CN115074590A - Refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy - Google Patents
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- 239000000956 alloy Substances 0.000 title claims abstract description 152
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 152
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 51
- 238000005245 sintering Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 10
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 44
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 238000001238 wet grinding Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 13
- 238000009837 dry grinding Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000007873 sieving Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- 238000002490 spark plasma sintering Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000003966 growth inhibitor Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011812 mixed powder Substances 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000011049 filling Methods 0.000 description 8
- 229910009043 WC-Co Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—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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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
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- 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
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- 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
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Abstract
The invention belongs to the technical field of hard alloys, and discloses a refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy and a preparation method thereof. The refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy takes a refractory high-entropy alloy as a binding phase and takes tungsten carbide as a hard phase; the refractory high-entropy alloy comprises at least five elements of Nb, Re, Mo, Sc, Ta and Y, and the atomic percent of each element is 5-30%. The method comprises the following steps: mixing refractory high-entropy alloy powder and WC powder, and then carrying out discharge plasma sintering molding to obtain the refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy. The tungsten carbide hard alloy has fine crystal grains and good comprehensive mechanical property; no crystal grain growth inhibitor is needed to be added; obviously reduces the consumption of cobalt and has high service temperature.
Description
Technical Field
The invention relates to a refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy and a preparation method thereof, belonging to the technical field of hard alloys.
Background
The hard alloy has high hardness, good high-temperature strength and fracture toughness, and is widely applied to industries such as metal cutting tools, drill bits, drawing dies and the like, thus being praised as 'industrial teeth'. Cemented carbides are produced by powder metallurgy processes from a hard phase that provides the cemented carbide with high hardness and a binder phase that provides it with toughness, and fracture toughness generally decreases with increasing hardness. In order to improve the comprehensive properties of cemented carbide and meet the requirements of development of aerospace industry and extreme service conditions, a great deal of research is carried out on the preparation of ultrafine/nanocrystalline cemented carbide and the development of novel binder phases. Although the preparation of the ultra-fine/nano-crystalline cemented carbide can improve the comprehensive performance of the cemented carbide, the process is complex, and the ultra-fine/nano-crystalline cemented carbide powder rapidly grows during the sintering process so that the ultra-fine/nano-crystalline characteristics are lost, thus a grain growth inhibitor needs to be added. On the other hand, although some new binder phases have been developed, cobalt, which is magnetic and toxic and a strategic resource, remains the most widely used binder phase at present, which is also a significant challenge in preparing new binder phases.
Therefore, in order to further improve the comprehensive mechanical property and the service temperature of the hard alloy and develop a binder phase with excellent performance capable of replacing Co, the invention provides a method for preparing the superfine tungsten carbide hard alloy with good comprehensive mechanical property by using the refractory high-entropy alloy as the binder phase and adopting spark plasma sintering.
Disclosure of Invention
In order to overcome the defects of the existing tungsten carbide hard alloy, the invention aims to provide the superfine tungsten carbide hard alloy with good comprehensive mechanical property and the preparation method thereof.
The bonding phase in the refractory high-entropy alloy bonding phase superfine tungsten carbide hard alloy is solid solution refractory high-entropy alloy, and WC is a hard phase. Co element can be completely replaced by adjusting the components and the content thereof in the refractory high-entropy alloy binding phase, and the comprehensive performance and the service temperature are improved. The invention utilizes the inhibition effect of the refractory high-entropy alloy on the growth of WC grains, can realize the preparation of the superfine tungsten carbide hard alloy without adding a grain growth inhibitor, and the hard alloy has good comprehensive mechanical properties.
The purpose of the invention is realized by the following technical scheme:
a refractory high-entropy alloy bonding phase superfine tungsten carbide hard alloy takes a refractory high-entropy alloy as a bonding phase and takes tungsten carbide (WC) as a hard phase; the refractory high-entropy alloy comprises at least five elements (components) of Nb, Re, Mo, Sc, Ta and Y, and the atomic percentage of each element is 5-30%.
The mass percentage of the refractory high-entropy alloy in the refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy is 5-20%.
The preparation method of the refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy comprises the following steps:
mixing refractory high-entropy alloy powder and WC powder, and then carrying out discharge plasma sintering molding to obtain the refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy. The sintering conditions are as follows: the sintering pressure is more than or equal to 40 MPa; the sintering temperature is 1450-1550 ℃.
