A wide-temperature-range lubricating and protective coating as well as a preparation method and application thereof, and a wide-temperature-range lubricating and protective coating

Abstract

The application provides a wide-temperature-range lubricating and protective coating, a preparation method and application thereof, and a wide-temperature-range lubricating and protective coating, and belongs to the field of protective coatings. The wide-temperature-range lubricating and protective coating comprises the following raw materials in parts by mass: a silicon-based polymer ceramic precursor 5.0-15.0 parts, molybdenum disulfide 10.0-30.0 parts, graphite 2.0-8.0 parts, MXene 2.0-8.0 parts, inorganic oxyacid salt 1.0-5.0 parts, high-entropy ceramic 1.0-5.0 parts, zirconium boride 1.0-5.0 parts, boron carbide 1.0-5.0 parts, aluminum oxide 1.0-5.0 parts, a dispersion medium 40.0-60.0 parts, and an additive 1.0-5.0 parts. The wide-temperature-range lubricating and protective coating prepared from the wide-temperature-range lubricating and protective coating has not only a low friction coefficient and wear rate in a wide temperature range, but also excellent temperature resistance, wear resistance, good adhesion to a substrate and other advantages.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of protective coating, in particular to a wide-temperature-range lubricating and protective coating material, a preparation method and application thereof, and a wide-temperature-range lubricating and protective coating. BACKGROUND

[0002] In recent years, with the rapid development of high-end equipment, the friction and wear characteristics of precision basic parts such as air foil bearings, gas turbine seals, low heat dissipation diesel engine piston rings and cylinder walls, and large thrust bearing assemblies involved in extreme working conditions have a great influence on the system reliability and service life. In particular, how to ensure the normal operation of high-end equipment in high-temperature environments and wide temperature range changes has always been a difficult problem and is one of the bottlenecks restricting the development of key equipment in high-end technical fields. Conventional lubricants, such as liquid lubricants, polymer lubricants and some traditional solid lubricants, will lose their lubricating properties due to oxidation at high temperatures. Therefore, the high performance, high efficiency and durability of the core moving parts and technologies of these high-end equipment depend on wide-temperature-range solid lubricating coating materials. Therefore, it is particularly important to prepare a solid lubricating coating material with low friction and wear properties in a wide temperature range.

[0003] Silicon-based ceramic precursors have been developed due to their unique structural properties, which can be converted into SiCNO, SiCN, SiC, SiNx or silicon dioxide ceramic materials at high temperatures. Compared with the adhesives of traditional adhesive coatings, the silicon-based ceramic precursors as adhesives have the advantages of strong bonding force with the substrate, good temperature resistance, simple preparation process, uniform stress distribution, etc. At present, the polymer precursor conversion method has been applied in ceramic matrix composites, porous materials, functional ceramics, protective coatings, adhesives, etc., which has benefited the development of aerospace, microelectronics, information storage and other fields. The high-temperature-resistant lubricating and protective coating prepared by using polymer precursors as adhesives has a low friction coefficient and wear rate at high temperatures. In order to meet the development needs of modern industry, it is urgent to develop a coating material with low friction coefficient and wear rate from low temperature to high temperature. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a wide-temperature-range lubricating and protective coating material, a preparation method and application thereof, and a wide-temperature-range lubricating and protective coating. The wide-temperature-range lubricating and protective coating provided by the present application has good lubricating and wear-resistant properties in a wide temperature range.

[0005] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:

[0006] The present application provides a wide-temperature-range lubricating and protective coating material, which comprises the following raw materials in mass fraction:

[0007] The precursor binder 5.0-15.0 parts, molybdenum disulfide 10.0-30.0 parts, graphite 2.0-8.0 parts, MXene 2.0-8.0 parts, inorganic oxyacid salt 1.0-5.0 parts, high-entropy ceramic 1.0-5.0 parts, zirconium boride 1.0-5.0 parts, boron carbide 1.0-5.0 parts, aluminum oxide 1.0-5.0 parts, dispersion medium 40.0-60.0 parts and auxiliary agent 1.0-5.0 parts; the precursor binder includes a silicon-based polymer ceramic precursor.

[0008] Preferably, the silicon-based polymer ceramic precursor includes one or more of polysilane, polymethylsilane, polycarbosilane, hydrogenated polycarbosilane, allyl hydrogenated polycarbosilane, polyzirconium carbosilane, polysiloxane, polymethylsiloxane, polysilazane, polyurea silazane and polyborosilazane.

[0009] Preferably, the inorganic oxyacid salt includes one or more of molybdate, chromate, sulfate and tungstate.

[0010] Preferably, the molybdate includes one or more of silver molybdate, barium molybdate, calcium molybdate, lead molybdate and nickel molybdate; the chromate includes barium chromate; the sulfate includes strontium sulfate and / or calcium sulfate; the tungstate includes sodium tungstate.

