CN116815031B - A fine-grained cermet with a multi-principal alloy as a bonding metal and a preparation method thereof - Google Patents
A fine-grained cermet with a multi-principal alloy as a bonding metal and a preparation method thereofInfo
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- CN116815031B CN116815031B CN202310939711.4A CN202310939711A CN116815031B CN 116815031 B CN116815031 B CN 116815031B CN 202310939711 A CN202310939711 A CN 202310939711A CN 116815031 B CN116815031 B CN 116815031B
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- 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
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- 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
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- B22F9/00—Making metallic powder or suspensions thereof
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- 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
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- 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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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 flaking treatment technology of CoCrFeNi high-entropy alloy used for 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 CoCrFeMnNi multi-principal element alloy system, the equal atomic ratio CoCrFeNi high-entropy alloy and the CoCrNi entropy alloy both have extremely high strength and toughness, so that the alloy has high-quality potential of replacing bonding metal Ni/Co in hard alloy and TiCN-based cermet, and provides a new break for endowing the unique performance of hard alloy and cermet which is not known or realized.
Both CoCrFeNi high-entropy alloy and CoCrNi medium-entropy alloy contain Cr. Cr is an element which is extremely liable to form carbide, and various carbides such as Cr 3C2、Cr7C3、Cr23C6、Cr2 C, crC can be formed. 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 elemental powder raw materials to prepare Fe, co, cr, ni or Co, cr and Ni multicomponent metals as cemented metal (also called as 'cemented metal' in the literature) hard alloy or metal ceramic, which can solve the problem of particle size matching among powders, but the elemental Cr easily forms carbide in the sintering process due to the existence of carbon in the alloy, so the problems of obvious reduction of the physical and mechanical properties of the alloy, unstable performance and the like caused by the existence of a third phase of chromium carbide are very easy to occur.
The patent of the invention with the application number 201210321098.1, titanium carbonitride based metal ceramic based on high-entropy alloy binding phase and a preparation method thereof, 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 materials of the high-entropy alloy binding phase are 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 in high-energy ball milling.
The AlFeNiCoCr novel bonding metal powder related to the patent application number 201910722025.5 'novel binder-based metal ceramic, a preparation method and application' invention patent is obtained by adopting an elemental powder (elemental metal powder) high-energy ball milling process.
The invention relates to a Ti (C, N) -based cermet with high strength and toughness and an intermediate entropy alloy binding phase and a preparation method thereof, and discloses a method for preparing a cermet by mechanically alloying to prepare CoCrNi intermediate entropy alloy prefabricated powder and adopting a spark plasma sintering process for applying 30-45 MPa pressure. 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 CoCrNi entropy prealloy powder 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 invention with the application number 201810611621.1 of 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 binder metal, wherein the ultrafine high-entropy prealloy powder consists of Cr, ni, fe, co, al and M, the M is selected from at least one of Cu, zr, ti, mo and rare earth, and the preparation method of the ultrafine high-entropy prealloy powder comprises the steps of melting each component in vacuum or protective atmosphere, crushing, and adopting high-energy ball milling 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 high-strength high-entropy alloy ceramic and a preparation method thereof, and discloses a method for preparing metal ceramic with the mass fraction of high-entropy alloy powder up to 30-45wt% by adopting high-entropy alloy powder with the particle size less than or equal to 10 μm as a raw material. The comparative example shows that the cermet is prepared by mixing 18wt% of high-entropy alloy powder CoCrFeNi, 72wt% of Ti (C, N) matrix powder and 10wt% of WC+Mo 2 C strengthening additive powder, and the result shows that the alloy has the problems of uneven hardness distribution (HV 30 1804+/-15), low 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 usually 15-25%. The method is only suitable for preparing the metal ceramic with the mass fraction of high-entropy alloy bonding metal up to 30-45wt%, 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 aim, based on material calculation and a metal ceramic material design database established by the inventor and an alloy composition, microstructure