CN116815031A - Fine-grain metal ceramic with multi-principal element alloy as bonding metal and preparation method thereof - Google Patents
Fine-grain metal ceramic with multi-principal element alloy as bonding metal and preparation method thereof Download PDFInfo
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- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 5
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- 238000001816 cooling Methods 0.000 description 4
- 238000000713 high-energy ball milling Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
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- 229910052719 titanium Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
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- 229910052804 chromium Inorganic materials 0.000 description 2
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- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
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- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
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- 238000012795 verification Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides
-
- 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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
-
- 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
- B22F1/068—Flake-like particles
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/026—Spray drying of solutions or suspensions
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
- C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to a fine-grain cermet with multi-principal element alloy as bonding metal and a preparation method thereof, belonging to the field of hard materials. The invention aims to solve the problems of application of high and medium entropy alloy in the field of hard materials and high performance of metal ceramics. According to the invention, through the component optimization design of TiCN-based cermet, core technologies such as a scalization treatment technology of CoCrFeNi high-entropy alloy used as alloy bonding metal and CoCrNi medium-entropy alloy gas atomization powder, a two-stage pressure sintering technology for improving wettability of an alloy system through short-time high-temperature impact and the like are developed, so that the TiCN-based cermet with a homogeneous two-phase crystal structure, a hard phase average grain size smaller than 1.0 mu m and high comprehensive performance and strong adaptability to various service conditions is obtained.
Description
Technical Field
The invention relates to a fine-grain cermet with multi-principal element alloy as bonding metal and a preparation method thereof, belonging to the fields of powder metallurgy and hard materials.
Background
Achieving the contradictory unification of high strength and high toughness is an important goal of multi-principal element alloy, i.e., high-entropy alloy (HEA) and medium-entropy alloy (MEA) development. The material design concept and great technological progress of the high/medium entropy alloy greatly promote the rapid development of new materials, and provide a new opportunity for the development of hard materials such as novel hard alloy, novel metal ceramic and the like. In the single-phase face-centered cubic crystal structure alloy of the CoCrFeMnNi multi-principal element alloy system, the equal atomic ratio CoCrFeNi high-entropy alloy and the CoCrNi medium-entropy alloy both have extremely high strength and toughness, so that the alloy has high-quality potential of replacing bonded metal Ni/Co in hard alloy and TiCN-based cermet, and provides a new break for endowing the unique performance of the hard alloy and the cermet which is not yet recognized or realized.
Cr is contained in both the CoCrFeNi high-entropy alloy and the CoCrNi medium-entropy alloy. Cr is an element which is extremely easy to form carbide and can form Cr 3 C 2 、Cr 7 C 3 、Cr 23 C 6 、Cr 2 C. CrC, and the like. If the chromium carbide exists as an independent phase in the alloy, the chromium carbide is extremely easy to grow anisotropically and rapidly, thereby causing obvious microstructure defects and stress concentration to be formed in the alloy and obviously reducing the strength and toughness of the alloy. The hard material is prepared, strict requirements are imposed on the particle size matching among raw material powders, and the problems that the alloy is difficult to densify, the microstructure homogeneity is poor and the like are easily caused by the poor particle size matching degree. The method adopts the powder raw material of simple substance element to prepare Fe, co, cr, ni or Co, cr and Ni multicomponent metal as hard alloy or metal ceramic of bonding metal (also called as bonding metal in the literature), which can solve the problem of particle size matching between powders, but the simple substance Cr easily forms carbide in the sintering process due to the existence of carbon in the alloy, thus the alloy physics caused by the existence of third phase of chromium carbide is extremely easy to appearThe mechanical property is obviously reduced, and the performance is unstable.
The patent of the invention with the application number of 201210321098.1 is titanium carbonitride based cermet based on a high-entropy alloy binding phase and a preparation method thereof, and discloses that the high-entropy alloy binding phase consists of at least four of iron, cobalt, nickel, chromium, aluminum, vanadium, titanium, copper, zirconium, molybdenum, manganese and rare earth elements, and the raw material of the high-entropy alloy binding phase is simple substance powder or/and alloy powder thereof. The invention has 12 examples, and none of them adopts high-entropy alloy powder or high-entropy alloy prealloyed powder. It is known from the examples of this patent that the "alloy powders thereof" described in this patent refer to binary master alloy powders in the high entropy alloy component.
The addition of the Cr-containing high-entropy alloy powder and the Cr-containing medium-entropy alloy powder in a stable alloy form is an effective measure for avoiding the occurrence of a third phase of elemental chromium carbide in the sintering process. The most common method for preparing Cr-containing alloy powder is gas atomization powder preparation, and the most common method for preparing prealloy powder is a high-energy ball milling method, which is also called a mechanical alloying method. The Fe, co, cr, ni has high activity, easy oxygen inhalation and easy obvious oxygen enrichment and incomplete alloying and other problems.
The novel bonding metal powder of AlFeNiCoCr related to the patent application No. 201910722025.5 'novel bonding agent-based metal ceramic, and the preparation method and application thereof' is obtained by adopting an elemental powder (elemental metal powder) high-energy ball milling process.
