所对应的电化学参数如图3(a)、图5和表1所示。
对比例2
按照实施例2的方法制备磷酸盐复合涂层，区别在于未添加磁场，其它条件同实施例2，所得极化曲线图及极化曲线所对应的电化学参数如图5和表1所示。
对比例3
按照实施例3的方法制备磷酸盐复合涂层，区别在于未添加磁场，其它条件同实施例3，所得极化曲线图及极化曲线所对应的电化学参数如图5和表1所示。
对比例4
未涂覆磷酸盐复合涂层金属基体作为空白对照例，所采用的金属基体为钛合金，所得极化曲线图及极化曲线所对应的电化学参数如图5和表1所示。
对比例5
按照实施例3的方法制备磷酸盐复合涂层，区别在于六方氮化硼含量为32％、氧化锌1％、磷酸二氢铝67％，其它条件同实施例3。
对比例6
(1)将0.4g三(羟甲基)氨基甲烷溶液与300ml去离子水混合搅拌均匀， 滴入3滴盐酸将pH调至8.5，加入4g粒径10μm的六方氮化硼粉末，其微观形貌图参见图1(a)，超声30分钟，然后加入1.4g盐酸多巴胺，水浴60℃下搅拌6小时，得到的产物用去离子水洗涤3次，离心干燥得到经多巴胺修饰的六方氮化硼粉末。
(2)将1g六水三氯化铁分散到200ml乙二醇中，再加入5g聚乙二醇和1.5g经多巴胺修饰的六方氮化硼粉末，超声1小时后，加入18g醋酸钠，并在60℃搅拌2小时，之后放入聚四氟乙烯反应釜100℃保温加热2小时，调至180℃再次加热15小时，得到的产物用去离子水洗涤3次，离心干燥得到经四氧化三铁修饰的六方氮化硼粉末。
(3)称取经四氧化三铁修饰的六方氮化硼粉末、氧化锌和磷酸二氢铝。质量配比如下：经四氧化三铁修饰的六方氮化硼粉末22％、氧化锌2％、磷酸二氢铝76％。
(4)使用球磨机对经四氧化三铁修饰的六方氮化硼粉末、氧化锌进行混料，球磨时转速为250r·min-1，球磨时间为1h，球与料的质量比例为1.2:1，球采用玛瑙小球。
(5)向球磨后的粉末加磷酸二氢铝粘结剂，通过磁力搅拌使其充分混合均匀，搅拌时间1小时，得复合涂料。
(6)对金属基体表面进行粗糙化处理和清洗预处理。首先采用粗砂纸去除其表面锈斑和表面氧化层，接着经过流水初步冲刷表面磨屑；然后通过超声波清洗机超声清洗，清洗溶液为酒精，清洗时间为30分钟；最后利用吹风机干燥金属基体表面。
(7)通过刮涂法将复合涂料涂覆在经过处理的金属基体表面。
(8)对涂层进行固化处理，固化工艺为：先室温固化4小时，室温固化过 程中利用磁场强度为0.8T的弱磁场辅助作用控制经四氧化三铁修饰的六方氮化硼粉末的排列方向，磁场施加方向示意图参见图4，然后100℃、150℃、200℃、270℃各固化1小时，随炉冷却后，得到厚度为0.2mm的“砖-泥”层状结构耐腐蚀磷酸盐复合涂层，所得极化曲线图及极化曲线所对应的电化学参数如图5和表1所示。
表1为实施例1-5和对比例1-4、对比例6的电化学性能测试结果。
表1
从表1、图5可看出，相比于未涂覆磷酸盐复合涂层金属基体，涂覆本发明制备的“砖-泥”层状结构磷酸盐复合涂层后的金属基体，具备超高的物理隔绝效果以及更好的耐腐蚀特性，可以保护基体免受破坏，延长金属基体的使用寿命。随着六方氮化硼含量的增加，腐蚀电流密度降低，电阻值升高。但当六方氮化硼含量超过30％时，涂料内部颗粒感明显，难以搅拌均匀，并且粘度过高难以涂覆。对于同等含量的磷酸盐复合涂层，施加磁场的层状结构磷酸盐复合涂层耐腐蚀性能更高，主要归因于层状结构的引入将充分发挥片状填料对力学性能和隔绝效果的增强作用，进而显著提高涂层的耐腐蚀性能。
图2示出了未包覆二氧化硅的六方氮化硼杂化材料、包覆二氧化硅的六方氮 化硼杂化材料分散在磷酸二氢铝粘结剂中，静置0h和12h的照片。从图2、表1可看出，未包覆二氧化硅的六方氮化硼材料会与磷酸二氢铝反应，由于六方氮化硼经四氧化三铁修饰，将其置入磷酸二氢铝粘结剂中，会导致四氧化三铁与磷酸二氢铝发生置换反应，生成新的化学物质，失去磁性，进而影响“砖-泥”层状结构的构建，削弱涂层的耐腐蚀性能。二氧化硅的包覆可防止四氧化三铁与磷酸二氢铝粘结剂发生反应，进而有利于“砖-泥”层状结构的构建。
