CN115287645A - High-entropy alloy-based high-temperature solid lubricating coating and preparation method thereof - Google Patents
High-entropy alloy-based high-temperature solid lubricating coating and preparation method thereof 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
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- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
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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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- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
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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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- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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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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- C22C30/00—Alloys containing less than 50% by weight of each constituent
Abstract
The invention relates to a high-entropy alloy-based high-temperature solid lubricating coating and a preparation method thereof, belonging to the technical field of material surface treatment and solid lubrication. The coating comprises the following components in percentage by mass based on 100% of the raw material composition of the coating: coCrFeNiW 0.2~0.5 70-90% of high-entropy alloy powder and 10-30% of Ag powder; the coating is prepared by a cold air dynamic spraying technology, and the phase structure of the coating is as follows: FCC phase + intermetallic + Ag phase. By adopting the cold spraying technology, the metal powder can be always in a low-temperature state in the spraying process, the burning loss of alloy elements in the spraying process is avoided, and meanwhile, the prepared coating has a compact structure and can effectively improve the tribological performance and the bearing performance of the coating.
Description
Technical Field
The invention relates to a high-entropy alloy-based high-temperature solid lubricating coating and a preparation method thereof, belonging to the technical field of material surface treatment and solid lubrication.
Background
With the development of high and new technologies such as aviation, aerospace, nuclear energy and the like in China and the development of traditional industries such as automobiles, energy sources, metallurgy, electric power and the like, more and more mechanical equipment needs to realize reliable and stable work at high temperature. The problems of lubrication and wear resistance of moving parts at high temperature become bottlenecks affecting the reliability and service life of the system, and the development of high-performance lubrication technology and materials has important significance for improving the reliability, stability and service life of equipment and parts thereof.
The common high-temperature solid lubricating coating consists of a bonding phase, a lubricating phase and a reinforcing phase, wherein the bonding phase mainly consists of metal and alloy materials, and a common nickel-based alloy and a common cobalt-based alloy mainly play roles in storing the lubricating phase and the reinforcing phase, connecting a matrix and supporting load in the coating; the lubricating phase mainly comprises soft metal with lubricating property and a plurality of lubricants with a laminated structure, and mainly plays a role in reducing friction and abrasion; the reinforcing phase is mainly a ceramic material with high hardness and high wear resistance, such as nitride ceramic, oxide ceramic and carbide ceramic, and mainly plays a role in improving the high-temperature hardness and the high-temperature wear resistance of the coating.
At present, many studies on high-temperature solid lubricating coatings are made, but no report is found on the study on the preparation of the high-temperature solid lubricating coating by taking high-entropy alloy as a binding phase and cold spraying as a preparation method. The PS304 and PS400 high-temperature solid lubricating coatings reported by NASA adopt atmospheric plasma spraying, the two coatings respectively take NiCr alloy and NiMoAl alloy as coating binder phase, and in order to compensate the hardness of the nickel-based alloy binder phase at high temperature,Insufficient wear resistance by adding a certain amount of Cr 2 O 3 The reinforcing phase is improved, but the addition of the ceramic reinforcing phase causes the thermal expansion coefficient of the coating to be mismatched, so that the bonding strength and the cohesive strength of the coating are reduced; meanwhile, the process characteristics of atmospheric plasma spraying also determine that the PS304 and PS400 coatings have loose porous structures, so that the bearing capacity of the coatings is reduced, and the application range of the coatings is limited to a great extent.
The Chinese patent CN 104278227B discloses a preparation technology of an all-metal phase wide temperature range self-lubricating coating, and the NiCrAlY-Ag-Mo composite coating is prepared by adopting an atmospheric plasma spraying process, so that the problem that the cohesive strength and the bonding strength of the coating are damaged by adding a ceramic reinforcing phase in the coating can be solved. However, the NiCrAlY binder phase has low high-temperature hardness and limited wear resistance, and the long service life of the coating is influenced. Meanwhile, the lubricating coating prepared by atmospheric plasma spraying has the problems of loose structure and burning loss of alloy elements, and the improvement of the bearing performance and the tribological performance of the coating is restricted.
