目的 WC基金属陶瓷涂层因高硬度、抗磨损性能好和耐腐蚀性能好的特点广泛应用于船用柴油机和船用燃气轮机的轴系部件（如推力轴承）与阀类产品（如燃油控制阀、放气阀）,上述部件在海洋环境服役时面临高温摩擦、磨损的问题,将制约船舶动力装置在长周期、高可靠性要求场景下的应用。但WC基涂层在高温下易氧化的问题有待解决,且涂层的润滑性能不足亦有待提升。方法 为赋予WC基涂层高温抗氧化性能与自润滑性能,利用超音速火焰喷涂技术在Ti6Al4V钛合金表面制备WC-NiMoCrFeCo涂层(S1),结合激光织构与高温真空浸渍工艺制备WC-NiMoCrFeCo-B2O3复合涂层（S2）。对S2涂层分别在25、800 ℃下进行摩擦学性能研究。结果 复合涂层（S2）在800 ℃下被B2O3覆盖区域未被氧化,S2涂层表面的B2O3展现优异的高温抗氧化性能。未改性涂层（S1）表面在800 ℃下发生氧化反应,氧化产物的主要成分为NiWO4和WO3。B2O3在高温下呈现熔融液态,湿润性好,流体覆盖于涂层表面可以隔绝空气,与涂层紧密贴合阻碍氧化。复合涂层（S2）在25 ℃和800 ℃时较未改性涂层（S1）均展现更优异的润滑性能。复合涂层（S2）在25 ℃和800 ℃下的平均摩擦系数分别为0.195和0.123,较未改性涂层分别降低55.7%和63.2%。B2O3具备良好的润滑性能,润滑机制为“扩散系数-界面反应”。结论 激光织构与B2O3润滑剂协同作用的复合涂层表面设计赋予WC-NiMoCrFeCo涂层高温抗氧化与润滑性能,这项研究成果有望为金属陶瓷涂层在海洋工程领域的深入应用提供一定的理论参考。
Abstract
Coatings with high temperature tribological properties are very important for marine diesel engines and marine gas turbines equipped with marine engineering equipment. For example, the theoretical working temperature of the bleed valve, low pressure fuel pump and high pressure fuel pump inside the marine gas turbine can reach 600 ℃, and the theoretical working temperature of the fuel injector inside the marine gas turbine and the oil separator inside the fuel system of the marine diesel engine can reach 720 ℃, all the above components are faced with the problems of oxidation corrosion and friction and wear at high temperature, which greatly reduces the structural reliability of the product itself and seriously affects the service life of the product. It is urgent to develop an integrated coating preparation technology to meet the high temperature self-lubricating performance of all product parts. WC-NiMoCrFeCo is sprayed on the surface of Ti6Al4V titanium alloy by supersonic flame spraying, and hexagonal honeycomb grooves are machined on the surface of the WC-NiMoCrFeCo composite coating by laser texture processing, the B2O3 powders are evenly coated in the groove after laser texturing, and the WC-NiMoCrFeCo-B2O3 composite coating (S2) is prepared by high temperature vacuum impregnation progress, so as to obtain better high temperature friction performance. The materials characterization tests are carried out by field emission electron microscope, X-ray diffractometer and X-ray photo-electron spectrometer, etc., in order to study the oxidation phenomenon of the composite coating (S2) at 800 ℃ and the friction and wear properties of the composite coating (S2) at 25 ℃ and 800 ℃. Through the above experiments, it is found that: the lubricating phase of the composite coating (S2) is tightly filled, the distribution of the lubricating phase is uniform, the overall structure is compact, and there are no defects such as cracks on the surface, the coating has good spraying quality. The composite coating (S2) has no oxidation reaction at the position covered by B2O3 at 800 ℃, and oxidation reaction occurs at the position not covered by B2O3. This phenomenon shows that B2O3 has an important influence on the high temperature oxidation resistance of the composite coating (S2) at high temperature. B2O3 has a certain viscosity, diffusion coefficient and shear modulus at 800 ℃, and it migrates to the contact zone due to the influence of the shear force during friction, and B2O3 has chemical stability and high temperature oxidation resistance. The surface of the unmodified composite coating (S1) undergoes oxidation reaction at 800 ℃, the surface is accompanied by dense yellow oxide. The composition and micro-structure of the surface of the unmodified composition coating (S1) are analyzed, and it is known that the main oxides are NiWO4 and WO3. At the initial stage of the oxidation reaction, the oxygen content near the surface of the composite coating (S1) is sufficient, and the oxidation reaction is mainly dominated by the interface reaction. Tungsten on the surface of the composite coating (S1) preferentially reacts with oxygen to generate WO3, and the CO2 generated by the reaction enters the atmosphere. With the increase of the temperature, the energy of molecules gradually increases, the movement becomes more intense, the percentage of activated molecules increases, the inward diffusion of oxygen ions increases oxides, and the adsorption between molecules increases. Ni and WO3 undergo an oxidation reaction to generate NiWO4, which is effectively adsorbed on the coating surface, and WO3 particles are wrapped in cotton-like NiWO4 and melted together. The friction coefficient of the composite coating (S2) is lower than that of the unmodified composite coating (S1) at 25 ℃ and 800 ℃. The lubricity of the composite coating (S2) is better at 800 ℃ than that at 25 ℃. This phenomenon is due to the high temperature synergistic lubrication mechanism of the lubricating phase of the composite coating (S2). The surface design of the composite coating combined with texture grooves and B2O3 lubrication may meet the requirements of improving the high temperature tribological properties of the hard wear-resistant coating.
关键词
热喷涂技术 /
激光织构 /
WC-NiMoCrFeCo-B2O3复合涂层 /
高温抗氧化 /
高温摩擦学 /
自润滑机理
Key words
thermal spraying technology /
laser texture /
WC-NiMoCrFeCo-B2O3 composite coating /
high temperature oxidation resistance /
high temperature tribology /
self-lubricating mechanism
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基金
广东省基础与应用基础研究基金项目（2023A1515012765）
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