[0011] Preferably, the high-entropy ceramic includes one or more of (CoCuMgNiZn)O, (TiZrNbTaMo)C, (VNbTaMoW)C, (CrNbSiTiZr)C, (CrTaNbMoV)N and (AlCrNbSiTiMo)N.

[0012] Preferably, the particle size of the molybdenum disulfide is 1-10 μm; the particle size of the graphite is 1-10 μm; the particle size of the high-entropy ceramic is less than 10 μm; the particle size of the zirconium boride is 1-20 μm; the particle size of the boron carbide is 1-20 μm; the particle size of the aluminum oxide is 1-10 μm.

[0013] Preferably, the auxiliary agent includes wet dispersant, defoaming agent, leveling agent and anti-settling agent; the mass ratio of the wet dispersant, defoaming agent, leveling agent and anti-settling agent is (0.9-1.1):(1.0-1.2):(0.8-1.0):(0-0.8).

[0014] The application also provides a preparation method of the wide-temperature-range lubricating and protective coating.

[0015] The molybdenum disulfide, inorganic oxyacid salt, graphite, MXene, high-entropy ceramic, zirconium boride, boron carbide and aluminum oxide are first mixed, and then mixed with the first dispersion medium to obtain a first mixed slurry.

[0016] mixing the precursor binder and the second dispersion medium to obtain a precursor binder solution;

[0017] mixing the first mixed slurry, the precursor binder solution, the additive and the third dispersion medium to obtain the wide-temperature-range lubricating and protective coating; the total mass of the first dispersion medium, the second dispersion medium and the third dispersion medium is the mass of the dispersion medium.

[0018] The application further provides application of the wide-temperature-range lubricating and protective coating or the wide-temperature-range lubricating and protective coating prepared by the preparation method in preparation of a wide-temperature-range lubricating and protective coating layer.

[0019] A wide-temperature-range lubricating and protective coating layer is prepared by a method comprising the following steps:

[0020] After the wide-temperature-range lubricating and protective coating or the wide-temperature-range lubricating and protective coating prepared by the preparation method is sprayed on the surface of a metal substrate, heat curing and ceramic treatment in a special atmosphere are sequentially performed to obtain the wide-temperature-range lubricating and protective coating layer.

[0021] The special atmosphere comprises ammonia, nitrogen or argon.

[0022] The application provides a wide-temperature-range lubricating and protective coating, which comprises the following raw materials in mass fractions: 5.0-15.0 parts of a precursor binder, 10.0-30.0 parts of molybdenum disulfide, 2.0-8.0 parts of graphite, 2.0-8.0 parts of MXene, 1.0-5.0 parts of an inorganic oxyacid salt, 1.0-5.0 parts of high-entropy ceramic, 1.0-5.0 parts of zirconium boride, 1.0-5.0 parts of boron carbide, 1.0-5.0 parts of aluminum oxide, 40.0-60.0 parts of a dispersion medium and 1.0-5.0 parts of an additive; the precursor binder comprises a silicon-based polymer ceramic precursor.

[0023] Compared with the prior art, the application has the following beneficial effects:

[0024] In the present application, the silicon-based polymer ceramic precursor is an adhesive which not only has good processability and high-temperature resistance of inorganic ceramic formed by pyrolysis, but also can give the coating excellent wear resistance and good bonding ability with the metal substrate; the molybdenum disulfide can improve the lubrication and protection coating in a wide temperature range in the low and medium temperature (room temperature-300℃) sliding wear resistance; the graphite can effectively improve the friction reduction and wear resistance of the lubrication and protection coating in a wide temperature range in the medium and high temperature (300-500℃); the MXene has good mechanical and tribological properties; the inorganic oxyacid salt can form a continuous lubricating film on the wear surface at high temperature (500-800℃), thereby reducing the friction coefficient and wear rate of the material pair; the high-entropy ceramic has high-temperature stability, excellent mechanical properties, good wear resistance and corrosion resistance and toughness; the boron carbide and zirconium boride can compensate for the heat loss of the precursor adhesive, increase the coating mass through high-temperature oxidation reaction in the friction process, and improve the coating density, and the oxidation products are boron trioxide with high-temperature lubrication performance and zirconium dioxide with wear resistance; the aluminum trioxide can give the coating excellent corrosion resistance and wear resistance, and can also compensate for the defects caused by the volume shrinkage of the precursor polymer during the conversion to inorganic ceramic in a special atmosphere; the additives ensure that the lubrication and protection coating in a wide temperature range is not easy to settle, and the fillers such as molybdenum disulfide, graphite, MXene, inorganic oxyacid, high-entropy ceramic, zirconium boride, boron carbide, aluminum trioxide and the like are uniformly dispersed in the system and have good wetting and leveling properties on the substrate surface; the coating formed by the present application is dense, free of bubbles, nodules and other defects.

