CN111334742B - Method for preparing ceramic composite coating of refractory transition metal compound - Google Patents

Method for preparing ceramic composite coating of refractory transition metal compound Download PDF

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CN111334742B
CN111334742B CN202010178923.1A CN202010178923A CN111334742B CN 111334742 B CN111334742 B CN 111334742B CN 202010178923 A CN202010178923 A CN 202010178923A CN 111334742 B CN111334742 B CN 111334742B
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powder
silicon carbide
coating
carbide
composite
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CN111334742A (en
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杨勇
马玉夺
王星宇
孙文韦
崔宇航
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Hebei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131—Wire arc spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material

Abstract

The invention relates to a preparation method of a refractory compound ceramic composite coating of transition metals. The method comprises the following steps: firstly, preparing metal simple substance/silicon carbide composite powder; the metal elementary powder is any x of zirconium, titanium, hafnium, tantalum, niobium, vanadium, chromium, molybdenum or tungsten, and x is 1,2,3 or 4; secondly, pretreating the surface of the base material of the coating; thirdly, spraying the metal simple substance/silicon carbide composite powder on the surface of the substrate material by adopting a thermal spraying method, thereby synthesizing the refractory compound ceramic composite coating of the transition metal through in-situ reaction. The invention overcomes the defects of complex process, high cost, large pollution, low deposition efficiency, low coating thickness, poor coating performance and unsuitability for large-scale industrial production in the prior art for preparing the refractory compound ceramic composite coating of transition metals.

Description

Method for preparing ceramic composite coating of refractory transition metal compound
Technical Field
The technical scheme of the invention relates to plating of refractory carbide and silicide on materials, in particular to a preparation method of a transition metal refractory compound ceramic composite coating.
Background
The refractory carbide of transition metals (zirconium, titanium, hafnium, tantalum, niobium, vanadium, chromium, molybdenum and tungsten) has a plurality of excellent performances such as high melting point, good thermal stability, excellent thermal shock resistance, good oxidation and ablation resistance, becomes one of the most promising candidate materials for preparing novel high-temperature material structural members in the field of aerospace, and has important application value in the fields of machinery, metallurgy, aerospace, nuclear, military and the like. Among them, titanium carbide is a typical transition metal carbide, and titanium carbide is a most widely developed material among titanium, zirconium, and chromium transition metal carbides, and is widely applied in many fields such as machinery, electronics, chemical engineering, environmental protection, fusion reactors, national defense industry, and the like, and especially widely used as a protective coating for structural materials. Zirconium carbide, as a refractory metal carbide, has excellent characteristics of high melting point (3420 ℃), high hardness (25.5GPa), high thermal and electrical conductivity, high chemical stability and the like, and is widely applied to the fields of emitter surface coatings, nuclear fuel particle coatings, thermo-electro-optical radiator coatings, ultrahigh temperature refractory materials and the like. Niobium carbide has high melting point (3610 ℃), high hardness, high elastic modulus, high wear resistance, thermodynamic stability and other properties. Therefore, the niobium carbide coating is prepared on the surface of the metal workpiece substrate, the surface hardness of the niobium carbide coating can be greatly improved to be more than HV2800, and the working temperature of the workpiece is improved, so that the service life of the niobium carbide coating is prolonged, and the niobium carbide coating has important application value in the fields of machinery, metallurgy, aerospace, nuclear, military and the like. The tantalum carbide has a very high melting point (3985 ℃), and the tantalum carbide coating is an important high-temperature structural material with high strength, corrosion resistance and good chemical stability, has excellent high-temperature mechanical property, high-speed airflow scouring resistance and ablation resistance, and has good chemical compatibility and mechanical compatibility with graphite and carbon/carbon composite materials. Molybdenum carbide has high hardness, good thermal stability and corrosion resistance, can be used as a high-temperature material in a neutral or reducing atmosphere at a temperature of more than 2000 ℃, can resist corrosion of cold potassium hydroxide and sodium hydroxide solution, and has been applied in various mechanical fields with high temperature resistance, wear resistance and chemical corrosion resistance. Tungsten carbide, as a refractory metal carbide, has excellent characteristics of high melting point (2870 ℃), high hardness (2000HV), high thermal and electrical conductivity, high chemical stability and the like, is widely applied to the fields of emitter surface coatings, nuclear fuel particle coatings, thermophotovoltaic radiator coatings, ultrahigh temperature refractory materials and the like, is a main raw material for manufacturing hard alloys, has good chemical stability and thermal stability, and still has high thermal hardness in a 1000 ℃ working environment. The chromium carbide has the advantages of high-temperature hardness (HV 1500-2100), good wear resistance, good corrosion resistance, low density and the like, and particularly has a thermal expansion coefficient close to that of steel and good matching with a base body component. Chromium carbide is one of the most widely applied coating materials in the high-temperature (600-900 ℃) environment at present, and is widely applied to industries such as metallurgy, aviation, electric power, nuclear energy and the like. The chromium carbide phase increases the hardness of the coating, which can produce a dense protective film of chromium oxide at high temperatures. The chromium carbide has good wear resistance and corrosion resistance, and is widely applied to the protective coating of parts. Hafnium carbide has a very high melting point (3890 ℃), and is a good material for the lining of high melting point metal melting crucibles. Hafnium carbide has high hardness, can be used as an additive of hard alloy, and has been widely applied in the fields of cutting tools and dies; the material also has high elastic coefficient, good electric thermal conductivity, smaller thermal expansion coefficient and better impact property, is suitable for rocket nozzle materials, can be used for the nose cone part of a rocket, has important application in the field of aerospace, and also has important application in the aspects of spray pipes, high-temperature resistant linings, electric arcs or electrodes for electrolysis. The hafnium carbide has good solid phase stability and chemical corrosion resistance, and has great potential for being used in high temperature environment. In addition, the hafnium carbide film is evaporated on the surface of the carbon nanotube cathode, so that the field emission performance of the carbon nanotube cathode can be well improved; the introduction of hafnium carbide into the carbon/carbon composite material may improve its ablation resistance. Hafnium carbide has many excellent physical and chemical properties, which makes it very widely used in current ultra-high temperature materials.
However, the great brittleness, poor thermal shock resistance and poor high temperature oxidation resistance of carbide ceramic coatings have limited further applications to some extent. Researches show that the ceramic composite coating can reduce the brittleness of the single-phase refractory carbide ceramic coating and improve the thermal shock resistance and the high-temperature oxidation resistance of the single-phase refractory carbide ceramic coating, so that the transition metal refractory compound ceramic composite coating is attracted by people as a high-temperature structural material. The silicide (zirconium silicide, titanium silicide, chromium silicide, hafnium silicide, niobium silicide, tantalum silicide, vanadium silicide, tungsten silicide, etc.) has low density, good thermal stability and strong oxidation resistance. The addition of silicide to carbide can reduce the brittleness of carbide coating, raise its heat shock resistance and high temperature oxidation resistance and make the coating obtain self-healing capacity of crack. When the coating generates cracks in the service process of high-temperature severe environment, silicide on the surfaces of the cracks and nearby the cracks can be quickly oxidized to generate silicon dioxide (SiO)2) And another oxide, SiO2As mobile phase fillable packingPattern; on the other hand, the volume expansion of the oxidation reaction and the high thermal expansion coefficient of the silicide can make the crack under compressive stress, accelerate the healing of the crack, and thus the coating has better healing capability [ patent CN201410199003.2 ].