The high-entropy alloy is also called multi-principal element alloy, and is an alloy system with a simple solid solution structure, wherein the alloy system consists of 5 or more than 5 elements, and the atomic percent of each element is between 5 and 35 percent. The high-entropy alloy has a high-entropy effect, a slow diffusion effect, a lattice distortion effect and a 'cocktail' effect, and endows the high-entropy alloy with a plurality of excellent characteristics, such as high strength, high hardness, high-temperature softening resistance, radiation resistance, high wear resistance and the like. The Chinese patent CN111218603B discloses a preparation method of a high-entropy alloy-based high-temperature solid lubricating composite material, which comprises the steps of carrying out ball-milling and uniform mixing on AlCoCrFeNi high-entropy alloy powder and Ag powder in sequence, carrying out discharge plasma sintering, and cooling to room temperature to obtain the AlCoCrFeNi-Ag high-entropy alloy-based high-temperature solid lubricating composite material, wherein the composite material has good mechanical property, wide-temperature-range self-lubricating property and wear-resisting property, but the friction coefficient of the composite material reaches 0.74 at 800 ℃ along with the increase of temperature, and the tribological property is sharply reduced.
Disclosure of Invention
In view of the above, the present invention aims to provide a high-entropy alloy-based high-temperature solid lubricating coating and a preparation method thereof.
In order to realize the purpose, the technical scheme of the invention is as follows:
the high-entropy alloy-based high-temperature solid lubricating coating comprises the following components in percentage by mass, based on 100% of the raw material composition of the coating: coCrFeNiW 0.2~0.5 70-90% of high-entropy alloy powder and 10-30% of Ag powder; the coating is prepared by a cold air dynamic spraying technology, and the phase structure of the coating is as follows: FCC phase + intermetallic + Ag phase.
Preferably, the coating comprises the following components in percentage by mass based on 100% of the raw material composition of the coating: coCrFeNiW 0.2~0.5 80-85% of high-entropy alloy powder and 15-20% of silver powder.
The invention relates to a preparation method of a high-entropy alloy-based high-temperature solid lubricating coating, which comprises the following steps:
(1) CoCrFeNiW is respectively weighed according to the powder proportion 0.2~0.5 Uniformly mixing the high-entropy alloy powder and Ag powder to obtain mixed powder;
(2) Carrying out surface degreasing cleaning and sand blasting treatment on the surface of the high-temperature alloy part to be sprayed to obtain the high-temperature alloy part after surface treatment;
(3) Placing the mixed powder into a powder feeder of cold spraying equipment, clamping the surface-treated high-temperature alloy part on a cold spraying workbench, taking helium as accelerating gas, and setting cold spraying process parameters as follows: the gas pressure is more than or equal to 4MPa, the gas temperature is 500-600 ℃, the spraying distance is 25-30 mm, the powder feeding amount is 20-30 g/min, the spraying speed is 0.3-0.6 m/min, the cycle is more than 2 times, and the high-entropy alloy-based high-temperature solid lubricating coating is prepared on the surface of the high-temperature alloy part.
Preferably, in the step (1), the Ag powder is a spherical powder having a particle size distribution of 15 to 53 μm.
Preferably, in step (1), the CoCrFeNiW 0.2~0.5 The high-entropy alloy powder is spherical powder, and the particle size distribution is 15-53 mu m.
Preferably, in step (1), the CoCrFeNiW 0.2~0.5 The high-entropy alloy powder is prepared by a rotary electrode method.
Preferably, in the step (2), the surface roughness of the high-temperature alloy part after the surface treatment is Ra1.6-Ra3.2.
Preferably, in the step (3), the pressure is 4MPa to 5MPa, and the cycle number is 2 to 6.
