CN111254379B - Preparation method of high-entropy ceramic coating - Google Patents
Preparation method of high-entropy ceramic coating Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C14/00—Alloys based on titanium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- 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
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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
- C23C4/04—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
- C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
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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
- C23C4/04—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
- C23C4/08—Metallic material containing only metal elements
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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
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
Abstract
The invention relates to a preparation method of a high-entropy ceramic coating. The method comprises the following steps: firstly, mixing a plurality of single element compound raw material powders to obtain composite powder, and then mixing the composite powder with a binder to prepare multi-element composite powder for thermal spraying; the single element compound is carbide, nitride or diboride; the multiple elements are any five or more than five elements of zirconium, titanium, hafnium, tantalum, niobium, vanadium, chromium, molybdenum or tungsten; secondly, pretreating the surface of the base material of the coating; thirdly, spraying the multi-element composite powder on the surface of the substrate by adopting a thermal spraying method, thereby forming the high-entropy ceramic coating through in-situ synthesis. The high-entropy ceramic coating prepared by the invention has high density, hardness, wear resistance, corrosion resistance and high-temperature resistance and oxidation resistance.
Description
Technical Field
The technical scheme of the invention relates to plating of high-entropy ceramics on materials, in particular to a preparation method of a high-entropy ceramic coating.
Background
The refractory carbides, borides and nitrides of transition metals (zirconium, titanium, hafnium, tantalum, niobium, vanadium, chromium, molybdenum and tungsten) have a plurality of excellent performances such as high melting point, good thermal stability, excellent thermal shock resistance, good oxidation and ablation resistance and the like, and become one of the most promising candidate materials for preparing novel high-temperature material structural parts in the field of aerospace. However, with the development of the aerospace and nuclear industries, the materials required are required to be usable in more severe environments, and the materials in the past have not been able to meet the requirements. The high entropy ceramic is a novel multi-component (five or more components) ceramic which is solid-dissolved into a single-phase solid solution, and has a higher entropy value. Compared with the traditional ceramics, the high-entropy ceramics has high strength, hardness, good wear resistance and structural stability. To date, some high entropy ceramics, particularly non-oxide systems, have been discovered. Among them, carbides, borides and nitrides of transition metals are considered to be ultra-high temperature ceramics (UHTCs), and the development of high-entropy ultra-high temperature ceramics is of great importance to further broaden their applications as structural elements. The preparation method of the high-entropy ceramic is still in an exploration stage at present, and the current methods for preparing the high-entropy ceramic comprise the following steps: combining a high-energy ball milling method with heat treatment; a method combining a high-energy ball milling method and spark plasma sintering; magnetron sputtering, and the like. However, the density of the ceramics and the coatings prepared by the method is usually not enough, so that the ceramics and the coatings are easy to crack when stressed, and the performance is not obviously improved.
Disclosure of Invention
The invention aims to provide a preparation method of a high-entropy ceramic coating, aiming at the defects that the research on the preparation of the high-entropy ceramic coating is less and the prior art has defects. The method adopts thermal spraying in-situ synthesis to prepare the high-entropy ceramic coating for the first time, does not need to prepare high-entropy ceramic composite powder firstly, only needs to directly carry out thermal spraying after simply mixing various raw material powders, and synthesizes the high-entropy ceramic phase in situ in the thermal spraying process. The high-entropy ceramic coating prepared by the invention has high density, hardness, wear resistance, corrosion resistance and high-temperature resistance and oxidation resistance.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a preparation method of a high-entropy ceramic coating comprises the following steps:
firstly, preparing multi-element composite powder for thermal spraying:
mixing multiple single element compound raw material powders to obtain composite powder, and mixing with a binder to prepare multi-element composite powder for thermal spraying;
wherein each raw material powder accounts for 5-35% of the total mass of the composite powder, and the mass ratio of the raw material powder to the composite powder is as follows: the binder is 100: 0.1-2,
the single element compound is carbide, nitride or diboride; the multiple elements are any five or more than five elements of zirconium, titanium, hafnium, tantalum, niobium, vanadium, chromium, molybdenum or tungsten;
the binder is polyvinyl alcohol or methyl cellulose;
the granularity range of the raw material powder is between 0.001 and 10 microns;
secondly, the surface of the base material with the required coating is pretreated in one of the following two ways:
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 when the base material is an inorganic non-metallic material base, performing sand blasting or sand paper polishing;
step three, preparing the high-entropy ceramic coating:
spraying the multi-element composite powder for thermal spraying prepared in the first step on the surface of the base material pretreated in the second step by adopting a thermal spraying method, so as to form a high-entropy ceramic coating through in-situ synthesis; the thickness of the coating is 300-500 microns;
wherein, the technological parameters of the method adopting the thermal spraying are as follows: the flow of the powder feeding gas is 0.3-0.6 m3The arc power is 35-45 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 raw materials of the preparation method of the high-entropy ceramic coating 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 processes in the field.
