Preparation method of ultrafine-grained high-entropy carbide-based cermet

Abstract

The present invention discloses a preparation method of an ultrafine-grained high-entropy carbide-based cermet, comprising the following steps: Step 1, dispersing multi-component carbide powders or micron-scale high-entropy carbide powders in an organic solvent, adding phenolic resin, and ball-milling with ceramic grinding balls; Step 2, pre-sintering the dried high-entropy ceramic powders; Step 3, conventionally ball-milling the obtained high-entropy carbide ceramic powders with metal powders, adding 1-3 wt% of paraffin or rubber forming agent, using absolute ethanol as the ball-milling medium, and then spray granulating the mixture; Step 4, compacting the above granulated powders; Step 5, degreasing and sintering the green compact to obtain the ultrafine-grained high-entropy carbide-based cermet. The present invention can obtain an ultrafine-grained high-entropy carbide-based cermet material with a flexural strength superior to 2300 MPa, a fracture toughness superior to 9.5 MPa·m<supgt;0.5< / supgt;, and a Rockwell hardness superior to 92.0 HRA, which can be widely applied in fields such as bearing materials, cutting tools, and die materials.

Description

Technical Field

[0001] The present invention relates to the technical field of cermets, and particularly to a preparation method of an ultrafine-grained high-entropy carbide-based cermet. Background Art

[0002] High-entropy carbides are ceramic materials composed of 4-5 transition metal carbides with an equi-(near-equi) molar ratio of metal atoms, such as (TiWMoVNb)C, (TaZrNbWMo)C, etc. Due to their excellent chemical stability, high hot hardness, wear resistance, etc., they have become potential candidate materials for a new generation of cermets. Currently, high-entropy carbide ceramic powders are prepared by solid-phase reaction methods, which have high sintering temperatures and form coarse powder particle sizes, reducing the mechanical properties of the cermet. Based on this, developing a cermet with fine grains and a high-entropy carbide ceramic phase has good application value.

[0003] However, there are mainly two methods for preparing high-entropy cermets at present. The first method is to directly mix multi-component carbide powders and metal powders evenly, and then perform high-temperature liquid-phase sintering. Through the dissolution-precipitation mechanism, multi-component carbides are formed into single-phase high-entropy carbide ceramic grains. However, this method requires a relatively high sintering temperature to ensure sufficient reaction of each component carbide and form high-entropy carbide ceramics, which will lead to grain growth and the formation of intergranular pores, reducing the mechanical properties of the cermet. The second method is to pre-synthesize high-entropy carbide ceramic powders, and then directly mix the high-entropy carbide ceramic powders with a metal binder phase (iron, cobalt, nickel) evenly, and then sinter through conventional processes to obtain a high-entropy cermet with uniform structure and controllable phases. However, due to the coarseness of the synthesized carbide powders, it is difficult to obtain a high-performance cermet material with fine grains.

[0004] Therefore, to obtain an ultrafine-grained high-entropy carbide-based cermet, there are two easily conceivable methods available. The first method is to use ultrafine high-entropy ceramic powders as raw materials. However, this method is often a chemical synthesis method, such as co-precipitation method, high-entropy ceramic precursor synthesis method. This method has low production efficiency and high cost, and it is difficult to industrialize and mass-produce. The second method is to fully crush and refine multi-component carbide ceramic powders to form ultrafine mixed powders; or directly fully grind and crush multi-component carbide ceramic powders and metal powders. Since the powders have high sintering activity after activation, an ultrafine-grained high-entropy carbide-based cermet material can be obtained. However, this method is prone to introducing excessive oxygen content during high-energy ball milling, and the adsorbed oxygen needs to be completely reduced at a relatively high temperature and consumes the carbon content, which will cause closed pores inside the cermet; at the same time, to make up for the carbon deficiency, carbon black needs to be additionally added to the cermet, but it is difficult for carbon black to achieve uniform mixing at the micron level.

[0005] Therefore, due to the coarse grains of high-entropy cermets in the prior art, there are technical problems such as poor mechanical properties. Ultrafine high-entropy carbide ceramic powders can be prepared by mechanical crushing or chemical synthesis methods, but there are still the following problems that are difficult to solve.