and performance matching design principle, experiments prove that the following composition characteristics of the fine-grain metal ceramic with the multi-principal-element alloy as bonding metal are defined, wherein the mass fraction of the CoCrFeNi high-entropy alloy or the CoCrNi entropy alloy in the alloy composition is less than 25 percent, But is more than 15 percent, WC accounts for 25-40 percent of the mass fraction of TiC xN1-x, the total mass fraction of (NbC+TaC) accounts for 10-15 percent of the mass fraction of TiC xN1-x, nbC accounts for 0-30 percent of the total mass fraction of (NbC+TaC), mo 2 C accounts for 25-30 percent of the total mass fraction of bonded metal of a multi-element alloy, wherein TiC xN1-x refers to single TiC 0.5N0.5 or TiC 0.7N0.3 powder or mixed powder of TiC 0.5N0.5 and TiC 0.7N0.3, the multi-element alloy refers to CoCrFeNi high-entropy alloy or CoCrNi medium-entropy alloy, each alloy component has equal molar ratio and forms bonding phase of metal ceramic after sintering, the metal ceramic alloy structure consists of hard phase and bonding phase, wherein the bonding phase is uniformly distributed in the alloy, The alloy has no microscopic aggregation phenomenon, the average grain size of a hard phase in the alloy is less than 1.0 mu M, the hard phase and a bonding phase both have face-centered cubic crystal structures, the components of the hard phase are (Ti, M) C xN1-x, and the hard phase is formed by alloy components TiC 0.5N0.5 and/or TiC 0.7N0.3、WC、TaC、NbC、Mo2 C through a multi-element solid solution reaction in the sintering process, wherein X=0.5-0.7, M=W, Ta, nb, mo or m=w, ta, mo represent individual alloy components that are solid-solved in the hard phase lattice and occupy Ti atomic positions.
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, has a single phase component and a face-centered cubic crystal structure, and the multi-principal element alloy powder is subjected to screening treatment by-250 meshes, wherein the maximum particle size of the powder is less than or equal to 58 mu m.
The Fisher particle size of the TiC 0.5N0.5 and/or TiC 0.7N0.3、TaC、NbC、Mo2 C raw material powder is smaller than 1.5 mu m, the specific surface area average particle size of the WC raw material powder is smaller than 0.3 mu m, and the WC raw material powder has 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. The flaking treatment of the multi-principal element alloy gas atomized powder is realized by adopting a stirring ball milling and crushing process under the argon protection condition, and the wet-ground powder is dried by adopting a vacuum drying process, wherein the multi-principal element alloy gas atomized powder is CoCrFeNi high-entropy alloy or CoCrNi medium-entropy alloy powder, and each alloy component has an equimolar ratio;
B. The preparation of a wet-grinding mixture, namely mixing multi-principal-element alloy flake powder prepared in the step A and TiC xN1-x、WC、TaC、NbC、Mo2 C, adding a forming agent accounting for 2.3-2.5% of the total mass fraction of the powder, and carrying out wet-grinding, wherein the mixing result is that the mass fraction of an entropy alloy in CoCrFeNi high-entropy alloy or CoCrNi is less than 25% but more than 15%, WC accounts for 25-40% of the mass fraction of TiC xN1-x, the total mass fraction of (NbC+TaC) accounts for 10-15% of the mass fraction of TiC xN1-x, nbC accounts for 0-30% of the total mass fraction of (NbC+TaC), mo 2 C accounts for 25-30% of the total mass fraction of bonded metal of the multi-principal-element alloy, the TiC xN1-x refers to single TiC 0.5N0.5 or TiC 0.7N0.3 powder, or mixed powder of TiC 0.5N0.5 and TiC 0.7N0.3, the particle size of TiC 0.5N0.5 and/or TiC 3878C raw material powder is less than 1.5 μm, the average particle size of the TiC 0.5N0.5 and/or TiC 0.7N0.3、TaC、NbC、Mo2 C raw material powder is less than 1.5 μm, the average particle size of the mixed powder is preferably less than 0.5 μm, and the average particle size of the mixed powder is preferably less than 2.5 μm, and the average particle size of the mixed powder is less than the average particle size of TiC 0.7N0.3 powder is equal to 0.5 0.7, and 3 m is higher than average particle size;
C. Drying and granulating the wet-milled mixture, namely 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, namely selecting a forming mode according to the shape and the size of a product and the production requirement of a traditional metal ceramic blank, wherein the forming mode comprises compression molding;
E. The forming agent removing and sintering process comprises the steps of carrying out forming agent removing and sintering 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 in the first stage is 1540-1560 ℃, the heat preservation time is 10-15 minutes, the sintering temperature in the second stage is 1480-1500 ℃, the heat preservation time is 60-100 minutes, and introducing high-purity argon gas to raise the pressure in the sintering furnace after the sintering temperature in the second stage is reached, so that the pressure in the sintering furnace reaches 3.0-5.5 MPa in the last 40-80 minutes 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-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.
