CN111286664A - Superfine tungsten carbide hard alloy with high-entropy alloy as binder phase and preparation method thereof - Google Patents
Superfine tungsten carbide hard alloy with high-entropy alloy as binder phase and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of composite materials, and relates to a superfine tungsten carbide hard alloy taking a high-entropy alloy as a binding phase and a preparation method thereof, wherein the high-entropy alloy is a five-element high-entropy alloy of Co, Cr, Ni, Cu and Fe, the mass percentage of the high-entropy alloy accounts for 5-30 wt% of the total system, and the balance is WC. Firstly, preparing nanometer five-component high-entropy alloy powder and refining WC powder; secondly, mixing the nanometer five-component high-entropy alloy powder and the nanometer WC in a ball mill according to different mass ratios; prepressing the uniformly mixed powder; and annealing the prepressing piece. And finally, carrying out vacuum hot-pressing sintering, wherein the sintering pressure is 40-50 MPa, and the sintering temperature is 1200-1400 ℃. Then cooling and releasing pressure to prepare the superfine tungsten carbide hard alloy. And annealing the hard alloy sintered body after sintering. The invention provides a superfine tungsten carbide hard alloy taking high-entropy alloy as a binding phase and a preparation method thereof, which reduce the production cost and improve the performance of the tungsten carbide hard alloy.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a superfine tungsten carbide hard alloy taking high-entropy alloy as a binding phase 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 alloy-bonded tungsten carbide cemented carbide has been widely studied because of its excellent properties.
Dongding dryl, etc. using 3-35 wt.% CoNiCuFeCr high entropy alloy as strengthening phase, 0-30% Co, 0-30% Ni, 0-30% Fe, 0-15% Cr as binder phase, 55-97% WC, 0-10% TaC/NbC, 0-5% VC/ZrC, 0-5% Cr2C3The composite material is a hard phase, and the tungsten carbide hard alloy is prepared by ball milling, spray drying, die pressing into blanks, gradient process sintering and heat treatment, and has good wear resistance, toughness, oxidation resistance and excellent comprehensive performance mechanics and mechanical properties [ DongDing; 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 red bayberry and the like are subjected to intermittent planetary ball milling to prepare amorphous high-entropy alloy binding phase powder of Fe, Co, Ni, Cu, Cr, 1:1:1 (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 [ red bayberry ] is prepared by adopting discharge plasma sintering; rosy clouds; longjiaping, a preparation method of high-entropy alloy binding phase hard alloy 109161773A.University of Chengdu Physician 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. The Vickers hardness value of the prepared hard alloy is 1922-2127 HV30, and the fracture toughness value is 9.89-10.41 MPa.m1/2. The best comprehensive performance is as follows: the Vickers hardness value is 1922HV30, and the fracture toughness value is 10.41 MPa-m1/2[ 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. The Vickers hardness value of the prepared hard alloy is 1825-1900 HV30[ wear strength; 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]. Tryplon and the like adopt an argon atomization method to prepare AlxCrFeCoNi (x is 0.5,1) high-entropy alloy powder, the AlxCrFeCoNi high-entropy alloy powder is mixed with WC powder and subjected to high-energy ball milling to obtain WC-AlxCrFeCoNi composite powder, and the WC-AlxCrFeCoNi composite powder is hot-pressed into a bulk composite material. The results of the characterization of the microstructure, the mechanical property, the corrosion behavior and the like of the composite material show that the AlxCrFeCoNi high-entropy alloy can be used for replacing Co as a binding phase to inhibit the growth of WC grains and play a role in refining the grains. Compared with the traditional WC-10Co alloy, the ultra-fine grain WC-AlxCrFeCoNi composite material has higher hardness and good fracture toughness. Wherein the WC-10AlCrFeCoNi composite material has the highest Hardness (HV) reaching 20.3GPa, and the WC-10Al0.5CrFeCoNi has the maximum fracture toughness of 12 MPa.m1/2. Compared with WC-10Co traditional hard alloy, the WC-10AlxCrFeCoNi composite material has better corrosion resistance [ trypan, Xiaoshihong, Zhongpengfei, et AlxCrFeCoNi composite material and its structure and performance [ J ]]Science and engineering of powder metallurgy materials, 2019,11(30):95-103]。
The high-entropy alloy bonding agent and the preparation method thereof adopted in the research have limited effect on improving the performance of the WC hard alloy, mainly improve the mechanical properties such as hardness and toughness of the WC hard alloy, and have limited improvement. Aiming at the problem, the invention mixes, heats and sinters Co, Cr, Ni, Cu and Fe five-component high-entropy alloy (the molar ratio of each component is 1-1.5) powder as a bonding agent with nanometer WC powder to synthesize the superfine WC hard alloy. Not only improves the mechanical property, but also improves the room temperature friction and wear property, especially the high temperature friction and wear property, thereby widening the application range of the WC hard alloy.
Disclosure of Invention
According to the technical problems, the invention uses five-component high-entropy alloy (the molar ratio of each component is 1-1.5) of Co, Cr, Ni, Cu and Fe as a binder of the tungsten carbide hard alloy, and prepares the tungsten carbide hard alloy by adopting a hot-pressing sintering method. Aims to reduce the sintering temperature of the hard alloy and improve the comprehensive performance of the hard alloy. And provides a superfine tungsten carbide hard alloy taking high-entropy alloy as a binding phase and a preparation method thereof.
