Preparation method of high-entropy composite hard wear-resistant material

Abstract

The application belongs to the field of powder metallurgy and relates to a preparation method of high-entropy composite hard wear-resistant material. 0.25 The WC powder, the high-entropy alloy CoCrFeNiAl, the Co powder and the grain growth inhibitor powder are put into an acoustic resonance mixer, acoustic resonance mixing is carried out according to a preset process, then the uniformly mixed powder is put into a graphite mold covered with graphite paper, pre-pressing is carried out, and then three-step temperature rising discharge plasma sintering is carried out. The powder mixing method adopted in the application is more efficient, cleaner and more uniform and stable compared with traditional methods, and is particularly suitable for mixing between hard phase and metal bonding phase micro-nano ultrafine powder. After uniform mixing, three-step temperature rising discharge plasma sintering is used, which can effectively prevent the decarburization of WC, and large-size materials with a diameter of 10mm-150mm, uniform texture, good wear resistance, hardness and fracture toughness can be sintered.

Description

Technical Field

[0001] This invention belongs to the field of powder metallurgy and relates to a method for preparing a high-entropy composite hard wear-resistant material, which can be applied to high-precision cutting tools, wear-resistant parts, molds and other fields. Background Technology

[0002] Cemented carbide, with its high hardness, excellent wear resistance, good strength and toughness, is known as the "teeth of industry" and is widely used in cutting tools, aerospace, bioelectronics, and wear-resistant parts. Most cemented carbides use Co as the binder phase; however, Co is a globally scarce resource and a strategic metal for many countries, making the discovery of effective substitutes of paramount importance.

[0003] In recent years, cemented carbides using high-entropy alloys instead of Co as the binder phase have been widely studied by scholars both domestically and internationally. Due to their superior performance and minimal Co content, they significantly reduce Co usage and improve product economics. However, cemented carbides prepared solely using high-entropy alloys as the binder phase exhibit poor performance in terms of toughness and wear resistance. Furthermore, the "powder mixing" process is a crucial step in cemented carbide preparation, and its quality ultimately affects the overall performance of the cemented carbide. If the powder mixing is uneven, it will lead to uneven texture in the sintered body during sintering, thus affecting the mechanical properties, wear resistance, and corrosion resistance of the cemented carbide, and even causing problems such as cracking and deformation.

[0004] Common high-entropy composite cemented carbide powders are mainly composed of WC powder and high-entropy alloy powder. However, their geometry and density (WC powder: 15.63-15.77 g / cm³) are different. 3 High-entropy alloy CoCrFeNiAl 0.25 7.8-8.1 g / cm³ 3 The large differences in particle size make it difficult to achieve uniform mixing using traditional powder mixing methods. For example, scholars such as Zou Qin et al. used the high-entropy alloy CoCrFeNiAl... 0.25WC-CoCrNiCuFe cemented carbide was prepared by ball milling powder and WC powder in an argon-filled glove box for 2-6 hours and then sintering by vacuum hot pressing (Patent Publication No.: CN111286664A, 2020-06-16). Nie Xiaowu et al. added NbCr2 powder and the process control agent n-heptane to WCrRuTaV high-entropy cemented carbide powder under argon protection, ball milled and mixed for 20-30 hours, and then sintered by spark plasma to obtain NbCr2-bonded WCrRuTaV refractory high-entropy cemented carbide (Patent Publication No.: CN1146064). (06A, 2022-06-10.) Sun Jialin et al. prepared suspensions by adding anhydrous ethanol and polyethylene glycol to high-entropy ceramic hard phase and high-entropy alloy FeCoNiCrMn powder, respectively. These suspensions were then ultrasonically dispersed in a water bath at over 100℃ for 1 hour. The high-entropy alloy powder FeCoNiCrMn suspension was then dropwise added to the high-entropy ceramic powder suspension while stirring, and ultrasonic dispersion continued for another hour. After ball milling for 24 hours, a high-entropy cemented carbide tool material was finally prepared using a two-step spark plasma sintering process (Patent Publication No.: CN115595463A, 2023-01-13.). Although the cemented carbide preparation processes selected in the above studies differed, they all employed the traditional ball milling mixing method. Ball milling mixing mainly involves the friction and collision between the grinding balls and powder in the milling jar as the container rotates, resulting in powder mixing. However, friction and collision can lead to a certain degree of impurity contamination. Moreover, during ball milling, powder particles tend to aggregate due to centrifugal force, thus affecting the uniformity of the material. The ball milling process generates a significant amount of heat. Since high-entropy alloys are unstable phases, excessively high temperatures and prolonged ball milling can affect their instability and may even cause powder oxidation, thus impacting the material's properties and stability. Furthermore, because W₂C is a stable phase at high temperatures (T>1200℃), WC can react with W to form W₂C. Therefore, temperature control is crucial during sintering. Thus, selecting a superior method for preparing high-entropy composite cemented carbides is essential. Summary of the Invention