At present, the technical problems of preparing the refractory compound ceramic composite coating of the transition metal are as follows:
(1) the disadvantages of chemical vapor deposition are: 1) the obtained coating has too small thickness, low deposition efficiency, low production efficiency and difficult preparation of thicker coatings; 2) it is difficult to deposit a thin film on a substrate locally or on a surface; 3) the reaction source participating in the deposition reaction and the residual gas after the reaction are mostly toxic, flammable and explosive gases, are dangerous to operate and pollute the environment; 4) the equipment requirements are strict, and the equipment is required to have corrosion resistance, so that the preparation cost is high.
(2) The disadvantages of the physical vapor deposition method are: 1) the deposition efficiency is low, and the production efficiency is low; 2) the film-base binding force is weak, the coated film is not wear-resistant, and chemical impurities are difficult to remove; 3) the method has complex equipment and large one-time investment.
(3) The disadvantages of the laser cladding method are: 1) the equipment has large one-time investment and high operation cost, and particularly, when large-area cladding is carried out, the probability of metallurgical defects is increased because the size of a light spot is small and a lapping process measure must be adopted; 2) in the process of laser cladding of the ceramic coating, the cracking phenomenon is easy to generate, so that the quality of the coating is reduced.
(4) The disadvantages of the slurry coating method are: 1) the slurry coating method is imperfect, and the coating thickness of the part is difficult to be uniform; 2) the coating properties depend to a large extent on the technical proficiency of the operator; under the condition of same thickness and same components, the slurry method coating has lower fracture resistance because of not compact; 3) the coating prepared by the method has poor bonding force with a matrix, poor thermal shock resistance, high sintering temperature and easy introduction of impurities.
(5) The disadvantages of the embedding method are: the embedding process usually needs to put the matrix material in a high-temperature environment for heat preservation (2000 ℃ -3000 ℃), so the defects of large heat damage to the matrix and high cost exist; meanwhile, the deposition and diffusion speeds of different elements are different, so that the thickness of the coating cannot be controlled and the uniformity of components in the coating cannot be ensured; in addition, the embedding technique is difficult to meet for preparing coatings on large-sized parts, subject to the crucible size and the influence of heat sources.
(6) The thermal spraying method is a method of heating a spray material to a molten or semi-molten state using a heat source and spray-depositing the spray material onto a pretreated substrate surface at a relatively high speed to form a coating layer. However, the problem with thermal spray processes for direct spraying of transition metal refractory ceramic powders to produce transition metal refractory ceramic composite coatings is that: 1) because the melting point of the refractory compounds (carbides and silicides) of the transition metals is very high, the residence time of the powder in the hot spraying high-temperature flame flow is short, the melting effect is not ideal, the deposition efficiency is low, and the porosity of the coating is high; 2) the carbide and the silicide are easily oxidized and decomposed by thermal spraying under the atmospheric condition or the oxidizing atmosphere; 3) the strong covalent bonding force in carbide and silicide crystals can cause that the diffusion sintering phenomenon is difficult to generate among particles during deposition in the thermal spraying process, so that the carbide and the silicide particles are isolated and not bonded with each other, are in a loose state and have high porosity of a coating.
Disclosure of Invention
The invention aims to provide a preparation method of a refractory compound ceramic composite coating of transition metals aiming at the defects in the prior art. The method adopts thermal spraying in-situ reaction synthesis, metal simple substances and silicon carbide are mixed and then thermally sprayed, and the metal simple substances and the silicon carbide react in situ to generate carbide and silicide phases in the thermal spraying process, so that the ceramic composite coating (carbide-silicide composite coating) of the refractory compound of the transition metal is obtained. The invention overcomes the defects of complex process, high cost, large pollution, low deposition efficiency, low coating thickness, poor coating performance and unsuitability for large-scale industrial production in the prior art for preparing the refractory compound ceramic composite coating of transition metals. Meanwhile, the invention also overcomes the defects that in the prior art, the raw materials are required to be added with simple substance carbon sources (such as graphite powder and the like) and silicon sources (such as silicon powder and the like) in the process of preparing the refractory carbide ceramic composite coating of the transition metal, and heat treatment is required after the coating is obtained by spraying.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a preparation method of a transition metal refractory compound ceramic composite coating comprises the following steps:
firstly, preparing metal simple substance/silicon carbide composite powder for thermal spraying:
mixing metal simple substance powder and silicon carbide powder into composite powder, and then mixing the composite powder with a binder to prepare the metal simple substance/silicon carbide composite powder for thermal spraying;
wherein the mass ratio of the metal simple substance powder to the silicon carbide powder is 50-90: 10-50; the weight ratio of the composite powder to the binder is 100: 0.1-2; the metal elementary powder is any x of zirconium, titanium, hafnium, tantalum, niobium, vanadium, chromium, molybdenum or tungsten, and x is 1,2,3 or 4; when x is 2,3 or 4, each elementary substance accounts for 5-95% of the total metal elementary substance powder by mass.
The binder is polyvinyl alcohol or methyl cellulose;
the particle size of the metal simple substance powder and the silicon carbide powder is 0.001-10 microns;
secondly, the surface of the base material with the required coating is pretreated in one of the following two ways:
1) when the base material is a metal base material, firstly, sand blasting is adopted, and then a bonding layer is sprayed on the surface of the metal base material after the sand blasting;
or, 2) when the base material is an inorganic non-metallic material base, adopting sand blasting or sand paper polishing treatment;
thirdly, preparing the ceramic composite coating of the refractory compound of the transition metal:
spraying the metal simple substance/silicon carbide composite powder for thermal spraying prepared in the first step on the surface of the substrate material pretreated in the second step by adopting a thermal spraying method, so as to synthesize a transition metal refractory compound ceramic composite coating through in-situ reaction; the thickness of the coating is 200-500 microns;
said miningThe technological parameters of the method for thermal spraying are as follows: the flow of the powder feeding gas is 0.3-0.6 m3The arc power is 32-45 KW, and the distance between spray guns is 80-120 mm; the powder feeding gas is argon;
the metal material matrix is steel, cast iron, aluminum alloy, copper alloy, titanium alloy, magnesium alloy, nickel-based superalloy, nickel-chromium alloy, cobalt-based superalloy or intermetallic compound.
The inorganic non-metallic material matrix is graphite, a carbon/carbon composite material, a carbon/silicon carbide composite material or a silicon carbide/silicon carbide composite material.
The bonding layer material is: NiAl, NiCrAl, FeAl, NiCrAlY, CoCrAlY, CoNiCrAlY, NiCoCrAlYTa or NiCrBSi.
The preparation method of the transition metal refractory compound ceramic composite coating is characterized in that the related raw materials are all obtained from commercial sources, and the sand blasting process, the sand paper sanding process and the bonding layer spraying process are all well known in the prior art.