The technical means adopted by the invention are as follows:
a superfine tungsten carbide hard alloy taking high-entropy alloy as a binder phase is characterized in that: the raw material formula comprises nanometer five-component high-entropy alloy powder and nanometer WC powder, wherein the molar ratio of each component of Co, Cr, Ni, Cu and Fe is 1-1.5, and the hard alloy comprises the following components in percentage by mass: the five-component high-entropy alloy accounts for 5-30 wt.%, and the balance is WC.
The grain diameter of the nanometer five-component high-entropy alloy powder is 150nm or less; the grain diameter of the nanometer WC is 150nm so as to be fine, and the purity is more than 99%.
The invention also provides a preparation method of the superfine tungsten carbide hard alloy taking the high-entropy alloy as the binder phase, which comprises the following steps:
s1, preparing nanometer five-component high-entropy alloy powder: mixing Co, Cr, Ni, Cu and Fe according to the molar ratio range of 1-1.5 of each component 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 30-60 h, stopping the machine for 30min for heat dissipation every 10h, scraping and uniformly mixing the raw materials adhered to the grinding balls and the inner wall of the tank every 10h, then adding an absolute ethyl alcohol dispersing agent of 0.2ml/10g of mixed powder, and continuing ball milling to prepare 150nm fine nanometer five-component high-entropy alloy powder;
s2, preparing nano 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 300-450 r/min, the ball milling time is 20-40 h, and the machine is stopped for 30min every 10h to carry out heat dissipation to prepare nano WC powder with the fineness of 150 nm;
s3, mixing materials: weighing 5-30 wt.% of nanometer five-component high-entropy alloy powder prepared in the step S1 in a glove box filled with argon, adding the nanometer five-component high-entropy alloy powder into the nanometer WC powder prepared in the step S2, and then performing ball milling and mixing, wherein the mass ratio of balls to materials is 5: 1-10: 1, the rotating speed is 250-350 r/min, the ball milling time is 2-6 h, and the glove box is shut down for 10min for heat dissipation every 1 h;
s4: preparing by vacuum hot-pressing sintering: prepressing the mixture prepared in the step S3 at 200-400 MPa for 1-3 minutes, annealing the prepressed piece at 300-500 ℃ after prepressing, keeping the temperature for 10-30 min, then carrying out vacuum hot-pressing sintering at the vacuum degree of 40Pa and the sintering pressure of 40-50 MPa, the sintering temperature of 1200-1400 ℃, the heating rate of 10-30 ℃/min and the heat preservation time of 10-30 min, then cooling and releasing the pressure to prepare the superfine tungsten carbide hard alloy, and carrying out annealing treatment at 350-600 ℃ on the hard alloy sintered body after sintering, keeping the temperature for 20-60 min to prepare the superfine tungsten carbide hard alloy taking high entropy as a binder phase.
Furthermore, the purity of the Co powder, the Cr powder, the Ni powder, the Cu powder and the 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 Ni powder, the Cu powder and the Fe 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, and 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 1000 ℃ at a heating rate of 20 ℃/min, and preserving the heat at 1000 ℃ for 20 min; and then heating the alloy to 1200-1400 ℃ from 1000 ℃ at a heating rate of 10-30 ℃/min, preserving heat for 10-30 min, cooling the alloy along with a furnace to obtain a blank, and carrying out surface grinding and deburring treatment on the prepared blank to obtain the superfine tungsten carbide hard alloy taking the high-entropy alloy as a binding phase.
Compared with the prior art, the invention has the following advantages:
(1) the five-component (Co, Cr, Ni, Cu and Fe) high-entropy alloy has excellent comprehensive performance which exceeds the comprehensive performance of WC hard alloy bonded by other high-entropy alloys.
(2) The WC hard alloy combined by the five-component high-entropy alloy prepared by the method has excellent frictional wear performance at room temperature and 500 ℃.
For the reasons, the invention can be widely popularized in the fields of composite materials and the like.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The described embodiments are only some embodiments of the invention, not all 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 should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The described embodiments are only some embodiments of the invention, not all 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. The relative arrangement of the steps set forth in these embodiments does not limit the scope of the invention unless specifically stated otherwise. 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 particular value, in all examples shown and discussed herein, should be construed as exemplary only and not as limiting. Thus, other examples of the exemplary embodiments may have different values.
A superfine tungsten carbide hard alloy taking high-entropy alloy as a binder phase is characterized in that: the raw material formula comprises five-component high-entropy alloy powder of nano CoCrNiCuFe, wherein the molar ratio of Co, Cr, Ni, Cu and Fe is 1-1.5, and nano WC powder, and the hard alloy comprises the following components in percentage by mass: the five-component high-entropy alloy accounts for 5-30 wt.%, and the balance is WC.
The grain diameter of the nanometer five-component high-entropy alloy powder is 150nm or less; the grain diameter of the nanometer WC is 150nm so as to be fine, and the purity is more than 99%.
