CN115595463A - High-entropy hard alloy cutter material and preparation method and application thereof - Google Patents
High-entropy hard alloy cutter material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of hard alloy materials, and relates to a high-entropy hard alloy cutter material as well as a preparation method and application thereof. The preparation method comprises the following steps: the single-phase high-entropy carbide ceramic is used as a hard phase, the single-phase high-entropy alloy is used as a binding phase, and a two-step discharge plasma sintering method is adopted for processing to obtain the high-entropy carbide ceramic; wherein the single-phase high-entropy carbide ceramic is (Hf) 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )C、(W 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) C or (W) 0.2 V 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) C; the single-phase high-entropy alloy is FeCoNiCrMn high-entropy alloy. Book (notebook)The high-entropy hard alloy cutter material provided by the invention has excellent performances of high-temperature hardness, high wear resistance, high cutting speed and precision, high toughness and the like.
Description
Technical Field
The invention belongs to the technical field of hard alloy materials, and relates to a high-entropy hard alloy cutter material as well as a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Research on cemented carbide tool materials is continuously evolving with advances in material science and related disciplines. In order to solve the contradiction between the hardness and the toughness of the hard alloy cutter material, the method which can be adopted at present mainly comprises the following steps: 1) Preparing the super-class nano hard alloy cutter material by reducing the size of powder particles; 2) Introducing a gradient structure to prepare a gradient hard alloy cutter material; 3) Preparing a coating hard alloy cutter material by using a coating technology; 4) Developing a novel Co-substituted binding phase hard alloy cutter material. However, until now, there has been no cemented carbide tool material that can satisfy the requirements of high-speed cutting for excellent mechanical properties (high hardness, high toughness, high strength, etc.), oxidation resistance, chemical stability, etc. of the tool at the same time. For example, although the research on the cemented carbide tool material replacing the Co binder phase goes through three stages of a metal replacing the Co binder phase, an intermetallic compound replacing the Co binder phase and a ceramic replacing the Co binder phase, the hardness, the wear resistance, the corrosion resistance and the oxidation resistance of the cemented carbide tool material replacing the Co binder phase are insufficient, and the toughness of the intermetallic compound and the ceramic binder phase cemented carbide is poor.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a high-entropy hard alloy cutter material and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on one hand, the preparation method of the high-entropy hard alloy cutter material is obtained by treating a single-phase high-entropy carbide ceramic as a hard phase and a single-phase high-entropy alloy as a binding phase by a two-step discharge plasma sintering method;
wherein the single-phase high-entropy carbide ceramic is (Hf) 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )C、(W 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) C or (W) 0.2 V 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )C；
The single-phase high-entropy alloy is FeCoNiCrMn high-entropy alloy.
The high-entropy material has higher stability and flexibility in the aspect of microstructure control, and can realize the combination of various excellent performances in the aspect of performance. The invention aims to use the single-phase high-entropy carbide ceramic as the hard phase of the hard alloy and the single-phase high-entropy alloy as the binder phase of the hard alloy, thereby hopefully overcoming the defects of the traditional hard alloy and breaking through the bottleneck of the traditional hard alloy. However, in the preparation of high-entropy cemented carbide materials based on mechanical alloying and powder metallurgy, it is difficult to form high-entropy cemented carbide in which the hard phase is a single-phase high-entropy carbide and the binder phase is a single-phase high-entropy alloy. Experiments show that when HfC, zrC, taC, nbC and TiC (or WC, zrC, taC, nbC and TiC or WC, VC, taC, nbC and TiC) five carbide ceramic powder and Fe, co, ni, cr and Mn five metal powder are used as raw materials, the high-entropy hard alloy with single-phase high-entropy carbide as a mass phase and single-phase high-entropy alloy as a binding phase can be obtained when two-step discharge plasma sintering is carried out. When using HfC, nbC, taC, tiC, VC (or NbC, taC, tiC, VC, zrC or HfC, nbC, taC, VC, WC or HfC, taC, tiC, WC, zrC or HfC, taC, tiC, VC, zrC) five carbide ceramic powders and Fe, co, ni, cr, mn five metal powders as raw materials, and performing two-step discharge plasma sintering, the hard phase cannot form single-phase high-entropy carbide, i.e. high-entropy hard alloy cannot be formed.