According to the preparation method of the transition metal refractory compound ceramic composite coating, when the metal elemental powder is any one of zirconium, titanium, hafnium, tantalum, niobium, vanadium, chromium, molybdenum or tungsten, the prepared coating mainly comprises carbide and silicide phases, wherein the carbide and the silicide are formed by in-situ reaction, each phase interface is pure, the interphase combination is tight, and the cohesive strength of the coating is high; the silicide formed in situ in the coating can not only improve the high-temperature resistance and the oxidation resistance of the coating, but also enable the coating to obtain the crack self-healing capability; when the raw material metal simple substance powder is used by two or more metal simple substances at the same time, more than two carbides generated in situ in the prepared coating are solid-dissolved, the coating has high cohesive strength, and the hardness, wear resistance, corrosion resistance and high-temperature resistance and oxidation resistance of the coating are further improved.
The prominent substantive features of the invention are:
in the prior art, if a coating material with one component needs to be prepared, the material with the component is selected as a raw material for thermal spraying (or called spraying feed), for example, if an aluminum oxide-titanium oxide composite coating is to be obtained, aluminum oxide and titanium oxide powder are selected as spraying raw materials; however, the transition metal compound (with high melting point) has the refractory characteristics in conventional spraying, which affects the application of the compound in the preparation of ceramic coating. The idea of the thermal spraying in-situ reaction is to adopt relatively cheap raw materials, generate a target component (generally a refractory compound) by the reaction of the raw materials at a high temperature in the spraying process, only mix a metal simple substance and silicon carbide and then perform thermal spraying, react the metal simple substance and the silicon carbide at the high temperature of a thermal spraying flame flow in the thermal spraying process to generate a carbide and a silicide phase in situ, and thus obtain the carbide-silicide composite coating by the thermal spraying in-situ reaction.
The invention has the following beneficial effects:
(1) the invention adopts the metal simple substance (zirconium, titanium, chromium, hafnium, tantalum, niobium, vanadium, molybdenum or tungsten) and the silicon carbide composite powder to prepare the transition metal refractory compound ceramic composite coating, the selected raw material powder has rich resources and low price, and the thermal spraying technical process is adopted to prepare the ceramic composite coating by one-step forming, so the preparation process is simple and the cost is low, and the invention provides a novel method for preparing the transition metal refractory compound ceramic composite coating.
(2) The method for preparing the transition metal refractory compound ceramic composite coating overcomes the defects that carbide and silicide particles are isolated from each other and are not bonded in a loose state, and each phase, namely the carbide and the silicide, in the prepared transition metal refractory compound ceramic composite coating is formed by in-situ reaction, the interfaces of each phase are pure, and the phases are combined tightly; when two or more than two metal simple substances are adopted as raw materials, carbides generated in situ in the prepared coating are solid-dissolved, and the coating has high cohesive strength.
(3) The refractory transition metal compound ceramic composite coating prepared by the method has uniform components, wider element proportion adjusting space, high density, high hardness, high wear resistance, high corrosion resistance and high temperature resistance and high oxidation resistance; the existence of the silicide in the coating can not only improve the high-temperature resistance and the oxidation resistance of the coating, but also ensure that the coating can obtain the crack self-healing capability; when the elemental metal powder is two or more of zirconium, titanium, hafnium, tantalum, niobium, vanadium, chromium, molybdenum or tungsten as a raw material, carbide generated in situ in the prepared coating is solid-dissolved; the binary or multi-element solid solution phase can play a role in solid solution strengthening, so that the hardness, wear resistance, corrosion resistance and high-temperature resistance and oxidation resistance of the coating are further improved; the defects of complex process, high cost, large energy consumption, large pollution, low efficiency, low coating thickness, low coating density and poor coating performance of the ceramic composite coating of the refractory transition metal compound prepared by the prior art are overcome.
(4) In order to obtain the transition metal refractory compound ceramic composite coating with excellent performance, a raw material system is optimized, the inventor team successfully adopts the method to prepare the transition metal refractory compound ceramic composite coating after years of intensive research and hundreds of repeated experiments, the preparation process is simple, the performance of the obtained transition metal refractory compound ceramic composite coating is good, and unexpected technical effects and obvious economic benefits are obtained.
Compared with the oxidation resistance and ablation resistance of boride and carbide coatings prepared by a thermal spraying process, the ceramic composite coating prepared by the invention has the oxidation resistance (1000 ℃, 24 hours, mass percent gain) which is improved by 38 percent at most than that of coatings prepared by thermal spraying of zirconium carbide powder, zirconium boride-zirconium carbide composite powder, titanium carbide powder, zirconium/boron carbide composite powder and zirconium oxide/boron carbide/aluminum composite powder; the ceramic composite coating prepared by the invention has ablation resistance (heat flux of 4.02 MW/m) compared with coatings obtained by thermally spraying zirconium carbide powder, zirconium boride-zirconium carbide composite powder, titanium carbide powder, zirconium/boron carbide composite powder and zirconium oxide/boron carbide/aluminum composite powder240s mass ablation rate,%) increased by 6.61% at most.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is an XRD pattern of a refractory transition metal compound ceramic composite coating (zirconium carbide-zirconium silicide composite coating) prepared in example 2.
FIG. 2 is an SEM image of a refractory transition metal compound ceramic composite coating (zirconium carbide-zirconium silicide composite coating) prepared in example 2.
FIG. 3 is an XRD pattern of a refractory transition metal compound ceramic composite coating (titanium carbide-titanium silicide composite coating) prepared in example 5.
FIG. 4 is an SEM image of the refractory transition metal compound ceramic composite coating (titanium carbide-titanium silicide composite coating) prepared in example 5.
FIG. 5 is an XRD pattern of the refractory transition metal compound ceramic composite coating (chromium carbide-chromium silicide composite coating) prepared in example 8.
FIG. 6 is an SEM image of the refractory transition metal compound ceramic composite coating (chromium carbide-chromium silicide composite coating) prepared in example 8.
FIG. 7 is an XRD pattern of a refractory transition metal compound ceramic composite coating (niobium carbide-niobium silicide composite coating) prepared in example 11.
FIG. 8 is an SEM image of a transition metal refractory compound ceramic composite coating (niobium carbide-niobium silicide composite coating) prepared in example 11.
Detailed Description
Example 1
The first step, preparing zirconium/silicon carbide composite powder for thermal spraying:
uniformly mixing zirconium powder with the particle size range of 0.001-10 microns and silicon carbide powder with the particle size range of 0.001-10 microns into composite powder, wherein the mass ratio of the zirconium powder to the silicon carbide powder is 50:50, and uniformly mixing a binder (methyl cellulose, the same as in examples 2-10) into the composite powder, wherein the use amount of the binder is that the mass ratio of the composite powder to the binder is 100:0.1, so that the zirconium/silicon carbide composite powder for thermal spraying is prepared;
secondly, preprocessing a base material:
the base material is 1Cr18Ni9Ti steel, the pretreatment mode adopts sand blasting, and then a NiCrAlY bonding bottom layer with the thickness of 50 microns is sprayed on the surface of the heat-resistant steel base material after the sand blasting;
thirdly, preparing the zirconium carbide-zirconium silicide composite coating:
an atmospheric plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.3m3H, the arc power is 32KW, the distance of the spray gun is 80mm, and the powder feeding gas is argon (the same as the powder feeding gas in the following embodiments); and spraying the zirconium/silicon carbide composite powder prepared in the first step for thermal spraying on the surface of the 1Cr18Ni9Ti steel matrix material pretreated in the second step to form a zirconium carbide-zirconium silicide composite coating with the thickness of 200 microns.