The invention also provides a preparation method of the superfine tungsten carbide hard alloy taking the high-entropy alloy as the binder phase, which comprises the following steps:
s1, preparing nanometer five-component high-entropy alloy powder: mixing Co, Cr, Ni, Cu and Fe in a glove box filled with argon in a molar ratio range of 1-1.5, 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 30-60 h, stopping the machine for 30min for heat dissipation every 10h, scraping off and uniformly mixing the raw materials adhered to the grinding balls and the inner wall of the tank every 10h, then adding an absolute ethyl alcohol dispersing agent of 0.2ml/10g of mixed powder, and continuing ball milling to prepare 150nm fine nano CoCrNiCuFe powder;
s2, preparing nano 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 300-450 r/min, the ball milling time is 20-40 h, and the machine is stopped for 30min every 10h to carry out heat dissipation to prepare nano WC powder with the fineness of 150 nm;
s3, mixing materials: weighing 5-30 wt.% of nanometer five-component high-entropy alloy powder prepared in the step S1 in a glove box filled with argon, adding the nanometer five-component high-entropy alloy powder into the nanometer WC powder prepared in the step S2, and then performing ball milling and mixing, wherein the mass ratio of balls to materials is 5: 1-10: 1, the rotating speed is 250-350 r/min, the ball milling time is 2-6 h, and the glove box is shut down for 10min for heat dissipation every 1 h;
s4: preparing by vacuum hot-pressing sintering: prepressing the mixture prepared in the step S3 at 200-400 MPa for 1-3 minutes, annealing the prepressed piece at 300-500 ℃ after prepressing, keeping the temperature for 10-30 min, then carrying out vacuum hot-pressing sintering at the vacuum degree of 40Pa and the sintering pressure of 40-50 MPa, the sintering temperature of 1200-1400 ℃, the heating rate of 10-30 ℃/min and the heat preservation time of 10-30 min, then cooling and releasing the pressure to prepare the superfine tungsten carbide hard alloy, and carrying out annealing treatment at 350-600 ℃ on the hard alloy sintered body after sintering, keeping the temperature for 20-60 min to prepare the superfine tungsten carbide hard alloy taking high entropy as a binder phase.
Furthermore, the purity of the Co powder, the Cr powder, the Ni powder, the Cu powder and the 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 Ni powder, the Cu powder and the Fe 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, and 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 1000 ℃ at a heating rate of 20 ℃/min, and preserving the heat at 1000 ℃ for 20 min; and then heating the alloy to 1200-1400 ℃ from 1000 ℃ at a heating rate of 10-30 ℃/min, preserving heat for 10-30 min, cooling the alloy along with a furnace to obtain a blank, and carrying out surface grinding and deburring treatment on the prepared blank to obtain the superfine tungsten carbide hard alloy taking the high-entropy alloy as a binding phase. (in all the following examples, "temperature rise from room temperature to 1000 ℃ at a temperature rise rate of 20 ℃/min; temperature hold at 1000 ℃ for 20 min;" description will not be repeated)
Further, the mixture prepared by step S3 is put into a graphite mold for pre-pressing in step S4.
The ball mill used in all the following examples of the present invention was model QM-3SP4 (china).
The model of the hot-pressing sintering instrument adopted in all the embodiments of the invention is ZRY-120 (China).
The graphite molds used in all the examples are currently commercially available products.
The detection equipment in all the following embodiments of 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.
The model of the friction and wear tester described in all the following embodiments of the present invention is MMU-10G (China). The grinding piece is made of 45# steel, and the hardness value is HRC 50. The test conditions were: the load is 300N, the rotating speed is 300r/min, the grinding time is 10min, the temperature is room temperature and 500 ℃.
Example 1
A method for preparing superfine tungsten carbide hard alloy with high-entropy alloy as a binding phase comprises the following steps of mixing raw materials according to a ratio shown in a table,
TABLE 1 raw materials for preparing CoCrNiCuFe and their mass ratios
TABLE 2 raw materials for preparing 40g of WC cemented carbide and their mixture ratio
The preparation method comprises the following steps:
s1, weighing 2.039g of Co, 1.799g of Cr, 2.031g of Ni, 2.199g of Cu and 1.932g of Fe according to the table 1 in a glove box filled with argon, mixing and filling 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 300r/min, the ball milling time is 60h, stopping the machine for 30min for heat dissipation every 10h, scraping and uniformly mixing the raw materials adhered to the grinding balls and the inner wall of the tank every 10h, then adding an absolute ethyl alcohol dispersing agent of 0.2ml/10g of mixed powder, and continuing ball milling to prepare fine CoCrNiCuFe powder with the particle size of 150 nm.
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 40h, the machine is stopped for 30min every 10h 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 were weighed into a WC cemented carbide ball mill pot according to Table 2. The mass ratio of the balls to the materials is 5:1, the rotating speed is 350r/min, the ball milling time is 2.5h, and the machine is stopped for 10min for heat dissipation every 1h of rotation.
And S4, putting the mixture into a hard alloy die for prepressing, wherein the prepressing pressure is 200MPa, and the prepressing time is 1 min. And annealing the pre-pressing piece at 300 ℃ after pre-pressing, and keeping the temperature for 10 min. Then carrying out vacuum hot-pressing sintering, wherein the vacuum degree is 40Pa, the sintering pressure is 40MPa, the sintering temperature is 1200 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 10 min. Then cooling and releasing pressure to prepare the superfine tungsten carbide hard alloy. And after sintering, annealing the hard alloy sintered body at 350 ℃ for 20 min.