The patent of the application number 202111215023.0, a high-strength and high-toughness medium-entropy alloy binding phase Ti (C, N) -based metal ceramic and a preparation method thereof, discloses a method for preparing a metal ceramic by adopting a spark plasma sintering process of applying 30-45 MPa pressure to prepare a CoCrNi medium-entropy alloy prefabricated powder through mechanical alloying. The method is obviously different from the traditional sintering mechanism, in the spark plasma sintering process, under the action of high pressure and external field, oxygen in the entropy prealloy powder in the CoCrNi prepared by mechanical alloying can be subjected to rapid carbothermic reduction, but the product with complex shape cannot be prepared under the constraint of a forming mode. Because the metal ceramic is mainly used as a cutting tool and a wear-resistant part, the industrial application of the metal ceramic is obviously limited by adopting a spark plasma sintering process.
The patent of the application number 201810611621.1 'ultrafine high-entropy alloy binder phase metal ceramic and a preparation method thereof' discloses a method for taking ultrafine high-entropy prealloy powder as metal ceramic binding metal, wherein the ultrafine high-entropy prealloy powder consists of Cr, ni, fe, co, al and M, and the M is at least one of Cu, zr, ti, mo and rare earth; the preparation method of the superfine high-entropy prealloy powder comprises the following steps: the components are melted and crushed under vacuum or protective atmosphere, and high-energy ball milling is adopted to obtain powder with the particle size less than or equal to 0.4 mu m. The comparative example results in the patent show that the alloy prepared from the elemental powder raw material has obviously lower performance. The components are melted and crushed under vacuum or protective atmosphere, and the powder with the particle diameter less than or equal to 0.4 mu m is obtained by adopting a high-energy ball milling method, so that the problems of obviously insufficient fine powder obtaining rate and obvious oxidation of the powder are solved. The method has obvious inapplicability for CoCrFeNi high-entropy alloy with high toughness and difficult breaking and CoCrNi medium-entropy alloy.
The invention relates to 202110476018.9' a high-strength and high-toughness high-entropy alloy ceramic and a preparation method thereof, and discloses a method for preparing a metal ceramic with the mass fraction of high-entropy alloy powder up to 30-45 wt% by adopting high-entropy alloy powder with the particle size less than or equal to 10 mu m as a raw material. In the comparative example, it is shown that CoCrFeNi as an 18wt% high entropy alloy powder, 72wt% Ti (C, N) base powder, 10wt% WC+Mo 2 C strengthening additive powder proportioning for preparing metal ceramic, and the result shows that the alloy has uneven hardness distribution (HV 30 1804+/-15), lower strength (bending strength 1434+/-50 MPa) and the like. The mass fraction of the bonded metal in the alloy which is TiCN cermet or WC-based hard alloy can meet the actual application requirement is less than or equal to 30 percent, and is usually less than or equal to 25 percent. TiCN has a theoretical density of less than 1/3 of WC theoretical density. The key parameter affecting the hardness and toughness of hard materials is the volume fraction of the binder phase in the alloy, not the mass fraction. According to the conversion relation between the mass fraction and the volume fraction, the mass fraction of the bonding metal in the TiCN-based metal ceramic capable of meeting the actual application requirement is generally 15-25%. Due to the collection of the Chinese charactersThe method is only suitable for preparing the metal ceramic with the mass fraction of high-entropy alloy bonding metal up to 30-45 wt%, and obviously the application field of the method is limited.
The screen corresponding to the particle size of 10 μm is 1600 meshes. The gas atomization powder preparation can realize complete alloying, but has the problems that the particles are coarse, the powder with the particle size smaller than 10 mu m is difficult to separate, and the particle size matching with other raw material powder of hard alloy or metal ceramic is difficult to realize.
Disclosure of Invention
The first aim of the invention is to develop a fine-grain cermet with uniform and fine microstructure, excellent comprehensive performance and better meeting the practical application requirements by using multi-principal element alloy as bonding metal.
In order to achieve the above object, based on the material calculation and the design database of the metal ceramic material established by the inventor, and the design principle of alloy composition, microstructure and performance matching, the following composition characteristics of the fine-grain metal ceramic with the multi-principal element alloy as bonding metal are clarified through experimental verification: in the alloy component, the mass fraction of the CoCrFeNi high-entropy alloy or the CoCrNi medium-entropy alloy is less than 25 percent but more than 15 percent, and WC accounts for TiC x N 1-x 25-40% of the mass fraction, and the total mass fraction of (NbC+TaC) accounts for TiC x N 1-x 10 to 15 percent of NbC accounting for 0 to 30 percent of the total mass fraction of (NbC+TaC) and Mo 2 C accounts for 25-30% of the total mass fraction of the multi-principal element alloy bonding metal; the TiC is x N 1-x Refers to single TiC 0.5 N 0.5 Or TiC 0.7 N 0.3 Powder, or TiC 0.5 N 0.5 And TiC 0.7 N 0.3 Is a mixed powder of (a) and (b); the multi-principal element alloy is CoCrFeNi high-entropy alloy or CoCrNi medium-entropy alloy, the alloy components have equal molar ratio, and the bonding phase of the metal ceramic is formed after sintering; the metal ceramic alloy structure consists of a hard phase and a binding phase, wherein the binding phase is uniformly distributed in the alloy, no microscopic aggregation phenomenon exists, and the average grain size of the hard phase in the alloy is smaller than 1.0 mu m; the hard phase and the binder phase both have face-centered cubic crystal structures; the hard phaseThe component is (Ti, M) C x N 1-x TiC is an alloy component in the sintering process 0.5 N 0.5 And/or TiC 0.7 N 0.3 、WC、TaC、NbC、Mo 2 C is formed by a multiple solid solution reaction, where x=0.5 to 0.7, m= W, ta, nb, mo or m=w, ta, mo, representing each alloy element solid-dissolved in the hard phase lattice, occupying the Ti atomic position.