The preparation method of the refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy specifically comprises the following steps of (1) preparing refractory high-entropy alloy powder by ball milling, uniformly mixing Nb, Re, Mo, Sc, Ta and Y powder according to a proportion, and carrying out ball milling to obtain refractory high-entropy alloy powder; the ball milling is carried out in an inert atmosphere, wherein the inert atmosphere is argon; the ball milling refers to dry milling and then wet milling, and drying is needed after wet milling;
(2) ball milling mixing material
Mixing refractory high-entropy alloy powder and WC powder uniformly, ball-milling and sieving to obtain a mixture; the ball milling is carried out in an inert atmosphere, wherein the inert atmosphere is argon; the ball milling refers to dry milling and then wet milling, and drying is needed after wet milling;
(3) spark plasma sintering forming
Prepressing the mixture obtained in the step (2), then placing the mixture in a discharge plasma sintering furnace for discharge plasma sintering, and cooling to obtain refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy; the sintering conditions are as follows: the sintering pressure is more than or equal to 40 MPa; the sintering temperature is 1450-1550 ℃.
And the sintering specifically comprises vacuumizing, adjusting sintering pressure, heating to 1050-1100 ℃, preserving heat, and continuously heating to 1450-1550 ℃ for heat preservation and sintering. And raising the temperature to 1050-1100 ℃, preferably raising the temperature to 1080 ℃, and preserving the heat. The heat preservation time is 2-3 min. And the time of the heat preservation sintering at 1450-1550 ℃ is 4-7 min.
Compared with the prior art, the invention has the following advantages and effects:
(1) the refractory high-entropy alloy bonding phase superfine tungsten carbide hard alloy adopts the refractory high-entropy alloy as the bonding phase, and Co can be partially or completely replaced by adjusting the components and the content thereof in the refractory high-entropy alloy bonding phase, so that the service temperature is improved while the performance of the hard alloy is ensured, and the requirement under an extreme service condition is met.
(2) The refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy adopts the refractory high-entropy alloy as the binding phase, and utilizes the inhibition effect of the refractory high-entropy alloy on the growth of WC grains in the sintering process, so that the superfine WC hard alloy can be obtained without adding a grain growth inhibitor.
(3) The refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy is solidified and formed by adopting a spark plasma sintering process. Because the spark plasma sintering has the advantages of high heating rate, short sintering time, low sintering temperature, high cooling rate and the like, the hard alloy with good density can be obtained by short-time sintering at lower sintering temperature, the growth of WC crystal grains in the sintering process can be obviously inhibited, and the comprehensive mechanical property of the hard alloy is effectively improved.
(4) According to the refractory high-entropy alloy bonding phase superfine tungsten carbide hard alloy, when 10 mass percent of NbReMoScTaY refractory high-entropy alloy is used as a bonding phase, under the process conditions that the sintering pressure is 40MPa, the sintering temperature is 1250 ℃ and the sintering time is 6 minutes, the WC average grain size of the hard alloy is 209nm, the Vickers hardness is 2610HV30, and the fracture toughness is 10.18 MPa-m 1/2 . Replacing the binder phase with 10% Re under the same process conditions 0.5 The MoScTaY refractory high-entropy alloy has the WC average grain size of 204nm, the Vickers hardness of 2650HV30 and the fracture toughness of 10.08 MPa-m 1/2 。
Drawings
FIG. 1 is an X-ray diffraction pattern of a binder phase ultrafine tungsten carbide hard alloy based on a refractory high-entropy alloy obtained in example 1;
FIG. 2 is a scanning electron microscope image of the ultra-fine tungsten carbide cemented carbide based on the refractory high-entropy alloy binder phase obtained in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy comprises the following steps:
1) nb, Re, Mo, Sc, Ta and Y powders with purity of more than 99.9% and average grain diameter of less than 45 μm are mixed according to a molar ratio
Weighing according to the ratio of 1:1:1:1:1, uniformly mixing, putting into a hard alloy ball milling tank, and putting into a hard alloy ball milling tank according to the ball-to-material ratio of 10:1