And (3) grinding and polishing the sintered tungsten carbide hard alloy sample, and then carrying out structure and performance detection, wherein the technical parameters of the obtained sintered body are shown in table 3.
TABLE 3 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 1
Example 2
A method for preparing superfine tungsten carbide hard alloy with high-entropy alloy as a binding phase comprises the following steps of mixing raw materials according to a ratio shown in a table,
table 4 raw materials for preparing CoCrNiCuFe and mass ratio thereof
TABLE 5 raw materials for preparing 40g of WC cemented carbide and their mixture ratio
The preparation method comprises the following steps:
s1, weighing 2.039g of Co, 1.799g of Cr, 2.031g of Ni, 2.199g of Cu and 1.932g of Fe according to the weight ratio of table 4 in a glove box filled with argon, mixing, putting 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 55h, stopping the machine for 30min for heat dissipation every 10h, scraping and uniformly mixing the raw materials adhered to the grinding balls and the inner wall of the tank every 10h, adding 0.2ml/10g of an absolute ethyl alcohol dispersing agent of mixed powder, and continuing ball milling to prepare fine CoCrNiCuFe powder with the particle size of 150 nm.
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 38h, the machine is stopped for 30min every 10h 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 were weighed into a WC cemented carbide ball mill jar according to Table 5. The mass ratio of the balls to the materials is 5:1, the rotating speed is 300r/min, the ball milling time is 4.5h, and the machine is stopped for 10min for heat dissipation every 1h of rotation.
And S4, putting the mixture into a hard alloy die for prepressing, wherein the prepressing pressure is 200MPa, and the prepressing time is 1 min. And after prepressing, annealing the prepressed piece at 300 ℃ for 30 min. Then carrying out vacuum hot-pressing sintering, wherein the vacuum degree is 40Pa, the sintering pressure is 50MPa, the sintering temperature is 1300 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 10 min. Then cooling and releasing pressure to prepare the superfine tungsten carbide hard alloy. And after sintering, annealing the hard alloy sintered body at 350 ℃ for 30 min.
And (3) grinding and polishing the sintered tungsten carbide hard alloy sample, and then carrying out structure and performance detection, wherein the technical parameters of the obtained sintered body are shown in a table 6.
TABLE 6 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 2
Example 3
A method for preparing superfine tungsten carbide hard alloy with high-entropy alloy as a binding phase comprises the following steps of mixing raw materials according to a ratio shown in a table,
TABLE 7 raw materials for preparing CoCrNiCuFe and their mass ratios
TABLE 8 raw materials for preparing 40g of WC cemented carbide and their mixture ratio
The preparation method comprises the following steps:
s1, weighing 2.039g of Co, 1.799g of Cr, 2.031g of Ni, 2.199g of Cu and 1.932g of Fe according to the weight ratio of table 7 in a glove box filled with argon, mixing, putting 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 45h, stopping the machine for 30min for heat dissipation every 10h, scraping and uniformly mixing the raw materials adhered to the grinding balls and the inner wall of the tank every 10h, adding 0.2ml/10g of an absolute ethyl alcohol dispersing agent of mixed powder, and continuing ball milling to prepare fine CoCrNiCuFe powder with the particle size of 150 nm.
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 400r/min, the ball milling is performed for 35 hours, the machine is stopped for 30 minutes every 10 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 were weighed into a WC cemented carbide ball mill jar according to Table 8. The mass ratio of the balls to the materials is 5:1, the rotating speed is 250r/min, the ball milling time is 6h, and the machine is stopped for 10min for heat dissipation every 1h of rotation.
And S4, putting the mixture into a hard alloy die for prepressing, wherein the prepressing pressure is 400MPa, and the prepressing is carried out for 2 min. And after prepressing, annealing the prepressed piece at 350 ℃ for 15 min. Then carrying out vacuum hot-pressing sintering, wherein the vacuum degree is 40Pa, the sintering pressure is 50MPa, the sintering temperature is 1400 ℃, the heating rate is 30 ℃/min, and the heat preservation time is 15 min. Then cooling and releasing pressure to prepare the superfine tungsten carbide hard alloy. And after sintering, annealing the hard alloy sintered body at 400 ℃ for 40 min.
And (3) grinding and polishing the sintered tungsten carbide hard alloy sample, and then carrying out structure and performance detection, wherein the technical parameters of the obtained sintered body are shown in a table 9.
TABLE 9 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 3
Example 4
A method for preparing superfine tungsten carbide hard alloy with high-entropy alloy as a binding phase comprises the following steps of mixing raw materials according to a ratio shown in a table,
TABLE 10 raw materials for preparing CoCrNiCuFe and their mass ratios
TABLE 11 raw materials for preparing 40g of WC cemented carbide and their mixture ratio
The preparation method comprises the following steps:
s1, in a glove box filled with argon, weighing 2.039g of Co, 1.799g of Cr, 2.031g of Ni, 2.199g of Cu and 1.932g of Fe according to the table 10, mixing and loading 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 600r/min, the ball milling time is 30h, stopping the machine for 30min for heat dissipation every 10h, stopping the machine every 10h to scrape off and uniformly mix the raw materials adhered to the grinding balls and the inner wall of the tank, then adding 0.2ml/10g of an absolute ethyl alcohol dispersing agent of mixed powder, and continuing ball milling to prepare fine CoCrNiCuFe powder with the particle size of 150 nm.