[0005] This invention proposes a method for preparing high-entropy composite hard wear-resistant materials. This method reduces processing costs, greatly improves processing efficiency, and overcomes the problems of uneven and unstable mixing of cemented carbide powder, long processing time, and low cemented carbide preparation efficiency in existing technologies.

[0006] The present invention specifically adopts the following technical solution: This invention provides a method for preparing a high-entropy composite hard wear-resistant material, wherein the high-entropy composite hard wear-resistant material is composed of the following raw materials: WC powder, high-entropy alloy CoCrFeNiAl 0.25 Powder, Co powder, grain growth inhibitor powder. Includes the following steps: S1: Weighing: Weigh WC powder and high-entropy alloy CoCrFeNiAl. 0.25 The powder and Co powder, and grain growth inhibitor powder, in the following weight ratios: WC powder 84.5 wt.%-91.9 wt.%; high entropy alloy CoCrFeNiAl 0.25 Powder and Co powder 8 wt.%-15 wt.%; Grain growth inhibitor powder 0.1 wt.%-0.5 wt.%; S2: Mixed Powder: The WC powder, grain growth inhibitor powder, and high-entropy alloy CoCrFeNiAl obtained in step S1 are mixed together. 0.25 After drying, the powder and Co powder are mixed evenly using an acoustic resonance mixer. S3: Pre-compression: The uniform powder obtained in step S2 is loaded into a graphite mold lined with graphite paper and pre-compressed using a cold press. The graphite mold has an inner diameter of Φ30mm and an outer diameter of Φ45mm. The pre-compression pressure is 25-50MPa and the pre-compression time is 60s-90s. S4: Spark Plasma Sintering: The graphite mold containing the mixed powder after cold pressing is placed into the furnace cavity, and a vacuum pump is used to vacuum it. Then, spark plasma sintering is carried out according to the steps of "heating-holding-second heating-holding-third heating-holding-cooling".

[0007] In step S1, the high-entropy alloy CoCrFeNiAl 0.25 Powder purity ≥99%, high entropy alloy CoCrFeNiAl 0.25 The powder particle size is 1-2 μm, the Co powder purity is ≥99.5%, the Co powder particle size is 1-2 μm, and the high-entropy alloy CoCrFeNiAl is produced. 0.25 The ratio of powder to Co powder is 3:1 to 1:1.

[0008] In step S1, the WC powder has a particle size of 200 nm-1 μm and a purity of ≥99.5%, while the grain growth inhibitor powder has a particle size of 500 nm-25 μm and a purity of ≥99.5%. The grain growth inhibitor powder includes, but is not limited to, vanadium carbide and TiC.

[0009] In step S2 above, the powder is mixed using an acoustic resonance mixing process. The specific process steps are as follows: After freeze-drying the raw material powder weighed in step S1, it is placed in a hard alloy mixing tank that is evacuated and purged with argon gas. During mixing, 3-5 mL of anhydrous ethanol is added for every 100 g of raw material powder for dispersion. The resonant frequency is 60 Hz, and the acoustic resonance acceleration is 80-100 g (gravitational acceleration). After acoustic resonance for 3-5 min, the acceleration is switched to 15-25 g (gravitational acceleration), and acoustic resonance is maintained for 1-3 min. Then, the acoustic resonance acceleration is switched again to 80-100 g (gravitational acceleration), and acoustic resonance is maintained for 5-10 min. Afterward, the mixing tank is water-cooled for 2-5 min, and then the powder is removed and vacuum-dried to obtain a uniformly mixed high-entropy composite hard wear-resistant material powder.

