CN110846547A - High-entropy alloy combined tungsten carbide hard alloy and preparation method thereof - Google Patents

High-entropy alloy combined tungsten carbide hard alloy and preparation method thereof Download PDF

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CN110846547A
CN110846547A CN201911215980.6A CN201911215980A CN110846547A CN 110846547 A CN110846547 A CN 110846547A CN 201911215980 A CN201911215980 A CN 201911215980A CN 110846547 A CN110846547 A CN 110846547A
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ball milling
hard alloy
tungsten carbide
cocrnicufe
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邹芹
李艳国
王明智
赵玉成
李晓普
熊建超
袁东方
张萌蕾
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Yanshan University
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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
    • C22C29/06—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 carbides, but not containing other metal compounds
    • C22C29/08—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 carbides, but not containing other metal compounds based on tungsten carbide
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    • 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
    • B22F3/10—Sintering only
    • B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
    • 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
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    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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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
    • 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
    • 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
    • C22C29/06—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 carbides, but not containing other metal compounds
    • C22C29/067—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 carbides, but not containing other metal compounds comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • 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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Abstract

The invention provides a high-entropy alloy combined tungsten carbide hard alloy and a preparation method thereof, wherein the hard alloy comprises the following components in percentage by mass: the CoCrNiCuFe accounts for 5-30 wt.%, and the balance is WC. Firstly, preparing CoCrNiCuFe powder by adopting a ball milling method and refining WC powder; then mixing CoCrNiCuFe powder and WC powder in a ball mill according to different mass ratios; uniformly mixing, filling into a graphite mold and prepressing; and then, performing discharge plasma sintering on the pre-pressed sample to prepare the tungsten carbide hard alloy combined with the high-entropy alloy. The method of the invention effectively reduces the production cost and improves the hardness and the fracture toughness of the tungsten carbide hard alloy.

Description

High-entropy alloy combined tungsten carbide hard alloy and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a high-entropy alloy-combined tungsten carbide hard alloy and a preparation method thereof.
Background
The tungsten carbide hard alloy has excellent heat resistance, corrosion resistance, high hardness and wear resistance, and is widely applied to materials such as cutters, molds, rollers and the like. Usually, WC is used as a main hard phase, Co is used as a binder, and the material is synthesized by a powder metallurgy method. However, metallic cobalt is expensive and toxic, so that the cemented carbide industry needs to find a substitute for Co binder to reduce production cost and promote sustainable development of the industry. In recent years, high-entropy alloys (HEA) have been widely studied because of their excellent properties. The HEA composed of a plurality of main elements has a series of characteristics such as high entropy effect, lattice distortion effect, retarded diffusion effect, cocktail effect and the like, so that the HEA has excellent physical, chemical and mechanical properties such as high strength, high hardness, high wear resistance, high corrosion resistance, high low-temperature toughness and the like, and is a substitute of a potential tungsten carbide hard alloy Co binder.
At present, the current state of development regarding different high entropy alloys as binders is as follows:
the influence of Mo content on the performance of WC-CoCrCuFeNiMo hard alloy is researched by sheep citizen and the like, and the research shows that the WC crystal grain size tends to become smaller along with the increase of Mo content. Meanwhile, the increase of Mo content can strengthen the binding phase, so that the hardness and the bending strength of the alloy are improved. Influence of sheep on performance of sintered WC-CoCrCuFeNiMo hard alloy [ J ] material heat treatment journal, 2018,11(39):46-51 ]
Preparation of ultrafine crystal WC-Al by using trypan and the like through hot pressingxCrFeCoNi hard alloy, research shows that Al is usedxThe CrFeCoNi high-entropy alloy replaces Co to be used as a binding phase, so that the growth of WC grains can be inhibited, and the effect of refining the grains is achieved. Compared with the traditional WC-10Co alloy, the superfine crystal WC-AlxThe CrFeCoNi composite material has higher hardness and good fracture toughness. Wherein the WC-10AlCrFeCoNi composite material has the highest Hardness (HV) which reaches 20.3GPa and WC-10Al0.5CrFeCoNi has maximum fracture toughness of 12 MPa.m1/2。WC-10AlxCompared with WC-10Co traditional hard alloy, the CrFeCoNi composite material has better corrosion resistance. [ Zhongpan, Xiaoshihong, Zhongpengfei, et Al, Hot pressing method for preparing superfine crystal WC-AlxCrFeCoNi composite material and its structure and performance [ J ]]Powder metallurgy materials science and engineering, 2019,11(30):95-103.]