Example 2
The first step, preparing zirconium/silicon carbide composite powder for thermal spraying:
uniformly mixing zirconium powder with the granularity ranging from 0.001 micron to 10 microns and silicon carbide powder with the granularity ranging from 0.001 micron to 10 microns into composite powder, wherein the mass ratio of the zirconium powder to the silicon carbide powder is 78: 22, and uniformly mixing a binder, wherein the weight ratio of the composite powder to the binder is 100: 1, so as to prepare zirconium/silicon carbide composite powder for thermal spraying;
secondly, preprocessing a base material:
the base material is a titanium-aluminum intermetallic compound Ti-48Al-2Cr-2Nb, the pretreatment mode adopts sand blasting, and then a NiCoCrAlYTa bonding layer with the thickness of 50 microns is sprayed on the surface of the titanium-aluminum intermetallic compound base material after the sand blasting;
thirdly, preparing the zirconium carbide-zirconium silicide composite coating:
an atmospheric plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.5m3And h, the electric arc power is 35KW, the distance between spray guns is 100mm, and the zirconium/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the titanium-aluminum intermetallic compound Ti-48Al-2Cr-2Nb base material pretreated in the second step, so that the zirconium carbide-zirconium silicide composite coating with the thickness of 200 microns is formed.
Fig. 1 is an XRD pattern of the zirconium carbide-zirconium silicide composite coating obtained in this example, from which it can be seen that the zirconium carbide-zirconium silicide composite coating is mainly composed of two phases of zirconium carbide and zirconium silicide, and secondly a silicon carbide phase is present. It can be seen that the zirconium carbide-zirconium silicide composite coating with zirconium carbide and zirconium silicide as main components can be successfully prepared by using zirconium/silicon carbide composite powder as a raw material and adopting a plasma spraying method.
Fig. 2 is an SEM image of the zirconium carbide-zirconium silicide composite coating layer obtained in the present example. It can be seen that the thickness of the zirconium carbide-zirconium silicide composite coating reaches more than 200 microns, the coating has high density, and the coating is well combined with the matrix.
Example 3
The first step, preparing zirconium/silicon carbide composite powder for thermal spraying:
uniformly mixing zirconium powder with the granularity ranging from 0.001 micron to 10 microns and silicon carbide powder with the granularity ranging from 0.001 micron to 10 microns into composite powder, wherein the mass ratio of the zirconium powder to the silicon carbide powder is 90: 10, and uniformly mixing a binder, wherein the weight ratio of the composite powder to the binder is 100: 2, so as to prepare zirconium/silicon carbide composite powder for thermal spraying;
secondly, preprocessing a base material:
the matrix material is a silicon carbide/silicon carbide composite material (silicon carbide fiber toughened silicon carbide ceramic matrix composite material), and the pretreatment mode adopts sand blasting;
thirdly, preparing the zirconium carbide-zirconium silicide composite coating:
the plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.6m3And h, the electric arc power is 45KW, the distance between spray guns is 120mm, and the zirconium/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the silicon carbide/silicon carbide composite material substrate pretreated in the second step, so that the zirconium carbide-zirconium silicide composite coating with the thickness of 300 microns is formed.
Example 4
The first step, preparing titanium/silicon carbide composite powder for thermal spraying:
uniformly mixing titanium powder with the granularity range of 0.001-10 microns and silicon carbide powder with the granularity range of 0.001-10 microns into composite powder, wherein the mass ratio of the titanium powder to the silicon carbide powder is 50:50, and uniformly mixing a binder, wherein the weight ratio of the composite powder to the binder is 100:0.1, so as to prepare the titanium/silicon carbide composite powder for thermal spraying;
secondly, preprocessing a base material:
the base material is heat-resistant steel, the pretreatment mode adopts sand blasting, and then a NiCrAlY bonding bottom layer with the thickness of 50 microns is sprayed on the surface of the heat-resistant steel base material after the sand blasting;
thirdly, preparing the titanium carbide-titanium silicide composite coating:
an atmospheric plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.3m3And h, the electric arc power is 35KW, the distance between spray guns is 110mm, and the titanium/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the heat-resistant steel matrix material pretreated in the second step, so that the titanium carbide-titanium silicide composite coating with the thickness of 400 microns is formed.
Example 5
The first step, preparing titanium/silicon carbide composite powder for thermal spraying:
uniformly mixing titanium powder with the granularity range of 0.001-10 microns and silicon carbide powder with the granularity range of 0.001-10 microns into composite powder, wherein the mass ratio of the titanium powder to the silicon carbide powder is 64: 36, and uniformly mixing a binder, wherein the weight ratio of the composite powder to the binder is 100: 1, so as to prepare the titanium/silicon carbide composite powder for thermal spraying;
secondly, preprocessing a base material:
the base material is a titanium-aluminum intermetallic compound, the pretreatment mode adopts sand blasting, and then a NiCoCrAlYTa bonding layer with the thickness of 50 microns is sprayed on the surface of the titanium-aluminum intermetallic compound base material after the sand blasting;
thirdly, preparing the zirconium carbide-zirconium silicide composite coating:
by atmospheric airThe plasma spraying method comprises the following process parameters: the flow of the powder feeding gas is 0.4m3And h, the electric arc power is 38KW, the distance between spray guns is 100mm, and the titanium/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the titanium-aluminum intermetallic compound matrix material pretreated in the second step, so that the titanium carbide-titanium silicide composite coating with the thickness of 200 microns is formed.
Fig. 3 is an XRD pattern of the titanium carbide-titanium silicide composite coating prepared in this example, from which it can be seen that the titanium carbide-titanium silicide composite coating is mainly composed of two phases of titanium carbide and titanium silicide, and secondly, a silicon carbide phase exists. It can be seen that the titanium carbide-titanium silicide composite coating with the main components of titanium carbide and titanium silicide can be successfully prepared by using the titanium/silicon carbide composite powder as the raw material and adopting a plasma spraying method.
Fig. 4 is an SEM image of the titanium carbide-titanium silicide composite coating layer obtained in the present example. It can be seen that the titanium carbide-titanium silicide composite coating has high density, fine structure and good combination of the coating and the matrix.
Example 6
The first step, preparing titanium/silicon carbide composite powder for thermal spraying:
uniformly mixing titanium powder with the granularity range of 0.001-10 microns and silicon carbide powder with the granularity range of 0.001-10 microns into composite powder, wherein the mass ratio of the titanium powder to the silicon carbide powder is 90: 10, and uniformly mixing a binder, wherein the weight ratio of the composite powder to the binder is 100: 2, so as to prepare the titanium/silicon carbide composite powder for thermal spraying;
secondly, preprocessing a base material:
the base material is heat-resistant steel, the pretreatment mode adopts sand blasting, and then a NiCrAlY bonding bottom layer with the thickness of 50 microns is sprayed on the surface of the heat-resistant steel base material after the sand blasting;
thirdly, preparing the titanium carbide-titanium silicide composite coating:
an atmospheric plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.6m3H, work of arcThe rate is 40KW, the distance between spray guns is 90mm, and the titanium/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the heat-resistant steel matrix material pretreated in the second step, so that the titanium carbide-titanium silicide composite coating with the thickness of 500 microns is formed.