And E, after the forming agent is removed, performing vacuum sintering, and when the temperature is raised to 1430-1450 ℃, introducing high-purity argon to enable the pressure in the sintering furnace to reach 5-7 kPa, and maintaining the pressure until the temperature in the sintering furnace reaches the temperature point of 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 milling balls to the mixture is (4:1) - (5:1), and the wet milling time is 50-60 hours.
The critical rotation speed V Critical of ＝42.4×D-1/2 of the ball mill, D is the diameter of the inner wall of the ball mill 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 material exhaustion and compliance, and develops the scalization treatment technology of the air atomization powder of the high-entropy alloy CoCrFeNi and the high-entropy alloy CoCrNi based on the characteristics of high strength, high toughness and high oxidation resistance of the high-entropy alloy CoCrFeNi and the medium-entropy alloy CoCrNi according to the working principle of stirring and ball milling, thereby realizing the matching of the particle sizes of the high-entropy alloy CoCrFeNi and the medium-entropy alloy CoCrNi prepared at low cost and the other raw material powder of the cermet in one-dimensional scale. Because CoCrFeNi high-entropy alloy and CoCrNi medium-entropy alloy have excellent plastic deformation capability, the high-entropy alloy is easy to deform under forming pressure, high-strength pressed blanks with uniform density can be obtained, and sintering densification is facilitated. 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 a-250 mesh CoCrNi.
FIG. 2 is a scanning electron micrograph of the entropy alloy powder of CoCrNi after flaking.
FIG. 3 is a scanning electron micrograph of the microstructure of TiC 0.5N0.5-13.0WC-5.3TaC-2.2NbC-6.5Mo2 C-22.0CoCrNi cermet in example 1.
FIG. 4 is a scanning electron micrograph of a-250 mesh CoCrFeNi high-entropy alloy aerosolized powder.
FIG. 5 is a scanning electron micrograph of the microstructure of TiC 0.7N0.3-19.0WC-5.0TaC-5.5Mo2 C-22.0CoCrFeNi cermet in example 2.
FIG. 6 is an X-ray diffraction pattern of TiC 0.5N0.5-25.0TiC0.7N0.3-16.0WC-6.0TaC-1.5NbC-5.0Mo2 C-18.0CoCrFeNi cermet (4 # alloy) (bottom position) and aerosolized CoCrFeNi high entropy alloy atomized powder (top position) of example 4 and its analysis results.
Detailed Description
The invention is further described below with reference to examples and figures.
Example 1
Scanning electron microscope pictures of the powder are shown in figure 1 by adopting entropy alloy powder in-250 mesh gas atomization CoCrNi as a raw material. 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 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 grinding medium, the liquid level is controlled to be 6 cm, the wet grinding time is 15 hours, a ball milling barrel jacket is cooled by cooling water, and the wet ground powder is dried by adopting a vacuum drying process. Scanning electron microscope pictures of the entropy alloy powder in CoCrNi after the flaking treatment are shown in figure 2.
The method is characterized in that the powder of the entropy alloy flake in CoCrNi after the flaking treatment is adopted, the powder of TiC 0.5N0.5、TaC、NbC、Mo2 C with the Fisher granularity of 1.3, 1.2, 1.4 and 1.3 mu m respectively and the WC powder with the specific surface area average particle size of 0.25 mu m are adopted as raw materials to prepare TiC 0.5N0.5-13.0WC-5.3TaC-2.2NbC-6.5Mo2 C-22.0CoCrNi cermet, and the numerical values listed in the alloy components 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 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 500 ℃ forming agent is removed, vacuum sintering is carried out, the temperature rising rate is 10 ℃ per minute, the temperature is respectively kept for 30 minutes 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 kept for 15 minutes, then the temperature is reduced to 1480 ℃ at the temperature reducing rate of 10 ℃ per minute, high-purity argon is introduced to enable the pressure in the sintering furnace to be raised to 5.5MPa, the temperature is kept for 80 minutes at the temperature, the total heat-preserving time of 1480 ℃ is controlled to be 100 minutes, 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 obtained by adopting-250-mesh aerosolized 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-element alloy gas atomized powder is 20:1, the liquid level is controlled to be 3 cm, the wet milling time is 10 hours, a ball milling barrel jacket is cooled by cooling water, and the wet milled powder is dried by adopting a vacuum drying process.