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 35h, the machine is stopped for 30min every 10h for heat dissipation, 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 were weighed into a WC cemented carbide ball mill jar according to Table 11. The mass ratio of the ball to the material is 8:1, the rotating speed is 350r/min, the ball milling time is 2.2h, and the machine is stopped for 10min for heat dissipation every 1 h.
And S4, putting the mixture into a hard alloy die for prepressing, wherein the prepressing pressure is 300MPa, and the prepressing is carried out for 2 min. And after prepressing, annealing the prepressed piece at 350 ℃ for 15 min. Then carrying out vacuum hot-pressing sintering, wherein the vacuum degree is 40Pa, the sintering pressure is 50MPa, the sintering temperature is 1400 ℃, the heating rate is 30 ℃/min, and the heat preservation time is 15 min. Then cooling and releasing pressure to prepare the superfine tungsten carbide hard alloy. And after sintering, annealing the hard alloy sintered body at 400 ℃ for 50 min.
And (3) grinding and polishing the sintered tungsten carbide hard alloy sample, and then carrying out structure and performance detection, wherein the technical parameters of the obtained sintered body are shown in a table 12.
TABLE 12 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 4
Example 5
A method for preparing superfine tungsten carbide hard alloy with high-entropy alloy as a binding phase comprises the following steps of mixing raw materials according to a ratio shown in a table,
TABLE 13 preparation of Co1.1Cr1.1NiCu1.2Fe1.3The raw materials and the mass ratio thereof
TABLE 14 raw materials for preparing 40g of WC cemented carbide and their compounding ratio
The preparation method comprises the following steps:
s1, in a glove box filled with argon, weighing 1.967g of Co, 1.735g of Cr, 1.781g of Ni, 2.314g of Cu and 2.203g of Fe according to the table 13, mixing and filling 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 40h, the tank is stopped for 30min for heat dissipation every 10h, the raw materials adhered to the grinding balls and the inner wall of the tank are scraped and uniformly mixed every 10h, then 0.2ml/10g of absolute ethyl alcohol dispersing agent of mixed powder is added for continuous ball milling, and the fine Co with the particle size of 150nm is prepared1.1Cr1.1NiCu1.2Fe1.3And (3) 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 350r/min, the ball milling is performed for 33h, the machine is stopped for 30min every 10h for heat dissipation, and the fine WC powder with the particle size of 150nm is prepared.
S3, in a glove box filled with argon, 4g of Co was weighed according to Table 141.1Cr1.1NiCu1.2Fe1.3And 36g of WC were charged into a WC cemented carbide ball mill jar. The mass ratio of the ball to the material is 8:1, the rotating speed is 300r/min, the ball milling time is 4.2h, and the machine is stopped for 10min for heat dissipation every 1 h.
And S4, putting the mixture into a hard alloy die for prepressing, wherein the prepressing pressure is 200MPa, and the prepressing is performed for 3 min. And after prepressing, annealing the prepressed piece at 400 ℃ for 20 min. Then carrying out vacuum hot-pressing sintering, wherein the vacuum degree is 40Pa, the sintering pressure is 50MPa, the sintering temperature is 1400 ℃, the heating rate is 30 ℃/min, and the heat preservation time is 20 min. Then cooling and releasing pressure to prepare the superfine tungsten carbide hard alloy. And after sintering, annealing the hard alloy sintered body at 450 ℃ for 60 min.
And (3) grinding and polishing the sintered tungsten carbide hard alloy sample, and then carrying out structure and performance detection, wherein the technical parameters of the obtained sintered body are shown in a table 15.
TABLE 15 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 5
Example 6
A method for preparing superfine tungsten carbide hard alloy with high-entropy alloy as a binding phase comprises the following steps of mixing raw materials according to a ratio shown in a table,
TABLE 16 preparation of CoCr1.2Ni1.3CuFe1.5The raw materials and the mass ratio thereof
TABLE 17 raw materials for preparing 40g of WC cemented carbide and their compounding ratio
The preparation method comprises the following steps:
s1, in a glove box filled with argon, weighing 1.708g of Co, 1.809g of Cr, 2.212g of Ni, 1.842g of Cu and 2.429g of Fe according to the table 16, mixing and filling 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 50h, stopping the machine for 30min for heat dissipation every 10h, uniformly scraping off the raw materials adhered to the grinding balls and the inner wall of the tank every 10h, then adding 0.2ml/10g of absolute ethyl alcohol dispersant of mixed powder for continuous ball milling to prepare 150nm fine CoCr1.2Ni1.3CuFe1.5And (3) 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 450r/min, the ball milling is performed for 25h, the machine is stopped for 30min every 10h 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 CoCr was weighed according to Table 171.2Ni1.3CuFe1.5And 32g of WC were charged in a WC cemented carbide ball mill jar. The mass ratio of the ball to the material is 8:1, the rotating speed is 250r/min, the ball milling time is 5.5h, and the machine is stopped for 10min for heat dissipation every 1 h.