The CoCrFeNi high-entropy alloy or CoCrNi medium-entropy alloy, namely the multi-principal element alloy, is prepared by adopting a melt atomization powder preparation industrialization technology in an argon atmosphere with low preparation cost, and has a single phase component and a face-centered cubic crystal structure; the multi-principal element alloy powder is subjected to screening treatment by-250 meshes, and the maximum particle size of the powder is less than or equal to 58 mu m.
The TiC is 0.5 N 0.5 And/or TiC 0.7 N 0.3 、TaC、NbC、Mo 2 The Fisher particle size of the raw material powder C is less than 1.5 mu m; the WC raw material powder has a specific surface area average particle diameter smaller than 0.3 mu m and high reactivity in the sintering process.
The design of the alloy system not only considers the matching of hardness and toughness, but also considers the complementary effect of volume expansion and the minimum stress of products generated by oxidation at high temperature and the galvanic corrosion inhibition effect in the microstructure of the alloy in the presence of corrosive liquid medium, so that the alloy has strong adaptability to various service conditions and has strong economical efficiency.
The second purpose of the invention is to develop a low-cost industrialized preparation technology of fine-grain cermet with uniform and fine microstructure, excellent comprehensive performance and capability of better meeting the practical application requirements and using multi-principal element alloy as bonding metal, thereby promoting the quality upgrading of the cermet and the expansion of application fields.
In order to achieve the above object, the present invention provides a method for preparing a fine-grain cermet using a multi-principal-element alloy as a binder metal, comprising the steps of:
A. and (3) flaking treatment of multi-principal element alloy gas atomization powder: adopting a stirring ball milling and crushing process under the argon protection condition to realize scalization treatment, and adopting a vacuum drying process to dry the wet-ground powder; the multi-principal element alloy gas atomization powder is CoCrFeNi high-entropy alloy or CoCrNi medium-entropy alloy powder, and each alloy component has an equimolar ratio; the aerosolized powder is subjected to screening treatment with a mesh of-250 meshes, and the maximum particle size of the powder is less than or equal to 58 mu m;
B. wet milling mixture preparation: c, preparing multi-principal element alloy flake powder and TiC by the step A x N 1-x 、WC、TaC、NbC、Mo 2 C, proportioning, and adding a forming agent accounting for 2.3-2.5% of the total mass of the powder for wet grinding; the result of the batching is that the mass fraction of the CoCrFeNi high-entropy alloy or the entropy alloy in the CoCrNi is less than 25 percent but more than 15 percent, and WC accounts for TiC in the metal ceramic alloy component x N 1-x 25-40% of the mass fraction, and the total mass fraction of (NbC+TaC) accounts for TiC x N 1-x 10 to 15 percent of NbC accounting for 0 to 30 percent of the total mass fraction of (NbC+TaC) and Mo 2 C accounts for 25-30% of the total mass fraction of the multi-principal element alloy bonding metal; the TiC is x N 1-x Refers to single TiC 0.5 N 0.5 Or TiC 0.7 N 0.3 Powder, or TiC 0.5 N 0.5 And TiC 0.7 N 0.3 X=0.5 to 0.7; the TiC is 0.5 N 0.5 And/or TiC 0.7 N 0.3 、TaC、NbC、Mo 2 The Fisher particle size of the raw material powder C is less than 1.5 mu m, and the specific surface area average particle size of the raw material powder WC is less than 0.3 mu m; preferably, the mass fraction of the CoCrFeNi high-entropy alloy or the CoCrNi medium-entropy alloy is 18-22%;
C. drying and granulating the wet-grinding mixture: preparing a spherical mixture with the average particle size smaller than 150 mu m by adopting a spray drying granulation or vacuum drying and mechanical granulation process;
D. powder forming: selecting a forming mode according to the shape and the size of the product and the production requirement of the traditional metal ceramic blank, wherein the forming mode comprises compression molding; if the product is a bar, the dry bag can be selected for cold isostatic pressing and extrusion molding besides the compression molding;
E. removing and sintering a forming agent: the forming agent is removed and sintered in a pressure sintering furnace; adopting a two-stage pressure sintering process for improving wettability of an alloy system by short-time high-temperature impact, wherein the sintering temperature of the first stage is 1540-1560 ℃ and the heat preservation time is 10-15 minutes; the sintering temperature of the second stage is 1480-1500 ℃ and the heat preservation time is 60-100 minutes; after the sintering temperature of the second stage is reached, high-purity argon is introduced to raise the pressure in the sintering furnace to 3.0-5.5 MPa in the final 40-80 min of the heat preservation stage.
In the step A, the rotation speed of a stirring paddle of the stirring ball mill is 250-300 revolutions per minute, the mass ratio of the hard alloy grinding ball to the multi-principal element alloy gas atomized powder is (15-20): 1, alcohol is adopted as a wet grinding medium, the liquid level is controlled to be 3-6 cm, the wet grinding time is 10-15 hours, and a ball mill barrel jacket is cooled by cooling water.