[0010] The specific process and parameters of spark plasma sintering in step S4 are as follows: the sintering pressure is 10-40 MPa, then the temperature is increased from room temperature to 600℃ at a heating rate of 40-100℃ / min, held at 600℃ for 5-15 min, then increased from 600℃ to 1100-1200℃ at a heating rate of 80-100℃ / min, and held for 5-10 min; finally, the temperature is increased to 1350-1450℃ at a heating rate of 100℃ / min, held for 30-60 s, and then cooled and depressurized at a cooling rate of 40-60℃ / min to obtain a high-entropy composite hard wear-resistant material.

[0011] The above-mentioned high-entropy alloy CoCrFeNiAl 0.25 The powder preparation process is as follows: Co powder, Cr powder, Fe powder, Ni powder, and Al powder are weighed according to the molar ratio of Co:Cr:Fe:Ni:Al = 1:1:1:1:0.25; wherein the particle size of Co powder is <20μm, Cr powder is <25μm, Fe powder is <25μm, Ni powder is <20μm, and Al powder is 20μm-30μm; the purity of Co, Cr, Fe, Ni, and Al powders is ≥99.5%. The purified metal powders are then sequentially cleaned with acetone, deionized water, anhydrous ethanol, and freeze-dried. The mixture is placed in a cemented carbide ball mill jar under vacuum and argon purging, and then mounted on a ball mill for variable-speed ball milling. Cemented carbide grinding balls are used, with a ball-to-material mass ratio of 10:1. 0.2mL of anhydrous ethanol is added for dispersion per 10g of material. Ball milling was performed at 600-900 r / min for 25-40 h. After ball milling for 30 min, the mill was stopped and cooled for 10-15 min before being reversed. Finally, the mixture was vacuum dried to prepare high-entropy alloy powder with a particle size of 1-2 μm. The purity of the prepared high-entropy alloy powder was ≥99%, and the particle size was 1-2 μm.

[0012] The present invention has the following beneficial effects: (1) This invention employs acoustic resonance mixing to mix raw materials, suitable for mixing hard phase and metallic binder phase micro / nano ultrafine powders, as well as materials with large density differences. During acoustic resonance mixing, the weightlessness state of the powder is altered by controlling acceleration, and the powder can achieve resonance during the mixing process. During resonance, the powder particles vibrate and move rapidly, leading to collisions and friction between particles. This interaction between particles makes the powder particle distribution more uniform, thus achieving powder mixing and homogenization. Since WC powder particles have high hardness and wear resistance, the interaction between particles is complex. Higher frequency acoustic resonance mixing, compared to traditional mixing methods, can accelerate the collisions and interactions between particles, thereby increasing the mixing rate and promoting uniform mixing of WC powder with other components. Compared to traditional ball milling, it is more efficient (only 10-20 minutes), cleaner and more environmentally friendly, and the mixed powder is more uniform and stable.

[0013] (2) The present invention uses “three-step heating” discharge plasma sintering. The heat is kept at 1100-1200℃ for a period of time and the final heat holding time is shortened to effectively prevent W from reacting with WC and converting into W2C after WC decarburization. Large-sized materials with uniform texture and good wear resistance with diameter of 10mm-150mm can be sintered.

[0014] (3) In this invention, a high-entropy alloy CoCrFeNiAl doped with Co powder is selected. 0.25 Powder is used as a binder phase. By adjusting the ratio between the two, cemented carbide with high hardness, high fracture toughness and excellent wear resistance can be prepared.

[0015] (4) The present invention has efficient, uniform and stable powder mixing, and the prepared cemented carbide has good wear resistance, density, hardness and fracture toughness, and can be applied to high precision cutting tools, wear-resistant parts, molds and other fields. Attached Figure Description

[0016] Figure 1 This is a process flow diagram of the present invention.