[0025] The present application also provides a lubrication and protection coating in a wide temperature range, which, when used as a lubricating coating for high-end equipment under extreme harsh conditions, not only has a low friction coefficient and wear rate in a wide temperature range, but also has excellent temperature resistance, wear resistance, good adhesion to the substrate and other advantages. DETAILED DESCRIPTION

[0026] The present application provides a lubrication and protection coating in a wide temperature range, which comprises the following raw materials by mass:

[0027] The precursor adhesive is 5.0-15.0 parts, the molybdenum disulfide is 10.0-30.0 parts, the graphite is 2.0-8.0 parts, the MXene is 2.0-8.0 parts, the inorganic oxyacid salt is 1.0-5.0 parts, the high-entropy ceramic is 1.0-5.0 parts, the zirconium boride is 1.0-5.0 parts, the boron carbide is 1.0-5.0 parts, the aluminum trioxide is 1.0-5.0 parts, the dispersing medium is 40.0-60.0 parts, and the additive is 1.0-5.0 parts; and the precursor adhesive comprises a silicon-based polymer ceramic precursor.

[0028] In the present application, all the raw materials for preparation are commercially available products well known to those skilled in the art unless otherwise specified.

[0029] The wide-temperature-range lubricating and protective coating according to the present application comprises 5.0-15.0 parts by weight, preferably 6.0-12.0 parts by weight, and more preferably 8.0-10.0 parts by weight of a precursor binder. In the present application, the precursor binder is a silicon-based polymer ceramic precursor; the silicon-based polymer ceramic precursor preferably comprises one or more of polysilane, polymethylsilane, polycarbosilane, hydrogenated polycarbosilane, allyl hydrogenated polycarbosilane, polyzirconocarbosilane, polysiloxane, polymethylsiloxane, polysilazane, polyureasilazane, and polyborosilazane; when the silicon-based polymer ceramic precursor is preferably two or more of the above specific choices, the present application does not have any special limitation on the ratio of the above specific substances, and any ratio can be mixed. In the present application, the silicon-based polymer ceramic precursor can be heat-crosslinked and cured under special atmosphere protection, and can form a ceramic phase with functions of heat-resistant ablation resistance, heat insulation, and wear resistance after pyrolysis.

[0030] The wide-temperature-range lubricating and protective coating according to the present application comprises 10.0-30.0 parts by mass, preferably 15.0-25.0 parts by mass, and more preferably 18.0-22.0 parts by mass of molybdenum disulfide based on the mass of the precursor binder. In the present application, the particle size of the molybdenum disulfide is preferably 1-10 μm, more preferably 2-8 μm, and most preferably 4-6 μm. In the present application, the molybdenum disulfide has excellent lubricating properties and good adhesion.

[0031] The wide-temperature-range lubricating and protective coating according to the present application comprises 2.0-8.0 parts by mass, preferably 3.0-7.0 parts by mass, and more preferably 4.0-5.0 parts by mass of graphite based on the mass of the precursor binder. In the present application, the particle size of the graphite is preferably 1-10 μm, more preferably 2-8 μm, and most preferably 4-6 μm. In the present application, the graphite has strong binding force and excellent lubricating properties.

[0032] The wide-temperature-range lubricating and protective coating according to the present application comprises 2.0-8.0 parts by mass, preferably 4.0-7.0 parts by mass, and more preferably 5.0-6.0 parts by mass of MXene based on the mass of the precursor binder. In the present application, the MXene has good mechanical and tribological properties.

[0033] The wide-temperature-range lubricating and protective coating of the present application comprises 1.0-5.0 parts by mass of inorganic oxyacid salt, preferably 2.0-4.0 parts, and more preferably 2.5-3.5 parts, based on the mass of the precursor binder. In the present application, the inorganic oxyacid salt preferably comprises one or more of molybdate, chromate, sulfate and tungstate, the molybdate preferably comprises one or more of silver molybdate, barium molybdate, calcium molybdate, lead molybdate and nickel molybdate; the chromate preferably comprises barium chromate; the sulfate preferably comprises strontium sulfate and / or calcium sulfate; and the tungstate preferably comprises sodium tungstate. When the inorganic oxyacid salt preferably comprises two or more of the above-mentioned specific substances, the present application does not have any special limitation on the ratio of the above-mentioned specific substances, and the mixing can be performed in any ratio. In the present application, the inorganic oxyacid salt can form a continuous lubricating film on the worn surface at high temperature, thereby reducing the friction coefficient and wear rate of the mating material.