In the step B, the forming agent added in the preparation of the wet-milling mixture is polyethylene glycol or paraffin wax, and a roller ball milling process is adopted.
In the step E, after the forming agent is removed, vacuum sintering is carried out; when the temperature is raised to 1430-1450 ℃, high-purity argon is introduced to enable the pressure in the sintering furnace to reach 5-7 kPa, and the pressure is maintained until the temperature in the sintering furnace reaches the temperature point of the second-stage sintering.
The roller ball milling process adopts an alcohol wet milling medium, the liquid level height is controlled to be 3-6 cm, the rotation speed of the ball mill is 60-70% of the critical rotation speed of the ball mill, the mass ratio of the hard alloy grinding balls to the mixture is (4:1) - (5:1), and the wet milling time is 50-60 hours.
Critical rotation speed V of the ball mill Critical of ＝42.4×D -1/2 And D is the diameter of the inner wall of the ball milling barrel, and the unit is meter.
The stirring type ball mill and the roller type ball mill are commercial standard equipment.
The invention is based on the basic concept of material design and preparation based on the complete property and compliance of materials, and based on the characteristics of high strength, high toughness and high oxidation resistance of CoCrFeNi high-entropy alloy and CoCrNi medium-entropy alloy, according to the working principle of stirring ball milling, the flaking treatment technology of the gas atomized powder of the CoCrFeNi high-entropy alloy and the CoCrNi medium-entropy alloy is developed, and the CoCrFeNi high-entropy alloy and the CoCrNi medium-entropy alloy powder which are prepared at low cost and have uniform components are matched with the particle sizes of other raw material powder of the cermet in one dimension. Because the CoCrFeNi high-entropy alloy and the CoCrNi medium-entropy alloy have excellent plastic deformation capability, the alloy is easy to deform under the forming pressure, and a high-strength pressed compact with uniform density can be obtained, which is beneficial to sintering densification. Based on the characteristic parameters of the liquid phase occurrence temperature and the liquid phase vapor pressure of an alloy system, the characteristic parameters of wettability improvement limit and the high-efficiency inhibition property of the slow diffusion effect of high-entropy alloy and medium-entropy alloy on the growth of hard phase grains, a two-stage pressure sintering process for improving the wettability of the alloy system by short-time high-temperature impact is developed, the wettability optimization of the alloy system is realized, the rapid diffusion among hard phase alloy components is promoted, the rapid sintering densification of the alloy is promoted under the condition of lower liquid phase volume fraction, the evaporation of the binder phase alloy components is effectively inhibited, the bonding state of the high-entropy alloy and medium-entropy alloy components is effectively stabilized, the growth of the hard phase grains is effectively inhibited, and the formation of a third phase of chromium carbide in the alloy is effectively inhibited.
Drawings
FIG. 1 is a scanning electron micrograph of an entropy alloy aerosolized powder in-250 mesh CoCrNi.
FIG. 2 is a scanning electron micrograph of entropy alloy powder in CoCrNi after flaking.
FIG. 3 is TiC in example 1 0.5 N 0.5 -13.0WC-5.3TaC-2.2NbC-6.5Mo 2 Scanning electron microscope photograph of C-22.0CoCrNi metal ceramic microstructure.
FIG. 4 is a scanning electron micrograph of a-250 mesh CoCrFeNi high entropy alloy aerosolized powder.
FIG. 5 is TiC in example 2 0.7 N 0.3 -19.0WC-5.0TaC-5.5Mo 2 Scanning electron microscope photograph of C-22.0CoCrFeNi metal ceramic microstructure.
FIG. 6 is TiC in example 4 0.5 N 0.5 -25.0TiC 0.7 N 0.3 -16.0WC-6.0TaC-1.5NbC-5.0Mo 2 C-18.0CoCrFeNi cermet (4) # Alloy) (lower position) and X-ray diffraction of aerosolized CoCrFeNi high entropy alloy atomized powder (upper position)And (5) performing jet superposition mapping and analysis results thereof.
Detailed Description
The invention is further described below with reference to examples and figures.
Example 1
Scanning electron microscope pictures of the powder, which adopts entropy alloy powder in-250 mesh gas atomization CoCrNi as a raw material, are shown in figure 1. Performing scalization treatment on the powder by adopting a stirring ball milling and crushing process under the argon protection condition, wherein the rotating speed of a stirring paddle is 250 revolutions per minute, the mass ratio of a hard alloy grinding ball to multi-principal-element alloy gas atomized powder is 15:1, alcohol is adopted as a wet milling medium, the liquid level is controlled to be 6 cm, the wet milling time is 15 hours, and a ball milling barrel jacket is cooled by cooling water; and drying the wet-ground powder by adopting a vacuum drying process. Scanning electron microscope pictures of entropy alloy powder in CoCrNi after being subjected to flaking treatment are shown in figure 2.
Adopting the CoCrNi medium entropy alloy flake powder after the flaking treatment, wherein the Fisher particle sizes are 1.3, 1.2, 1.4 and 1.3 mu m TiC respectively 0.5 N 0.5 、TaC、NbC、Mo 2 Preparing TiC by using WC powder with specific surface area average particle size of 0.25 μm as raw material 0.5 N 0.5 -13.0WC-5.3TaC-2.2NbC-6.5Mo 2 The C-22.0CoCrNi metal ceramic comprises the following alloy components in percentage by mass.