The DongDigan alloy is prepared by using 3-35% (mass fraction, the same below) of high-entropy alloy as a strengthening phase, using 0-30% of Co, 0-30% of Ni, 0-30% of Fe and 0-15% of Cr as a binding phase, using 55-97% of WC, 0-10% of TaC/NbC, 0-5% of VC/ZrC and 0-5% of Cr2C3 as a hard phase, and performing ball milling, spray drying, die pressing to form a blank, gradient process sintering and heat treatment. [ Dongding dry; grandfather is grandfather; moving to new; yangwei WC-based hard alloy material based on high-entropy alloy and preparation method thereof 108950343A. Sichuan institute of technology 2018-12-07 ]
The waxberry and the like adopt intermittent planetary ball milling to prepare amorphous high-entropy alloy binding phase powder of Fe, Co, Ni, Cu, Cr, 1, 0.4-0.6 and 0.4-0.6, then the high-entropy alloy binding phase powder and hard phase powder are subjected to ball milling and mixing, and the high-entropy alloy binding phase hard alloy is prepared by adopting discharge plasma sintering. [ Myrica rubra; rosy clouds; longjiaping, preparation method of high-entropy alloy binder phase hard alloy, 109161773A, university of Chengdu studys, 2019-01-08 ]
In the Liuyun medium, high-entropy alloy with at least five of Al, Co, Cr, Cu, Fe and Ni as components is used as a binding phase, the atomic percent of each element is 5-35%, and the high-entropy alloy binding phase superfine tungsten carbide hard alloy is obtained through spark plasma sintering. [ Liu Hua; the characters are rich in the characters of Rouwen; shenjunjian, a high-entropy alloy binding phase superfine tungsten carbide hard alloy and a preparation method thereof, 109252081A, university of south China's science and engineering, 2019-01-22
The wear strength takes high-entropy alloy composed of elementary-substance metals of iron, cobalt, chromium, nickel, aluminum, vanadium, titanium, copper, zirconium, manganese and the like as a binder, and WC-based hard alloy is prepared by three different sintering methods. [ wearing quality is strong; liu Xiao Qiang (well-known diseases); guo-trade family; hongchunfu; frequently sending; tianjun; wangwang, preparation method of WC-based hard alloy with high-entropy alloy powder as binder, CN109371307A, Fujian engineering academy, 2019-02-22 ]
Based on the above research, different high-entropy alloys have different effects on the preparation of tungsten carbide, and for the purposes of reducing the sintering temperature of the cemented carbide, reducing the production cost and improving the hardness and fracture toughness of the tungsten carbide cemented carbide, it is necessary to provide a high-entropy alloy with better performance as a binder to solve the above requirements.
Disclosure of Invention
According to the technical problems of reducing the sintering temperature of the hard alloy, reducing the production cost and improving the hardness and fracture toughness of the tungsten carbide hard alloy, the high-entropy alloy-combined tungsten carbide hard alloy and the preparation method thereof are provided. The invention mainly adopts CoCrNiCuFe high-entropy alloy as a binder, and adopts a discharge plasma sintering method to prepare the tungsten carbide hard alloy, wherein metal simple substances are all the binders or important addition elements of common tungsten carbide hard alloy, the wettability to WC is good, and the performance of the prepared tungsten carbide hard alloy is good.
The technical means adopted by the invention are as follows:
the high-entropy alloy-bonded tungsten carbide hard alloy is characterized by comprising the following components in percentage by mass: the CoCrNiCuFe accounts for 5-30 wt.%, and the balance is WC.
Further, the particle size of the CoCrNiCuFe is 150nm to be fine; the purity of WC is more than 99%, and the grain diameter is 150 nm.
The invention also discloses a preparation method of the tungsten carbide hard alloy combined with the high-entropy alloy, which is characterized by comprising the following steps,
s1, preparation of CoCrNiCuFe powder: mixing Co, Cr, Ni, Cu and Fe according to a molar ratio of 1:1:1:1:1 in a glove box filled with argon, filling the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 300-600 r/min, the ball milling time is 20-50 h, stopping the machine for 30min for heat dissipation every 5h of rotation, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank and uniformly mixing the raw materials every 10h of stop, and then continuing ball milling to prepare fine CoCrNiCuFe powder with the particle size of 150 nm;
s2, preparing WC powder: carrying out ball milling and thinning on WC powder, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 250-400 r/min, the ball milling time is 10-40 h, and the machine is stopped for 30min every 5h to carry out heat dissipation to prepare fine WC powder with the particle size of 150 nm;
s3, mixing materials: in a glove box filled with argon, 5-30 wt.% of CoCrNiCuFe powder prepared in the step S1 is weighed, added into WC powder prepared in the step S2 and subjected to ball milling and mixing, the ball-material mass ratio is 5: 1-10: 1, the rotating speed is 200-350 r/min, the ball milling time is 2-5 h, and the glove box is stopped for 10min for heat dissipation every 1 h;
s4, sintering preparation: putting the mixture mixed in the step S3 into a graphite die for prepressing, wherein the prepressing pressure is 10-30 MPa, and the prepressing is 60S; then, carrying out spark plasma sintering, wherein the vacuum degree is 40Pa, the sintering pressure is 40-50 MPa, the sintering temperature is 1100-1400 ℃, the heating rate is 30-100 ℃/min, and the heat preservation time is 3-30 min; and then cooling and relieving pressure to prepare the high-entropy alloy-combined tungsten carbide hard alloy.
Furthermore, the purity of the Co, Cr, Ni, Cu and Fe powder is more than 99%, wherein the grain diameter of the Co powder is 1-3 mu m, the grain diameter of the Cr powder is less than 75 mu m, and the grain diameter of the rest metal simple substance powder is less than 45 mu m.
Furthermore, the grain size of the WC powder is 1-3 mu m, and the purity is more than 99%.
Further, the ball milling processes of the steps S1, S2 and S3 all adopt three large, medium and small WC hard alloy balls with the diameters of 8mm, 5mm and 2mm respectively, wherein the mass ratio of the large, medium and small WC hard alloy balls is 3:1: 1.
Further, the specific sintering process in step S4 is: firstly, slowly applying pressure to a sample to 40-50 MPa; then, the vacuum degree is pumped to 40 Pa; then, heating from room temperature to 600 ℃ for 5min, and preserving the heat at 600 ℃ for 10 min; then heating from 600 ℃ to 1100-1400 ℃ at a heating rate of 30-100 ℃/min, and preserving heat for 3-30 min; cooling along with the furnace to obtain a blank; and (3) carrying out surface grinding and deburring treatment on the prepared blank to obtain the high-entropy alloy combined tungsten carbide hard alloy.