[0034] The wide-temperature-range lubricating and protective coating of the present application comprises 1.0-5.0 parts by mass of high-entropy ceramic, preferably 2.0-4.0 parts, and more preferably 2.5-3.5 parts, based on the mass of the precursor binder. In the present application, the particle size of the high-entropy ceramic is preferably less than 10 μm, more preferably 1-8 μm, and most preferably 3-6 μm. In the present application, the high-entropy ceramic preferably comprises one or more of (CoCuMgNiZn)O, (TiZrNbTaMo)C, (VNbTaMoW)C, (CrNbSiTiZr)C, (CrTaNbMoV)N and (AlCrNbSiTiMo)N. When the high-entropy alloy preferably comprises two or more of the above-mentioned specific choices, the present application does not have any special limitation on the ratio of the above-mentioned specific substances, and the mixing can be performed in any ratio. In the present application, the high-entropy ceramic has high-temperature stability, excellent mechanical properties, good wear resistance and corrosion resistance, and toughness.

[0035] The wide-temperature-range lubricating and protective coating of the present application comprises 1.0-5.0 parts by mass of zirconium boride, preferably 2.0-4.0 parts, and more preferably 2.5-3.5 parts, based on the mass of the precursor binder. In the present application, the particle size of the zirconium boride is preferably 1-20 μm, more preferably 5-15 μm, and most preferably 8-10 μm.

[0036] The wide-temperature-range lubricating and protective coating of the present application comprises 1.0-5.0 parts by mass of boron carbide, preferably 2.0-4.0 parts, and more preferably 2.5-3.5 parts, based on the mass of the precursor binder. In the present application, the particle size of the boron carbide is preferably 1-20 μm, more preferably 5-15 μm, and most preferably 8-10 μm.

[0037] In the present application, the zirconium boride and boron carbide can make up for the heat loss of the precursor binder, improve the ceramic yield, increase the coating quality through high-temperature oxidation reaction, and improve the coating density, and the oxidation products are boron trioxide with high-temperature lubricating property and zirconium dioxide with wear-resistant property.

[0038] In the present application, the wide-temperature-range lubricating and protective coating includes 1.0-5.0 parts of aluminum oxide by mass fraction of the precursor binder, preferably 2.0-4.0 parts, and more preferably 2.5-3.5 parts. In the present application, the particle size of the aluminum oxide is preferably 1-10 μm, more preferably 2-8 μm, and most preferably 4-6 μm. In the present application, the aluminum oxide can impart excellent corrosion resistance and wear resistance to the coating, and can also make up for the defects caused by the volume shrinkage of the precursor polymer during the conversion to inorganic ceramic in a special atmosphere.

[0039] In the present application, the wide-temperature-range lubricating and protective coating includes 40.0-60.0 parts of the dispersing medium by mass fraction of the precursor binder, preferably 45.0-55.0 parts, and more preferably 48.0-52.0 parts. In the present application, the dispersing medium preferably includes one or more of n-butyl ether, dimethylbenzene, 1,1,2-trichlorotrifluoroethane, and propylene glycol methyl ether acetate; when the dispersing medium is preferably two or more of the above specific choices, the present application does not have any special limitation on the ratio of the above specific substances, and mixing in any ratio can be performed.

[0040] In the present application, the high-temperature-resistant lubricating and protective coating includes 1.0-5.0 parts of the additive by mass fraction of the precursor binder, more preferably 2.0-4.0 parts, and most preferably 2.5-3.5 parts; in the present application, the additive preferably includes a wetting dispersant, a defoaming agent, a leveling agent, and an anti-settling agent; the mass ratio of the wetting dispersant, the defoaming agent, the leveling agent, and the anti-settling agent is preferably (0.9-1.1):(1.0-1.2):(0.8-1.0):(0-0.8), and more preferably 1:1:1:0, 1:1.1:1:0, or 1.1:1.2:0.9:0. In the present application, the wetting dispersant preferably includes Tech-5061 and / or Tech-5063; the defoaming agent preferably includes Tech-367N and / or Tech-341; the leveling agent preferably includes Tech-154N and / or Tech-2730; and the anti-settling agent preferably includes silicon dioxide and / or organic bentonite.

[0041] The present application also provides a preparation method of the wide-temperature-range lubricating and protective coating according to the above technical solution, which includes the following steps:

[0042] The molybdenum disulfide, inorganic oxyacid salt, graphite, MXene, high-entropy ceramic, zirconium boride, boron carbide and aluminum oxide are first mixed to obtain a first mixed slurry, and then mixed with a first dispersion medium.

[0043] The precursor binder and the second dispersion medium are second mixed to obtain a precursor binder solution.

[0044] The first mixed slurry, the precursor binder solution, the auxiliary agent and a third dispersion medium are third mixed to obtain the wide-temperature-range lubricating and protective coating; the total mass of the first dispersion medium, the second dispersion medium and the third dispersion medium is the mass of the dispersion medium.