[0017] Figure 2 Comparison of the morphology of the mixed powders. The left image shows the powder milling process after 8 hours in a planetary ball mill, and the right image shows the powder milling process after 16 minutes in an acoustic resonance mill.

[0018] Figure 3 This is the XRD pattern of WC-H1-grain growth inhibitor.

[0019] Figure 4 This is a comparison diagram of wear sections.

[0020] In the diagram, "H1" refers to the high-entropy alloy CoCrFeNiAl. 0.25 A mixture with Co. Detailed Implementation

[0021] The present invention will now be described in more detail through specific embodiments to facilitate understanding of the technical solution of the present invention, but this is not intended to limit the scope of protection of the present invention.

[0022] like Figure 1 As shown, the preparation method of a high-entropy composite hard wear-resistant material of the present invention mainly includes the following process: First, WC powder and high-entropy alloy CoCrFeNiAl are mixed in a certain proportion. 0.25 The powder and the grain growth inhibitor powder are placed in an acoustic resonance mixer and mixed according to the preset process. After pre-pressing, the mixture is then subjected to "three-step heating" discharge plasma sintering (discharge plasma sintering).

[0023] The high-entropy alloy CoCrFeNiAl used in the examples 0.25 The powder was prepared using the following method: 25.38g of Co powder, 22.4g of Cr powder, 24.05g of Fe powder, 25.27g of Ni powder, and 2.9g of Al powder were weighed. The purified metal powders were then sequentially cleaned with acetone, deionized water, anhydrous ethanol, and freeze-dried. The mixture was placed in a cemented carbide ball mill jar evacuated and purged with argon, and then mounted on a ball mill for variable-speed ball milling. Cemented carbide grinding balls were used, with a ball-to-powder mass ratio of 10:1. 0.2mL of anhydrous ethanol was added for dispersion for every 10g of material. The milling was performed at 750r / min for 35h, with a 10min cooling period after every 30min of milling, followed by reverse rotation. Finally, vacuum drying was performed to obtain high-entropy alloy powder with a particle size of 1-2μm.

[0024] Example 1 The specific steps for preparing high-entropy composite hard wear-resistant materials are as follows: S1: Weighing raw materials: Weigh 42.25g of WC powder with a purity of ≥99.5%, 0.25g of vanadium carbide powder with a purity greater than 99.5%, and 4.75g of high-entropy alloy CoCrFeNiAl with a purity greater than 99%. 0.25 Powder and 2.75g of Co powder with a purity greater than 99.5%; S2: Powder Mixing: After freeze-drying the raw material powder weighed in step S1, place it into a 0.7L volume hard alloy mixing container evacuated and purged with argon. During mixing, add 3mL of anhydrous ethanol for every 100g of raw material powder for dispersion. The resonant frequency is 60Hz, and the acoustic resonance acceleration is 80g (gravitational acceleration). After 5 minutes of acoustic resonance, switch the acceleration to 15g (gravitational acceleration) and continue acoustic resonance for 3 minutes. Then, switch the acoustic resonance acceleration back to 80g (gravitational acceleration) and continue acoustic resonance for 8 minutes. After this, water-cool the mixing container for 3 minutes, then remove the powder and vacuum dry it to obtain a uniformly mixed high-entropy composite hard wear-resistant material powder. The morphology of the powder after acoustic resonance mixing is shown in the figure. Figure 2 As shown on the right.

[0025] Figure 2 (Left) The powder was mixed by ball milling using a planetary ball mill. The ball milling process was as follows: cemented carbide grinding balls were used, with a ball-to-powder mass ratio of 10:1. 0.2 mL of anhydrous ethanol was added as a dispersant for every 10 g of powder. The rotation speed was 750 r / min, and the ball milling was carried out for 8 hours. The mill was stopped and cooled for 15 minutes after every 30 minutes of ball milling. Finally, the cemented carbide mixed powder was prepared by vacuum drying.

[0026] Depend on Figure 2 As we can see, compared with the traditional ball milling method that mixes powder for 8 hours, the acoustic resonance mixing method of this invention has higher mixing efficiency and more uniform mixing.