The method is characterized in that the powder of the entropy alloy flake in CoCrFeNi after the flaking treatment is adopted, tiC 0.7N0.3、TaC、Mo2 C powder with the Fisher granularity of 1.4, 1.2 and 1.3 mu m respectively and WC powder with the specific surface area average particle size of 0.25 mu m are adopted as raw materials to prepare TiC 0.7N0.3-19.0WC-5.0TaC-5.5Mo2 C-22.0CoCrFeNi cermet, and the numerical values listed in the alloy components 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 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 500 ℃ forming agent is removed, vacuum sintering is carried out, the temperature rising rate is 10 ℃ per minute, the temperature is respectively kept for 30 minutes at 780 ℃ and 1250 ℃, 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 temperature is kept for 10 minutes, then the temperature is reduced to 1500 ℃ at the temperature reducing rate of 10 ℃ per minute, high-purity argon is introduced to enable the pressure in the sintering furnace to be raised to 3.0MPa, the temperature is kept for 40 minutes under the pressure, the total heat-preserving time of 1500 ℃ is controlled to be 60 minutes, 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 entropy alloy powder in-250 mesh gas atomization CoCrNi as raw material. 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 280 r/min, the mass ratio of a hard alloy grinding ball to multi-element alloy gas atomized powder is 18:1, alcohol is adopted as a wet grinding medium, the liquid level is controlled to be 4 cm, the wet grinding time is 12 hours, a ball milling barrel jacket is cooled by cooling water, and the wet ground powder is dried by adopting a vacuum drying process.
The method is characterized in that the powder of the entropy alloy flake in CoCrNi after the flaking treatment is adopted, tiC 0.7N0.3、TaC、Mo2 C powder with the Fisher granularity of 1.4, 1.2 and 1.3 mu m respectively and WC powder with the specific surface area average particle size of 0.25 mu m are adopted as raw materials to prepare TiC 0.7N0.3-16.0WC-6.5TaC-5.0Mo2 C-18.0CoCrNi cermet, and the numerical values listed in the alloy components 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 500 ℃ forming agent is removed, vacuum sintering is carried out, the temperature rising rate is 10 ℃ per minute, the heat preservation is carried out for 30 minutes at 750 ℃ and 1200 ℃ respectively, when the temperature rises to 1440 ℃, high-purity argon is introduced to enable the pressure in the sintering furnace to reach 6kPa, the temperature continues to rise to 1550 ℃, the heat preservation is carried out for 10 minutes, then the temperature is reduced to 1490 ℃ at the temperature reducing rate of 10 ℃ per minute, high-purity argon is introduced to enable the pressure in the sintering furnace to rise to 4MPa, the heat preservation is carried out for 60 minutes at the temperature, the total heat preservation time of 1490 ℃ is controlled to be 80 minutes, and then the 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. 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 280 r/min, the mass ratio of a hard alloy grinding ball to multi-element alloy gas atomized powder is 18:1, alcohol is adopted as a wet grinding medium, the liquid level is controlled to be 5 cm, the wet grinding time is 12 hours, a ball milling barrel jacket is cooled by cooling water, and the wet ground powder is dried by adopting a vacuum drying process.
Preparing TiC 0.5N0.5-25.0TiC0.7N0.3-16.0WC-6.0TaC-1.5NbC-5.0Mo2 C-18.0CoCrFeNi metal ceramic by adopting the above-mentioned CoCrFeNi entropy alloy flake powder with Fisher granularity of 1.3, 1.4, 1.2, 1.4 and 1.3 μm TiC 0.5N0.5、TiC0.7N0.3、TaC、NbC、Mo2 C powder and WC powder with specific surface area average particle diameter of 0.25 μm as raw materials, wherein the values listed in the alloy components 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 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 500 ℃ forming agent is removed, vacuum sintering is carried out, the temperature rising rate is 10 ℃ per minute, the temperature is respectively kept for 30 minutes at 780 ℃ and 1250 ℃, 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 temperature is kept for 10 minutes, then the temperature is reduced to 1500 ℃ at the temperature reducing rate of 10 ℃ per minute, high-purity argon is introduced to enable the pressure in the sintering furnace to be raised to 4.0MPa, the temperature is kept for 40 minutes under the pressure, the total heat-preserving time of 1500 ℃ is controlled to be 60 minutes, 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.