[0045] The molybdenum disulfide, inorganic oxyacid salt, graphite, MXene, high-entropy ceramic, zirconium boride, boron carbide and aluminum oxide are first mixed to obtain a first mixed slurry.

[0046] The present application does not have any special limitation on the process of the first mixing, and the process known to those skilled in the art can be used.

[0047] In the present application, the mixing with the first dispersion medium is preferably first adding part of the first dispersion medium to the mixture obtained by the first mixing, then sequentially performing first stirring and grinding, and then adding the remaining first dispersion medium for second stirring. In the present application, the total of the part of the first dispersion medium and the remaining first dispersion medium is the first dispersion medium. The present application does not have any special limitation on the mass ratio of the part of the first dispersion medium and the remaining first dispersion medium, and any ratio can be mixed. In the present application, the present application does not have any special limitation on the process of the first stirring and the second stirring, and the process known to those skilled in the art can be used. In the present application, the rotation speed of the grinding is preferably 400 rpm, the time is preferably 6-24 h, more preferably 8-18 h, and most preferably 12-16 h. In the present application, the grinding is preferably performed in a ball mill.

[0048] After the second stirring is completed, the present application further preferably includes filtering; the filter cloth used in the filtering is preferably a 200-mesh filter cloth.

[0049] After obtaining the first mixed slurry, the present application second mixes the precursor binder and the second dispersion medium to obtain a precursor binder solution.

[0050] The present application does not have any special limitation on the way of the second mixing, and the way known to those skilled in the art can be used.

[0051] After obtaining the precursor binder solution, the first mixed slurry, the precursor binder solution, the auxiliary agent and the third dispersion medium are mixed to obtain the wide-temperature-range lubricating and protective coating.

[0052] In the present application, the third mixing is preferably mixing the first mixed slurry and the precursor binder solution first, and then adding the third dispersion medium and the auxiliary agent. The present application does not have any special limitation on the way of the third mixing, which can be carried out in a manner known to those skilled in the art.

[0053] The present application does not have any special limitation on the ratio of the first dispersion medium, the second dispersion medium and the third dispersion medium, which can be mixed in any ratio.

[0054] The present application also provides the use of the wide-temperature-range lubricating and protective coating prepared by the above technical solution or the wide-temperature-range lubricating and protective coating prepared by the preparation method to prepare a wide-temperature-range lubricating and protective coating.

[0055] The present application provides a wide-temperature-range lubricating and protective coating prepared by a method comprising the following steps:

[0056] After the wide-temperature-range lubricating and protective coating prepared by the above technical solution or the wide-temperature-range lubricating and protective coating prepared by the preparation method is sprayed on the surface of the metal substrate, heat curing and ceramic treatment under a special atmosphere are carried out in sequence to obtain the wide-temperature-range lubricating and protective coating.

[0057] The special atmosphere includes ammonia, nitrogen or argon.

[0058] In the present application, before the spraying, the present application also preferably includes sandblasting treatment of the metal substrate.

[0059] In the present application, the surface roughness of the metal substrate after the sandblasting treatment is preferably 0.5-4.0 μm, and more preferably 1.0-3.0 μm. The present application does not have any special limitation on the conditions of the sandblasting treatment, which can be ensured to meet the above requirements of the surface roughness of the metal substrate in a manner known to those skilled in the art.

[0060] The present application does not have any special limitation on the type of the metal substrate, which can be used in a manner known to those skilled in the art.

[0061] The present application does not have any special limitation on the process of the spraying, which can be used in a manner known to those skilled in the art, and preferably the thickness of the coating obtained by the spraying is in the range of 10-40 μm.

[0062] In the present application, the temperature of the heat curing is preferably 70-150°C, more preferably 80-120°C, and most preferably 90-100°C; and the time is preferably 1-6h, more preferably 2-4h.

[0063] In the present application, the temperature of the ceramicization treatment is preferably 300-900°C, more preferably 400-800°C, and most preferably 500-600°C; and the time is preferably 0.5-3h, more preferably 1-2h.

[0064] The technical solutions in the present application will be described clearly and completely below in combination with the embodiments in the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0065] Embodiment 1

[0066] After 3.6g of molybdenum disulfide (particle size 5-8μm), 0.8g of graphite (particle size 5-8μm), 1.0g of MXene, 0.5g of silver molybdate and barium chromate with a mass ratio of 1:1, 0.5g of (CoCuMgNiZn)O high-entropy ceramic, 0.5g of zirconium boride, 0.5g of boron carbide and 0.5g of aluminum oxide are mixed, 4.0g of dimethylbenzene and 1.0g of propylene glycol methyl ether acetate are added and stirred uniformly, and then the mixture is ground (at a speed of 400rpm) for 12h, 1.0g of dimethylbenzene and 1.0g of propylene glycol methyl ether acetate are added and stirred fully, and then the mixture is filtered with a 200-mesh filter cloth to obtain a first mixed slurry;

[0067] 1.6g of polysilazane and 2.5g of dimethylbenzene are mixed and stirred to dilute the polysilazane, and a polysilazane solution is obtained.