Preferably, the thickness of the coating is 200 to 300 μm.
Advantageous effects
The invention provides a high-entropy alloy-based high-temperature solid lubricating coating, which is formed by using CoCrFeNiW as a coating material 0.2~0.5 The high-entropy alloy is a bonding phase, and the alloy can still keep good hardness, strength and wear resistance at 1000 ℃, so that a ceramic reinforcing phase is not required to be added to improve the high-temperature mechanical property and wear resistance of the coating, the coating with the all-metal phase structure can obviously improve the bonding strength and cohesive strength of the coating, and meanwhile, the thermal expansion coefficients of the coating and a high-temperature alloy matrix are more matched, so that the bearing capacity and the service life of the coating are favorably improved; w is a metal element having the highest melting point, and CoCrFeNiW can be increased as an alloy element 0.2~0.5 Melting point, strength and hardness in high entropy alloys, and its oxidation product at high temperatures WO 3 The coating has a low friction coefficient, and is beneficial to comprehensively improving the high-temperature mechanical property and the tribological property of the coating; the coating mainly plays a role in lubrication by Ag at medium and low temperatures, and plays a role in lubrication by a multi-element composite oxide generated by oxidizing Ag and alloy elements at high temperatures, so that the coating can be ensured to have lower friction coefficient and wear rate in the range of room temperature to 1000 ℃.
The invention provides a preparation method of a high-entropy alloy-based high-temperature solid lubricating coating, which adopts a cold spraying technology to keep metal powder in a low-temperature state all the time in a spraying process, avoids burning loss of alloy elements in the spraying process, and can effectively improve the tribological performance and the bearing performance of the coating due to a compact structure of the prepared coating.
The high-entropy alloy-based high-temperature solid lubricating coating provided by the invention is suitable for application in high-temperature working conditions such as brush seal of an aero-engine, piston of a Stirling engine, gas foil bearing, missile high-temperature gas servo system and the like.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
In examples 1 to 3 and comparative example 1 below, the high-entropy alloy powder was prepared by the rotary electrode method, and the manufacturer was Beijing, mingpeng, new materials science and technology Co., ltd.
Example 1
(1) The coating comprises the following components in percentage by mass based on 100% of the raw material composition of the coating: coCrFeNiW 0.2 90% of high-entropy alloy powder and 10% of Ag powder; the CoCrFeNiW 0.2 The high-entropy alloy powder is spherical powder prepared by a rotating electrode method, and the particle size distribution is 15-53 mu m; the silver powder is spherical powder, and the particle size distribution is 15-53 mu m. And weighing the powder according to the proportion, and putting the powder into a V-shaped mixer for mixing for 3 hours.
(2) And carrying out sand blasting treatment on the surface of the GH4169 high-temperature alloy substrate to remove surface oxides, wherein the roughness of the surface of the substrate after sand blasting is Ra1.6-Ra3.2.
(3) Placing the obtained mixed powder into a powder feeder of cold spraying equipment, clamping the surface-treated high-temperature alloy part on a cold spraying workbench, taking helium as accelerating gas, and setting cold spraying process parameters as follows: the gas pressure is 4MPa, the gas temperature is 500 ℃, the spraying distance is 25mm, the powder feeding amount is 20g/min, the spraying speed is 0.3m/min, and the high-entropy alloy-based high-temperature solid lubricating coating is prepared by circularly spraying on the surface of the high-temperature alloy matrix for 2 times.