On the other hand, the high-entropy hard alloy cutter material is obtained by the preparation method.
In a third aspect, the high-entropy hard alloy cutter material is applied to the preparation of high-speed cutting tools.
The invention has the beneficial effects that:
(1) The invention selects high entropy carbide ceramic (Hf) 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )C、(W 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) C or (W) 0.2 V 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) C is used as a hard phase, feCoNiCrMn high-entropy alloy is selected as a binding phase, and the high-entropy hard alloy is prepared by adopting two-step discharge plasma sintering, so that the design bottleneck of the traditional hard alloy material is broken through, and the high-entropy hard alloy has high stability and flexibility in the aspect of microstructure control.
(2) The high-entropy hard alloy cutter material prepared by the invention can realize combination of various excellent performances in the aspect of performance, and based on the cocktail effect of the high-entropy material, the high-entropy hard alloy and the high-entropy binder phase with different performances can be obtained by controlling the element types, so that the performance of the hard alloy can be regulated and controlled, and the design of the hard alloy cutter material based on performance driving can be realized. Compared with the traditional WC-Co hard alloy, the hardness, the strength and the toughness of the high-entropy hard alloy are greatly improved at the same time.
(3) The two-step discharge plasma sintering method adopted by the invention can realize the complete densification of the high-entropy hard alloy cutter material under the condition of inhibiting the growth of crystal grains.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows (Hf) in example 1 of the present invention 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) XRD pattern of C-6FeCoNiCrMn high entropy hard alloy cutter material.
FIG. 2 shows the results of example 2 of the present invention (W) 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) XRD pattern of C-6FeCoNiCrMn high entropy hard alloy cutter material.
FIG. 3 shows (W) in example 3 of the present invention 0.2 V 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) XRD pattern of C-6FeCoNiCrMn high entropy hard alloy cutter material.
FIG. 4 is an XRD pattern of a comparative example of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, the traditional hard alloy cutter material is difficult to simultaneously meet the requirements of high-speed cutting on excellent mechanical properties (high hardness, high toughness, high strength and the like), oxidation resistance, chemical stability and the like of the cutter, and the invention provides a high-entropy hard alloy cutter material and a preparation method and application thereof.
The invention provides a typical implementation mode of a high-entropy hard alloy cutter material, which is obtained by treating a single-phase high-entropy carbide ceramic serving as a hard phase and a single-phase high-entropy alloy serving as a bonding phase by a two-step discharge plasma sintering method;
wherein the single-phase high-entropy carbide ceramic is (Hf) 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )C、(W 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) C or (W) 0.2 V 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )C；
The single-phase high-entropy alloy is FeCoNiCrMn high-entropy alloy.
In some embodiments, the binder phase is present in a mass fraction of 5 to 20%.
In some embodiments, the single-phase high entropy carbide ceramic is a powder with an average particle size of 100 to 500nm.
In some embodiments, the single-phase high entropy alloy is a powder with an average particle size of 100 to 500nm.
In some embodiments, the process of the two-step spark plasma sintering process is: keeping the vacuum degree below 10Pa, heating to 1500-1600 ℃ at the speed of 120-140 ℃/min, preserving the heat for 1-5 min, cooling to 1300-1400 ℃ at the speed of 120-140 ℃/min, preserving the heat for 20-60 min, cooling to 750-850 ℃ at the speed of 120-140 ℃/min, and furnace-cooling; the pressure intensity of the applied pressure is kept between 10 and 20MPa between 750 and 850 ℃ and between 40 and 50MPa between 1300 and 1600 ℃ during the temperature between 750 and 850 ℃.