The drum-type ball milling process and an alcohol wet milling medium are adopted, the liquid level height is controlled to be 6 cm, the rotation speed of the ball mill is 60% of the critical rotation speed of the ball mill, the mass ratio of the hard alloy grinding ball to the mixture is 4:1, the wet milling time is 60 hours, and the polyvinyl alcohol forming agent accounting for 2.3% of the total mass fraction of the powder is added during wet milling. And preparing a spherical mixture with the average particle size smaller than 150 mu m by adopting spray drying granulation. The round bar sample was prepared by a dry bag cold isostatic pressing forming process. The removal of the forming agent and sintering are carried out in a pressure sintering furnace. After the forming agent is removed at 500 ℃, vacuum sintering is carried out, the heating rate is 10 ℃/min, the heat is preserved for 30 min at 750 ℃ and 1200 ℃, when the temperature is raised to 1430 ℃, high-purity argon is introduced to enable the pressure in the sintering furnace to reach 7kPa, the temperature is continuously raised to 1540 ℃, the temperature is preserved for 15 min, then the temperature is reduced to 1480 ℃ at the cooling rate of 10 ℃/min, high-purity argon is introduced to enable the pressure in the sintering furnace to be raised to 5.5MPa, the temperature is preserved for 80 min at the pressure, the total heat preservation time at 1480 ℃ is controlled to be 100 min, and then the furnace is cooled. Cutting the sintered round bar product into a B-type sample for bending strength test by adopting a diamond cutting tool. The scanning electron microscope photograph of the microstructure of the metal ceramic in the embodiment is shown in fig. 3. The test results showed that the average grain size of the hard phase in the alloy was 0.8 μm.
Example 2
Scanning electron microscope pictures of the powder, which adopts-250 mesh gas atomization CoCrFeNi high-entropy alloy powder as a raw material, are shown in figure 4. The powder is subjected to flaking treatment by adopting a stirring ball milling and crushing process under the argon protection condition, the rotating speed of a stirring paddle is 300 revolutions per minute, the mass ratio of a hard alloy grinding ball to multi-principal-element alloy gas atomized powder is 20:1, the liquid level is controlled to be 3 cm, the wet milling time is 10 hours, and a ball milling barrel jacket is cooled by cooling water; and drying the wet-ground powder by adopting a vacuum drying process.
Adopting the CoCrFeNi medium entropy alloy flake powder after the flaking treatment, and TiC with Fisher granularity of 1.4, 1.2 and 1.3 mu m respectively 0.7 N 0.3 、TaC、Mo 2 Preparing TiC by using WC powder with specific surface area average particle size of 0.25 μm as raw material 0.7 N 0.3 -19.0WC-5.0TaC-5.5Mo 2 The C-22.0CoCrFeNi metal ceramic has the values listed in the alloy components of the mass percent of each powder component.
The drum-type ball milling process and an alcohol wet milling medium are adopted, the liquid level height is controlled to be 6 cm, the rotation speed of the ball mill is 70% of the critical rotation speed of the ball mill, the mass ratio of the hard alloy grinding ball to the mixture is 5:1, the wet milling time is 50 hours, and the paraffin wax forming agent accounting for 2.5% of the total mass fraction of the powder is added during wet milling. And adopting a vacuum drying and mechanical granulating process to prepare the spherical mixture with the average particle size smaller than 150 mu m. And preparing a B-type sample for bending strength test by adopting a compression molding process. The removal of the forming agent and sintering are carried out in a pressure sintering furnace. After the forming agent is removed at 500 ℃, vacuum sintering is carried out, the heating rate is 10 ℃/min, the heat is preserved for 30 min at 780 ℃ and 1250 ℃ respectively, when the temperature is raised to 1450 ℃, high-purity argon is introduced to enable the pressure in the sintering furnace to reach 5kPa, the temperature is continuously raised to 1560 ℃, the heat is preserved for 10 min, then the temperature is reduced to 1500 ℃ at the cooling rate of 10 ℃/min, high-purity argon is introduced to enable the pressure in the sintering furnace to be raised to 3.0MPa, the heat is preserved for 40 min at the pressure, the total heat preservation time at 1500 ℃ is controlled to be 60 min, and then the furnace is cooled. The scanning electron microscope photograph of the microstructure of the metal ceramic of this example is shown in fig. 5. The test results showed that the average grain size of the hard phase in the alloy was 0.7 μm.
Example 3
Adopts-250 mesh gas atomization CoCrNi medium entropy alloy powder as a raw material. Performing scalization treatment on the powder by adopting a stirring ball milling and crushing process under the argon protection condition, wherein the rotating speed of a stirring paddle is 280 r/min, the mass ratio of a hard alloy grinding ball to multi-principal-element alloy gas atomized powder is 18:1, alcohol is adopted as a wet milling medium, the liquid level is controlled to be 4 cm, the wet milling time is 12 hours, and a ball milling barrel jacket is cooled by cooling water; and drying the wet-ground powder by adopting a vacuum drying process.
Adopting the CoCrNi medium entropy alloy flake powder after the flaking treatment, and TiC with Fisher granularity of 1.4, 1.2 and 1.3 mu m respectively 0.7 N 0.3 、TaC、Mo 2 Preparing TiC by using WC powder with specific surface area average particle size of 0.25 μm as raw material 0.7 N 0.3 -16.0WC-6.5TaC-5.0Mo 2 C-18.0CoCrNi cermet, the values listed in the alloy composition are the mass fraction of each powder component,%.