[0006] The mechanical crushing method is a commonly used technology in industrial production. However, to grind micron-sized high-entropy carbide ceramic powders or multi-component carbide elemental powders (4-5 kinds of carbide powders) to dozens to hundreds of nanometers requires high-energy ball milling. During this ball milling process, it is easy to cause many lattice defects on the powder surface, resulting in difficult control of the sintered structure, excessive oxygen adsorption on the powder, and it is difficult to eliminate during the subsequent sintering process. The excessive oxygen content will consume the total carbon of the cermet, and there is also a problem of uneven carbon content distribution when compensating for carbon by mixing. Summary of the Invention

[0007] The purpose of the present invention is to solve the deficiencies in the prior art, and a preparation method of ultrafine-grained high-entropy carbide-based cermet is proposed. This method has low cost, can be industrially produced, and effectively solves the problems of adsorbed oxygen and uneven distribution of carbon compensation during the crushing process.

[0008] To achieve the above purpose, a preparation method of ultrafine-grained high-entropy carbide-based cermet includes the following steps:

[0009] Step 1, disperse multi-component carbide powders or micron-sized high-entropy carbide powders in an organic solvent. The multi-component carbide powders and the micron-sized high-entropy carbide powders are both composed of at least 4 of TiC, WC, Mo 2 C, TaC, NbC, ZrC, VC, and HfC in transition metal carbides. The ratio difference of each metal element is ≤10wt%. Add 1-5wt% of phenolic resin, then add ceramic grinding balls. The ball-to-material ratio is 10-25:1, the particle size of the balls is 0.2-1.0 mm, the ball milling time is 24-60h, and the ball milling speed is 100-300r / min;

[0010] Step 2, pre-sinter the high-entropy ceramic powder after high-energy ball milling and drying in Step 1. The pre-sintering atmosphere is argon with a purity better than 99.999%. The pre-sintering temperature is 1300-1500°C, and the holding time is 1-5h;

[0011] Step 3, conventionally ball mill the high-entropy carbide ceramic powder obtained in Step 2 with metal powder. Add 1-3wt% of paraffin or rubber forming agent. The ball milling medium is anhydrous ethanol. Use cemented carbide balls. The ball-to-material ratio is 5-8:1, and the ball milling time is 24-60h; then spray granulate the mixture. The particle size of the granulated powder is 20-100μm;

[0012] Step 4: Compact the powder granulated in Step 3, with the compaction pressure being 50 - 200 MPa;

[0013] Step 5: Debind and sinter the green compact to obtain the ultrafine-grained high-entropy carbide-based cermet; the sintering is vacuum sintering or gas pressure sintering. For vacuum sintering, the vacuum degree is 5 - 50 Pa; if it is gas pressure sintering, the protective gas is argon, and the gas pressure is 0.5 - 5 MPa; the sintering temperature is 1400 - 1500 °C, and the sintering time is 1 - 3 h.

[0014] Preferably, in Step 1, the organic solvent is anhydrous ethanol or acetone.

[0015] Preferably, in Step 1, the ceramic grinding balls are alumina grinding balls or zirconia grinding balls.

[0016] Preferably, in Step 1, the addition amount of the phenolic resin is 2 - 4 wt%.

[0017] Preferably, in Step 1, the ball-to-powder ratio is 15 - 20:1, the ball milling time is 30 - 48 h, the ball milling speed is 150 - 200 r / min. Subsequently, vacuum dry the powder after high-energy grinding, and after drying is completed, perform vacuum packaging and storage.

[0018] Preferably, in Step 2, the pre-sintering temperature is preferably 1350 - 1400 °C, the holding time is 2 - 3 h. After this step, the particle size of the obtained high-entropy carbide ceramic powder is 100 - 300 nm, and the oxygen content of the powder is ≤ 0.8 wt%.

[0019] Preferably, in Step 3, the ball milling time is 30 - 48 h.

[0020] Preferably, in Step 3, the particle size of the granulated powder is 30 - 50 μm.

[0021] Preferably, in Step 5, the debinding temperature is 300 - 500 °C, and the debinding time is 2 - 5 h.

[0022] Preferably, in Step 1, the multi-component carbide powder uses commercial carbide powder, the micron-sized high-entropy carbide powder uses micron-sized high-entropy carbide powder synthesized by conventional solid-state reaction. Both the multi-component carbide powder and the micron-sized high-entropy carbide powder are composed of at least 4 kinds of TiC, WC, Mo 2 C, TaC, NbC, ZrC, VC, and HfC in transition metal carbides. To maintain the high-entropy system, the molar ratios of the metal elements of each additive phase are similar, and the difference in the ratios of each metal element is ≤ 10 wt%. The metal powder used is at least one of iron, cobalt, and nickel, and the content of the metal powder is 15 - 25 wt%.