In some embodiments, the high-entropy carbide ceramic powder, the high-entropy alloy powder and polyethylene glycol are added into absolute ethyl alcohol to be heated and ultrasonically dispersed to obtain a high-entropy hard alloy powder suspension, ball milling and drying are carried out to obtain the high-entropy hard alloy powder, and the high-entropy hard alloy powder is treated by adopting two-step discharge plasma sintering.
In some embodiments, the single-phase high-entropy carbide ceramic is prepared by: adding five carbides (TaC, nbC, tiC, hfC and ZrC or TaC, nbC, tiC, WC and VC) into absolute ethyl alcohol containing polyethylene glycol to prepare five carbide suspensions respectively, mixing the five carbide suspensions, heating and ultrasonically dispersing to obtain high-entropy carbide ceramic suspensions, and performing ball milling and drying to obtain high-entropy carbide ceramic powder. The five carbides were added in equimolar amounts. The temperature in the heating ultrasonic dispersion process is 95-105 ℃, and the time is 50-70 min. After the high-entropy carbide ceramic suspension is obtained, continuing to perform ultrasonic dispersion for 50-70 min, and then performing ball milling. The ball milling time is 23-25 h.
The preparation process of the single-phase high-entropy alloy is the same as that of the single-phase high-entropy carbide ceramic, namely the preparation process comprises the following steps: respectively adding Fe powder, co powder, ni powder, cr powder and Mn powder into absolute ethyl alcohol containing polyethylene glycol to prepare five metal powder suspensions, mixing the five metal powder suspensions, carrying out heating ultrasonic dispersion to obtain a high-entropy alloy suspension, carrying out ball milling, and drying to obtain the high-entropy alloy powder. Fe powder, co powder, ni powder, cr powder and Mn powder are added in equal molar weight. The temperature in the heating ultrasonic dispersion process is 95-105 ℃, and the time is 50-70 min. After the high-entropy alloy suspension is obtained, continuing to perform ultrasonic dispersion for 50-70 min, and then performing ball milling. The ball milling time is 23-25 h.
According to another embodiment of the invention, a high-entropy hard alloy cutter material is provided, and is obtained by the preparation method.
According to a third embodiment of the invention, the application of the high-entropy hard alloy cutter material in preparing a high-speed cutting tool is provided.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
(1) Taking 0.5 mu m HfC, zrC, taC, nbC and TiC five carbide ceramic powders as raw materials, and mixing the raw materials according to an equal molar ratio. Adopting absolute ethyl alcohol as a dispersing solvent and polyethylene glycol as a dispersing medium to respectively prepare five carbide suspensions, and heating in a water bath at 100 ℃ and ultrasonically dispersing for 1h. Under the conditions of mechanical stirring and ultrasonic dispersion, mixing the five carbide suspensions to obtain a high-entropy carbide ceramic suspension, and continuing ultrasonic dispersion for 1h. Adding grinding balls according to a certain ball-material ratio, carrying out ball milling for 24h, then drying in a vacuum drying oven, and sieving to obtain the well-dispersed high-entropy ceramic hard phase powder.
(2) Taking five metal powders of Fe, co, ni, cr and Mn of 0.5 mu m as raw materials, and mixing the raw materials according to an equal molar ratio. The five metal powder suspensions are respectively prepared by adopting absolute ethyl alcohol as a dispersing solvent and polyethylene glycol as a dispersing medium, and are subjected to ultrasonic dispersion for 1h by heating in a water bath at the temperature of 100 ℃. Under the conditions of mechanical stirring and ultrasonic dispersion, five metal powder suspensions are mixed to obtain a high-entropy alloy suspension, and the ultrasonic dispersion is continued for 1 hour. Adding grinding balls according to a certain ball-to-material ratio, carrying out ball milling for 24h, then drying in a vacuum drying oven, and sieving to obtain well-dispersed high-entropy alloy binding phase powder.