Example 7
The first step, preparing chromium/silicon carbide composite powder for thermal spraying:
uniformly mixing chromium powder with the granularity range of 0.001-10 microns and silicon carbide powder with the granularity range of 0.001-10 microns into composite powder, wherein the mass ratio of the chromium powder to the silicon carbide powder is 50:50, and uniformly mixing a binder, wherein the weight ratio of the composite powder to the binder is 100:0.1, so as to prepare the chromium/silicon carbide composite powder for thermal spraying;
secondly, preprocessing a base material:
the base material is heat-resistant steel, the pretreatment mode adopts sand blasting, and then a NiCrAlY bonding bottom layer with the thickness of 50 microns is sprayed on the surface of the heat-resistant steel base material after the sand blasting;
thirdly, preparing the chromium carbide-chromium silicide composite coating:
an atmospheric plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.3m3And h, the electric arc power is 34KW, the distance between spray guns is 80mm, and the chromium/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the heat-resistant steel matrix material pretreated in the second step, so that the chromium carbide-chromium silicide composite coating with the thickness of 200 microns is formed.
Example 8
The first step, preparing chromium/silicon carbide composite powder for thermal spraying:
uniformly mixing chromium powder with the granularity range of 0.001-10 microns and silicon carbide powder with the granularity range of 0.001-10 microns into composite powder, wherein the mass ratio of the chromium powder to the silicon carbide powder is 85: 15, and uniformly mixing a binder, wherein the weight ratio of the composite powder to the binder is 100: 1, so as to prepare the chromium/silicon carbide composite powder for thermal spraying;
secondly, preprocessing a base material:
the base material is a titanium-aluminum intermetallic compound, the pretreatment mode adopts sand blasting, and then a NiCoCrAlYTa bonding layer with the thickness of 50 microns is sprayed on the surface of the titanium-aluminum intermetallic compound base material after the sand blasting;
thirdly, preparing the chromium carbide-chromium silicide composite coating:
an atmospheric plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.4m3And h, the electric arc power is 36KW, the distance between spray guns is 110mm, and the chromium/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the titanium-aluminum intermetallic compound matrix material pretreated in the second step, so that the chromium carbide-chromium silicide composite coating with the thickness of 200 microns is formed.
Fig. 5 is an XRD pattern of the chromium carbide-chromium silicide composite coating prepared in this example, from which it can be seen that the chromium carbide-chromium silicide composite coating is mainly composed of two phases of chromium carbide and chromium silicide, and secondly, chromium, silicon carbide and chromium oxide phases exist. It can be seen that the chromium carbide-chromium silicide composite coating with the main components of chromium carbide and chromium silicide can be successfully prepared by using the chromium/silicon carbide composite powder as the raw material and adopting a plasma spraying method.
Fig. 6 is an SEM image of the chromium carbide-chromium silicide composite coating layer obtained in the present example. It can be seen that the thickness of the chromium carbide-chromium silicide composite coating reaches more than 200 microns, the density of the coating is high, and the coating is well combined with the matrix.
Example 9
The first step, preparing chromium/silicon carbide composite powder for thermal spraying:
uniformly mixing chromium powder with the granularity range of 0.001-10 microns and silicon carbide powder with the granularity range of 0.001-10 microns into composite powder, wherein the mass ratio of the chromium powder to the silicon carbide powder is 90: 10, and uniformly mixing a binder, wherein the weight ratio of the composite powder to the binder is 100: 2, so as to prepare the chromium/silicon carbide composite powder for thermal spraying;
secondly, preprocessing a base material:
the matrix material is a silicon carbide/silicon carbide composite material, and the pretreatment mode adopts sand blasting treatment;
thirdly, preparing the chromium carbide-chromium silicide composite coating:
the plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.6m3And h, the electric arc power is 42KW, the distance between spray guns is 120mm, and the chromium/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the silicon carbide/silicon carbide composite material substrate pretreated in the second step, so that the chromium carbide-chromium silicide composite coating with the thickness of 200 microns is formed.
Example 10
First, preparing niobium/silicon carbide composite powder for thermal spraying:
uniformly mixing niobium powder with the granularity ranging from 0.001 micrometer to 10 micrometers and silicon carbide powder with the granularity ranging from 0.001 micrometer to 10 micrometers into composite powder, wherein the mass ratio of the niobium powder to the silicon carbide powder is 50:50, and uniformly mixing a binder, wherein the binder is used in a weight ratio of the composite powder to the binder of 100:0.1, so as to prepare the niobium/silicon carbide composite powder for thermal spraying;
secondly, preprocessing a base material:
the base material is heat-resistant steel, the pretreatment mode adopts sand blasting, and then a NiCrAlY bonding bottom layer with the thickness of 50 microns is sprayed on the surface of the heat-resistant steel base material after the sand blasting;
thirdly, preparing the niobium carbide-niobium silicide composite coating:
an atmospheric plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.3m3And h, the electric arc power is 32KW, the distance between spray guns is 80mm, and the niobium/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the heat-resistant steel matrix material pretreated in the second step, so that the niobium carbide-niobium silicide composite coating with the thickness of 200 microns is formed.
Example 11
First, preparing niobium/silicon carbide composite powder for thermal spraying:
uniformly mixing niobium powder with the granularity range of 0.001-10 microns and silicon carbide powder with the granularity range of 0.001-10 microns into composite powder, wherein the mass ratio of the niobium powder to the silicon carbide powder is 85: 15, and uniformly mixing a binder (polyvinyl alcohol, the same as in the following embodiment) into the composite powder, wherein the use amount of the binder is that the weight ratio of the composite powder to the binder is 100: 1, so that the niobium/silicon carbide composite powder for thermal spraying is prepared;
secondly, preprocessing a base material:
the base material is a titanium-aluminum intermetallic compound, the pretreatment mode adopts sand blasting, and then a NiCoCrAlYTa bonding layer with the thickness of 50 microns is sprayed on the surface of the titanium-aluminum intermetallic compound base material after the sand blasting;
thirdly, preparing the niobium carbide-niobium silicide composite coating:
an atmospheric plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.5m3And h, the electric arc power is 36KW, the distance between spray guns is 100mm, and the niobium/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the titanium-aluminum intermetallic compound matrix material pretreated in the second step, so that the niobium carbide-niobium silicide composite coating with the thickness of 200 microns is formed.
Fig. 7 is an XRD pattern of the niobium carbide-niobium silicide composite coating prepared in this example, from which it can be seen that the niobium carbide-niobium silicide composite coating is mainly composed of niobium carbide and niobium silicide phases, and secondly niobium and niobium oxide phases exist. It can be seen that the niobium carbide-niobium silicide composite coating with the main components of niobium carbide and niobium silicide can be successfully prepared by using the niobium/silicon carbide composite powder as the raw material and adopting a plasma spraying method.
Fig. 8 is an SEM image of the niobium carbide-niobium silicide composite coating layer obtained in the present example. It can be seen that the thickness of the niobium carbide-niobium silicide composite coating reaches more than 200 microns, the coating has high density, and the coating is well combined with the matrix.