[0023] Preferably, in step one, the transition metal carbide contains at least two phases of TiC and WC.

[0024] Preferably, in step one, the average particle size of the commercial carbide powder is 0.5 - 5.0 microns, the particle size of the high-entropy carbide powder is 5 - 10 microns, and the average particle size of the metal powder is 1.0 - 3.0 microns.

[0025] The present invention adopts a high-energy ball milling-pre-sintering treatment process to eliminate the lattice defects of the micro-nano high-entropy carbide powder and the oxygen content adsorbed in the powder; high-energy ball milling is to ball mill and crush the micron-sized high-entropy carbide ceramic powder or a variety of carbide powders to obtain nano-sized high-entropy carbide ceramic powder; and the pre-sintering treatment is to pre-sinter the nano-sized powder in a protective atmosphere to 1300 - 1500 °C, allowing atoms to diffuse through the defects to eliminate the intragranular defects, and at the same time, the adsorbed oxygen can react with the carbon on the powder surface to be eliminated. By uniformly mixing and coating the phenolic resin with a high carbon content on the surface of the high-entropy carbide ceramic powder, its dispersion is uniform, and the total carbon content in the cermet can be better controlled.

[0026] Compared with the prior art, the beneficial effects of the present invention are as follows;

[0027] 1. The present invention uses a chemical mixing method, that is, dissolving the phenolic resin with a high carbon content in an organic solvent and mixing and coating it with the high-entropy carbide ceramic powder. After drying, the phenolic resin is uniformly distributed on the surface of the high-entropy carbide ceramic powder; compared with the traditional method of adding carbon black for carbon supplementation and mixing, its dispersion uniformity is better.

[0028] 2. The present invention adopts a high-energy ball milling-pre-sintering process to obtain high-entropy carbide ceramic powder with a complete grain structure and a grain size of 100 - 300 nm. The oxygen content of this powder is ≤0.8 wt%, and it has good sintering activity and microstructure.

[0029] 3. The present invention can obtain an ultra-fine grain high-entropy carbide-based cermet material with a flexural strength better than 2300 MPa, a fracture toughness better than 9.5 MPa·m 0.5 , and a Rockwell hardness better than 92.0 HRA, which can be widely used in fields such as bearing materials, cutting tools, and die materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the embodiments.

[0031] Figure 1 It is a flowchart of a preparation method of an ultra-fine grain high-entropy carbide-based cermet.

[0032] Figure 2 Transmission electron microscopic morphologies of the high-entropy carbide ceramic powder after high-energy ball milling and the high-entropy carbide ceramic powder after pre-sintering at 1350°C in Example 1 of the present invention. Among them, (a) and (c) are the high-entropy carbide ceramic powder after high-energy ball milling, and there are many defects in its lattice; while (b) and (d) are the high-entropy carbide ceramic powder after pre-sintering at 1350°C, and the surface of its grains is curved and the lattice structure is complete.

[0033] Figure 3 Microscopic morphology of the ultrafine-grained high-entropy carbide-based cermet in Example 1 of the present invention. Detailed implementation manners

[0034] To make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below in combination with specific implementation manners and with reference to the accompanying drawings. It should be understood that these descriptions are merely exemplary and are not intended to limit the scope of the present invention. In addition, in the following description, the descriptions of well-known structures and technologies are omitted to avoid unnecessarily confusing the concepts of the present invention.

[0035] Example 1

[0036] As Figures 1-3 shown, composition: 85(Ti,W,Ta,Nb,Mo)C-15Ni cermet, where the atomic ratio of Ti:W:Ta:Nb:Mo = 1.0:1:1.1:0.9:1.0.

[0037] The mass fraction of the cermet composition is 85 parts of high-entropy carbide ceramic powder and 15 parts of binder phase. Among them, the average particle size of the high-entropy carbide powder is 5.0 microns, and the particle size of the nickel powder is 1.0 micron.