The X-ray phase analysis results show that the CoCrFeNi high-entropy alloy and the CoCrNi entropy alloy both have single phase components and face-centered cubic crystal structures, the four groups of alloys do not contain a third phase, and the alloys consist of a hard phase of the face-centered cubic crystal structure and a binding phase of the face-centered cubic crystal structure. The results of the X-ray diffraction phase analysis of the alloy of example 4 (identified as 4 # alloy) are shown in fig. 6. In fig. 6, the X-ray diffraction pattern of the aerosolized CoCrFeNi high-entropy alloy powder is superimposed on top of the 4 # alloy X-ray diffraction pattern in example 4. The PDF card of TiC 0.7N0.3 is selected because the X-ray diffraction database has no PDF card of TiC 0.5N0.5. Since there is no CoCrFeNi high-entropy alloy PDF card, a Ni PDF card is selected. The standard peak positions of the X-ray diffraction of Ni are marked by the dotted lines in the figure, and the unidentified peak positions all correspond to TiC 0.7N0.3. The X-ray diffraction patterns of the 4 # alloy and the CoCrFeNi high-entropy alloy corresponding to the comparative example show that the peak position of the 4 # alloy binding phase has better correspondence with the strongest and second 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 steps of carrying out vacuum sintering after a 500 ℃ forming agent is removed, keeping the temperature rising rate at 10 ℃ per minute, respectively keeping the temperature at 750 ℃ and 1200 ℃ for 30 minutes, when the temperature rises to 1430 ℃, introducing high-purity argon to enable the pressure in a sintering furnace to reach 7kPa, continuously heating to 1540 ℃, introducing high-purity argon to enable the pressure in the sintering furnace to rise to 5.5MPa, keeping the temperature at the pressure for 80 minutes, controlling the total heat-preserving time at 1540 ℃ to be 100 minutes, and then cooling along with the furnace. 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 steps of carrying out vacuum sintering after a 500 ℃ forming agent is removed, keeping the temperature at the rising speed of 10 ℃ per minute, respectively keeping the temperature at 750 ℃ and 1200 ℃ for 30 minutes, when the temperature rises to 1430 ℃, introducing high-purity argon to enable the pressure in a sintering furnace to reach 7kPa, continuously rising the temperature to 1480 ℃, introducing high-purity argon to enable the pressure in the sintering furnace to rise to 5.5MPa, keeping the temperature at the pressure for 80 minutes, controlling the total heat-preserving time at 1480 ℃ to be 100 minutes, and then cooling along with the furnace. 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 1802-2114 MPa, 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 scalization 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 (6)
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 entropy alloy, each alloy component has an equimolar ratio, and after sintering, the bonding phase of the cermet is formed, wherein the mass fraction of the entropy alloy in the CoCrFeNi high-entropy alloy or CoCrNi is smaller than 25 percent but larger than 15 percent, WC accounts for 25-40 percent of the mass fraction of TiC xN1–x, the total mass fraction of (NbC+TaC) accounts for 10-15 percent of the mass fraction of TiC xN1–x, nbC accounts for 0-30 percent of the total mass fraction of (NbC+TaC), mo 2 C accounts for 25-30 percent of the mass fraction of the entropy alloy in the 6896 high-entropy alloy or the TiC xN1–x, the TiC xN1–x is single TiC 0.5N0.5 or TiC 0.7N0.3 powder, or mixed powder of TiC 0.5N0.5 and TiC 0.7N0.3, the bonding phase is formed by uniformly distributing the bonding phase in the cermet, and does not exist in the mass fraction of TiC xN1–x, the bonding phase accounts for 10-15 percent of the total mass fraction of (NbC+TaC) and the grain size of the ceramic is equal to 3.M=3, and the average grain size of the crystal grain size of the ceramic is equal to that in the Ti phase is 3 m=3, and the crystal grain size of the sintered phase is equal to 3 m=3;
the preparation method of the fine-grain cermet with the multi-principal element alloy as the bonding metal comprises the following steps:
A. The flaking treatment of the multi-principal element alloy gas atomized powder is realized by adopting a stirring ball milling and crushing process under the argon protection condition, and the wet-ground powder is dried by adopting a vacuum drying process, wherein the multi-principal element alloy gas atomized powder is CoCrFeNi high-entropy alloy or CoCrNi medium-entropy alloy powder, and each alloy component has an equimolar ratio, and the gas atomized powder is subjected to 250-mesh screening treatment, and the maximum particle size of the powder is less than or equal to 58 mu m;