According to the preparation method of the high-entropy ceramic coating, the high-entropy ceramic phase generated in situ in the prepared coating is a solid solution phase of a compound (carbide or nitride or diboride) of any five or more elements of zirconium, titanium, hafnium, tantalum, niobium, vanadium, chromium, molybdenum or tungsten, the coating has high cohesive strength, and the hardness, wear resistance, corrosion resistance and high-temperature resistance and oxidation resistance of the coating are improved.
The invention has the substantive characteristics that:
in the current high-entropy ceramic preparation technology, firstly, because the ceramic is in a starting stage, the used method is the original ceramic preparation method, namely high-temperature sintering, and the high-temperature sintering capable of enabling a five-element ceramic phase to form a solid solution is achieved; secondly, for preparing the high-entropy ceramic coating by thermal spraying, the preparation of the high-entropy ceramic coating by thermal spraying of the high-entropy ceramic powder is the most direct method considering the traditional method. Therefore, the idea of preparing high-entropy ceramic (or high-entropy ceramic coating) is to firstly prepare five ceramic raw materials (for example, five different carbide powders) into high-entropy ceramic composite powder (single-phase solid solution) through high-temperature sintering, and then prepare the high-entropy ceramic powder into a ceramic block or coating through sintering and other methods.
The core innovation point of the invention is that the high-entropy ceramic coating is prepared by adopting thermal spraying in-situ synthesis for the first time, namely, the high-entropy ceramic composite powder is not required to be prepared firstly, only five raw material powders are simply mixed and then are directly subjected to thermal spraying, and the high-entropy ceramic phase is synthesized in situ in the thermal spraying process.
In the thermal spraying in-situ synthesis high-entropy ceramic coating, the high-temperature action of thermal spraying flame flow is utilized to melt and uniformly mix multi-component composite powder, a liquid uniform high-temperature melt is rapidly quenched and deposited on the surface of a base material under the action of high-speed jet flow, the melt is deposited and solidified to form a single-phase solid solution (namely a high-entropy ceramic phase), and meanwhile, the deposition and solidification processes of the liquid high-temperature melt are completed in a very short time, the supercooling degree is very high, so that the nucleation rate is very high in the solidification process of the melt, and crystal nuclei are not in time to grow, and the high-entropy ceramic coating with a fine crystal structure is synthesized in situ. The high-entropy ceramic coating has high density, high hardness, wear resistance, corrosion resistance and high-temperature resistance and oxidation resistance.
The invention has the following beneficial effects:
(1) the invention firstly adopts the hot spraying in-situ synthesis of the high-entropy ceramic coating (the hot spraying of the composite powder of various raw materials directly synthesizes the coating with the high-entropy ceramic phase as the main part), has simple preparation process and low cost, and provides a novel method for preparing the high-entropy ceramic coating.