[0038] The preparation steps of the high-entropy carbide-based cermet are as follows: (1) Dispersing multi-component carbide powders or micron-sized high-entropy carbide powders in absolute ethanol, adding 2 wt% of phenolic resin, then adding alumina ceramic grinding balls with a ball-to-material ratio of 15:1, a ball diameter of 0.5 mm, a ball milling time of 30 h, and a ball milling speed of 150 r / min; subsequently, the powder after high-energy grinding is vacuum dried, and after drying, it is vacuum-packed and stored. (2) Pre-sintering the high-entropy ceramic powder after the above high-energy ball milling and drying, with an argon atmosphere for pre-sintering, a pre-sintering temperature of 1350 °C, and a holding time of 2 h. (3) Conventionally ball milling the high-entropy carbide ceramic powder obtained above with metal powder, adding 2 wt% of paraffin forming agent, using absolute ethanol as the ball milling medium, using cemented carbide balls with a ball-to-material ratio of 5:1, and a ball milling time of 48 h; subsequently, the mixture is spray granulated, and the particle size of the granulated powder is 30 μm. (4) Compacting the above granulated powder, with a compaction pressure of 80 MPa. (5) The green compact is degreased and sintered to obtain an ultrafine-grained high-entropy carbide-based cermet; the sintering is vacuum sintering with a vacuum degree of 10 Pa; the sintering temperature is 1450 °C, and the sintering time is 1 h. The temperature of the degreasing is 400 °C, and the degreasing time is 2 h.

[0039] After the above steps, the particle size of the high-entropy carbide ceramic powder obtained by the high-energy ball milling-pre-sintering method is 120 nm, and the oxygen content of the powder is 0.8 wt%. After sintering, the grain size of the high-entropy carbide ceramic is 0.6 microns, its porosity is at the A04B00C00 level, the flexural strength of the material is 2450 MPa, the fracture toughness is 9.8 MPa·m 0.5 , and the Rockwell hardness is 92.5 HRA, which is a cermet tool and die material with wide application potential.

[0040] Example 2

[0041] As Figure 1 shown, the composition: 80(W, Mo,Ti, V, Nb)C-20Co cermet, where the atomic ratio of W: Mo:Ti:V:Nb = 1:0.9:1.0:1.0:0.9.

[0042] The mass fraction of the cermet composition is 80 parts of high-entropy carbide ceramic powder and 20 parts of metal binder phase. The high-entropy carbide powder is added in the form of elemental carbide powders, including WC, Mo2C, TiC, VC, and NbC. The average particle sizes of the above powders are 2.5, 3.0, 1.8, 2.5, and 1.6 microns respectively, and the particle size of the cobalt powder is 2.5 microns.

[0043] The preparation steps of the high-entropy carbide-based cermet are as follows: (1) Dispersing multi-component carbide powders in absolute ethanol, adding 3 wt% of phenolic resin, then adding zirconia ceramic grinding balls with a ball-to-powder ratio of 20:1, a ball diameter of 0.8 mm, a ball milling time of 36 h, and a ball milling speed of 180 r / min; subsequently, vacuum drying the powders after high-energy grinding, and after drying, packing them under vacuum for storage. (2) Pre-sintering the high-entropy ceramic powders after the above high-energy ball milling and drying, with an argon atmosphere, a pre-sintering temperature of 1400 °C, and a holding time of 1 h. (3) Conventionally ball milling the high-entropy carbide ceramic powders obtained above with metal powders, adding 3 wt% of a rubber forming agent, using absolute ethanol as the ball milling medium, using cemented carbide balls, with a ball-to-powder ratio of 6:1, and a ball milling time of 35 h; subsequently, spray granulating the mixture, and the particle size of the granulated powder is 50 μm. (4) Compacting the above granulated powder, with a compaction pressure of 150 MPa. (5) The green compact is degreased and sintered to obtain an ultrafine-grained high-entropy carbide-based cermet; the sintering is atmosphere pressure sintering, with argon as the inert gas and a gas pressure of 2 MPa; the sintering temperature is 1480 °C, and the sintering time is 1 h. The temperature of the degreasing is 450 °C, and the time of the degreasing is 2 h.

[0044] After the above steps, the particle size of the high-entropy carbide ceramic powders obtained by the high-energy ball milling-pre-sintering method is 200 nm, and the oxygen content of the powders is 0.6 wt%. After sintering, the grain size of the high-entropy carbide ceramic is 0.8 microns, its porosity is at the A04B00C00 level, the flexural strength of the material is 2320 MPa, the fracture toughness is 10.2 MPa·m 0.5 , and the Rockwell hardness is 92.2 HRA, which is a cermet tool and die material with wide application potential.

[0045] Example 3

[0046] As Figure 1 shown, the composition: 75(Ti,W, Nb, V, Zr)C-10Fe-15Ni cermet, where the atomic ratio of Ti:W:Nb:V:Zr = 1:1.0:1.0:1.0:1.0.