Example 12
First, preparing niobium/silicon carbide composite powder for thermal spraying:
uniformly mixing niobium powder with the granularity ranging from 0.001 micrometer to 10 micrometers and silicon carbide powder with the granularity ranging from 0.001 micrometer to 10 micrometers into composite powder, wherein the mass ratio of the niobium powder to the silicon carbide powder is 90: 10, and uniformly mixing a binder, wherein the weight ratio of the composite powder to the binder is 100: 2, so as to prepare the niobium/silicon carbide composite powder for thermal spraying;
secondly, preprocessing a base material:
the matrix material is a silicon carbide/silicon carbide composite material, and the pretreatment mode adopts sand blasting treatment;
thirdly, preparing the niobium carbide-niobium silicide composite coating:
the plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.6m3And h, the electric arc power is 38KW, the distance between spray guns is 110mm, and the niobium/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the silicon carbide/silicon carbide composite material substrate pretreated in the second step, so that the niobium carbide-niobium silicide composite coating with the thickness of 200 microns is formed.
Example 13
The first step, preparing hafnium/silicon carbide composite powder for thermal spraying:
uniformly mixing hafnium powder with the particle size range of 0.001-10 microns and silicon carbide powder with the particle size range of 0.001-10 microns into composite powder, wherein the mass ratio of the hafnium powder to the silicon carbide powder is 50:50, and uniformly mixing a binder, wherein the use amount of the binder is that the weight ratio of the composite powder to the binder is 100:0.1, so as to prepare the hafnium/silicon carbide composite powder for thermal spraying;
secondly, preprocessing a base material:
the base material is heat-resistant steel, the pretreatment mode adopts sand blasting, and then a NiCrAlY bonding bottom layer with the thickness of 50 microns is sprayed on the surface of the heat-resistant steel base material after the sand blasting;
thirdly, preparing the hafnium carbide-hafnium silicide composite coating:
an atmospheric plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.4m3And h, the electric arc power is 35KW, the distance between spray guns is 90mm, and the hafnium/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the heat-resistant steel matrix material pretreated in the second step, so that the hafnium carbide-hafnium silicide composite coating with the thickness of 200 microns is formed.
Example 14
The first step, preparing hafnium/silicon carbide composite powder for thermal spraying:
uniformly mixing hafnium powder with the particle size range of 0.001-10 microns and silicon carbide powder with the particle size range of 0.001-10 microns into composite powder, wherein the mass ratio of the hafnium powder to the silicon carbide powder is 85: 15, and uniformly mixing a binder, wherein the weight ratio of the composite powder to the binder is 100: 1, so as to prepare the hafnium/silicon carbide composite powder for thermal spraying;
secondly, preprocessing a base material:
the base material is a titanium-aluminum intermetallic compound, the pretreatment mode adopts sand blasting, and then a NiCoCrAlYTa bonding layer with the thickness of 50 microns is sprayed on the surface of the titanium-aluminum intermetallic compound base material after the sand blasting;
thirdly, preparing the hafnium carbide-hafnium silicide composite coating:
an atmospheric plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.5m3And h, the electric arc power is 38KW, the distance between spray guns is 100mm, and the hafnium/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the titanium-aluminum intermetallic compound substrate material pretreated in the second step, so that the hafnium carbide-hafnium silicide composite coating with the thickness of 200 microns is formed.
Example 15
The first step, preparing hafnium/silicon carbide composite powder for thermal spraying:
uniformly mixing hafnium powder with the particle size range of 0.001-10 microns and silicon carbide powder with the particle size range of 0.001-10 microns into composite powder, wherein the mass ratio of the hafnium powder to the silicon carbide powder is 90: 10, and uniformly mixing a binder, wherein the weight ratio of the composite powder to the binder is 100: 2, so as to prepare the hafnium/silicon carbide composite powder for thermal spraying;
secondly, preprocessing a base material:
the matrix material is a silicon carbide/silicon carbide composite material, and the pretreatment mode adopts sand blasting treatment;
thirdly, preparing the hafnium carbide-hafnium silicide composite coating:
the plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.6m3And h, the electric arc power is 45KW, the distance between spray guns is 120mm, and the hafnium/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the silicon carbide/silicon carbide composite material substrate pretreated in the second step, so that the hafnium carbide-hafnium silicide composite coating with the thickness of 200 microns is formed.
Example 16
Firstly, preparing tantalum/silicon carbide composite powder for thermal spraying:
tantalum powder with the granularity range of 0.001-10 microns and silicon carbide powder with the granularity range of 0.001-10 microns are uniformly mixed into composite powder, wherein the mass ratio of the tantalum powder to the silicon carbide powder is 50:50, and then a binder is uniformly mixed into the composite powder, wherein the use amount of the binder is that the weight ratio of the composite powder to the binder is 100:0.1, so that the tantalum/silicon carbide composite powder for thermal spraying is prepared;
secondly, preprocessing a base material:
the base material is heat-resistant steel, the pretreatment mode adopts sand blasting, and then a NiCrAlY bonding bottom layer with the thickness of 50 microns is sprayed on the surface of the heat-resistant steel base material after the sand blasting;
thirdly, preparing the tantalum carbide-tantalum silicide composite coating:
an atmospheric plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.5m3/h，And the electric arc power is 40KW, the distance of a spray gun is 100mm, and the tantalum/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the heat-resistant steel matrix material pretreated in the second step, so that the tantalum carbide-tantalum silicide composite coating with the thickness of 200 microns is formed.
Example 17
Firstly, preparing tantalum/silicon carbide composite powder for thermal spraying:
tantalum powder with the granularity range of 0.001-10 microns and silicon carbide powder with the granularity range of 0.001-10 microns are uniformly mixed into composite powder, wherein the mass ratio of the tantalum powder to the silicon carbide powder is 85: 15, then a binder is uniformly mixed, the use amount of the binder is that the weight ratio of the composite powder to the binder is 100: 1, and the tantalum/silicon carbide composite powder for thermal spraying is prepared;
secondly, preprocessing a base material:
the base material is a titanium-aluminum intermetallic compound, the pretreatment mode adopts sand blasting, and then a NiCoCrAlYTa bonding layer with the thickness of 50 microns is sprayed on the surface of the titanium-aluminum intermetallic compound base material after the sand blasting;
thirdly, preparing the tantalum carbide-tantalum silicide composite coating:
an atmospheric plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.5m3And h, the electric arc power is 42KW, the distance between spray guns is 90mm, and the tantalum/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the titanium-aluminum intermetallic compound substrate material pretreated in the second step, so that the tantalum carbide-tantalum silicide composite coating with the thickness of 200 microns is formed.