Compared with the prior art, the invention has the following advantages:
1. the CoCrNiCuFe high-entropy alloy selected by the invention has excellent comprehensive performance, and is mainly reflected in that all metal simple substances in the CoCrNiCuFe high-entropy alloy are common bonding agents or important addition elements of tungsten carbide hard alloy, so that the CoCrNiCuFe high-entropy alloy has good wettability to WC. Moreover, the hardness and the bending strength of the CoCrNiCuFe high-entropy alloy sintered body are respectively 420HV and 1800MPa, and the hardness and the bending strength of the CoCrNiCuFe high-entropy alloy sintered body exceed those of the traditional metal binders such as Co, Ni, Fe and the like, so that the hardness and the toughness of the tungsten carbide hard alloy can be improved. Secondly, in the embodiment of the invention, most CoCrNiCuFe high-entropy alloy can stably exist in a hard alloy system.
2. The preparation method provided by the invention can reduce the use of metal Co resources, reduce the production cost and reduce the pollution to the environment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an XRD pattern of a tungsten carbide cemented carbide of a high entropy alloy provided by the present invention, wherein, (a) the XRD pattern of the tungsten carbide cemented carbide in example 6; (b) XRD pattern of tungsten carbide cemented carbide in example 7; (c) XRD pattern of tungsten carbide cemented carbide in example 8.
Fig. 2 is an FESEM view of a tungsten carbide cemented carbide surface of a high entropy alloy provided by the present invention, wherein, (a) an FESEM view of a tungsten carbide cemented carbide surface in example 6; (b) FESEM image of tungsten carbide cemented carbide surface in example 7; (c) FESEM image of the tungsten carbide cemented carbide surface in example 8.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
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.
The relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise. Meanwhile, it should be understood that the sizes of the respective portions shown in the drawings are not drawn in an actual proportional relationship for the convenience of description. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate. Any specific values in all examples shown and discussed herein are to be construed as exemplary only and not as limiting. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
The invention provides a tungsten carbide hard alloy combined with high entropy alloy, wherein the mass percent of CoCrNiCuFe in the hard alloy is 5-30 wt.%, and the balance is WC. Wherein the particle size of the CoCrNiCuFe is 150nm to be fine; the purity of WC is more than 99%, and the grain diameter is 150 nm.
The invention also provides a preparation method of the tungsten carbide hard alloy combined with the high-entropy alloy, which comprises the following steps,
s1, preparation of CoCrNiCuFe powder: mixing Co, Cr, Ni, Cu and Fe according to a molar ratio of 1:1:1:1:1 in a glove box filled with argon, filling the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 300-600 r/min, the ball milling time is 20-50 h, stopping the machine for 30min for heat dissipation every 5h of rotation, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank and uniformly mixing the raw materials every 10h of stop, and then continuing ball milling to prepare fine CoCrNiCuFe powder with the particle size of 150 nm; the purity of the Co, Cr, Ni, Cu and Fe powder is more than 99%, wherein the grain diameter of the Co powder is 1-3 mu m, the grain diameter of the Cr powder is less than 75 mu m, and the grain diameter of the rest metal simple substance powder is less than 45 mu m.
S2, preparing WC powder: carrying out ball milling and thinning on WC powder, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 250-400 r/min, the ball milling time is 10-40 h, and the machine is stopped for 30min every 5h to carry out heat dissipation to prepare fine WC powder with the particle size of 150 nm; wherein the grain diameter of the WC powder is 1-3 μm, and the purity is more than 99%.
S3, mixing materials: in a glove box filled with argon, 5-30 wt.% of CoCrNiCuFe powder prepared in the step S1 is weighed, added into WC powder prepared in the step S2 and subjected to ball milling and mixing, the ball-material mass ratio is 5: 1-10: 1, the rotating speed is 200-350 r/min, the ball milling time is 2-5 h, and the glove box is stopped for 10min for heat dissipation every 1 h;
the ball milling processes of the steps S1, S2 and S3 all adopt three large, medium and small WC hard alloy balls with the diameters of 8mm, 5mm and 2mm respectively, wherein the mass ratio of the large, medium and small WC hard alloy balls is 3:1: 1.
S4, sintering preparation: putting the mixture mixed in the step S3 into a graphite die for prepressing, wherein the prepressing pressure is 10-30 MPa, and the prepressing is 60S; then, performing discharge plasma sintering, and firstly, slowly applying pressure to a sample to 40-50 MPa; then, the vacuum degree is pumped to 40 Pa; and then, determining a temperature rising mode according to the SPS sintering characteristics as follows: heating to 600 deg.C from room temperature for 5min, and maintaining the temperature at 600 deg.C for 10 min; then heating from 600 ℃ to 1100-1400 ℃ at a heating rate of 30-100 ℃/min, and preserving heat for 3-30 min; cooling along with the furnace to obtain a blank; and (3) carrying out surface grinding and deburring treatment on the prepared blank to obtain the high-entropy alloy combined tungsten carbide hard alloy. Specifically, in the sintering process, at the stage that the temperature is below 600 ℃, gas adsorbed on the surfaces of alloy powder particles is gradually desorbed, the performance of an alloy matrix is not fundamentally changed, and the temperature is rapidly increased at the stage, so that the sintering time can be shortened, and energy can be saved; the 600 ℃ heat preservation stage has two functions, namely, the large power adjustment caused by the rapid temperature rise in the previous stage is stabilized, and the surface of alloy particles is diffused to eliminate the thermal stress in the matrix so as to prepare for later sintering; in the stage of raising the temperature to the set sintering temperature at 600 ℃, alloy particles begin to bond, the sintering neck is expanded, air holes are gradually communicated with each other, the grain boundary begins to move, the grains begin to grow normally, and the stage is mainly based on the diffusion of the grain boundary and crystal lattices; in the final heat preservation stage, the sintering reaction is fully carried out, the change of each component, the evaporation-condensation mass transfer of the surface of the solid-phase particles and the plastic rheological process all reach the optimal state in the stage, and the sintering gradually enters the later stage. In the cooling stage, the hardness and strength of the product can be directly influenced by the cooling speed, the cooling speed is high, the alloy particles cannot grow long enough, the crystals are fine, and the fine-grain strengthening effect is achieved.