Testing the thickness of the coating by using a coating thickness tester, wherein the thickness is 100 +/-10 mu m; the bonding strength of the coating tested according to the GB/T8642 standard method is 34.7MPa; the Vickers hardness of the coating at room temperature and 1000 ℃ is respectively 324HV and 190HV when tested under 30kgf load by adopting an HVZHT-30 type high-temperature hardness tester; GH4169 high-temperature alloy balls with the diameter of phi 8mm are matched with a pair, the test load is 5N, and the friction coefficients of the coating tested by an ASTM G133-02 standard method at 25 ℃, 500 ℃ and 1000 ℃ are 0.35 and 0 respectively under the test condition of the sliding speed of 1 m/s.33 and 0.29, wear rates of 8.3X 10 at the three temperatures, respectively -6 mm 3 /N·m、5.6×10 -5 mm 3 N.m and 5.1X 10 -5 mm 3 /N·m。
Example 2
(1) The coating comprises the following raw materials in percentage by mass, based on 100 percent of the raw materials of the coating: coCrFeNiW 0.5 85% of high-entropy alloy powder and 15% of Ag powder; the CoCrFeNiW 0.5 The high-entropy alloy powder is spherical powder prepared by a rotating electrode method, and the particle size distribution is 15-53 mu m; the silver powder is spherical powder, and the particle size distribution is 15-53 mu m. And weighing the powder according to the proportion, and putting the powder into a V-shaped mixer for mixing for 3 hours to obtain mixed powder.
(2) And carrying out sand blasting treatment on the surface of the GH4169 high-temperature alloy substrate to remove surface oxides, wherein the roughness of the surface of the substrate after sand blasting is Ra1.6-Ra3.2.
(3) Placing the obtained mixed powder into a powder feeder of cold spraying equipment, clamping the surface-treated high-temperature alloy part on a cold spraying workbench, taking helium as accelerating gas, and setting cold spraying process parameters as follows: the gas pressure is 5MPa, the gas temperature is 600 ℃, the spraying distance is 30mm, the powder feeding amount is 30g/min, the spraying speed is 0.6m/min, and the high-entropy alloy-based high-temperature solid lubricating coating is prepared by spraying on the surface of the high-temperature alloy substrate for 6 times in a circulating manner.
Testing the thickness of the coating layer by using a coating thickness gauge, wherein the thickness is 300 +/-10 mu m; the bonding strength of the coating tested according to the GB/T8642-2002 standard method is 36.6MPa; the Vickers hardness of the coating at room temperature and 1000 ℃ was determined to be 355HV and 203HV, respectively, using a high temperature durometer model HVZHT-30, under a load of 30 kgf; GH4169 high-temperature alloy ball with the diameter of 8mm is matched with a pair of balls, the test load is 5N, the friction coefficients of the coating tested by the ASTM G133-02 standard method at 25 ℃, 500 ℃ and 1000 ℃ are 0.33, 0.30 and 0.21 respectively under the test conditions of the sliding speed of 1m/s, and the wear rates at the three temperatures are 2.1 multiplied by 10 respectively -6 mm 3 /N·m、7.5×10 -6 mm 3 N.m and 8.3X 10 -6 mm 3 /N·m。
Example 3
(1) The coating comprises the following components in percentage by mass based on 100% of the raw material composition of the coating: coCrFeNiW 0.5 70% of high-entropy alloy powder and 30% of Ag powder; the CoCrFeNiW 0.5 The high-entropy alloy powder is spherical powder prepared by a rotating electrode method, and the particle size distribution is 15-53 mu m; the silver powder is spherical powder, and the particle size distribution is 15-53 mu m. And weighing the powder according to the proportion, and putting the powder into a V-shaped mixer for mixing for 3 hours to obtain mixed powder.
(2) And carrying out sand blasting treatment on the surface of the GH4169 high-temperature alloy matrix to remove surface oxides, wherein the roughness of the surface of the matrix after sand blasting is Ra1.6-Ra3.2.
(3) Placing the obtained mixed powder into a powder feeder of cold spraying equipment, clamping the surface-treated high-temperature alloy part on a cold spraying workbench, taking helium as accelerating gas, and setting cold spraying process parameters as follows: the gas pressure is 4.5MPa, the gas temperature is 550 ℃, the spraying distance is 25mm, the powder feeding amount is 25g/min, the spraying speed is 0.5m/min, and the high-entropy alloy-based high-temperature solid lubricating coating is prepared by circularly spraying on the surface of the high-temperature alloy matrix for 2 times.