[0047] The mass fraction of the cermet composition is 75 parts of high-entropy carbide ceramic powders and 15 parts of the binder phase. The average particle size of the high-entropy carbide powders is 8.0 microns, the particle size of the iron powder is 2.0 microns, and the particle size of the nickel powder is 3.0 microns.

[0048] The preparation steps of the high-entropy carbide-based cermet are as follows: (1) Dispersed micron-scale high-entropy carbide powder in acetone, added 3 wt% phenolic resin, then added alumina ceramic grinding balls with a ball-to-powder ratio of 20:1, a ball diameter of 0.8 mm, a ball-milling time of 48 h, and a ball-milling speed of 180 r / min; Subsequently, the powder after high-energy grinding was vacuum dried, and after drying, it was vacuum-packed and stored. (2) The high-entropy ceramic powder after high-energy ball milling and drying above was pre-sintered with an argon atmosphere, a pre-sintering temperature of 1350 °C, and a holding time of 1 h. (3) The high-entropy carbide ceramic powder obtained above was ball milled with metal powder conventionally, added 2 wt% paraffin forming agent, with absolute ethanol as the ball-milling medium, using cemented carbide balls, a ball-to-powder ratio of 8:1, and a ball-milling time of 30 h; Subsequently, the mixture was spray granulated, and the particle size of the granulated powder was 50 μm. (4) The granulated powder above was pressed into shape with a pressing pressure of 100 MPa. (5) The green compact was degreased and sintered to obtain the ultrafine-grained high-entropy carbide-based cermet; the sintering was vacuum sintering with a vacuum degree of 10 Pa; the sintering temperature was 1500 °C, and the sintering time was 2 h. The degreasing temperature was 400 °C, and the degreasing time was 2 h.

[0049] After the above steps, the particle size of the high-entropy carbide ceramic powder obtained by the high-energy ball milling-pre-sintering method is 250 nm, and the oxygen content of the powder is 0.6 wt%. After sintering, the grain size of the high-entropy carbide ceramic is 0.8 microns, its porosity is at the A04B00C00 level, the flexural strength of the material is 2280 MPa, the fracture toughness is 10.5 MPa·m 0.5 and the Rockwell hardness is 92.2 HRA, which is a cermet tool and die material with wide application potential.

[0050] Comparative Example 1

[0051] Other conditions are the same as those in Example 1, except that the high-entropy ceramic powder added is directly mixed with the metal binder phase after high-energy ball milling without going through step two, pre-sintering.

[0052] After testing, the particle size of the high-entropy carbide ceramic powder obtained by the high-energy ball milling method is 60 nm, and the oxygen content of the powder is 3.2 wt%. After sintering, the grain size of the high-entropy carbide ceramic is 1.5 microns, its porosity is at the A08B02C00 level, the flexural strength of the material is 2050 MPa, the fracture toughness is 8.2 MPa·m 0.5 and the Rockwell hardness is 91.3 HRA, which is difficult to meet the industrial requirements for tool and die products.

[0053] Comparative Example 2

[0054] Other conditions were the same as in Example 2, except that phenolic resin was not added to the organic solvent, but 1.8 wt% of pyrolytic carbon black (residual carbon content of phenolic resin was -60%) was directly added.

[0055] It was detected that the particle size of the high-entropy carbide ceramic powder obtained by the high-energy ball milling-pre-sintering method was 200 nm, and the oxygen content of the powder was 1.2 wt%. After sintering, the size of the high-entropy carbide ceramic grains was 1.0 μm, its porosity was at the A08B00C00 level, the flexural strength of the material was 2140 MPa, and the fracture toughness was 9.2 MPa·m 0.5 and the Rockwell hardness was 91.2 HRA, which was difficult to meet the industrial requirements for tooling products.

[0056] Comparative Example 3

[0057] Other conditions were the same as in Example 3, except that the atomic ratio of Ti:W:Nb:V:Zr in the preparation was 1:0.7:1.0:1.0:0.9.

[0058] It was detected that the particle size of the high-entropy carbide ceramic powder obtained by the high-energy ball milling-pre-sintering method was 230 nm, and the oxygen content of the powder was 0.8 wt%. After sintering, the size of the high-entropy carbide ceramic grains was 0.9 μm, its porosity was at the A06B00C00 level, the flexural strength of the material was 2180 MPa, and the fracture toughness was 8.2 MPa·m 0.5 and the Rockwell hardness was 92.5 HRA, which was difficult to meet the industrial requirements for tooling products.