The ball mill of the invention has the model of QM-3SP4 (China).
The model of the spark plasma sintering instrument is LABOXTM-110 (Japan).
The graphite mold is a product sold in the current market.
The detection equipment provided by the invention is an instrument used by a conventional detection means in a college laboratory, such as an X-ray diffractometer, a sclerometer, a scanning electron microscope and the like.
Example 1
As shown in table 1, the raw materials for preparing CoCrNiCuFe and the mass ratio thereof are shown; as shown in table 2, the raw material formulations were weighed in the following percentages:
TABLE 1 raw materials for preparing CoCrNiCuFe and their mass ratios
Figure BDA0002299515130000081
TABLE 2 raw materials for preparing 40g of WC cemented carbide and their mixture ratio
Figure BDA0002299515130000082
S1, mixing 2.039g of Co, 1.799g of Cr, 2.031g of Ni, 2.199g of Cu and 1.932g of Fe in a glove box filled with argon, putting the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 10:1, the rotating speed is 600r/min, the ball milling time is 30h, stopping the machine for 30min for heat dissipation every 5h of rotation, stopping the machine every 10h, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank, uniformly mixing, and then continuing ball milling to obtain 150nm fine CoCrNiCuFe powder.
S2, performing ball milling and refining on the WC powder, wherein the mass ratio of balls to materials is 10:1, the rotating speed is 250r/min, the ball milling is performed for 40h, the machine is stopped for 30min every 5h for ball milling, and the fine WC powder with the particle size of 150nm is prepared.
S3, in a glove box filled with argon, 2g of CoCrNiCuFe and 38g of WC are weighed and loaded into a WC cemented carbide ball milling pot. The mass ratio of the balls to the materials is 5:1, the rotating speed is 350r/min, the ball milling time is 5h, and the machine is stopped for 10min for heat dissipation every 1h of rotation.
S4, firstly, putting the mixture into a graphite die for prepressing, wherein the prepressing pressure is 10MPa, and the prepressing is 60S; then, the vacuum degree is pumped to 40Pa, and the pressure is increased to 40 MPa; then, heating from room temperature to 600 ℃ for 5min, and preserving the heat at 600 ℃ for 10 min; then the temperature is raised from 600 ℃ to 1200 ℃ at the temperature raising rate of 30 ℃/min, and the temperature is preserved for 30 min. And cooling along with the furnace to obtain a blank. And (3) carrying out surface grinding and deburring treatment on the prepared blank to obtain the high-entropy alloy combined tungsten carbide hard alloy.
After grinding and polishing the sintered tungsten carbide hard alloy sample, carrying out structure and performance detection, wherein the technical parameters of the obtained sintered body are shown in a table 3:
TABLE 3 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 1
Figure BDA0002299515130000091
Example 2
The compositions in table 1 and table 2 were used for preparation, and the ball milling speed, time, etc. were adjusted:
s1, mixing 2.039g of Co, 1.799g of Cr, 2.031g of Ni, 2.199g of Cu and 1.932g of Fe in a glove box filled with argon, putting the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 15:1, the rotating speed is 300r/min, the ball milling time is 50h, stopping the machine for 30min for heat dissipation every 5h of rotation, stopping the machine every 10h, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank, uniformly mixing, and continuing ball milling to obtain 150nm fine CoCrNiCuFe powder.
S2, performing ball milling and refining on the WC powder, wherein the mass ratio of balls to materials is 10:1, the rotating speed is 300r/min, the ball milling is performed for 30h, the machine is stopped for 30min every 5h for ball milling, and the fine WC powder with the particle size of 150nm is prepared.
S3, in a glove box filled with argon, 2g of CoCrNiCuFe and 38g of WC are weighed and loaded into a WC cemented carbide ball milling pot. The mass ratio of the balls to the materials is 5:1, the rotating speed is 300r/min, the ball milling time is 4h, and the machine is stopped for 10min for heat dissipation every 1 h.
S4, firstly, putting the mixture into a graphite die for prepressing, wherein the prepressing pressure is 10MPa, and the prepressing is 60S; then, the vacuum degree is pumped to 40Pa, and the pressure is increased to 50 MPa; then, heating from room temperature to 600 ℃ for 5min, and preserving the heat at 600 ℃ for 10 min; then heating from 600 ℃ to 1300 ℃ at the heating rate of 50 ℃/min, and preserving the heat for 5 min. And cooling along with the furnace to obtain a blank. And (3) carrying out surface grinding and deburring treatment on the prepared blank to obtain the high-entropy alloy combined tungsten carbide hard alloy.