And S4, putting the mixture into a hard alloy die for prepressing, wherein the prepressing pressure is 250MPa, and the prepressing is carried out for 3 min. And after prepressing, annealing the prepressed piece at 400 ℃ for 20 min. Then carrying out vacuum hot-pressing sintering, wherein the vacuum degree is 40Pa, the sintering pressure is 40MPa, the sintering temperature is 1300 ℃, the heating rate is 20 ℃/min, and the heat preservation time is 20 min. Then cooling and releasing pressure to prepare the superfine tungsten carbide hard alloy. And after sintering, annealing the hard alloy sintered body at 450 ℃ for 20 min.
And (3) grinding and polishing the sintered tungsten carbide hard alloy sample, and then carrying out structure and performance detection, wherein the technical parameters of the obtained sintered body are shown in a table 18.
TABLE 18 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 6
Example 7
A method for preparing superfine tungsten carbide hard alloy with high-entropy alloy as a binding phase comprises the following steps of mixing raw materials according to a ratio shown in a table,
TABLE 19 preparation of CoCrNi1.2Cu1.5Raw material of Fe and mass ratio thereof
TABLE 20 raw materials for preparing 40g of WC cemented carbide and their compounding ratio
The preparation method comprises the following steps:
s1, in a glove box filled with argon, weighing 1.772g of Co, 1.564g of Cr, 2.118g of Ni, 2.867g of Cu and 1.679g of Fe according to the table 19, mixing and filling 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 600r/min, the ball milling time is 30h, the tank is stopped for 30min for heat dissipation every 10h, the raw materials adhered to the grinding balls and the inner wall of the tank are scraped and uniformly mixed every 10h, then 0.2ml/10g of absolute ethyl alcohol dispersing agent of mixed powder is added for continuous ball milling, and the CoCrNi fine powder with the particle size of 150nm is prepared1.2Cu1.5And (3) Fe 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 450r/min, performing ball milling for 20h, stopping the ball milling machine for 30min every 10h, and performing heat dissipation to obtain fine WC powder with the particle size of 150 nm.
S3, in a glove box filled with argon, 8g of CoCrNi was weighed according to Table 201.2Cu1.5Fe and 32g WC were charged into a WC cemented carbide ball mill jar. The mass ratio of the ball to the material is 10:1, the rotating speed is 350r/min, the ball milling time is 2h, and the machine is stopped for 10min for heat dissipation every 1 h.
And S4, putting the mixture into a hard alloy die for prepressing, wherein the prepressing pressure is 250MPa, and the prepressing is carried out for 3 min. And annealing the pre-pressing piece at 450 ℃ after pre-pressing, and keeping the temperature for 25 min. Then carrying out vacuum hot-pressing sintering, wherein the vacuum degree is 40Pa, the sintering pressure is 40MPa, the sintering temperature is 1400 ℃, the heating rate is 20 ℃/min, and the heat preservation time is 25 min. Then cooling and releasing pressure to prepare the superfine tungsten carbide hard alloy. And after sintering, annealing the hard alloy sintered body at 500 ℃ for 30 min.
And (3) grinding and polishing the sintered tungsten carbide hard alloy sample, and then carrying out structure and performance detection, wherein the technical parameters of the obtained sintered body are shown in a table 21.
TABLE 21 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 7
Example 8
A method for preparing superfine tungsten carbide hard alloy with high-entropy alloy as a binding phase comprises the following steps of mixing raw materials according to a ratio shown in a table,
TABLE 22 preparation of Co1.5Cr1.5Ni1.3Cu1.1Fe1.4The raw materials and the mass ratio thereof
TABLE 23 raw materials for preparing 40g of WC cemented carbide and their compounding ratio
The preparation method comprises the following steps:
s1, in a glove box filled with argon, weighing 2.262g of Co, 1.996g of Cr, 1.952g of Ni, 1.789g of Cu and 2.001g of Fe according to the table 22, mixing and filling 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 35h, stopping the machine for 30min for heat dissipation every 10h, stopping the machine every 10h to scrape off and uniformly mix the raw materials adhered to the grinding balls and the inner wall of the tank, then adding 0.2ml/10g of absolute ethyl alcohol dispersant of mixed powder for continuous ball milling to prepare the fine Co with the particle size of 150nm1.5Cr1.5Ni1.3Cu1.1Fe1.4And (3) 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 400r/min, the ball milling is performed for 25h, the machine is stopped for 30min every 10h 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 Co was weighed according to Table 231.5Cr1.5Ni1.3Cu1.1Fe1.4And 32g of WC were charged in a WC cemented carbide ball mill jar. The mass ratio of the ball to the material is 10:1, 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.
And S4, putting the mixture into a hard alloy die for prepressing, wherein the prepressing pressure is 300MPa, and the prepressing is carried out for 2 min. And annealing the pre-pressing piece at 450 ℃ after pre-pressing, and keeping the temperature for 25 min. Then carrying out vacuum hot-pressing sintering, wherein the vacuum degree is 40Pa, the sintering pressure is 40MPa, the sintering temperature is 1400 ℃, the heating rate is 20 ℃/min, and the heat preservation time is 25 min. Then cooling and releasing pressure to prepare the superfine tungsten carbide hard alloy. And after sintering, annealing the hard alloy sintered body at 500 ℃ for 40 min.
And (3) grinding and polishing the sintered tungsten carbide hard alloy sample, and then carrying out structure and performance detection, wherein the technical parameters of the obtained sintered body are shown in a table 24.