[0027] S3: Pre-compression: The uniform powder obtained in step S2 is loaded into a graphite mold lined with graphite paper and pre-compressed using a cold press. The graphite mold has an inner diameter of Φ30mm and an outer diameter of Φ45mm. The pre-compression pressure is 25MPa and the pre-compression time is 90s. S4: Spark Plasma Sintering: The sintering process is as follows: the sintering pressure is 30 MPa, then the temperature is increased from room temperature to 600℃ at a rate of 60℃ / min, held at 600℃ for 10 min, then increased from 600℃ to 1100℃ at a rate of 100℃ / min, held for 5 min; finally, the temperature is increased to 1350℃ at a rate of 100℃ / min, held for 60 s, and then cooled and depressurized at a rate of 50℃ / min to obtain a high-entropy composite hard wear-resistant material. The obtained hard alloy sample was polished and then subjected to microstructure and property testing. The results show that the hardness is 2832.6 HV, the density is 97.41%, the flexural strength is 2134.6 MPa, and the fracture toughness is 12.846 MPa·m. 1 / 2 .

[0028] Example 2 The specific steps for preparing high-entropy composite hard and wear-resistant materials are as follows: S1: Weighing raw materials: Weigh 44.75g of WC powder with a purity of ≥99.5%, 0.25g of vanadium carbide powder with a purity greater than 99.5%, and 3.75g of high-entropy alloy CoCrFeNiAl with a purity greater than 99%. 0.25 Powder and 1.25g of Co powder with a purity greater than 99.5%; S2: Mixing Powder: After freeze-drying the raw material powder weighed in step S1, place it into a 0.7L volume hard alloy mixing tank evacuated and purged with argon. During mixing, add 4mL of anhydrous ethanol for every 100g of raw material powder to disperse it. The resonant frequency is 60Hz, the acoustic resonance acceleration is 90g (gravitational acceleration), and after 4min of acoustic resonance, switch the acceleration to 20g (gravitational acceleration) and acoustic resonance for 2min. Then switch the acoustic resonance acceleration to 90g (gravitational acceleration) again and acoustic resonance for 10min. After that, water cool the mixing tank for 4min, and then take out the powder and vacuum dry it to obtain a uniformly mixed high-entropy composite hard wear-resistant material powder.

[0029] S3: Pre-compression: The uniform powder obtained in step S2 is loaded into a graphite mold lined with graphite paper and pre-compressed using a cold press. The graphite mold has an inner diameter of Φ30mm and an outer diameter of Φ45mm. The pre-compression pressure is 40MPa and the pre-compression time is 75s. S4: Spark Plasma Sintering: The sintering process is as follows: the sintering pressure is 35 MPa, then the temperature is increased from room temperature to 600℃ at a rate of 60℃ / min, held at 600℃ for 12 min, then increased from 600℃ to 1150℃ at a rate of 80℃ / min, and held for 8 min; finally, the temperature is increased to 1400℃ at a rate of 100℃ / min, held for 45 s, and then cooled and depressurized at a rate of 60℃ / min to obtain a high-entropy composite hard wear-resistant material. The obtained hard alloy sample was polished and then subjected to microstructure and property testing. The results show that the hardness is 2793.6 HV, the density is 98.62%, the flexural strength is 1929 MPa, and the fracture toughness is 12.462 MPa·m. 1 / 2 The XRD pattern of the sample obtained in this embodiment is as follows. Figure 3 As shown in the figure, it can be clearly seen that a strong WC diffraction peak appears in the sample, no other impurities are observed, and no obvious decarburization phenomenon occurs in the sintered sample.