(2) The high-entropy ceramic 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 in-situ generated high-entropy ceramic phase in the coating is a solid solution phase of carbide or nitride or diboride of any five or more elements used in zirconium, titanium, hafnium, tantalum, niobium, vanadium, chromium, molybdenum or tungsten, and 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, high energy consumption, high pollution, low efficiency, low coating thickness, low coating density, poor bonding force between the coating and a matrix, easy cracking and unsuitability for large-scale industrial production in the prior art for preparing the high-entropy ceramic coating are overcome.
(3) In order to obtain the high-entropy ceramic coating with excellent performance, the inventor team successfully adopts the method to prepare the high-entropy ceramic coating after years of intensive research and nearly hundred repeated experiments, so that the preparation process is simple, the obtained high-entropy ceramic coating has excellent performance, and unexpected technical effects and obvious economic benefits are obtained.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is an XRD spectrum of the high entropy ceramic coating prepared in example 1.
FIG. 2 is an SEM image of the high entropy ceramic coating obtained in example 1.
FIG. 3 is a graph comparing the hardness of the high-entropy ceramic coating obtained in example 1 with that of a coating obtained by thermally spraying zirconium carbide, titanium carbide, niobium carbide, chromium carbide and vanadium carbide powders.
Detailed Description
Example 1
Firstly, preparing multi-element composite powder for thermal spraying: uniformly mixing five raw material powders of zirconium carbide, titanium carbide, niobium carbide, chromium carbide and vanadium carbide with the granularity of 0.001-10 microns into composite powder, wherein the raw material powders of zirconium carbide, titanium carbide, niobium carbide, chromium carbide and vanadium carbide account for the total mass ratio of the composite powder of 27:15:27:15:16, and uniformly mixing a binder (methyl cellulose) with the use amount of the binder, and the weight ratio of the composite powder to the binder is 100:0.1, thereby preparing the multi-component composite powder for thermal spraying;
secondly, preprocessing the surface of the base material:
the base material is heat-resistant steel 1Cr18Ni9Ti steel, 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 sand-blasted 1Cr18Ni9Ti steel base material;
step three, preparing the high-entropy ceramic coating:
and spraying the multi-element composite powder for thermal spraying prepared in the first step on the surface of the 1Cr18Ni9Ti steel matrix material pretreated in the second step by adopting a thermal spraying method, so as to synthesize the high-entropy ceramic coating with the thickness of 300 microns in situ.
According to the preparation method of the high-entropy ceramic coating, the technological parameters of the thermal spraying method are as follows: the flow of the powder feeding gas is 0.3m3H, the arc power is 35KW,the distance of the spray gun is 100mm, and the powder feeding gas is argon.
Fig. 1 is an XRD pattern of the high-entropy ceramic coating prepared in this example, and it can be seen from the XRD pattern that the main phase of the ceramic coating is the peak of (ZrTiNbCrV) C solid solution with FCC structure, which proves that the high-entropy ceramic coating with the solid solution phase with FCC structure as the main phase is obtained after the multi-component composite powder is thermally sprayed. Comparing with standard PDF cards of ZrC and NbC, 65-0332 and 65-7964, the peak of (ZrTiNbCrV) C shifts to a high angle, which proves that five elements are mutually dissolved in solid solution, so that the lattice constant is reduced, and the diffraction peak shifts. It can be seen that the high-entropy ceramic coating with the main component of FCC structure solid solution phase can be successfully synthesized in situ by adopting the thermal spraying method by taking the zirconium carbide, the titanium carbide, the niobium carbide, the chromium carbide and the vanadium carbide multi-component composite powder as the raw materials. FIG. 2 is an SEM image of the high-entropy ceramic coating prepared in the present example. It can be seen that the thickness of the high-entropy ceramic coating reaches 300 microns, the density of the coating is high, and the coating is well combined with a matrix. In addition, compared with the coating (comparative examples 1-5) obtained by thermally spraying zirconium carbide, titanium carbide, niobium carbide, chromium carbide and vanadium carbide unit powder, the (ZrTiNbCrV) C high-entropy ceramic coating prepared by thermal spraying in-situ synthesis has higher density, hardness, wear resistance, corrosion resistance and high-temperature oxidation resistance. As can be seen from FIG. 3, the Hardness (HV) of the thermal sprayed zirconium carbide, titanium carbide, niobium carbide, chromium carbide and vanadium carbide coatings0.1) 1043, 1089, 905, 1126 and 964, the hardness of the (ZrTiNbCrV) C high-entropy ceramic coating obtained in the embodiment is 1397, and the hardness of the high-entropy ceramic coating obtained in the embodiment is improved by 24-45% compared with that of the zirconium carbide, titanium carbide, niobium carbide, chromium carbide and vanadium carbide coatings.