TABLE 24 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 8
Example 9
A method for preparing superfine tungsten carbide hard alloy with high-entropy alloy as a binding phase comprises the following steps of mixing raw materials according to a ratio shown in a table,
TABLE 25 preparation of CoCrNi1.2Cu1.5Raw material of Fe and mass ratio thereof
TABLE 26 raw materials for preparing 40g of WC cemented carbide and their compounding ratio
The preparation method comprises the following steps:
s1, in a glove box filled with argon, weighing 1.772g of Co, 1.564g of Cr, 2.118g of Ni, 2.867g of Cu and 1.679g of Fe according to the table 25, mixing and filling 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 10h, scraping and uniformly mixing the raw materials adhered to the grinding balls and the inner wall of the tank every 10h, then adding an absolute ethyl alcohol dispersing agent of 0.2ml/10g of mixed powder, and continuing ball milling to prepare fine CoCrNi1.2Cu1.5Fe powder with the particle size of 150 nm.
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 30h, the machine is stopped for 30min every 10h for heat dissipation, and the fine WC powder with the particle size of 150nm is prepared.
S3, in a glove box filled with argon, 12g of CoCrNi1.2Cu1.5Fe and 28g of WC were weighed into a WC cemented carbide ball mill pot according to Table 26. The mass ratio of the ball to the material is 10:1, the rotating speed is 280r/min, the ball milling time is 5h, and the machine is stopped for 10min for heat dissipation every 1 h.
And S4, putting the mixture into a hard alloy die for prepressing, wherein the prepressing pressure is 300MPa, and the prepressing is carried out for 2 min. And after prepressing, annealing the prepressed piece at 500 ℃ for 30 min. Then carrying out vacuum hot-pressing sintering, wherein the vacuum degree is 40Pa, the sintering pressure is 40MPa, the sintering temperature is 1300 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 30 min. Then cooling and releasing pressure to prepare the superfine tungsten carbide hard alloy. And (3) annealing the hard alloy sintered body at 550 ℃ after sintering, wherein the heat preservation time is 50 min.
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 27.
TABLE 27 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 9
Example 10
The preparation method of the superfine tungsten carbide hard alloy taking the high-entropy alloy as the binder phase comprises the following raw materials and the mixture ratio shown in the table 28.
TABLE 28 preparation of CoCr1.2Ni1.3CuFe1.5The raw materials and the mass ratio thereof
TABLE 29 raw materials for preparing 40g of WC cemented carbide and their compounding ratio
The preparation method comprises the following steps:
s1, in a glove box filled with argon, weighing 1.708g of Co, 1.809g of Cr, 2.212g of Ni, 1.842g of Cu and 2.429g of Fe according to the table 28, mixing and filling 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 50h, stopping the machine for 30min for heat dissipation every 10h, scraping and uniformly mixing the raw materials adhered to the grinding balls and the inner wall of the tank every 10h, then adding 0.2ml/10g of an absolute ethyl alcohol dispersing agent of mixed powder, and continuing ball milling to prepare 150nm fine CoCr1.2Ni1.3CuFe1.5 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 32h, the machine is stopped for 30min every 10h for heat dissipation, and the fine WC powder with the particle size of 150nm is prepared.
S3, 12g of cocr1.2ni1.3cufe1.5 and 28g of WC were weighed into a WC cemented carbide ball mill pot according to table 29 in a glove box filled with argon. The mass ratio of the ball to the material is 10:1, the rotating speed is 250r/min, the ball milling time is 5.2h, and the machine is stopped for 10min for heat dissipation every 1 h.
And S4, putting the mixture into a hard alloy die for prepressing, wherein the prepressing pressure is 400MPa, and the prepressing is carried out for 2 min. And after prepressing, annealing the prepressed piece at 500 ℃ for 30 min. Then carrying out vacuum hot-pressing sintering, wherein the vacuum degree is 40Pa, the sintering pressure is 50MPa, the sintering temperature is 1300 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 30 min. Then cooling and releasing pressure to prepare the superfine tungsten carbide hard alloy. And after sintering, annealing the hard alloy sintered body at 600 ℃ for 60 min.
And (3) grinding and polishing the sintered tungsten carbide hard alloy sample, and then carrying out structure and performance detection, wherein the technical parameters of the obtained sintered body are shown in a table 30.
TABLE 30 PERFORMANCE PARAMETERS AND SPECIFIC NUMERALS OF TUNGSTEN CARBIDE HARD ALLOY IN EXAMPLE 10
It is clear from examples 1, 2 and 3 that the sintering temperature is increased, the hardness is slightly decreased, the toughness is increased, and the frictional wear performance at room temperature and 500 ℃ is improved. As is clear from examples 1, 3 and 4, the combination properties are good when the pre-pressing pressure is high and the pre-pressing time is long. As is clear from examples 8, 9 and 10, the heat retention time was prolonged, the hardness was slightly lowered, the toughness was increased, and the frictional wear properties at room temperature and 500 ℃ were improved. As is clear from examples 1, 3, 5 and 7, the powder annealing temperature and the annealing time have little influence on the performance. From examples 2, 4, 6 and 9, it is clear that the overall performance is better when the bulk annealing temperature is lower and the annealing time is shorter.