(3) Proportioning according to the mass proportion of a 94 high-entropy ceramic hard phase-6 high-entropy alloy binding phase. The high-entropy ceramic hard phase dispersion adopts absolute ethyl alcohol as a dispersion solvent, polyethylene glycol with the mass of 0.8 percent of that of the high-entropy ceramic powder is added to prepare a suspension, and the suspension is subjected to water bath heating and ultrasonic dispersion for 1 hour at the temperature of 100 ℃. The dispersion process of the high-entropy alloy binding phase is the same as the dispersion process of the high-entropy ceramic hard phase. Then, the high-entropy alloy powder suspension is dropwise added to the high-entropy ceramic powder suspension under the state of strong stirring, and the ultrasonic dispersion is continued for 1 hour. Adding grinding balls according to a certain ball-material ratio, ball-milling for 24 hours, then drying in a vacuum drying oven, and sieving to obtain the high-entropy hard alloy powder with uniformly distributed phases.
(4) Adopting a two-step discharge plasma sintering process, keeping the vacuum degree below 10Pa, heating to 1550 ℃ at a speed of 130 ℃/min, preserving heat for 5min, then cooling to 1350 ℃ at a speed of 130 ℃/min, preserving heat for 60min, then cooling to 800 ℃ at a speed of 130 ℃/min, and then cooling along with a furnace; the pressure was maintained at 15MPa,800-1550 ℃ and 45MPa during the temperature range from room temperature to 800 ℃.
After the sintering process is finished, the high-entropy hard alloy cutter material with the hard phase of single-phase high-entropy ceramics and the bonding phase of single-phase high-entropy alloy can be obtained, as shown in figure 1. The mechanical properties are as follows: vickers hardness HV 3 3049.9kgf/mm 2 Fracture toughness of 12.3 MPa.m 1/2 。
Example 2
(1) Five carbide ceramic powders of WC, zrC, taC, nbC and TiC with the particle size of 0.5 μm are used as raw materials and are mixed according to an equal molar ratio. Adopting absolute ethyl alcohol as a dispersing solvent and polyethylene glycol as a dispersing medium to respectively prepare five carbide suspensions, and heating in a water bath at 100 ℃ to perform ultrasonic dispersion for 1 hour. Under the conditions of mechanical stirring and ultrasonic dispersion, mixing the five carbide suspensions to obtain a high-entropy carbide ceramic suspension, and continuing ultrasonic dispersion for 1h. Adding grinding balls according to a certain ball-material ratio, carrying out ball milling for 24h, then drying in a vacuum drying oven, and sieving to obtain the well-dispersed high-entropy ceramic hard phase powder.
(2) Taking five metal powders of Fe, co, ni, cr and Mn of 0.5 mu m as raw materials, and mixing the raw materials according to an equal molar ratio. The five metal powder suspensions are respectively prepared by adopting absolute ethyl alcohol as a dispersing solvent and polyethylene glycol as a dispersing medium, and are subjected to ultrasonic dispersion for 1h by heating in a water bath at the temperature of 100 ℃. Under the conditions of mechanical stirring and ultrasonic dispersion, five kinds of metal powder suspension are mixed to obtain high-entropy alloy suspension, and the ultrasonic dispersion is continued for 1 hour. Adding grinding balls according to a certain ball-material ratio, carrying out ball milling for 24h, then drying in a vacuum drying oven, and sieving to obtain well-dispersed high-entropy alloy binder phase powder.