[0068] The first mixed slurry and the polysiloxane solution are mixed, 0.5g of propylene glycol methyl ether acetate, 0.17g of Tech-5061, 0.17g of Tech-341 and 0.16g of Tech-2730 are added, and the wide-temperature-range lubricating and protective coating is obtained.

[0069] The metal substrate (high-temperature alloy C276) is subjected to sand blasting treatment to make the surface roughness of the metal substrate 2.5μm.

[0070] The wide-temperature-range lubricating and protective coating is obtained by spraying the wide-temperature-range lubricating and protective coating on the surface of the sand-blasted metal substrate (with a thickness of 30μm), heat curing at 70°C for 2h, and ceramicization at 700°C under nitrogen atmosphere protection for 2h.

[0071] Embodiment 2

[0072] After 3.6 g of molybdenum disulfide (particle size 5-8 μm), 0.8 g of graphite (particle size 5-8 μm), 1.0 g of MXene, 0.5 g of silver molybdate, calcium molybdate and barium molybdate with a mass ratio of 1:1:1, 0.5 g of (TiZrNbTaMo)C high-entropy ceramic, 0.5 g of zirconium boride, 0.5 g of boron carbide and 0.5 g of aluminum oxide are mixed, 4.0 g of dimethylbenzene and 1.0 g of propylene glycol methyl ether acetate are added and stirred uniformly, then grinded (the rotation speed of grinding is 400 rpm) for 12 h, 1.0 g of dimethylbenzene and 1.0 g of propylene glycol methyl ether acetate are added and stirred fully, then filtered with a 200-mesh filter cloth, a first mixed slurry is obtained;

[0073] 1.6 g of polyborosilazane and 2.5 g of dimethylbenzene are mixed and stirred to dilute the polyborosilazane, and a polyborosilazane solution is obtained;

[0074] The first mixed slurry and the polyborosilazane solution are mixed, 0.5 g of propylene glycol methyl ether acetate, 0.17 g of Tech-5061, 0.17 g of Tech-341 and 0.16 g of Tech-2730 are added, and the wide-temperature-range lubricating and protective coating is obtained;

[0075] The metal substrate (high-temperature alloy C276) is subjected to sand blasting treatment, so that the surface roughness of the metal substrate is 2.5 μm;

[0076] The wide-temperature-range lubricating and protective coating is obtained by spraying the wide-temperature-range lubricating and protective coating on the surface of the sand-blasted metal substrate (thickness is 30 μm), hot curing at 70 ℃ for 2 h, and ceramicizing at 700 ℃ under the protection of ammonia atmosphere for 2 h.

[0077] Example 3

[0078] After 3.6 g of molybdenum disulfide (particle size 5-8 μm), 0.8 g of graphite (particle size 5-8 μm), 1.0 g of MXene, 0.5 g of silver molybdate, potassium molybdate and nickel molybdate with a mass ratio of 1:1:1, 0.5 g of (AlCrNbSiTiMo)N and (CoCuMgNiZn)O high-entropy ceramic with a mass ratio of 1:1, 0.5 g of zirconium boride, 0.5 g of boron carbide and 0.5 g of aluminum oxide are mixed, 4.0 g of dimethylbenzene and 1.0 g of propylene glycol methyl ether acetate are added and stirred uniformly, then grinded (the rotation speed of grinding is 400 rpm) for 12 h, 1.0 g of dimethylbenzene and 1.0 g of propylene glycol methyl ether acetate are added and stirred fully, then filtered with a 200-mesh filter cloth, a first mixed slurry is obtained;

[0079] 1.6 g of polycarbosilane and polysiloxane with a mass ratio of 1:1 were mixed with 2.5 g of xylene to dilute the polycarbosilane and polysiloxane, and a polycarbosilane and polysiloxane solution was obtained;

[0080] The first mixed slurry and the polycarbosilane and polysiloxane solution were mixed, and 0.5 g of propylene glycol methyl ether acetate, 0.17 g of Tech-5061, 0.17 g of Tech-341, and 0.16 g of Tech-2730 were added to obtain the wide-temperature-range lubrication and protection coating;

[0081] The metal substrate (high-temperature alloy C276) was sandblasted to have a surface roughness of 2.5 μm;

[0082] After the wide-temperature-range lubrication and protection coating was sprayed on the surface of the sandblasted metal substrate (30 μm thick), 70°C thermal curing for 2 h, and ceramicization at 700°C in an argon atmosphere for 2 h, the wide-temperature-range lubrication and protection coating was obtained.