Testing the thickness of the coating by using a coating thickness tester, wherein the thickness is 120 +/-10 mu m; the bonding strength of the coating tested according to the GB/T8642-2002 standard method is 19.5MPa; the Vickers hardness of the coating at room temperature and 1000 ℃ was tested at 30kgf load using a HVZHT-30 type high temperature durometer to 297HV and 149HV, respectively; GH4169 superalloy balls with the diameter of phi 8mm are matched with pairs, the test load is 5N, the friction coefficients of a coating tested by an ASTM G133-02 standard method at 25 ℃, 500 ℃ and 1000 ℃ are 0.28, 0.31 and 0.22 respectively under the test condition of the sliding speed of 1m/s, and the wear rates at the three temperatures are 2.7 multiplied by 10 respectively -5 mm 3 /N·m、6.9×10 -4 mm 3 N.m and 6.2X 10 -4 mm 3 /N·m。
Comparative example 1
(1) The coating comprises the following raw materials in percentage by mass, based on 100 percent of the raw materials of the coating: coCrFeNiW 0.6 85% of high-entropy alloy powder and Ag powderThe last 15 percent; the CoCrFeNiW 0.6 The high-entropy alloy powder is spherical powder prepared by a rotating electrode method, and the particle size distribution is 15-53 mu m; the silver powder is spherical powder, and the particle size distribution is 15-53 mu m. And weighing the powder according to the proportion, and putting the powder into a V-shaped mixer for mixing for 3 hours to obtain mixed powder.
(2) And carrying out sand blasting treatment on the surface of the GH4169 high-temperature alloy substrate to remove surface oxides, wherein the roughness of the surface of the substrate after sand blasting is Ra1.6-Ra3.2.
(3) Placing the obtained mixed powder into a powder feeder of cold spraying equipment, clamping the surface-treated high-temperature alloy part on a cold spraying workbench, taking helium as accelerating gas, and setting cold spraying process parameters as follows: the gas pressure is 5MPa, the gas temperature is 600 ℃, the spraying distance is 20mm, the powder feeding amount is 20g/min, the spraying speed is 0.3m/min, the powder can not be deposited on the high-temperature alloy matrix to form a coating after being sprayed on the surface of the high-temperature alloy matrix for 6 times in a circulating way.
Comparative example 2
Co, cr, fe, ni and W element particles with the purity of more than 99.95 percent are used as raw materials, and the vacuum arc melting technology is adopted to prepare the CoCrFeNiW 0.6 High-entropy alloy ingot casting and sample preparation are carried out, a CMT-5202 type universal material testing machine is adopted to test CoCrFeNiW according to the GB/T7314-2005 requirement 0.6 The compressive mechanical property of the alloy shows that the plasticity is poor, the sample is broken in the compression process, and the yield strength and the breaking strain are 863MPa and 21 percent respectively; coCrFeNiW was tested at a load of 30kgf using a HVZHT-30 type high temperature durometer 0.6 The Vickers hardness of the alloy at room temperature and 1000 ℃ is 507HV and 330HV respectively.
In summary, the invention includes but is not limited to the above embodiments, and any equivalent substitutions or partial modifications made under the spirit and principle of the invention are considered to be within the protection scope of the invention.
Claims (10)
1. A high-entropy alloy-based high-temperature solid lubricating coating is characterized in that: the coating comprises the following components in percentage by mass based on 100 percent of the raw material composition of the coatingComprises the following steps: coCrFeNiW 0.2~0.5 70-90% of high-entropy alloy powder and 10-30% of Ag powder; the coating is prepared by a cold air dynamic spraying technology, and the phase structure of the coating is as follows: FCC phase + intermetallic + Ag phase.