And (3) grinding and polishing the sintered tungsten carbide hard alloy sample, and then detecting the structure and the performance, wherein the technical parameters of the obtained sintered body are shown in a table 4:
table 4 performance parameters and specific values for tungsten carbide cemented carbide in example 2
Figure BDA0002299515130000092
Example 3
The raw material formulations were weighed according to the following percentages in table 5:
TABLE 5 raw materials for preparing 40g of WC cemented carbide and their mixture ratio
Figure BDA0002299515130000101
S1, mixing 2.039g of Co, 1.799g of Cr, 2.031g of Ni, 2.199g of Cu and 1.932g of Fe in a glove box filled with argon, putting the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 20:1, the rotating speed is 300r/min, the ball milling time is 45h, stopping the machine for 30min for heat dissipation every 5h of rotation, stopping the machine every 10h, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank, uniformly mixing, and then continuing ball milling to obtain 150nm fine CoCrNiCuFe powder.
S2, performing ball milling and refining on the WC powder, wherein the mass ratio of balls to materials is 10:1, the rotating speed is 350r/min, the ball milling is performed for 20 hours, the machine is stopped for 30 minutes every 5 hours of rotation, and the fine WC powder with the particle size of 150nm is prepared.
S3, in a glove box filled with argon, 4g of CoCrNiCuFe and 36g of WC are weighed and loaded into a WC cemented carbide ball milling pot. The mass ratio of the ball to the material is 8:1, the rotating speed is 200r/min, the ball milling time is 4.5h, and the machine is stopped for 10min for heat dissipation every 1 h.
S4, firstly, putting the mixture into a graphite die for prepressing, wherein the prepressing pressure is 30MPa, and the prepressing is 60S; then, the vacuum degree is pumped to 40Pa, and the pressure is increased to 50 MPa; then, heating from room temperature to 600 ℃ for 5min, and preserving the heat at 600 ℃ for 10 min; then heating from 600 ℃ to 1300 ℃ at the heating rate of 30 ℃/min, and preserving the heat for 10 min. And cooling along with the furnace to obtain a blank. And (3) carrying out surface grinding and deburring treatment on the prepared blank to obtain the high-entropy alloy combined tungsten carbide hard alloy.
After grinding and polishing the sintered tungsten carbide hard alloy sample, carrying out structure and performance detection, wherein the technical parameters of the obtained sintered body are shown in table 6:
TABLE 6 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 3
Example 4
The compositions in table 1 and table 5 were used for preparation, and the ball milling speed, time, etc. were adjusted:
s1, mixing 2.039g of Co, 1.799g of Cr, 2.031g of Ni, 2.199g of Cu and 1.932g of Fe in a glove box filled with argon, putting the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 10:1, the rotating speed is 500r/min, the ball milling time is 40h, stopping the machine for 30min for heat dissipation every 5h of rotation, stopping the machine every 10h, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank, uniformly mixing, and then continuing ball milling to obtain 150nm fine CoCrNiCuFe powder.
S2, ball milling and refining the WC powder, wherein the mass ratio of balls to materials is 10:1, the rotating speed is 400r/min, ball milling is carried out for 15h, stopping the machine for 30min every 5h for ball milling, and heat dissipation is carried out to obtain fine WC powder with the particle size of 150 nm.
S3, in a glove box filled with argon, 4g of CoCrNiCuFe and 36g of WC are weighed and loaded into a WC cemented carbide ball milling pot. The mass ratio of the ball to the material is 8:1, the rotating speed is 250r/min, the ball milling time is 5h, and the machine is stopped for 10min for heat dissipation every 1 h.
S4, firstly, putting the mixture into a graphite die for prepressing, wherein the prepressing pressure is 30MPa, and the prepressing is 60S; then, the vacuum degree is pumped to 40Pa, and the pressure is increased to 50 MPa; then, heating from room temperature to 600 ℃ for 5min, and preserving the heat at 600 ℃ for 10 min; then heating from 600 ℃ to 1200 ℃ at the heating rate of 50 ℃/min, and preserving the heat for 5 min. And cooling along with the furnace to obtain a blank. And (3) carrying out surface grinding and deburring treatment on the prepared blank to obtain the high-entropy alloy combined tungsten carbide hard alloy.
After grinding and polishing the sintered tungsten carbide hard alloy sample, carrying out structure and performance detection, wherein the technical parameters of the obtained sintered body are shown in table 7:
TABLE 7 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 4
Figure BDA0002299515130000111
Example 5
The compositions in table 1 and table 5 were used for preparation, and the ball milling speed, time, etc. were adjusted:
s1, mixing 2.039g of Co, 1.799g of Cr, 2.031g of Ni, 2.199g of Cu and 1.932g of Fe in a glove box filled with argon, putting the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 10:1, the rotating speed is 400r/min, the ball milling time is 50h, stopping the machine for 30min for heat dissipation every 5h of rotation, stopping the machine every 10h, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank, uniformly mixing, and then continuing ball milling to obtain 150nm fine CoCrNiCuFe powder.
S2, performing ball milling and refining on the WC powder, wherein the mass ratio of balls to materials is 15:1, the rotating speed is 250r/min, the ball milling is performed for 35 hours, the machine is stopped for 30 minutes every 5 hours of rotation, and the fine WC powder with the particle size of 150nm is prepared.
S3, in a glove box filled with argon, 4g of CoCrNiCuFe and 36g of WC are weighed and loaded into a WC cemented carbide ball milling pot. The mass ratio of the ball to the material is 8:1, the rotating speed is 300r/min, the ball milling time is 3h, and the machine is stopped for 10min for heat dissipation every 1 h.