[0030] Example 3 The specific steps for preparing high-entropy composite hard and wear-resistant materials are as follows: S1: Weighing raw materials: Weigh 89.5g of WC powder with a purity of 99.5% or higher, 0.3g of vanadium carbide powder with a purity greater than 99.5%, and 6.12g of high-entropy alloy CoCrFeNiAl with a purity greater than 99%. 0.25 Powder and 4.08g of Co powder with a purity greater than 99.5%; S2: Mixing Powder: After freeze-drying the raw material powder weighed in step S1, place it into a 0.7L volume hard alloy mixing tank evacuated and purged with argon. During mixing, add 5mL of anhydrous ethanol for every 100g of raw material powder to disperse it. The resonant frequency is 60Hz, the acoustic resonance acceleration is 100g (gravitational acceleration), and after 3min of acoustic resonance, switch the acceleration to 25g (gravitational acceleration) and acoustic resonance for 1.5min. Then switch the acoustic resonance acceleration to 100g (gravitational acceleration) again and acoustic resonance for 5min. After that, water cool the mixing tank for 5min, and then take out the powder and vacuum dry it to obtain a uniformly mixed high-entropy composite hard wear-resistant material powder.

[0031] S3: Pre-compression: The uniform powder obtained in step S2 is loaded into a graphite mold lined with graphite paper and pre-compressed using a cold press. The graphite mold has an inner diameter of Φ30mm and an outer diameter of Φ45mm. The pre-compression pressure is 50MPa and the pre-compression time is 60s. S4: Spark Plasma Sintering: The sintering process is as follows: the sintering pressure is 40 MPa, then the temperature is increased from room temperature to 600℃ at a rate of 75℃ / min, held at 600℃ for 15 min, then increased from 600℃ to 1200℃ at a rate of 100℃ / min, held for 10 min; finally, the temperature is increased to 1450℃ at a rate of 100℃ / min, held for 30 s, and then cooled and depressurized at a rate of 60℃ / min to obtain a high-entropy composite hard wear-resistant material. The obtained hard alloy sample was polished and then subjected to microstructure and property testing. The results show that the hardness is 2884.2 HV, the density is 98.86%, the flexural strength is 1984.8 MPa, and the fracture toughness is 12.146 MPa·m. 1 / 2 .

[0032] Example 4 Comparative Example S1: Weigh the raw materials: Weigh 89.5g of WC powder with a purity of 99.5% or higher, 0.3g of vanadium carbide powder with a purity of 99.5% or higher, and 10.02g of Co powder with a purity of 99.5% or higher; S2: Mixing Powder: After freeze-drying the powder weighed in step S1, place it into a 0.7L volume hard alloy mixing tank evacuated and purged with argon. During mixing, add 5ml of anhydrous ethanol for every 100g of raw material powder for dispersion. The resonant frequency is 60Hz, the acoustic resonance acceleration is 100g (gravitational acceleration), and after 3 minutes of acoustic resonance, switch the acceleration to 25g (gravitational acceleration) and continue acoustic resonance for 1.5 minutes. Then, switch the acoustic resonance acceleration back to 100g (gravitational acceleration) and continue acoustic resonance for 5 minutes. After that, water-cool the mixing tank for 5 minutes, and then remove the powder and vacuum dry it to obtain a uniformly mixed high-entropy composite hard wear-resistant material powder.

[0033] S3: Pre-compression: The uniform powder obtained in step S2 is loaded into a graphite mold lined with graphite paper and pre-compressed using a cold press. The graphite mold has an inner diameter of Φ30mm and an outer diameter of Φ45mm. The pre-compression pressure is 50MPa and the pre-compression time is 60s. S4: Spark Plasma Sintering: The sintering process is as follows: the sintering pressure is 40 MPa, then the temperature is increased from room temperature to 600℃ at a heating rate of 75℃ / min, held at 600℃ for 15 min, then increased from 600℃ to 1200℃ at a heating rate of 100℃ / min, and held for 10 min; finally, the temperature is increased to 1450℃ at a heating rate of 100℃ / min, held for 30 s, and then cooled and depressurized at a cooling rate of 60℃ / min to obtain a high-entropy composite hard wear-resistant material.

[0034] The sample prepared in Example 4 (WC-Co-vanadium carbide) and the sample prepared in Example 3 (WC-H1-vanadium carbide) were subjected to friction experiments under the same experimental parameters: Si3N4 ceramic balls were used as the friction pair, the load was 80 N, the speed was 9.6 m / min (4 Hz), and dry friction was performed. The wear cross-section comparison diagram is shown below. Figure 4 As shown, it is clear that "WC-Co-vanadium carbide" has superior wear resistance compared to "WC-H1-vanadium carbide".