(3) Proportioning according to the mass proportion of a 94 high-entropy ceramic hard phase-6 high-entropy alloy binding phase. The high-entropy ceramic hard phase dispersion adopts absolute ethyl alcohol as a dispersion solvent, and polyethylene glycol with the mass of 0.8 percent of that of the high-entropy ceramic powder is added to prepare a suspension which is subjected to water bath heating and ultrasonic dispersion for 1 hour at the temperature of 100 ℃. The dispersion process of the high-entropy alloy binding phase is the same as the dispersion process of the high-entropy ceramic hard phase. Then, the high-entropy alloy powder suspension is dropwise added to the high-entropy ceramic powder suspension under the state of strong stirring, and the ultrasonic dispersion is continued for 1 hour. Adding grinding balls according to a certain ball-material ratio, carrying out ball milling for 24 hours, then drying in a vacuum drying oven, and sieving to obtain the high-entropy hard alloy powder with uniformly distributed phases.
(4) Adopting a two-step discharge plasma sintering process, keeping the vacuum degree below 10Pa, heating to 1550 ℃ at a speed of 130 ℃/min, preserving heat for 5min, then cooling to 1350 ℃ at a speed of 130 ℃/min, preserving heat for 60min, then cooling to 800 ℃ at a speed of 130 ℃/min, and then cooling along with a furnace; the pressure was maintained at 15MPa and at 800-1550 ℃ for a period of room temperature to 800 ℃ at 45MPa.
After the sintering process is finished, the high-entropy hard alloy cutter material with the hard phase of single-phase high-entropy ceramics and the bonding phase of single-phase high-entropy alloy can be obtained, as shown in figure 2. The mechanical properties are as follows: vickers hardness HV 3 3007.2kgf/mm 2 Fracture toughness of 11.7 MPa.m 1/2 。
Example 3
(1) Five carbide ceramic powders of WC, VC, taC, nbC and TiC with the particle size of 0.5 μm are used as raw materials and are proportioned according to the equal molar ratio. Adopting absolute ethyl alcohol as a dispersing solvent and polyethylene glycol as a dispersing medium to respectively prepare five carbide suspensions, and heating in a water bath at 100 ℃ to perform ultrasonic dispersion for 1 hour. Under the conditions of mechanical stirring and ultrasonic dispersion, mixing the five carbide suspensions to obtain a high-entropy carbide ceramic suspension, and continuing ultrasonic dispersion for 1h. Adding grinding balls according to a certain ball-to-material ratio, carrying out ball milling for 24h, then drying in a vacuum drying oven, and sieving to obtain the well-dispersed high-entropy ceramic hard phase powder.
(2) Five metal powders of Fe, co, ni, cr and Mn with the particle size of 0.5 μm are used as raw materials and are mixed according to the equal molar ratio. The five metal powder suspensions are respectively prepared by adopting absolute ethyl alcohol as a dispersing solvent and polyethylene glycol as a dispersing medium, and are subjected to ultrasonic dispersion for 1h by heating in a water bath at the temperature of 100 ℃. Under the conditions of mechanical stirring and ultrasonic dispersion, five metal powder suspensions are mixed to obtain a high-entropy alloy suspension, and the ultrasonic dispersion is continued for 1 hour. Adding grinding balls according to a certain ball-to-material ratio, carrying out ball milling for 24h, then drying in a vacuum drying oven, and sieving to obtain well-dispersed high-entropy alloy binding phase powder.
(3) Proportioning according to the mass proportion of a 94 high-entropy ceramic hard phase-6 high-entropy alloy binding phase. The high-entropy ceramic hard phase dispersion adopts absolute ethyl alcohol as a dispersion solvent, polyethylene glycol with the mass of 0.8 percent of that of the high-entropy ceramic powder is added to prepare a suspension, and the suspension is subjected to water bath heating and ultrasonic dispersion for 1 hour at the temperature of 100 ℃. The dispersion process of the high-entropy alloy binding phase is the same as the dispersion process of the high-entropy ceramic hard phase. Then, the high-entropy alloy powder suspension is dropwise added to the high-entropy ceramic powder suspension under the state of strong stirring, and the ultrasonic dispersion is continued for 1 hour. Adding grinding balls according to a certain ball-material ratio, ball-milling for 24 hours, then drying in a vacuum drying oven, and sieving to obtain the high-entropy hard alloy powder with uniformly distributed phases.