S4, firstly, putting the mixture into a graphite die for prepressing, wherein the prepressing pressure is 30MPa, and the prepressing is 60S; then, the vacuum degree is pumped to 40Pa, and the pressure is increased to 50 MPa; then, heating from room temperature to 600 ℃ for 5min, and preserving the heat at 600 ℃ for 10 min; then heating from 600 ℃ to 1400 ℃ at the heating rate of 100 ℃/min, and preserving the heat for 3 min. And cooling along with the furnace to obtain a blank. And (3) carrying out surface grinding and deburring treatment on the prepared blank to obtain the high-entropy alloy combined tungsten carbide hard alloy.
After grinding and polishing the sintered tungsten carbide hard alloy sample, carrying out structure and performance detection, wherein the technical parameters of the obtained sintered body are shown in table 8:
TABLE 8 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 5
Figure BDA0002299515130000121
Example 6
The raw material formulations were weighed according to the following percentages in table 9:
TABLE 9 raw materials for preparing 40g of WC cemented carbide and their mixture ratio
Figure BDA0002299515130000122
S1, mixing 2.039g of Co, 1.799g of Cr, 2.031g of Ni, 2.199g of Cu and 1.932g of Fe in a glove box filled with argon, putting the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 15:1, the rotating speed is 400r/min, the ball milling time is 45h, stopping the machine for 30min for heat dissipation every 5h of rotation, stopping the machine every 10h, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank, uniformly mixing, and continuing ball milling to obtain 150nm fine CoCrNiCuFe powder.
S2, performing ball milling and refining on the WC powder, wherein the mass ratio of balls to materials is 15:1, the rotating speed is 300r/min, the ball milling is performed for 25h, the machine is stopped for 30min every 5h for ball milling, and the fine WC powder with the particle size of 150nm is prepared.
S3, in a glove box filled with argon, 8g of CoCrNiCuFe and 32g of WC are weighed and loaded into a WC cemented carbide ball milling pot. The mass ratio of the ball to the material is 10:1, the rotating speed is 350r/min, the ball milling time is 2.5h, and the machine is stopped for 10min for heat dissipation every 1 h.
S4, firstly, putting the mixture into a graphite die for prepressing, wherein the prepressing pressure is 30MPa, and the prepressing is 60S; then, the vacuum degree is pumped to 40Pa, and the pressure is increased to 40 MPa; then, heating from room temperature to 600 ℃ for 5min, and preserving the heat at 600 ℃ for 10 min; then heating from 600 ℃ to 1200 ℃ at the heating rate of 50 ℃/min, and preserving the heat for 10 min. And cooling along with the furnace to obtain a blank. And (3) carrying out surface grinding and deburring treatment on the prepared blank to obtain the high-entropy alloy combined tungsten carbide hard alloy.
After grinding and polishing the sintered tungsten carbide hard alloy sample, carrying out structure and performance detection, wherein the technical parameters of the obtained sintered body are shown in table 10:
TABLE 10 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 6
Figure BDA0002299515130000131
Example 7
The compositions in table 1 and table 9 were used for preparation, and the ball milling speed, time, etc. were adjusted:
s1, mixing 2.039g of Co, 1.799g of Cr, 2.031g of Ni, 2.199g of Cu and 1.932g of Fe in an argon-filled glove box, putting the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 15:1, the rotating speed is 500r/min, the ball milling time is 35h, stopping the machine for 30min for heat dissipation every 5h of rotation, stopping the machine every 10h, scraping off raw materials adhered to the grinding balls and the inner wall of the tank, uniformly mixing, and then continuing ball milling to obtain 150nm fine CoCrNiCuFe powder.
S2, ball milling and refining the WC powder, wherein the mass ratio of balls to materials is 15:1, the rotating speed is 400r/min, ball milling is carried out for 10 hours, and the machine is stopped for 30 minutes every 5 hours of rotation to carry out heat dissipation, so that the fine WC powder with the particle size of 150nm is prepared.
S3, in a glove box filled with argon, 8g of CoCrNiCuFe and 32g of WC are weighed and loaded into a WC cemented carbide ball milling pot. The mass ratio of the ball to the material is 10:1, the rotating speed is 300r/min, the ball milling time is 3h, and the machine is stopped for 10min for heat dissipation every 1 h.
S4, firstly, putting the mixture into a graphite die for prepressing, wherein the prepressing pressure is 30MPa, and the prepressing is 60S; then, the vacuum degree is pumped to 40Pa, and the pressure is increased to 40 MPa; then, heating from room temperature to 600 ℃ for 5min, and preserving the heat at 600 ℃ for 10 min; then heating from 600 ℃ to 1300 ℃ at the heating rate of 50 ℃/min, and preserving the heat for 15 min. And cooling along with the furnace to obtain a blank. And (3) carrying out surface grinding and deburring treatment on the prepared blank to obtain the high-entropy alloy combined tungsten carbide hard alloy.
After the sintered tungsten carbide hard alloy sample is polished, the structure and the performance are detected, and the technical parameters of the obtained sintered body are shown in a table 11:
TABLE 11 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 7
Figure BDA0002299515130000141
Example 8
The compositions in table 1 and table 9 were used for preparation, and the ball milling speed, time, etc. were adjusted:
s1, mixing 2.039g of Co, 1.799g of Cr, 2.031g of Ni, 2.199g of Cu and 1.932g of Fe in a glove box filled with argon, putting the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 20:1, the rotating speed is 400r/min, the ball milling time is 40h, stopping the machine for 30min for heat dissipation every 5h of rotation, stopping the machine every 10h, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank, uniformly mixing, and then continuing ball milling to obtain 150nm fine CoCrNiCuFe powder.
S2, ball milling and refining the WC powder, wherein the mass ratio of balls to materials is 20:1, the rotating speed is 250r/min, ball milling is carried out for 15h, stopping the machine for 30min every 5h for ball milling, and heat dissipation is carried out to obtain the fine WC powder with the particle size of 150 nm.