[0083] Example 4

[0084] After 3.6 g of molybdenum disulfide (particle size 5-8 μm), 0.8 g of graphite (particle size 5-8 μm), 1.0 g of MXene, 0.5 g of silver molybdate and sodium tungstate with a mass ratio of 1:1, 0.5 g of (CoCuMgNiZn)O and (TiZrNbTaMo)C high-entropy ceramic with a mass ratio of 1:1, 0.5 g of zirconium boride, 0.5 g of boron carbide, and 0.5 g of aluminum oxide were mixed, 4.0 g of xylene and 1.0 g of propylene glycol methyl ether acetate were added and stirred uniformly, and then ground (at a speed of 400 rpm) for 12 h, 1.0 g of xylene and 1.0 g of propylene glycol methyl ether acetate were added and stirred fully, and then filtered with a 200-mesh filter cloth to obtain a first mixed slurry;

[0085] 1.6 g of polycarbosilane and polysiloxane with a mass ratio of 1:1 were mixed with 2.5 g of xylene to dilute the polycarbosilane and polysiloxane, and a polycarbosilane and polysiloxane solution was obtained;

[0086] The first mixed slurry and the polycarbosilane and polysiloxane solution were mixed, and 0.5 g of propylene glycol methyl ether acetate, 0.17 g of Tech-5061, 0.17 g of Tech-341, and 0.16 g of Tech-2730 were added to obtain the wide-temperature-range lubrication and protection coating;

[0087] The metal substrate (high-temperature alloy C276) was sandblasted to have a surface roughness of 2.5 μm;

[0088] After the wide-temperature-range lubricating and protecting coating is sprayed on the surface of the sand-blasted metal substrate (30 μm in thickness), the wide-temperature-range lubricating and protecting coating is obtained after 70 ℃ heat curing for 2 h and ceramicization under the protection of a nitrogen atmosphere at 700 ℃ for 2 h.

[0089] Example 5

[0090] After 3.6 g of molybdenum disulfide (5-8 μm in particle size), 0.8 g of graphite (5-8 μm in particle size), 1.0 g of MXene, 0.5 g of calcium molybdate and barium molybdate at a mass ratio of 1:1, 0.5 g of (AlCrNbSiTiMo)N and (TiZrNbTaMo)C high-entropy ceramics at a mass ratio of 1:1, 0.5 g of zirconium boride, 0.5 g of boron carbide, and 0.5 g of aluminum oxide are mixed, 4.0 g of dimethylbenzene and 1.0 g of propylene glycol methyl ether acetate are added and stirred uniformly, and then the mixture is ground (at a rotation speed of 400 rpm) for 12 h, 1.0 g of dimethylbenzene and 1.0 g of propylene glycol methyl ether acetate are added and stirred fully, and then the mixture is filtered with a 200-mesh filter cloth to obtain a first mixed slurry;

[0091] After 1.6 g of polysilazane and polyzirconium carbosilane at a mass ratio of 1:1 are mixed with 2.5 g of dimethylbenzene and stirred, the polysilazane and polyzirconium carbosilane are diluted to obtain a polysilazane and polyzirconium carbosilane solution;

[0092] The first mixed slurry and the polysilazane and polyzirconium carbosilane solution are mixed, 0.5 g of propylene glycol methyl ether acetate, 0.17 g of Tech-5061, 0.17 g of Tech-341, and 0.16 g of Tech-2730 are added to obtain the wide-temperature-range lubricating and protecting coating.

[0093] A metal substrate (high-temperature alloy C276) is subjected to sand-blasting treatment to make the surface roughness of the metal substrate 2.5 μm.

[0094] After the wide-temperature-range lubricating and protecting coating is sprayed on the surface of the sand-blasted metal substrate (30 μm in thickness), the wide-temperature-range lubricating and protecting coating is obtained after 70 ℃ heat curing for 2 h and ceramicization under the protection of a nitrogen atmosphere at 700 ℃ for 2 h.

[0095] Test Example 1

[0096] The wide-temperature-range lubricating and protecting coatings described in Examples 1-5 are subjected to performance testing.

[0097] Thickness testing: The coating thickness is tested by a thickness tester according to the method of GB 1764-79 (89).

[0098] Bonding strength testing: The bonding strength is tested according to the cross-hatch method of GB / T 9286-1998.

[0099] Tribological performance test, test conditions: test temperature 25-800 DEG C, load 2N, Φ=3mm nickel-based superalloy, rotating mode speed 100rpm, test time 30min.

[0100] Neutral salt spray: according to the specification of GB / T 10125-2012, the neutral salt spray test is carried out on bare carbon steel and coating.