Example 2
Firstly, preparing multi-element composite powder for thermal spraying: uniformly mixing five raw material powders ZrC, HfC, TiC, NbC and TaC with the particle size range of 0.001-10 microns into composite powder, wherein the mass ratio of each raw material powder to the total composite powder is 20%, and uniformly mixing the raw material powders into a binder, wherein the weight ratio of the composite powder to the binder is 100: 1, so as to prepare the multi-component composite powder for thermal spraying;
secondly, preprocessing the surface of the 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 is sprayed on the surface of the titanium-aluminum intermetallic compound base material after sand blasting;
step three, preparing the high-entropy ceramic coating:
and spraying the multi-element composite powder for thermal spraying prepared in the first step on the surface of the titanium-aluminum intermetallic compound Ti-48Al-2Cr-2Nb base material pretreated in the second step by adopting a thermal spraying method, so as to synthesize the high-entropy ceramic coating in situ.
According to the preparation method of the high-entropy ceramic coating, the technological parameters of the thermal spraying method are as follows: the flow of the powder feeding gas is 0.4m3The arc power is 40KW, and the distance between the spray guns is 80 mm.
The high-entropy ceramic coating takes a (ZrHfTiNbTa) C solid solution phase with an FCC structure as a main phase, the coating has high density, and the coating is well combined with a matrix. In addition, compared with the coating obtained by thermally spraying ZrC, HfC, TiC, NbC and TaC unit powder, the (ZrHfTiNbTa) C high-entropy ceramic coating prepared by thermal spraying in-situ synthesis has higher density, hardness, wear resistance, corrosion resistance and high-temperature resistance and oxidation resistance.
Example 3
The other steps are the same as example 1, except that the raw material powders in the first step are six raw material powders: zirconium carbide, hafnium carbide, tantalum carbide, titanium carbide, niobium carbide and vanadium carbide are uniformly mixed into composite powder, wherein the raw material powder zirconium carbide, hafnium carbide, tantalum carbide, titanium carbide, niobium carbide and vanadium carbide account for the total mass ratio of the composite powder is 17: 17: 17: 17: 16: 16. the properties of the coating thus obtained are similar to those of example 1.
Example 4
The other steps are the same as example 1, except that the raw material powders in the first step are six raw material powders: zirconium carbide, molybdenum carbide, chromium carbide, titanium carbide, niobium carbide and tungsten carbide are uniformly mixed into composite powder, wherein the raw material powder zirconium carbide, molybdenum carbide, chromium carbide, titanium carbide, niobium carbide and tungsten carbide account for 17 of the total mass ratio of the composite powder: 16: 17: 17: 17: 16. the properties of the coating thus obtained are similar to those of example 1.
Comparative example 1
The base material is 1Cr18Ni9Ti steel, 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 1Cr18Ni9Ti steel base material after the sand blasting; zirconium carbide powder is sprayed on the surface of the pretreated 1Cr18Ni9Ti steel matrix material, and the thermal spraying process parameters 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 1Cr18Ni9Ti steel, 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 1Cr18Ni9Ti steel base material after the sand blasting; titanium carbide powder is sprayed on the surface of the pretreated 1Cr18Ni9Ti steel matrix material, and the thermal spraying process parameters 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 3
The base material is 1Cr18Ni9Ti steel, 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 1Cr18Ni9Ti steel base material after the sand blasting; spraying niobium carbide powder on the surface of the pretreated 1Cr18Ni9Ti steel matrix material, wherein the thermal spraying process parameters 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 niobium carbide coating having a thickness of 300 microns.