The process comprises the following steps of (1) carrying out mass alloy grinding ball, vacuumizing a ball milling tank, and filling high-purity argon; then carrying out dry milling for 40 hours at the rotating speed of 300 revolutions per minute, and then carrying out wet milling for 2 hours (the wet milling medium is ethanol) to obtain refractory high-entropy alloy powder; after the ball milling process is finished, putting the refractory high-entropy alloy powder into a vacuum drying oven, drying for 48 hours at the temperature of 80 ℃, sieving by a No. 300 sample sieve, and granulating;
2) placing 15g of the refractory high-entropy alloy powder obtained in the step 1) and 135g of WC powder with purity of more than 99.5% and average particle size of 0.8 μm into a tank, mixing the materials on a powder mixer for 5 hours, then carrying out dry grinding for 30 hours under the protection of argon gas, and then carrying out wet grinding for 2 hours; wherein the ball-material ratio during ball milling is 5:1, the wet milling medium is ethanol, and the rotation speed of the ball milling is 300 r/min; after the ball milling process is finished, putting the mixed powder into a vacuum drying oven for drying, sieving by a 100# sample sieve, and granulating to obtain mixed powder;
3) 25g of the mixed powder obtained in the step 2) is filled into a die cavity with a graphite die diameter of 20mm to be preliminarily pressed into a sample,
putting the sample into a discharge plasma sintering furnace, vacuumizing to less than 10Pa, adjusting the sintering pressure to 40MPa, and then adding 100 DEG C
Raising the temperature to 1080 ℃ at a temperature raising speed of less than ten minutes and preserving the heat for 3 minutes to facilitate the release of gas adsorbed in the powder, and raising the temperature to 1450 DEG C
Keeping the temperature for 6 minutes (the temperature rise speed is 100 ℃/min), and finally cooling to 100 ℃ along with the furnace to obtain the WC with the average grain size of 208nm and the Vickers hardness of 2630HV30, fracture toughness 10.04MPa m 1/2 The superfine tungsten carbide hard alloy based on the refractory high-entropy alloy binding phase. FIG. 1 is an X-ray diffraction pattern of a binder phase ultrafine tungsten carbide hard alloy based on a refractory high-entropy alloy obtained in example 1; FIG. 2 is a scanning electron microscope image of the ultra-fine tungsten carbide cemented carbide based on the refractory high-entropy alloy binder phase obtained in example 1.
Example 2
A preparation method of refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy comprises the following steps:
1) weighing Nb, Re, Mo, Sc, Ta and Y powder with the purity of more than 99.9 percent and the average grain diameter of less than 45 mu m according to the molar ratio of 1:1:1:1:1, uniformly mixing, putting into a hard alloy ball milling tank, filling into hard alloy grinding balls according to the ball-to-material ratio of 10:1, vacuumizing the ball milling tank, and filling high-purity argon; then carrying out dry milling for 40 hours at the rotating speed of 300 revolutions per minute, and then carrying out wet milling for 2 hours (the wet milling medium is ethanol) to obtain refractory high-entropy alloy powder; after the ball milling process is finished, putting the refractory high-entropy alloy powder into a vacuum drying oven, drying for 48 hours at the temperature of 80 ℃, sieving by a No. 300 sample sieve, and granulating;
2) 7.5g of the refractory high-entropy alloy powder of step 1) and 142.5g of a powder having a purity of more than 99.5% and an average particle size of 0.8 μm
Placing WC powder into a tank, mixing the WC powder for 5 hours on a powder mixer, then carrying out dry grinding for 30 hours under the protection of argon gas, and then carrying out wet grinding for 2 hours; wherein the ball-material ratio during ball milling is 5:1, the wet milling medium is ethanol, and the rotation speed of the ball milling is 300 r/min; after the ball milling process is finished, putting the mixed powder into a vacuum drying oven for drying, sieving by a 100# sample sieve, and granulating to obtain mixed powder;
3) weighing 25g of the mixed powder in the step 2), and filling the mixed powder into a die cavity with the diameter of 20mm of a graphite die to preliminarily press the mixed powder into a sample; putting the sample into a discharge plasma sintering furnace, pumping to vacuum of less than 10Pa, adjusting sintering pressure to 40MPa, heating to 1080 ℃ at a heating rate of 100 ℃/min, keeping the temperature for 3 minutes, facilitating the release of gas adsorbed in the powder, heating to 1450 ℃ (heating rate of 100 ℃/min), keeping the temperature for 6 minutes, and finally cooling to 100 ℃ along with the furnace to obtain the productWC average grain size is 223nm, Vickers hardness is 2670HV30, and fracture toughness is 9.54 MPa.m 1/2 The superfine tungsten carbide hard alloy based on the refractory high-entropy alloy binding phase.