此外，固化温度的不同也会影响涂层的耐腐蚀能力，当固化温度达到400℃时，涂层的耐腐蚀性能得到明显提升，但是当固化温度达到800℃时，涂层-基体腐蚀电流密度升高，电阻值降低，涂层-基体系统耐腐蚀性能也随之下降。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (8)

  1. 一种“砖-泥”层状结构耐腐蚀磷酸盐复合涂层，其特征在于：其各原料的重量百分比为：六方氮化硼杂化材料18％～30％、固化剂1％～10％、磷酸盐粘结剂70％～80％；
    所述六方氮化硼杂化材料的制备方法包括如下步骤：
    步骤一、将三(羟甲基)氨基甲烷溶液与去离子水混合均匀，调节pH为8.5，然后加入六方氮化硼，六方氮化硼与三(羟甲基)氨基甲烷溶液的质量比为(90～95):(5～10)，超声处理后加入盐酸多巴胺，盐酸多巴胺与六方氮化硼的质量比为(20～40):(60～80)，50～80℃加热搅拌反应后，经洗涤、干燥，得到经多巴胺修饰的六方氮化硼粉末；
    步骤二、将六水三氯化铁溶解于乙二醇中，通过超声波浴将聚乙二醇和经多巴胺修饰的六方氮化硼添加到上述溶液中，然后加入醋酸钠，并在60～80℃下剧烈搅拌2～3h，将所得混合物密封在反应釜内，80～100℃保温加热2h后，温度升至160～240℃继续加热15～20h，然后冷却至室温，经洗涤、干燥，得到经四氧化三铁修饰的六方氮化硼粉末；其中，各原料的重量百分比为：六水三氯化铁2～4％，聚乙二醇18～23％，经多巴胺修饰的六方氮化硼粉末3～7％，醋酸钠66～77％；
    步骤三、将经四氧化三铁修饰的六方氮化硼粉末和去离子水混合，搅拌均匀，调节pH为10，常温搅拌20～24h，搅拌过程中滴加质量浓度为30％的硅酸四乙酯溶液，经四氧化三铁修饰的六方氮化硼粉末与硅酸四乙酯溶液的用量比为(1～2)g:(5～10)mL，搅拌结束后，经洗涤、干燥，得到六方氮化硼杂化材料。
  2. 根据权利要求1所述的“砖-泥”层状结构耐腐蚀磷酸盐复合涂层，其特征在于：所述固化剂为氧化镁和(或)氧化锌。
  3. 根据权利要求1所述的“砖-泥”层状结构耐腐蚀磷酸盐复合涂层，其特 征在于：所述粘结剂为磷酸二氢铝。
  4. 根据权利要求1所述的“砖-泥”层状结构耐腐蚀磷酸盐复合涂层，其特征在于：所述六方氮化硼的粒度为5μm～15μm。
  5. 根据权利要求1-4任一项所述的“砖-泥”层状结构耐腐蚀磷酸盐复合涂层的制备方法，其特征在于：包括如下步骤：称取六方氮化硼杂化材料、固化剂和粘结剂，将六方氮化硼杂化材料、固化剂球磨混合后，将粉体和粘结剂混合搅拌均匀，涂覆在预处理的金属基体上，在弱磁场环境下室温固化4小时后，再在100℃、150℃、200℃、270℃～800℃各固化1小时，随炉冷却，得到“砖-泥”层状结构耐腐蚀磷酸盐复合涂层。
  6. 根据权利要求5所述的“砖-泥”层状结构耐腐蚀磷酸盐复合涂层的制备方法，其特征在于：所述球磨转速为250r·min-1，球磨总时间为1小时，球与料的质量比例为1.2:1。
  7. 根据权利要求5所述的“砖-泥”层状结构耐腐蚀磷酸盐复合涂层的制备方法，其特征在于：所述弱磁场环境磁场强度为0.5～1.0T。
  8. 根据权利要求5所述的“砖-泥”层状结构耐腐蚀磷酸盐复合涂层的制备方法，其特征在于：所述预处理具体过程如下：先采用粗砂纸去除金属表面锈斑和表面氧化层，冲刷干净后，置于酒精清洗液中超声清洗，取出后干燥即可。
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