Comparative example 4
The base material is 1Cr18Ni9Ti steel, 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 1Cr18Ni9Ti steel base material after the sand blasting; spraying chromium carbide powder on the above-mentioned raw materialThe surface of the pretreated 1Cr18Ni9Ti steel matrix material has the following thermal spraying process parameters: 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 chromium carbide coating having a thickness of 300 microns.
Comparative example 5
The base material is 1Cr18Ni9Ti steel, 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 1Cr18Ni9Ti steel base material after the sand blasting; vanadium carbide powder is sprayed on the surface of the pretreated 1Cr18Ni9Ti steel matrix material, and the thermal spraying process parameters 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 vanadium carbide coating having a thickness of 300 microns.
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 (3)
1. A preparation method of a high-entropy ceramic coating is characterized by comprising the following steps:
firstly, preparing multi-element composite powder for thermal spraying:
mixing multiple single element compound raw material powders to obtain composite powder, and mixing with a binder to prepare multi-element composite powder for thermal spraying;
wherein each raw material powder accounts for 5-35% of the total mass of the composite powder, the mass ratio of the composite powder to the binder is = 100: 0.1-2,
the single element compound is carbide, nitride or diboride; the multiple single elements are any five or more elements of zirconium, titanium, hafnium, tantalum, niobium, vanadium, chromium, molybdenum or tungsten;
secondly, the surface of the base material with the required coating is pretreated in one of the following two ways:
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 when the base material is an inorganic non-metallic material base, performing sand blasting or sand paper polishing;
step three, preparing the high-entropy ceramic coating:
spraying the multi-element composite powder for thermal spraying prepared in the first step on the surface of the base material pretreated in the second step by adopting a thermal spraying method, so as to form a high-entropy ceramic coating through in-situ synthesis; the thickness of the coating is 300-500 microns;
wherein, the technological parameters of the method adopting the thermal spraying are as follows: the flow of the powder feeding gas is 0.3-0.6 m3The arc power is 35-45 kW, and the distance between spray guns is 80-120 mm;
the binder is polyvinyl alcohol or methyl cellulose;
the granularity range of the raw material powder is between 0.001 and 10 microns;
the metal material matrix is steel, cast iron, aluminum alloy, copper alloy, titanium alloy, magnesium alloy, nickel-based superalloy, 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.
2. The method for preparing a high-entropy ceramic coating according to claim 1, wherein the bonding layer material is: NiAl, NiCrAl, FeAl, NiCrAlY, CoCrAlY, CoNiCrAlY, NiCoCrAlYTa or NiCrBSi.
3. The method for producing a high-entropy ceramic coating according to claim 1, wherein the powder feeding gas in the thermal spraying is argon gas.
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| US11840486B1 (en) * | 2022-06-16 | 2023-12-12 | The Florida International University Board Of Trustees | High-entropy ultra-high temperature ceramic (HE-UHTC) coatings and deposition methods thereof |
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| CN114920559A (en) * | 2022-06-07 | 2022-08-19 | 西北工业大学 | High-entropy oxide powder material for thermal barrier coating and preparation method and application thereof |
| CN115057715B (en) * | 2022-06-17 | 2023-07-04 | 中广核研究院有限公司 | Silicon carbide cladding connecting material, silicon carbide ceramic connecting piece, and manufacturing method and application thereof |
| CN116516337B (en) * | 2023-04-18 | 2024-01-05 | 哈尔滨工业大学 | High-entropy carbide protective coating for shielding high-energy electrons and high-energy protons and preparation method thereof |
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