[0059] It should be understood that the above specific embodiments of the present invention are only used for exemplary illustration or explanation of the principle of the present invention, and do not constitute a limitation to the present invention. Therefore, any modifications, equivalent replacements, improvements, etc. made without departing from the spirit and scope of the present invention shall be included within the protection scope of the present invention. In addition, the appended claims of the present invention are intended to cover all changes and modifications that fall within the scope and boundaries of the appended claims, or equivalent forms of such scope and boundaries.

Claims

1. A method for preparing an ultrafine grain high entropy carbide-based cermet, characterized in that: The steps include: Step 1, dispersing a multi-component carbide powder or a micron-sized high entropy carbide powder in an organic solvent, wherein the multi-component carbide powder and the micron-sized high entropy carbide powder are both composed of at least four of transition metal carbides including TiC, WC, Mo2C, TaC, NbC, ZrC, VC and HfC; adding 1-5wt% of phenolic resin, and then adding ceramic grinding balls, the ball-to-material ratio is 10-25:1, the ball particle size is 0.2-1.0 mm, the ball milling time is 24-60h, and the ball milling speed is 100-300r / min; Step 2, pre-sintering the high entropy ceramic powder after high-energy ball milling and drying in step 1, the pre-sintering atmosphere is argon gas, the purity of which is better than 99.999%, the pre-sintering temperature is 1300-1500°C, and the holding time is 1-5h; Step 3, conventionally ball-milling the high entropy carbide ceramic powder obtained in step 2 with metal powder, adding 1-3wt% paraffin or rubber forming agent, using anhydrous ethanol as the ball milling medium, using carbide balls, the ball-to-material ratio is 5-8:1, and the ball milling time is 24-60h; then spray granulating the mixture, the particle size of the powder after granulation is 20-100μm, and the metal powder used is at least one of iron, cobalt, and nickel; Step 4, pressing the powder granulated in step 3 into a shape at a pressing pressure of 50-200 MPa; Step 5: Degreasing and sintering the green compact to obtain an ultrafine-grained high-entropy carbide-based cermet; the sintering is vacuum sintering or atmosphere pressure sintering, the vacuum degree of the vacuum sintering is 5-50Pa, the protective gas of the atmosphere pressure sintering is argon, and the gas pressure is 0.5-5MPa; the sintering temperature is 1400-1500°C, the sintering time is 1-3h, and the fracture toughness of the ultrafine-grained high-entropy carbide-based cermet is better than 9.5 MPa·m 0.5 .

2. The method for preparing an ultrafine grain high entropy carbide-based cermet according to claim 1, characterized in that: In step 1, the multi-component carbide powder is commercial carbide powder, and the micron-sized high entropy carbide powder is micron-sized high entropy carbide powder synthesized by conventional solid phase reaction; the metal powder content is 15-25wt%.

3. The method for preparing an ultrafine grain high entropy carbide-based cermet according to claim 2, characterized in that: The transition metal carbide contains at least two phases, TiC and WC.

4. The method for preparing an ultrafine grain high entropy carbide-based cermet according to claim 2, characterized in that: The average particle size of the commercial carbide powder is 0.5-5.0 microns, the average particle size of the high entropy carbide powder is 5-10 microns, and the average particle size of the metal powder is 1.0-3.0 microns.

5. The method for preparing an ultrafine grain high entropy carbide-based cermet according to claim 1, characterized in that: In step 1, the ceramic grinding balls are alumina grinding balls or zirconia grinding balls, the ball-to-material ratio is 15-20:1, the ball milling time is 30-48 hours, and the ball milling speed is 150-200 r / min.

6. The method for preparing an ultrafine grain high entropy carbide-based cermet according to claim 1, characterized in that: In step 1, the organic solvent is anhydrous ethanol or acetone.

7. The method for preparing an ultrafine grain high entropy carbide-based cermet according to claim 1, characterized in that: In step 1, the amount of phenolic resin added is 2-4wt%.

8. The method for preparing an ultrafine grain high entropy carbide-based cermet according to claim 1, characterized in that: In step 2, the pre-sintering temperature is 1350-1400° C., and the holding time is 2-3 hours.

9. The method for preparing an ultrafine grain high entropy carbide-based cermet according to claim 1, characterized in that: In step three, the ball milling time is 30-48 hours, and the particle size of the powder after granulation is 30-50 μm.

10. The method for preparing an ultrafine grain high entropy carbide-based cermet according to claim 1, characterized in that: In step five, the degreasing temperature is 300-500° C., and the degreasing time is 2-5 hours.

Images