Example 18
Firstly, preparing tantalum/silicon carbide composite powder for thermal spraying:
tantalum powder with the granularity range of 0.001-10 microns and silicon carbide powder with the granularity range of 0.001-10 microns are uniformly mixed into composite powder, wherein the mass ratio of the tantalum powder to the silicon carbide powder is 90: 10, and then a binder is uniformly mixed into the composite powder, wherein the use amount of the binder is that the weight ratio of the composite powder to the binder is 100: 2, so that the tantalum/silicon carbide composite powder for thermal spraying is prepared;
secondly, preprocessing a base material:
the matrix material is a silicon carbide/silicon carbide composite material, and the pretreatment mode adopts sand blasting treatment;
thirdly, preparing the tantalum carbide-tantalum silicide composite coating:
the plasma spraying method is adopted, and the technological parameters are as follows: the flow of the powder feeding gas is 0.6m3And h, the electric arc power is 45KW, the distance between spray guns is 120mm, and the tantalum/silicon carbide composite powder for thermal spraying prepared in the first step is sprayed on the surface of the silicon carbide/silicon carbide composite material substrate pretreated in the second step, so that the tantalum carbide-tantalum silicide composite coating with the thickness of 200 microns is formed.
Example 19
Firstly, preparing binary metal simple substance/silicon carbide composite powder for thermal spraying: uniformly mixing binary metal simple substance powder with the granularity ranging from 0.001 micrometer to 10 micrometers and silicon carbide powder with the granularity ranging from 0.001 micrometer to 10 micrometers to form composite powder, wherein the mass ratio of Zr and Ti in the binary metal simple substance powder is 50:50, and the mass ratio of the binary metal simple substance powder to the silicon carbide powder is 70: 30; uniformly mixing the powder and the binder in a weight ratio of 100:0.1 to prepare binary metal simple substance/silicon carbide composite powder for thermal spraying;
secondly, preprocessing the surface of the base material:
the base material is TC4 titanium alloy, the pretreatment mode adopts sand blasting, and then a NiCoCrAlYTa bonding layer with the thickness of 50 microns is sprayed on the surface of the TC4 titanium alloy base material after the sand blasting;
thirdly, preparing the ceramic composite coating of the refractory compound of the transition metal:
and spraying the binary composite powder for thermal spraying prepared in the first step on the surface of the TC4 titanium alloy base material pretreated in the second step by adopting a thermal spraying method, so as to synthesize the transition metal refractory compound ceramic composite coating with the thickness of 200 microns in situ.
The preparation method of the transition metal refractory compound ceramic composite coating adopts the thermal spraying method, and the technological parameters are as follows: the flow of the powder feeding gas is 0.3m3The arc power is 38KW, and the spray gun distance is 100 mm.
The refractory transition metal compound ceramic composite coating is a refractory transition metal compound ceramic composite coating taking a (Zr, Ti) C solid solution phase as a main phase, and has high density and good combination with a substrate.
Example 20
Firstly, preparing ternary metal simple substance/silicon carbide composite powder for thermal spraying: uniformly mixing ternary metal simple substance powder with the granularity ranging from 0.001 micrometer to 10 micrometers and silicon carbide powder with the granularity ranging from 0.001 micrometer to 10 micrometers to form composite powder, wherein the mass ratio of Zr, Ti and Nb in the ternary metal simple substance powder is 34:33:33, and the mass ratio of the ternary metal simple substance powder to the silicon carbide powder is 75: 25; uniformly mixing the mixture with a binder, wherein the weight ratio of the binder to the composite powder is 100:0.1, and preparing ternary metal simple substance/silicon carbide composite powder for thermal spraying;
secondly, preprocessing the surface of the base material:
the base material is Inconel 718 nickel-based high-temperature alloy, the pretreatment mode is sand blasting, and then a NiCoCrAlYTa bonding layer with the thickness of 50 micrometers is sprayed on the surface of the Inconel 718 nickel-based high-temperature alloy base material after sand blasting;
thirdly, preparing the ceramic composite coating of the refractory compound of the transition metal:
and spraying the ternary composite powder for thermal spraying prepared in the first step on the surface of the Inconel 718 nickel-based high-temperature alloy base material pretreated in the second step by adopting a thermal spraying method, so as to in-situ synthesize the transition metal refractory compound ceramic composite coating with the thickness of 200 microns.
Of ceramic composite coatings of refractory compounds of the above-mentioned transition metalsThe preparation method comprises the following process parameters of the thermal spraying method: the flow of the powder feeding gas is 0.3m3The arc power is 40KW, and the distance between the spray guns is 100 mm.
The refractory transition metal compound ceramic composite coating is a refractory transition metal compound ceramic composite coating taking a (Zr, Ti, Nb) C solid solution phase as a main phase, and has high density and good combination with a substrate.
Example 21
Firstly, preparing quaternary metal simple substance/silicon carbide composite powder for thermal spraying: uniformly mixing quaternary metal simple substance powder with the granularity ranging from 0.001 micrometer to 10 micrometers and silicon carbide powder with the granularity ranging from 0.001 micrometer to 10 micrometers to form composite powder, wherein the mass ratio of the metal simple substance powder Zr, Ti, Nb and Cr to the total quaternary metal simple substance powder is 25:25:25:25, and the mass ratio of the quaternary metal simple substance powder to the silicon carbide powder is 80: 20; uniformly mixing the mixture into a binder, wherein the weight ratio of the binder to the composite powder is 100:0.1, and preparing the quaternary metal simple substance/silicon carbide composite powder for thermal spraying;
secondly, preprocessing the surface of the base material:
the base material is GH188 cobalt-based high-temperature alloy, the pretreatment mode adopts sand blasting, and then a NiCoCrAlYTa bonding layer with the thickness of 50 micrometers is sprayed on the surface of the GH188 cobalt-based high-temperature alloy base material after the sand blasting;
thirdly, preparing the ceramic composite coating of the refractory compound of the transition metal:
and spraying the quaternary composite powder for thermal spraying prepared in the first step on the surface of the GH188 cobalt-based high-temperature alloy base material pretreated in the second step by adopting a thermal spraying method, so as to synthesize the transition metal refractory compound ceramic composite coating with the thickness of 200 microns in situ.
The preparation method of the transition metal refractory compound ceramic composite coating adopts the thermal spraying method, and the technological parameters are as follows: the flow of the powder feeding gas is 0.3m3The arc power is 42KW, and the spray gun distance is 100 mm.
The refractory transition metal compound ceramic composite coating is a refractory transition metal compound ceramic composite coating taking a (Zr, Ti, Nb, Cr) C solid solution phase as a main phase, and has high density and good combination with a substrate.
Comparative example 1
The base material is TC4 titanium alloy, the pretreatment mode adopts sand blasting, and then NiCrAlY bonding bottom layer with the thickness of 50 microns is sprayed on the surface of the TC4 titanium alloy base material after the sand blasting; zirconium carbide powder is sprayed on the surface of the pretreated TC4 titanium alloy base material, and the parameters of the thermal spraying process are as follows: the flow of the powder feeding gas is 0.3m3H, the electric arc power is 35KW, the distance of a spray gun is 100mm, and the powder feeding gas is argon; thereby synthesizing a zirconium carbide coating having a thickness of 300 microns.
Comparative example 2
The base material is TC4 titanium alloy, the pretreatment mode adopts sand blasting, and then NiCrAlY bonding bottom layer with the thickness of 50 microns is sprayed on the surface of the TC4 titanium alloy base material after the sand blasting; zirconium boride powder is sprayed on the surface of the pretreated TC4 titanium alloy base material, and the parameters of the thermal spraying process are as follows: the flow of the powder feeding gas is 0.3m3H, the electric arc power is 35KW, the distance of a spray gun is 100mm, and the powder feeding gas is argon; thus synthesizing a zirconium boride coating having a thickness of 300 microns.