The drum-type ball milling process and an alcohol wet milling medium are adopted, the liquid level height is controlled to be 5 cm, the rotation speed of the ball mill is 65% of the critical rotation speed of the ball mill, the mass ratio of the hard alloy grinding ball to the mixture is 5:1, the wet milling time is 56 hours, and the paraffin wax forming agent accounting for 2.3% of the total mass fraction of the powder is added during wet milling. And adopting a vacuum drying and mechanical granulating process to prepare the spherical mixture with the average particle size smaller than 150 mu m. And preparing a B-type sample for bending strength test by adopting a compression molding process. The removal of the forming agent and sintering are carried out in a pressure sintering furnace. After the forming agent is removed at 500 ℃, vacuum sintering is carried out, the heating rate is 10 ℃/min, the heat is preserved for 30 min at 750 ℃ and 1200 ℃, when the temperature is raised to 1440 ℃, high-purity argon is introduced to enable the pressure in the sintering furnace to reach 6kPa, the temperature is continuously raised to 1550 ℃, the heat is preserved for 10 min, then the temperature is reduced to 1490 ℃ at the cooling rate of 10 ℃/min, high-purity argon is introduced to enable the pressure in the sintering furnace to be raised to 4MPa, the heat is preserved for 60 min at the pressure, the total heat preservation time at 1490 ℃ is controlled to be 80 min, and then the sintering furnace is cooled. The test results showed that the average grain size of the hard phase in the alloy was 0.8 μm.
Example 4
Adopts-250 mesh gas atomization CoCrFeNi high-entropy alloy powder as a raw material. Performing scalization treatment on the powder by adopting a stirring ball milling and crushing process under the argon protection condition, wherein the rotating speed of a stirring paddle is 280 r/min, the mass ratio of a hard alloy grinding ball to multi-principal-element alloy gas atomized powder is 18:1, alcohol is adopted as a wet milling medium, the liquid level is controlled to be 5 cm, the wet milling time is 12 hours, and a ball milling barrel jacket is cooled by cooling water; and drying the wet-ground powder by adopting a vacuum drying process.
Adopting the CoCrFeNi medium entropy alloy flake powder after the flaking treatment, wherein the Fisher particle sizes are 1.3, 1.4, 1.2, 1.4 and 1.3 mu m TiC respectively 0.5 N 0.5 、TiC 0.7 N 0.3 、TaC、NbC、Mo 2 Preparing TiC by using WC powder with specific surface area average particle size of 0.25 μm as raw material 0.5 N 0.5 -25.0TiC 0.7 N 0.3 -16.0WC-6.0TaC-1.5NbC-5.0Mo 2 The C-18.0CoCrFeNi metal ceramic comprises the following alloy components in percentage by mass.
The drum-type ball milling process and an alcohol wet milling medium are adopted, the liquid level height is controlled to be 5 cm, the rotation speed of the ball mill is 65% of the critical rotation speed of the ball mill, the mass ratio of the hard alloy grinding ball to the mixture is 5:1, the wet milling time is 50 hours, and the paraffin wax forming agent accounting for 2.5% of the total mass fraction of the powder is added during wet milling. And adopting a vacuum drying and mechanical granulating process to prepare the spherical mixture with the average particle size smaller than 150 mu m. And preparing a B-type sample for bending strength test by adopting a compression molding process. The removal of the forming agent and sintering are carried out in a pressure sintering furnace. After the forming agent is removed at 500 ℃, vacuum sintering is carried out, the heating rate is 10 ℃/min, the heat is preserved for 30 min at 780 ℃ and 1250 ℃ respectively, when the temperature is raised to 1450 ℃, high-purity argon is introduced to enable the pressure in the sintering furnace to reach 5kPa, the temperature is continuously raised to 1560 ℃, the heat is preserved for 10 min, then the temperature is reduced to 1500 ℃ at the cooling rate of 10 ℃/min, high-purity argon is introduced to enable the pressure in the sintering furnace to be raised to 4.0MPa, the heat is preserved for 40 min at the pressure, the total heat preservation time at 1500 ℃ is controlled to be 60 min, and then the furnace is cooled. The test results showed that the average grain size of the hard phase in the alloy was 0.7 μm.
X-ray phase analysis results show that the CoCrFeNi high-entropy alloy and the CoCrNi medium-entropy alloy both have single phase components and face-centered cubic crystal structures; all the four groups of alloys do not contain a third phase, and the alloys consist of a hard phase of a face-centered cubic crystal structure and a bonding phase of the face-centered cubic crystal structure. Example 4 alloy (identified as 4 # Alloy) is shown in fig. 6. In FIG. 6, in example 4, 4 # An X-ray diffraction pattern of the gas atomization CoCrFeNi high-entropy alloy powder is superimposed on the alloy X-ray diffraction pattern. Since there is no TiC in the X-ray diffraction database 0.5 N 0.5 Is selected from TiC 0.7 N 0.3 PDF card of (c). Since there is no PDF card of CoCrFeNi high entropy alloy, a PDF card of Ni is selected. The X-ray diffraction standard peak position of Ni in the figure is marked by a dotted line, and the unidentified peak position all corresponds to TiC 0.7 N 0.3 . Comparative example corresponding to 4 # X-ray diffraction patterns of the alloy and CoCrFeNi high-entropy alloy can be known, 4 # The peak position of the alloy bonding phase has better correspondence with the strongest and the next strongest peak positions of the CoCrFeNi high-entropy alloy. The observation results of the scanning electron microscope show that the corresponding alloy in the four embodiments has the obvious characteristic of uniform microstructure and has no microscopic aggregation phenomenon of the bonding phase.