(4) Adopting a two-step discharge plasma sintering process, keeping the vacuum degree below 10Pa, heating to 1550 ℃ at a speed of 130 ℃/min, preserving heat for 5min, then cooling to 1350 ℃ at a speed of 130 ℃/min, preserving heat for 60min, then cooling to 800 ℃ at a speed of 130 ℃/min, and then cooling along with a furnace; the pressure is kept at 15MPa and at 800-1550 ℃ for the period from room temperature to 800 ℃.
The high-entropy hard alloy with the hard phase of single-phase high-entropy ceramic and the bonding phase of single-phase high-entropy alloy can be obtained by the operation of the sintering procedureTool material, as shown in fig. 3. The mechanical properties are as follows: vickers hardness HV 3 2847.1kgf/mm 2 Fracture toughness of 10.3 MPa.m 1/2 。
Comparative example
(1) Taking 0.5 mu m HfC, nbC, taC, tiC and VC (or NbC, taC, tiC, VC, zrC or HfC, nbC, taC, VC, WC or HfC, taC, tiC, WC, zrC or HfC, taC, tiC, VC and ZrC) five carbide ceramic powders as raw materials, and mixing the raw materials according to an equal molar ratio. Adopting absolute ethyl alcohol as a dispersing solvent and polyethylene glycol as a dispersing medium to respectively prepare five carbide suspensions, and heating in a water bath at 100 ℃ to perform ultrasonic dispersion for 1 hour. Under the conditions of mechanical stirring and ultrasonic dispersion, mixing the five carbide suspensions to obtain a high-entropy carbide ceramic suspension, and continuing to perform ultrasonic dispersion for 1 hour. Adding grinding balls according to a certain ball-material ratio, carrying out ball milling for 24h, then drying in a vacuum drying oven, and sieving to obtain the well-dispersed high-entropy ceramic hard phase powder.
(2) Taking five metal powders of Fe, co, ni, cr and Mn of 0.5 mu m as raw materials, and mixing the raw materials according to an equal molar ratio. The five metal powder suspensions are respectively prepared by adopting absolute ethyl alcohol as a dispersing solvent and polyethylene glycol as a dispersing medium, and are subjected to ultrasonic dispersion for 1h by heating in a water bath at the temperature of 100 ℃. Under the conditions of mechanical stirring and ultrasonic dispersion, five metal powder suspensions are mixed to obtain a high-entropy alloy suspension, and the ultrasonic dispersion is continued for 1 hour. Adding grinding balls according to a certain ball-to-material ratio, carrying out ball milling for 24h, then drying in a vacuum drying oven, and sieving to obtain well-dispersed high-entropy alloy binding phase powder.
(3) Proportioning according to the mass proportion of a 94 high-entropy ceramic hard phase-6 high-entropy alloy binding phase. The high-entropy ceramic hard phase dispersion adopts absolute ethyl alcohol as a dispersion solvent, polyethylene glycol with the mass of 0.8 percent of that of the high-entropy ceramic powder is added to prepare a suspension, and the suspension is subjected to water bath heating and ultrasonic dispersion for 1 hour at the temperature of 100 ℃. The dispersion process of the high-entropy alloy binding phase is the same as the dispersion process of the high-entropy ceramic hard phase. Then the high-entropy alloy powder suspension is dropwise added to the high-entropy ceramic powder suspension under the strong stirring state to continue ultrasonic dispersion for 1 hour. Adding grinding balls according to a certain ball-material ratio, ball-milling for 24 hours, then drying in a vacuum drying oven, and sieving to obtain the high-entropy hard alloy powder with uniformly distributed phases.
(4) Adopting a two-step discharge plasma sintering process, keeping the vacuum degree below 10Pa, heating to 1550 ℃ at a speed of 130 ℃/min, preserving heat for 5min, then cooling to 1350 ℃ at a speed of 130 ℃/min, preserving heat for 60min, then cooling to 800 ℃ at a speed of 130 ℃/min, and then cooling along with a furnace; the pressure was maintained at 15MPa and 45MPa at 800-1550 ℃ during the temperature range from room temperature to 800 ℃.