Comparative example 3
The base material is TC4 titanium alloy, the pretreatment mode adopts sand blasting, and then NiCrAlY bonding bottom layer with the thickness of 50 microns is sprayed on the surface of the TC4 titanium alloy base material after the sand blasting; zirconium boride-zirconium carbide powder is sprayed on the surface of the pretreated TC4 titanium alloy base material, and the parameters of the thermal spraying process are as follows: the flow of the powder feeding gas is 0.3m3H, the electric arc power is 35KW, the distance of a spray gun is 100mm, and the powder feeding gas is argon; thereby synthesizing a zirconium boride-zirconium carbide coating having a thickness of 300 μm.
Comparative example 4
The base material is TC4 titanium alloy, the pretreatment mode adopts sand blasting, and then NiCrAlY bonding bottom layer with the thickness of 50 microns is sprayed on the surface of the TC4 titanium alloy base material after the sand blasting; spraying titanium carbide powder onThe thermal spraying process parameters of the pretreated TC4 titanium alloy base material surface are as follows: the flow of the powder feeding gas is 0.3m3H, the electric arc power is 35KW, the distance of a spray gun is 100mm, and the powder feeding gas is argon; thereby synthesizing a titanium carbide coating having a thickness of 300 microns.
Comparative example 5
The base material is TC4 titanium alloy, the pretreatment mode adopts sand blasting, and then NiCrAlY bonding bottom layer with the thickness of 50 microns is sprayed on the surface of the TC4 titanium alloy base material after the sand blasting; spraying zirconium/boron carbide composite powder on the surface of the pretreated TC4 titanium alloy matrix material, wherein the parameters of the thermal spraying process are as follows: the flow of the powder feeding gas is 0.3m3H, the electric arc power is 35KW, the distance of a spray gun is 100mm, and the powder feeding gas is argon; thereby synthesizing the zirconium boride-zirconium carbide composite coating with the thickness of 300 microns.
Comparative example 6
The base material is TC4 titanium alloy, the pretreatment mode adopts sand blasting, and then NiCrAlY bonding bottom layer with the thickness of 50 microns is sprayed on the surface of the TC4 titanium alloy base material after the sand blasting; spraying zirconium oxide/boron carbide/aluminum composite powder on the surface of the pretreated TC4 titanium alloy matrix material, wherein the parameters of the thermal spraying process are as follows: the flow of the powder feeding gas is 0.3m3H, the electric arc power is 35KW, the distance of a spray gun is 100mm, and the powder feeding gas is argon; thereby synthesizing the zirconium boride-zirconium carbide-alumina composite coating with the thickness of 300 microns.
As can be seen from the above examples and comparative examples, when compared with the oxidation resistance and ablation resistance of boride and carbide coatings prepared by thermal spraying, the oxidation resistance (1000 ℃, 24 hours, mass gain,%) of coatings obtained by thermal spraying zirconium carbide powder, zirconium boride-zirconium carbide composite powder, titanium carbide powder, zirconium/boron carbide composite powder and zirconium oxide/boron carbide/aluminum composite powder were 58, 56, 47, 65, 38 and 36, respectively, while the coatings of example 2 (zirconium carbide-zirconium silicide composite coating), example 5 (titanium carbide-titanium silicide composite coating), example 8 (chromium carbide-chromium silicide composite coating) and example 11 (niobium carbide-niobium silicide composite coating) were respectively obtainedCo-coat) has oxidation resistance of 29, 32, 27 and 34, respectively; ablation resistance (heat flux 4.02 MW/m) of coatings obtained by thermal spraying of zirconium carbide powder, zirconium boride-zirconium carbide composite powder, titanium carbide powder, zirconium/boron carbide composite powder and zirconium oxide/boron carbide/aluminum composite powder240s mass ablation (%), 8.16, 7.81, 6.33, 10.15, 4.99 and 4.74 respectively, whereas the coatings of example 2 according to the invention (zirconium carbide-zirconium silicide composite coating), of example 5 (titanium carbide-titanium silicide composite coating), of example 8 (chromium carbide-chromium silicide composite coating) and of example 11 (niobium carbide-niobium silicide composite coating) had an ablation resistance of 3.58, 3.61, 3.54 and 3.67 respectively. It can be seen that the refractory compound ceramic composite coating of transition metal prepared by the method of the invention has more excellent performance (including oxidation resistance and ablation resistance) than the corresponding boride and carbide coatings.
In the above examples, the raw materials are commercially available, and the sand blasting process, the sand sanding process, and the process of spraying the bonding layer are well known in the art.
The invention is not the best known technology.

Claims (6)

1. A method for preparing a ceramic composite coating of refractory compound of transition metal is characterized by comprising the following steps:
firstly, preparing metal simple substance/silicon carbide composite powder for thermal spraying:
mixing metal simple substance powder and silicon carbide powder into composite powder, and then mixing the composite powder with a binder to prepare the metal simple substance/silicon carbide composite powder for thermal spraying;
wherein the mass ratio of the metal simple substance powder to the silicon carbide powder is 50-90: 10-50; the weight ratio of the composite powder to the binder is 100: 0.1-2; the metal elementary powder is any x of zirconium, titanium, hafnium, tantalum, niobium, vanadium, chromium, molybdenum or tungsten, and x is 1,2,3 or 4;
secondly, the surface of the base material with the required coating is pretreated in one of the following two ways:
1) when the base material is a metal base material, firstly, sand blasting is adopted, and then a bonding layer is sprayed on the surface of the metal base material after the sand blasting;
or, 2) when the base material is an inorganic non-metallic material base, adopting sand blasting or sand paper polishing treatment;
thirdly, preparing the ceramic composite coating of the refractory compound of the transition metal:
spraying the metal simple substance/silicon carbide composite powder for thermal spraying prepared in the first step on the surface of the substrate material pretreated in the second step by adopting a thermal spraying method, so as to synthesize a transition metal refractory compound ceramic composite coating through in-situ reaction;
the technological parameters of the thermal spraying method are as follows: the flow of the powder feeding gas is 0.3-0.6 m3The arc power is 32-45 KW, and the distance between spray guns is 80-120 mm;
the binder is polyvinyl alcohol or methyl cellulose;
the particle size of the metal simple substance powder and the silicon carbide powder is 0.001-10 microns.
2. The method of claim 1, wherein when x is 2,3 or 4, the mass ratio of each element in the total metal powder is 5-95%.
3. The method of claim 1, wherein the powder gas is argon.
4. The method of claim 1, wherein the thickness of the coating obtained in the third step is 200-500 μm.
5. The method of claim 1, wherein the metal material substrate is steel, cast iron, aluminum alloy, copper alloy, titanium alloy, magnesium alloy, nickel-based superalloy, nickel-chromium alloy, cobalt-based superalloy, or intermetallic compound;
the inorganic non-metallic material matrix is graphite, a carbon/carbon composite material, a carbon/silicon carbide composite material or a silicon carbide/silicon carbide composite material.
6. The method of claim 1, wherein the bonding layer material is: NiAl, NiCrAl, FeAl, NiCrAlY, CoCrAlY, CoNiCrAlY, NiCoCrAlYTa or NiCrBSi.
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