The physical and mechanical properties of the alloy are tested according to the corresponding national standards, and the physical and mechanical properties of the alloy in the four examples are shown in table 1. The dimensions of the type B specimen for flexural strength test were (20.+ -. 1) mm (6.5.+ -. 0.25) mm (5.25.+ -. 0.25) mm. As can be seen from Table 1, the four groups of alloys all have excellent physical and mechanical properties.
TABLE 1 physical and mechanical Properties of alloys in four examples
Comparative example 1
The alloy composition and preparation process were the same as in example 1, except that the sintering process was different. The sintering process of the alloy comprises the following steps: after the forming agent is removed at 500 ℃, vacuum sintering is carried out, the heating rate is 10 ℃/min, the heat is preserved for 30 min at 750 ℃ and 1200 ℃, when the temperature is increased to 1430 ℃, high-purity argon is introduced to enable the pressure in the sintering furnace to reach 7kPa, the temperature is continuously increased to 1540 ℃, high-purity argon is introduced to enable the pressure in the sintering furnace to be increased to 5.5MPa, the heat is preserved for 80 min under the pressure, the total heat preservation time at 1540 ℃ is controlled to be 100 min, and then the furnace is cooled. Cutting the sintered round bar product into a B-type sample for bending strength test by adopting a diamond cutting tool. The observation and analysis detection show that the alloy has obvious overburning, and the obvious sintering deformation and the excessive porosity of the alloy are shown. The bending strength test result shows that the bending strength of the alloy is 1380-1790 MPa.
Comparative example 2
The alloy composition and preparation process were the same as in example 1, except that the sintering process was different. The sintering process of the alloy comprises the following steps: after the forming agent is removed at 500 ℃, vacuum sintering is carried out, the heating rate is 10 ℃/min, the heat is preserved for 30 min at 750 ℃ and 1200 ℃, when the temperature is increased to 1430 ℃, high-purity argon is introduced to enable the pressure in the sintering furnace to reach 7kPa, the temperature is continuously increased to 1480 ℃, high-purity argon is introduced to enable the pressure in the sintering furnace to be increased to 5.5MPa, the heat is preserved for 80 min under the pressure, the total heat preservation time at 1480 ℃ is controlled to be 100 min, and then the furnace is cooled. Cutting the sintered round bar product into a B-type sample for bending strength test by adopting a diamond cutting tool. The bending strength test result shows that the bending strength of the alloy is between 1802 and 2114MPa, which is obviously lower than that of the alloy in the embodiment 1.
Comparative example 3
The entropy alloy in CoCrNi is not subjected to flaking treatment, and other experimental raw materials, alloy components and preparation processes are the same as those in example 1. The bending strength test result shows that the bending strength of the alloy is 780-1305 MPa, which is obviously lower than that of the alloy in the embodiment 1.
Claims (9)
1. A fine-grain cermet using multi-principal element alloy as bonding metal is characterized in that: the multi-principal element alloy is CoCrFeNi high-entropy alloy or CoCrNi medium-entropy alloy, the alloy components have equal molar ratio, and the bonding phase of the metal ceramic is formed after sintering; in the metal ceramic alloy component, the mass fraction of the CoCrFeNi high-entropy alloy or the CoCrNi medium-entropy alloy is less than 25 percent but more than 15 percent, and WC accounts for TiC x N 1-x 25-40% of the mass fraction, and the total mass fraction of (NbC+TaC) accounts for TiC x N 1-x 10 to 15 percent of NbC accounting for 0 to 30 percent of the total mass fraction of (NbC+TaC) and Mo 2 C accounts for 25-30% of the total mass fraction of the multi-principal element alloy bonding metal; the TiC is x N 1-x Refers to single TiC 0.5 N 0.5 Or TiC 0.7 N 0.3 Powder, or TiC 0.5 N 0.5 And TiC 0.7 N 0.3 Is a mixed powder of (a) and (b); the metal ceramic alloy structure consists of a hard phase and a binding phase, wherein the binding phase is uniformly distributed in the alloy, no microscopic aggregation phenomenon exists, and the average grain size of the hard phase in the alloy is smaller than 1.0 mu m; the hard phase and the binder phase both have face-centered cubic crystal structures; the hard phase comprises (Ti, M) C x N 1-x TiC is an alloy component in the sintering process 0.5 N 0.5 And/or TiC 0.7 N 0.3 、WC、TaC、NbC、Mo 2 C is formed by a multiple solid solution reaction, where x=0.5 to 0.7, m= W, ta, nb, mo or m=w, ta, mo, representing each alloy element solid-dissolved in the hard phase lattice, occupying the Ti atomic position.
2. A multi-master alloy fine grain cermet for use as a bond metal according to claim 1 wherein: the multi-principal element alloy is prepared by adopting a melt atomization powder preparation method in an argon atmosphere, and has a single phase component and a face-centered cubic crystal structure; the multi-principal element alloy powder is subjected to screening treatment by-250 meshes, and the maximum particle size of the powder is less than or equal to 58 mu m.