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. A preparation method of superfine tungsten carbide hard alloy taking high-entropy alloy as a binder phase is characterized by comprising the following steps:
s1, preparing nanometer five-component high-entropy alloy powder: mixing five components of Co, Cr, Ni, Cu and Fe in a glove box filled with argon, and loading the mixture into a WC hard alloy ball milling tank, wherein the molar ratio of each component is 1-1.5, 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 30-60 h, the machine is stopped for 30min for heat dissipation every 10h, the machine is stopped every 10h to scrape off and mix the raw materials adhered to the grinding balls and the inner wall of the tank uniformly, then 0.2ml/10g of an absolute ethyl alcohol dispersing agent of mixed powder is added for continuous ball milling, and the fine nano five-component high-entropy alloy powder with the granularity of 150nm is prepared;
s2, preparing nano 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 300-450 r/min, the ball milling time is 20-40 h, and the machine is stopped for 30min every 10h to carry out heat dissipation to prepare nano WC powder with the fineness of 150 nm;
s3, mixing materials: weighing 5-30 wt.% of nanometer five-component high-entropy alloy powder prepared in the step S1 in a glove box filled with argon, adding the nanometer five-component high-entropy alloy powder into the nanometer WC powder prepared in the step S2, and then performing ball milling and mixing, wherein the mass ratio of balls to materials is 5: 1-10: 1, the rotating speed is 250-350 r/min, the ball milling time is 2-6 h, and the glove box is shut down for 10min for heat dissipation every 1 h;
s4: preparing by vacuum hot-pressing sintering: prepressing the mixture prepared in the step S3 at 200-400 MPa for 1-3 minutes, annealing the prepressed piece at 300-500 ℃ after prepressing, keeping the temperature for 10-30 min, then carrying out vacuum hot-pressing sintering at the vacuum degree of 40Pa and the sintering pressure of 40-50 MPa, the sintering temperature of 1200-1400 ℃, the heating rate of 10-30 ℃/min and the heat preservation time of 10-30 min, then cooling and releasing the pressure to prepare the superfine tungsten carbide hard alloy, and carrying out annealing treatment at 350-600 ℃ on the hard alloy sintered body after sintering, keeping the temperature for 20-60 min to prepare the superfine tungsten carbide hard alloy taking high entropy as a binder phase.
2. The preparation method of the ultrafine tungsten carbide hard alloy with the high-entropy alloy as the binder phase according to claim 1, is characterized in that:
the purities of the Co, Cr, Ni, Cu and Fe powders are all more than 99 percent,
wherein the particle size of the Co powder is 1-3 μm,
the grain diameter of Cr powder is less than 75 μm, and the grain diameters of Ni powder, Cu powder and Fe powder are all less than 45 μm.
3. The preparation method of the ultrafine tungsten carbide hard alloy with the high-entropy alloy as the binder phase according to claim 1, is characterized in that:
the WC powder has the grain diameter of 1-3 mu m and the purity of more than 99 percent.
4. The preparation method of the ultrafine tungsten carbide hard alloy with the high-entropy alloy as the binder phase according to claim 1, is characterized in that:
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, and the mass ratio of the large, medium and small WC hard alloy balls is 3:1: 1.
5. The preparation method of the ultrafine tungsten carbide hard alloy with the high-entropy alloy as the binder phase according to claim 1, is characterized in that:
the specific sintering process in step S4 is: firstly, applying pressure to a sample to 40-50 MPa; then, the vacuum degree is pumped to 40 Pa; then, heating from room temperature to 1000 ℃ at a heating rate of 20 ℃/min, and preserving the heat at 1000 ℃ for 20 min; and then heating the alloy to 1200-1400 ℃ from 1000 ℃ at a heating rate of 10-30 ℃/min, preserving heat for 10-30 min, cooling the alloy along with a furnace to obtain a blank, and carrying out surface grinding and deburring treatment on the prepared blank to obtain the superfine tungsten carbide hard alloy taking the high-entropy alloy as a binding phase.
6. The superfine tungsten carbide hard alloy prepared by the preparation method according to any one of claims 1 to 5 and taking the high-entropy alloy as a binder phase is characterized in that: the raw material formula comprises five nano-component high-entropy alloy of Co, Cr, Ni, Cu and Fe and nano WC powder, the molar ratio range of each component in the five-component high-entropy alloy of Co, Cr, Ni, Cu and Fe is 1-1.5, and the hard alloy comprises the following components in percentage by mass: the five-component high-entropy alloy powder accounts for 5-30 wt% of the total system, and the balance is WC.
7. The ultra-fine tungsten carbide hard alloy with high entropy alloy as binder phase according to claim 6, characterized in that: the grain diameter of the nanometer five-component high-entropy alloy powder is 150nm or less; the grain diameter of the nanometer WC is 150nm so as to be fine, and the purity is more than 99%.
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| CN112941391A (en) * | 2020-12-31 | 2021-06-11 | 厦门钨业股份有限公司 | NbC-containing high-density composite metal ceramic material and preparation method thereof |
| CN114309627A (en) * | 2022-03-15 | 2022-04-12 | 中南大学 | Preparation method of low-oxygen-content refractory high-entropy alloy powder |
| CN115011827A (en) * | 2022-05-11 | 2022-09-06 | 北京工业大学 | NbMoTaWCu high-entropy alloy and preparation method thereof |
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