S3, in a glove box filled with argon, 8g of CoCrNiCuFe and 32g of WC are weighed and loaded into a WC cemented carbide ball milling pot. The ball-material mass ratio is 10:1, the rotating speed is 200r/min, the ball milling time is 4h, and the machine is stopped for 10min for heat dissipation every 1 h.
S4, firstly, putting the mixture into a graphite die for prepressing, wherein the prepressing pressure is 10MPa, and the prepressing is 60S; then, the vacuum degree is pumped to 40Pa, and the pressure is increased to 40 MPa; then, heating from room temperature to 600 ℃ for 5min, and preserving the heat at 600 ℃ for 10 min; then heating from 600 ℃ to 1400 ℃ at the heating rate of 50 ℃/min, and preserving the heat for 20 min. And cooling along with the furnace to obtain a blank. And (3) carrying out surface grinding and deburring treatment on the prepared blank to obtain the high-entropy alloy combined tungsten carbide hard alloy.
After the sintered tungsten carbide hard alloy sample is polished, the structure and the performance are detected, and the technical parameters of the obtained sintered body are shown in table 12:
TABLE 12 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 8
Figure BDA0002299515130000151
Example 9
The raw material formulations were weighed according to the following percentages in table 13:
TABLE 13 raw materials for preparing 40g of WC cemented carbide and their compounding ratio
Figure BDA0002299515130000152
S1, mixing 2.039g of Co, 1.799g of Cr, 2.031g of Ni, 2.199g of Cu and 1.932g of Fe in a glove box filled with argon, putting the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 20:1, the rotating speed is 500r/min, the ball milling time is 30h, stopping the machine for 30min for heat dissipation every 5h of rotation, stopping the machine every 10h, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank, uniformly mixing, and then continuing ball milling to obtain 150nm fine CoCrNiCuFe powder.
S2, performing ball milling and refining on the WC powder, wherein the mass ratio of balls to materials is 20:1, the rotating speed is 300r/min, the ball milling is performed for 20h, the machine is stopped for 30min every 5h for ball milling, and the fine WC powder with the particle size of 150nm is prepared.
S3, in a glove box filled with argon, 12g of CoCrNiCuFe and 28g of WC are weighed into a WC cemented carbide ball mill pot. The mass ratio of the balls to the materials is 7:1, the rotating speed is 350r/min, the ball milling time is 4.5h, and the machine is stopped for 10min for heat dissipation every 1h of rotation.
S4, firstly, putting the mixture into a graphite die for prepressing, wherein the prepressing pressure is 20MPa, and the prepressing is 60S; then, the vacuum degree is pumped to 40Pa, and the pressure is increased to 40 MPa; then, heating from room temperature to 600 ℃ for 5min, and preserving the heat at 600 ℃ for 10 min; then heating from 600 ℃ to 1100 ℃ at the heating rate of 100 ℃/min, and preserving the heat for 5 min. And cooling along with the furnace to obtain a blank. And (3) carrying out surface grinding and deburring treatment on the prepared blank to obtain the high-entropy alloy combined tungsten carbide hard alloy.
After the sintered tungsten carbide hard alloy sample is polished, the structure and the performance are detected, and the technical parameters of the obtained sintered body are shown in table 14:
TABLE 14 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 9
Figure BDA0002299515130000161
Example 10
The compositions in table 1 and table 13 were used for preparation, and the ball milling speed, time, etc. were adjusted:
s1, mixing 2.039g of Co, 1.799g of Cr, 2.031g of Ni, 2.199g of Cu and 1.932g of Fe in a glove box filled with argon, putting the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 20:1, the rotating speed is 300r/min, the ball milling time is 45h, stopping the machine for 30min for heat dissipation every 5h of rotation, stopping the machine every 10h, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank, uniformly mixing, and then continuing ball milling to obtain 150nm fine CoCrNiCuFe powder.
S2, performing ball milling and refining on the WC powder, wherein the mass ratio of balls to materials is 20:1, the rotating speed is 350r/min, the ball milling is performed for 10 hours, the machine is stopped for 30 minutes every 5 hours of rotation, and the fine WC powder with the particle size of 150nm is prepared.
S3, in a glove box filled with argon, 12g of CoCrNiCuFe and 28g of WC are weighed into a WC cemented carbide ball mill pot. The mass ratio of the balls to the materials is 7:1, the rotating speed is 300r/min, the ball milling time is 3.5h, and the machine is stopped for 10min for heat dissipation every 1h of rotation.
S4, firstly, putting the mixture into a graphite die for prepressing, wherein the prepressing pressure is 20MPa, and the prepressing is 60S; then, the vacuum degree is pumped to 40Pa, and the pressure is increased to 50 MPa; then, heating from room temperature to 600 ℃ for 5min, and preserving the heat at 600 ℃ for 10 min; then heating from 600 ℃ to 1200 ℃ at the heating rate of 100 ℃/min, and preserving the heat for 5 min. And cooling along with the furnace to obtain a blank. And (3) carrying out surface grinding and deburring treatment on the prepared blank to obtain the high-entropy alloy combined tungsten carbide hard alloy.