3. A multi-master alloy bonded metal fine grain cermet according to claim 1 wherein: the TiC is 0.5 N 0.5 And/or TiC 0.7 N 0.3 、TaC、NbC、Mo 2 The Fisher particle size of the raw material powder C is less than 1.5 μm, and the specific surface area average particle size of the raw material powder WC is less than 0.3 μm.
4. A preparation method of fine-grain cermet with multi-principal element alloy as bonding metal is characterized by comprising the following steps: the method comprises the following steps:
A. and (3) flaking treatment of multi-principal element alloy gas atomization powder: adopting a stirring ball milling and crushing process under the argon protection condition to realize scalization treatment, and adopting a vacuum drying process to dry the wet-ground powder; the multi-principal element alloy gas atomization powder is CoCrFeNi high-entropy alloy or CoCrNi medium-entropy alloy powder, and each alloy component has an equimolar ratio; the aerosolized powder is subjected to screening treatment with a mesh of-250 meshes, and the maximum particle size of the powder is less than or equal to 58 mu m;
B. wet milling mixture preparation: mixing the multi-principal element alloy flake powder prepared in the step A with TiC x N 1-x 、WC、TaC、NbC、Mo 2 C, proportioning, and adding a forming agent accounting for 2.3-2.5% of the total mass of the powder for wet grinding; the result of the batching is that the mass fraction of the CoCrFeNi high-entropy alloy or the entropy alloy in the CoCrNi is less than 25 percent but more than 15 percent, and WC accounts for TiC in the metal ceramic alloy component x N 1-x 25-40% of the mass fraction, and the total mass fraction of (NbC+TaC) accounts for TiC x N 1-x 10 to 15 percent of NbC accounting for 0 to 30 percent of the total mass fraction of (NbC+TaC) and Mo 2 C accounts for 25-30% of the total mass fraction of the multi-principal element alloy bonding metal; the TiC is x N 1-x Refers to single TiC 0.5 N 0.5 Or TiC 0.7 N 0.3 Powder, or TiC 0.5 N 0.5 And TiC 0.7 N 0.3 X=0.5 to 0.7; the TiC is 0.5 N 0.5 And/or TiC 0.7 N 0.3 、TaC、NbC、Mo 2 The Fisher particle size of the raw material powder C is less than 1.5 mu m, and the specific surface area average particle size of the raw material powder WC is less than 0.3 mu m;
C. drying and granulating the wet-grinding mixture: preparing a spherical mixture with the average particle size smaller than 150 mu m by adopting a spray drying granulation or vacuum drying and mechanical granulation process;
D. powder forming: selecting a forming mode according to the shape and the size of the product and the production requirement of the traditional metal ceramic blank, wherein the forming mode comprises compression molding;
E. removing and sintering a forming agent: the forming agent is removed and sintered in a pressure sintering furnace; adopting a two-stage pressure sintering process for improving wettability of an alloy system by short-time high-temperature impact, wherein the sintering temperature of the first stage is 1540-1560 ℃ and the heat preservation time is 10-15 minutes; the sintering temperature of the second stage is 1480-1500 ℃ and the heat preservation time is 60-100 minutes; after the sintering temperature of the second stage is reached, high-purity argon is introduced to raise the pressure in the sintering furnace to 3.0-5.5 MPa in the final 40-80 min of the heat preservation stage.
5. The method for producing a fine-grain cermet having a binder metal made of a multi-component alloy according to claim 4, wherein: in the step A, the rotation speed of a stirring paddle of the stirring ball mill is 250-300 revolutions per minute, the mass ratio of the hard alloy grinding ball to the multi-principal element alloy gas atomized powder is (15-20): 1, alcohol is adopted as a wet grinding medium, the liquid level is controlled to be 3-6 cm, the wet grinding time is 10-15 hours, and a ball mill barrel jacket is cooled by cooling water.
6. The method for producing a fine-grain cermet having a binder metal made of a multi-component alloy according to claim 4, wherein: in the step B, the forming agent added in the preparation of the wet-milling mixture is polyethylene glycol or paraffin wax, and a roller ball milling process is adopted.
7. The method for producing a fine-grain cermet having a binder metal made of a multi-component alloy according to claim 4, wherein: in the step E, after the forming agent is removed, vacuum sintering is carried out; when the temperature is raised to 1430-1450 ℃, high-purity argon is introduced to enable the pressure in the sintering furnace to reach 5-7 kPa, and the pressure is maintained until the temperature in the sintering furnace reaches the temperature point of the second-stage sintering.
8. The method for producing a fine-grain cermet having a binder metal of a multi-component alloy as defined in claim 6, wherein: the roller ball milling process adopts an alcohol wet milling medium, the liquid level height is controlled to be 3-6 cm, the rotation speed of the ball mill is 60-70% of the critical rotation speed of the ball mill, the mass ratio of the hard alloy grinding balls to the mixture is (4:1) - (5:1), and the wet milling time is 50-60 hours.
9. The method for producing a fine-grain cermet having a binder metal of a multi-component alloy as defined in claim 8, wherein: critical rotation speed V of the ball mill Critical of ＝42.4×D -1/2 And D is the diameter of the inner wall of the ball milling barrel, and the unit is meter.
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