From the above to the end of the sintering process run, the single-phase high entropy carbide hard phase is not formed, but exists as a mixed phase of multiple binary carbides, as shown in fig. 4.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-entropy hard alloy cutter material is characterized in that single-phase high-entropy carbide ceramic is used as a hard phase, single-phase high-entropy alloy is used as a binding phase, and a two-step discharge plasma sintering method is adopted for processing to obtain the high-entropy hard alloy cutter material;
wherein the single-phase high-entropy carbide ceramic is (Hf) 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )C、(W 0.2 Zr 0.2 Ta 0.2 Nb 0.2 Ti 0.2 ) C or (W) 0.2 V 0.2 Ta 0.2 Nb 0.2 Ti 0.2 )C；
The single-phase high-entropy alloy is FeCoNiCrMn high-entropy alloy.
2. The method for producing a high-entropy hard alloy cutting tool material according to claim 1, wherein the mass fraction of the binder phase is 5 to 20%.
3. The method for preparing a high-entropy cemented carbide cutting tool material as claimed in claim 1, wherein the single-phase high-entropy carbide ceramic is in the form of powder having an average particle size of 100 to 500nm.
4. The method for preparing a high-entropy cemented carbide tool material as claimed in claim 1, wherein the single-phase high-entropy alloy is powder with an average particle size of 100 to 500nm.
5. The method for preparing a high-entropy cemented carbide tool material according to claim 1, wherein the two-step spark plasma sintering process comprises: keeping the vacuum degree below 10Pa, heating to 1500-1600 ℃ at the speed of 120-140 ℃/min, preserving the heat for 1-5 min, cooling to 1300-1400 ℃ at the speed of 120-140 ℃/min, preserving the heat for 20-60 min, cooling to 750-850 ℃ at the speed of 120-140 ℃/min, and furnace-cooling; the pressure intensity of the applied pressure is kept between 10 and 20MPa between 750 and 850 ℃ and between 40 and 50MPa between 750 and 850 ℃ and 1300 and 1600 ℃ during the temperature between 750 and 850 ℃.
6. The method for preparing a high-entropy hard alloy cutter material according to claim 1, wherein the high-entropy carbide ceramic powder, the high-entropy alloy powder and polyethylene glycol are added into absolute ethyl alcohol to be heated and ultrasonically dispersed to obtain a high-entropy hard alloy powder suspension, the high-entropy hard alloy powder suspension is obtained by ball milling and drying, and the high-entropy hard alloy powder is treated by two-step discharge plasma sintering.
7. The method for preparing the high-entropy hard alloy cutter material according to claim 1, wherein the method for preparing the single-phase high-entropy carbide ceramic comprises the following steps: respectively adding the five carbides into absolute ethyl alcohol containing polyethylene glycol to prepare five carbide suspensions, mixing the five carbide suspensions, carrying out heating ultrasonic dispersion to obtain high-entropy carbide ceramic suspensions, and carrying out ball milling and drying to obtain high-entropy carbide ceramic powder.
8. The method for preparing the high-entropy hard alloy cutter material according to claim 1, wherein the single-phase high-entropy alloy is prepared by the following steps: respectively adding Fe powder, co powder, ni powder, cr powder and Mn powder into absolute ethyl alcohol containing polyethylene glycol to prepare five metal powder suspensions, mixing the five metal powder suspensions, carrying out heating ultrasonic dispersion to obtain a high-entropy alloy suspension, carrying out ball milling, and drying to obtain the high-entropy alloy powder.
9. A high-entropy cemented carbide cutting tool material, which is obtained by the production method according to any one of claims 1 to 8.
10. Use of the high entropy cemented carbide tool material of claim 9 in the manufacture of high speed cutting tools.
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