[0035] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Therefore, all equivalent changes or modifications made to the structure, features and principles described in the claims of the present invention should be included within the scope of the present invention.

Claims

1. A method for preparing a high-entropy composite hard wear-resistant material, characterized in that, Includes the following steps: S1: Weighing raw materials: Weigh the high-entropy alloy CoCrFeNiAl 0.25 Powder, Co powder, WC powder, and grain growth inhibitor powder; the weight ratio of the raw materials is: WC powder 84.5wt.%-91.9wt.%; high entropy alloy CoCrFeNiAl 0.25 Powder and Co powder 8 wt.%-15 wt.%; grain growth inhibitor powder 0.1 wt.%-0.5 wt.%; among which, high-entropy alloy CoCrFeNiAl 0.25 The ratio of powder to Co powder is 3:1 to 1:1; S2: Mixing Powder: Place the powder weighed in step S1 into a mixing tank and mix it using an acoustic resonance mixing process to obtain a uniform powder. The acoustic resonance mixing process is as follows: After freeze-drying the raw material powder weighed in step S1, place it into a vacuum mixing tank purged with argon gas. During mixing, add 3-5 mL of anhydrous ethanol per 100 g of raw material powder for dispersion. The resonant frequency is 60 Hz, and the acoustic resonance acceleration is 80-100 gravitational acceleration. After acoustic resonance for 3-5 min, switch the acceleration to 15-25 gravitational acceleration and continue acoustic resonance for 1-3 min. Then, switch the acoustic resonance acceleration back to 80-100 gravitational acceleration and continue acoustic resonance for 5-10 min. After this, water-cool the mixing tank and then remove the powder and vacuum dry it to obtain a uniformly mixed high-entropy composite hard wear-resistant material powder. S3: Pre-compression: The uniform powder obtained in step S2 is loaded into a graphite mold for pre-compression; S4: Spark Plasma Sintering: A graphite mold containing mixed powder, after being cold-pressed, is placed into the furnace chamber and vacuumed using a vacuum pump. Then, spark plasma sintering is performed following the steps of "heating-holding-secondary heating-holding-third heating-holding-cooling". The specific process of spark plasma sintering is as follows: the sintering pressure is 10-40 MPa, the temperature is increased from room temperature to 600℃ at a heating rate of 40-100℃ / min, held at 600℃ for 5-15 min, then increased from 600℃ to 1100-1200℃ at a heating rate of 80-100℃ / min, and held for 5-10 min; finally, the temperature is increased to 1350-1450℃ at a heating rate of 100℃ / min, held for 30-60 s, and then cooled and depressurized at a cooling rate of 40-60℃ / min to obtain a high-entropy composite hard wear-resistant material.

2. The method for preparing a high-entropy composite hard wear-resistant material according to claim 1, characterized in that, In step S1, the high-entropy alloy CoCrFeNiAl 0.25 Powder purity ≥99%, high entropy alloy CoCrFeNiAl 0.25 The particle size of the powder is 1-2 μm.

3. The method for preparing a high-entropy composite hard wear-resistant material according to claim 1, characterized in that, In step S1, the purity of the Co powder is ≥99.5%, and the particle size of the Co powder is 1-2 μm.

4. The method for preparing a high-entropy composite hard wear-resistant material according to claim 1, characterized in that, In step S1, the WC powder has a particle size of 200 nm-1 μm and a purity of ≥99.5%.

5. The method for preparing a high-entropy composite hard wear-resistant material according to claim 1, characterized in that, In step S1, the grain growth inhibitor powder has a particle size of 500nm-25μm and a purity of ≥99.5%.

6. The method for preparing a high-entropy composite hard wear-resistant material according to claim 1, characterized in that, In step S1, the grain growth inhibitor is vanadium carbide or TiC.

7. The method for preparing a high-entropy composite hard wear-resistant material according to claim 1, characterized in that, In step S3, the pre-compression pressure is 25-50 MPa, and the pre-compression time is 60-90 seconds.

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