B. The preparation of a wet-grinding mixture, namely mixing multi-principal-element alloy flake powder prepared in the step A with TiC xN1–x、WC、TaC、NbC、Mo2 C, adding a forming agent accounting for 2.3-2.5% of the total mass fraction of the powder, and carrying out wet-grinding, wherein the mixing result is that the mass fraction of CoCrFeNi high-entropy alloy or entropy alloy in CoCrNi is less than 25%, but greater than 15%, WC accounts for 25-40% of TiC xN1–x mass fraction, the total mass fraction of (NbC+TaC) accounts for 10-15% of TiC xN1–x mass fraction, nbC accounts for 0-30% of the total mass fraction of (NbC+TaC), mo 2 C accounts for 25-30% of the total mass fraction of multi-principal-element alloy bonding metal, tiC xN1–x refers to single TiC 0.5N0.5 or TiC 0.7N0.3 powder, or mixed powder of TiC 0.5N0.5 and TiC 0.7N0.3, the Fisher particle size of TiC xN1–x、TaC、NbC、Mo2 C raw material powder is less than 1.5 mu m, and the specific surface area of WC raw material powder is less than 0.3 mu m;
C. drying and granulating the wet-milled mixture, namely 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, namely 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. The forming agent removing and sintering process includes the steps of forming agent removing and sintering in a pressure sintering furnace, vacuum sintering after the forming agent removing, introducing high-purity argon gas when the temperature is raised to 1430-1450 ℃, enabling the pressure in the sintering furnace to reach 5-7 kPa, maintaining the pressure until the temperature in the sintering furnace reaches the temperature point of second-stage sintering, adopting a short-time high-temperature impact two-stage pressure sintering process for improving wettability of an alloy system, enabling the sintering temperature in the first stage to be 1540-1560 ℃, enabling the heat preservation time to be 10-15 minutes, enabling the sintering temperature in the second stage to be 1480-1500 ℃, enabling the heat preservation time to be 60-100 minutes, introducing high-purity argon gas after the temperature reaches the second-stage sintering temperature, enabling the pressure in the sintering furnace to be raised, enabling the pressure in the sintering furnace to reach 3.0-5.5 MPa in the last 40-80 minutes of the heat preservation stage.
2. The fine-grain cermet for bonding metals prepared by adopting the multi-principal-element alloy as bonding 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, and the multi-principal-element alloy powder is subjected to 250-mesh screening treatment, and the maximum grain size of the powder is less than or equal to 58 mu m.
3. A fine-grain cermet using a multi-element alloy as bonding metal according to claim 1, wherein in the step A, the rotation speed of a stirring paddle of stirring ball milling is 250-300 rpm, the mass ratio of a hard alloy grinding ball to a multi-element alloy gas atomized powder is (15-20): 1, alcohol is adopted as a wet milling medium, the liquid level is controlled to be 3-6 cm, the wet milling time is 10-15 hours, and a ball milling barrel jacket is cooled by cooling water.
4. The fine-grain cermet for bonding metals with multi-component alloy according to claim 1, wherein in step B, the shaping agent added in the preparation of the wet-milling mixture is polyethylene glycol or paraffin wax, and a roller ball milling process is adopted.
5. The fine-grain cermet with multi-principal element alloy as bonding metal according to claim 4, wherein the roller ball milling process is characterized in that alcohol wet milling media are adopted, the liquid level height is controlled to be 3-6 cm, the rotation speed of the ball mill is controlled to be 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.
6. The fine grain cermet for metal bonding by using a multi-component alloy according to claim 5, wherein the critical rotation speed V Critical of =42.4×D–1/2 of the ball mill is the diameter of the inner wall of the ball mill barrel, and the unit is meter.
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| CN113265573A (en) * | 2021-04-29 | 2021-08-17 | 四川大学 | High-strength high-toughness high-entropy alloy ceramic and preparation method thereof |
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