[0101] Wear rate test: the surface profilometer is selected to measure the wear amount, and then the wear rate calculation formula is used for calculation as follows:

[0102]

[0103] In the formula, ΔV is the wear volume change, mm 3 ; S is the stroke, m; P is the load size, N;

[0104] The test results are shown in Table 1, and it can be known from Table 1 that the wide temperature range lubricating and protective coating prepared by the application not only has a low friction coefficient and wear rate in a wide temperature range, but also has excellent temperature resistance, wear resistance, good adhesion with the substrate and other advantages.

[0105] Table 1 Performance parameters of the wide temperature range lubricating and protective coating described in Examples 1-5

[0106]

[0107] The above only describes the preferred embodiments of the application, and does not limit the application in any form. It should be noted that for ordinary skilled persons in the art, without departing from the principles of the application, a number of improvements and refinements can be made, and these improvements and refinements should be considered as the protection scope of the application.

Claims

1. A wide temperature range lubricating and protective coating characterized in that, Specifically, the raw materials are as follows in mass fraction: The precursor binder 5.0-15.0 parts, molybdenum disulfide 10.0-30.0 parts, graphite 2.0-8.0 parts, MXene 2.0-8.0 parts, inorganic oxyacid salt 1.0-5.0 parts, high-entropy ceramic 1.0-5.0 parts, zirconium boride 1.0-5.0 parts, boron carbide 1.0-5.0 parts, aluminum oxide 1.0-5.0 parts, dispersion medium 40.0-60.0 parts and auxiliary agent 1.0-5.0 parts; the precursor binder comprises a silicon-based polymer ceramic precursor; The inorganic oxyacid salt is one or more of molybdate, chromate and tungstate.

2. The wide temperature range lubricating and protective coating of claim 1, wherein, The silicon-based polymer ceramic precursor comprises one or more of polysilane, polymethylsilane, polycarbosilane, hydrogenated polycarbosilane, allyl hydrogenated polycarbosilane, polyzirconium carbosilane, polysiloxane, polymethylsiloxane, polysilazane, polyurea silazane and polyborosilazane.

3. The wide temperature range lubricating and protective coating of claim 1, wherein, The molybdate comprises one or more of silver molybdate, barium molybdate, calcium molybdate, lead molybdate and nickel molybdate; the chromate comprises barium chromate; the tungstate comprises sodium tungstate.

4. The wide temperature range lubricating and protective coating of claim 1, wherein, The high-entropy ceramic comprises one or more of (CoCuMgNiZn)O, (TiZrNbTaMo)C, (VNbTaMoW)C, (CrNbSiTiZr)C, (CrTaNbMoV)N and (AlCrNbSiTiMo)N.

5. The wide temperature range lubricating and protective coating of claim 1, wherein, The particle size of the molybdenum disulfide is 1-10 μm; the particle size of the graphite is 1-10 μm; the particle size of the high-entropy ceramic is less than 10 μm; the particle size of the zirconium boride is 1-20 μm; the particle size of the boron carbide is 1-20 μm; the particle size of the aluminum oxide is 1-10 μm.

6. The wide temperature range lubricating and protective coating of claim 1, wherein, The auxiliary agent comprises a wetting dispersant, a defoaming agent, a leveling agent and an anti-settling agent; the mass ratio of the wetting dispersant, the defoaming agent, the leveling agent and the anti-settling agent is (0.9-1.1):(1.0-1.2):(0.8-1.0):(0-0.8).

7. A process for the preparation of a wide-temperature-range lubricating and protective coating according to any one of claims 1 to 6, characterized in that, The method comprises the following steps: The molybdenum disulfide, the inorganic oxyacid salt, the graphite, the MXene, the high-entropy ceramic, the zirconium boride, the boron carbide and the aluminum oxide are first mixed, and then mixed with a first dispersion medium to obtain a first mixed slurry; The precursor binder and a second dispersion medium are second mixed to obtain a precursor binder solution; The first mixed slurry, the precursor binder solution, the auxiliary agent and a third dispersion medium are third mixed to obtain the wide-temperature-range lubricating and protective coating; the total mass of the first dispersion medium, the second dispersion medium and the third dispersion medium is the mass of the dispersion medium.

8. Use of the wide-temperature-range lubricating and protective coating of any one of claims 1-6 or the wide-temperature-range lubricating and protective coating prepared by the preparation method of claim 7 in preparing a wide-temperature-range lubricating and protective coating layer.

9. A wide temperature range lubricating and protective coating characterized in that, The method comprises the following steps: The wide-temperature-range lubricating and protective coating prepared by the method of claim 7 is sprayed on the surface of a metal substrate, and then sequentially subjected to heat curing and ceramicization treatment in a special atmosphere to obtain the wide-temperature-range lubricating and protective coating. The special atmosphere comprises ammonia, nitrogen or argon.

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