2. The high-entropy alloy-based high-temperature solid lubricating coating as claimed in claim 1, wherein: the coating comprises the following raw materials in percentage by mass, based on 100 percent of the raw materials of the coating: coCrFeNiW 0.2~0.5 80-85% of high-entropy alloy powder and 15-20% of silver or gold powder.
3. A method for preparing a high-entropy alloy-based high-temperature solid lubricating coating as claimed in claim 1 or 2, characterized in that: the method comprises the following steps:
(1) Respectively weighing CoCrFeNiW according to the powder proportion 0.2~0.5 Uniformly mixing the high-entropy alloy powder and the Ag powder to obtain mixed powder;
(2) Carrying out surface degreasing cleaning and sand blasting treatment on the surface of the high-temperature alloy part to be sprayed to obtain a surface-treated high-temperature alloy part;
(3) Placing the mixed powder into a powder feeder of cold spraying equipment, clamping the surface-treated high-temperature alloy part on a cold spraying workbench, taking helium as accelerating gas, and setting cold spraying process parameters as follows: the gas pressure is more than or equal to 4MPa, the gas temperature is 500-600 ℃, the spraying distance is 25-30 mm, the powder feeding amount is 20-30 g/min, the spraying speed is 0.3-0.6 m/min, the cycle is more than 2 times, and the high-entropy alloy-based high-temperature solid lubricating coating is prepared on the surface of the high-temperature alloy part.
4. The preparation method of the high-entropy alloy-based high-temperature solid lubricating coating as claimed in claim 3, wherein: in the step (1), the Ag powder is spherical powder, and the particle size distribution is 15-53 mu m.
5. The preparation method of the high-entropy alloy-based high-temperature solid lubricating coating as claimed in claim 3The method is characterized in that: in the step (1), the CoCrFeNiW 0.2~0.5 The high-entropy alloy powder is spherical powder, and the particle size distribution is 15-53 mu m.
6. The method for preparing a high-entropy alloy-based high-temperature solid lubricating coating as claimed in claim 3 or 5, wherein: in the step (1), the CoCrFeNiW 0.2~0.5 The high-entropy alloy powder is prepared by a rotary electrode method.
7. The preparation method of the high-entropy alloy-based high-temperature solid lubricating coating as claimed in claim 3, wherein: in the step (2), the surface roughness of the high-temperature alloy part after surface treatment is Ra1.6-Ra3.2.
8. The preparation method of the high-entropy alloy-based high-temperature solid lubricating coating as claimed in claim 3, wherein: in the step (3), the gas pressure is 4 MPa-5 MPa, and the cycle time is 2-6 times.
9. The preparation method of the high-entropy alloy-based high-temperature solid lubricating coating as claimed in claim 8, wherein: the thickness of the coating is 90-300 mu m.
10. The preparation method of the high-entropy alloy-based high-temperature solid lubricating coating as claimed in claim 3, wherein: in the step (1), the Ag powder is spherical powder, and the particle size distribution is 15-53 mu m; the CoCrFeNiW 0.2~0.5 The high-entropy alloy powder is spherical powder, and the particle size distribution is 15-53 mu m; the CoCrFeNiW 0.2~0.5 The high-entropy alloy powder is prepared by a rotary electrode method;
in the step (2), the surface roughness of the high-temperature alloy part after surface treatment is Ra1.6-Ra3.2;
in the step (3), the gas pressure is 4 MPa-5 MPa, and the cycle time is 2-6 times;
the thickness of the coating is 90-300 mu m.
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CN115627403A (en) * | 2022-11-21 | 2023-01-20 | 中国科学院兰州化学物理研究所 | High-toughness and lubrication integrated high-entropy ceramic matrix composite and preparation method thereof |
CN115627403B (en) * | 2022-11-21 | 2023-11-10 | 中国科学院兰州化学物理研究所 | High-toughness lubrication integrated high-entropy ceramic matrix composite material and preparation method thereof |
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