After the sintered tungsten carbide hard alloy sample is polished, the structure and the performance are detected, and the technical parameters of the obtained sintered body are shown in table 15:
TABLE 15 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 10
Taking examples 6, 7 and 8 as examples, as shown in fig. 1, the tungsten carbide cemented carbide bonded with the high-entropy alloy all contained WC phase, FCC phase CoCrNiCuFe and Cr phase2O3Phase (1); the relative intensity of WC diffraction peak is increased gradually with the increase of sintering temperature and the prolonging of holding time. As shown in fig. 2, as the sintering temperature increases and the holding time is prolonged, part of WC grains gradually grow into polygons, WC is more tightly bonded, and the density first increases and then decreases.
Summary of experimental data: as can be seen from examples 1 to 10, the content, sintering temperature and holding time of the CoCrNiCuFe high-entropy alloy have great influence on the performance of the tungsten carbide hard alloy combined with the high-entropy alloy. From the examples 4 and 10, it is known that the content of the CoCrNiCuFe high-entropy alloy is increased, the hardness of the hard alloy is reduced, and the toughness and the compactness are improved. From examples 5 and 9, it is known that when the content of the CoCrNiCuFe high-entropy alloy is continuously increased, the toughness is slightly improved, the hardness is rapidly reduced, and the hard alloy sintered body with good comprehensive performance can be obtained only by ensuring that the content of the CoCrNiCuFe high-entropy alloy is in a proper range. It is clear from examples 6, 7 and 8 that the hardness, toughness and compactness of the cemented carbide increase first and then decrease as the sintering temperature increases and the holding time increases. It can be seen from examples 1 and 2 that the ball milling rotation speed and the ball milling time can be balanced with each other, and that increasing the rotation speed can shorten the ball milling time and increasing the ball milling time can reduce the rotation speed.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (7)

1. The high-entropy alloy-bonded tungsten carbide hard alloy is characterized by comprising the following components in percentage by mass: the CoCrNiCuFe accounts for 5-30 wt.%, and the balance is WC.
2. A high entropy alloy bonded tungsten carbide cemented carbide according to claim 1, characterized in that the particle size of the CoCrNiCuFe is 150nm fine; the purity of WC is more than 99%, and the grain diameter is 150 nm.
3. A method for producing a high-entropy alloy-bonded cemented tungsten carbide according to claim 1 or 2, characterized by comprising the steps of,
s1, preparation of CoCrNiCuFe powder: mixing Co, Cr, Ni, Cu and Fe according to a molar ratio of 1:1:1:1:1 in a glove box filled with argon, filling the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 300-600 r/min, the ball milling time is 20-50 h, stopping the machine for 30min for heat dissipation every 5h of rotation, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank and uniformly mixing the raw materials every 10h of stop, and then continuing ball milling to prepare fine CoCrNiCuFe powder with the particle size of 150 nm;
s2, preparing WC powder: carrying out ball milling and thinning on WC powder, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 250-400 r/min, the ball milling time is 10-40 h, and the machine is stopped for 30min every 5h to carry out heat dissipation to prepare fine WC powder with the particle size of 150 nm;
s3, mixing materials: in a glove box filled with argon, 5-30 wt.% of CoCrNiCuFe powder prepared in the step S1 is weighed, added into WC powder prepared in the step S2 and subjected to ball milling and mixing, the ball-material mass ratio is 5: 1-10: 1, the rotating speed is 200-350 r/min, the ball milling time is 2-5 h, and the glove box is stopped for 10min for heat dissipation every 1 h;
s4, sintering preparation: putting the mixture mixed in the step S3 into a graphite die for prepressing, wherein the prepressing pressure is 10-30 MPa, and the prepressing is 60S; then, carrying out spark plasma sintering, wherein the vacuum degree is 40Pa, the sintering pressure is 40-50 MPa, the sintering temperature is 1100-1400 ℃, the heating rate is 30-100 ℃/min, and the heat preservation time is 3-30 min; and then cooling and relieving pressure to prepare the high-entropy alloy-combined tungsten carbide hard alloy.
4. The preparation method according to claim 3, wherein the purity of the Co, Cr, Ni, Cu and Fe powder is more than 99%, wherein the grain diameter of the Co powder is 1-3 μm, the grain diameter of the Cr powder is less than 75 μm, and the grain diameter of the other metal simple substance powder is less than 45 μm.
5. The method according to claim 3, wherein the WC powder has a particle size of 1 to 3 μm and a purity of > 99%.
6. The preparation method according to claim 3, wherein the ball milling processes of the steps S1, S2 and S3 all use three large, medium and small WC hard alloy balls with the diameters of 8mm, 5mm and 2mm respectively, wherein the mass ratio of the large, medium and small WC hard alloy balls is 3:1: 1.
7. The preparation method according to claim 3, wherein the specific sintering process in step S4 is: firstly, slowly applying pressure to a sample to 40-50 MPa; then, the vacuum degree is pumped to 40 Pa; then, heating from room temperature to 600 ℃ for 5min, and preserving the heat at 600 ℃ for 10 min; then heating from 600 ℃ to 1100-1400 ℃ at a heating rate of 30-100 ℃/min, and preserving heat for 3-30 min; cooling along with the furnace to obtain a blank; and (3) carrying out surface grinding and deburring treatment on the prepared blank to obtain the high-entropy alloy combined tungsten carbide hard alloy.
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JP7103565B1 (en) * 2020-12-23 2022-07-20 住友電工ハードメタル株式会社 Cemented carbide and cutting tools containing it as a base material
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CN115305401A (en) * 2022-08-24 2022-11-08 燕山大学 High-entropy alloy-high-entropy ceramic combined tungsten carbide hard alloy and preparation method thereof
CN115305401B (en) * 2022-08-24 2023-05-26 燕山大学 High-entropy alloy-high-entropy ceramic combined tungsten carbide hard alloy and preparation method thereof

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