Example 3
A preparation method of refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy comprises the following steps:
1) weighing Nb, Re, Mo, Sc, Ta and Y powder with the purity of more than 99.9 percent and the average grain diameter of less than 45 mu m according to the molar ratio of 0.5:1:1:1:1, uniformly mixing, putting into a hard alloy ball milling tank, putting into hard alloy grinding balls according to the ball-to-material ratio of 10:1, vacuumizing the ball milling tank, and filling high-purity argon; then carrying out dry milling for 40 hours at the rotating speed of 300 revolutions per minute, and then carrying out wet milling for 2 hours (the wet milling medium is ethanol) to obtain refractory high-entropy alloy powder; after the ball milling process is finished, putting the refractory high-entropy alloy powder into a vacuum drying oven, drying for 48 hours at the temperature of 80 ℃, sieving by a No. 300 sample sieve, and granulating;
2) placing 15g of the refractory high-entropy alloy powder obtained in the step 1) and 135g of WC powder with purity of more than 99.5% and average particle size of 0.8 μm into a tank, mixing the materials on a powder mixer for 5 hours, then carrying out dry grinding for 30 hours under the protection of argon gas, and then carrying out wet grinding for 2 hours; wherein the ball-material ratio during ball milling is 5:1, the wet milling medium is ethanol, and the rotation speed of the ball milling is 300 r/min; after the ball milling process is finished, putting the mixed powder into a vacuum drying oven for drying, sieving by a 100# sample sieve, and granulating to obtain mixed powder;
3) weighing 25g of the mixed powder obtained in the step 2), placing the mixed powder into a die cavity with a graphite die diameter of 20mm, primarily pressing the mixed powder into a sample, placing the sample into a discharge plasma sintering furnace, pumping the sample until the vacuum is less than 10Pa, adjusting the sintering pressure to 40MPa, heating to 1080 ℃ at the heating rate of 100 ℃/min, keeping the temperature for 2 minutes to facilitate the release of gas adsorbed in the powder, heating to 1550 ℃ (the heating rate is 100 ℃/min), keeping the temperature for 5 minutes, cooling to 100 ℃ along with the furnace to obtain the WC average grain size of 213nm, the Vickers hardness of 2680HV30, and the fracture toughness of 10.12 MPa.m 1/2 The superfine tungsten carbide hard alloy based on the refractory high-entropy alloy binding phase.
Example 4
A preparation method of refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy comprises the following steps:
1) nb, Re, Mo, Sc, Ta and Y powders with purity of more than 99.9% and average grain diameter of less than 45 μm are mixed according to a molar ratio
Weighing according to the ratio of 1.5:1:1:1:1, uniformly mixing, putting into a hard alloy ball milling tank, and filling into the hard alloy ball milling tank according to the ball-material ratio of 10:1
And (3) hard alloy grinding balls, wherein the ball milling tank is vacuumized and then filled with high-purity argon. Followed by dry milling at 300 rpm for 40 hours,
then carrying out wet milling for 2 hours (a wet milling medium is ethanol) to obtain refractory high-entropy alloy powder; after the ball milling process is finished, putting the refractory high-entropy alloy powder into a vacuum drying oven, drying for 48 hours at the temperature of 80 ℃, sieving by a No. 300 sample sieve, and granulating;
2) placing 15g of the refractory high-entropy alloy powder obtained in the step 1) and 135g of WC powder with purity of more than 99.5% and average particle size of 0.8 μm into a tank, mixing the materials on a powder mixer for 5 hours, then carrying out dry grinding for 30 hours under the protection of argon gas, and then carrying out wet grinding for 2 hours; wherein the ball-material ratio during ball milling is 5:1, the wet milling medium is ethanol, and the rotation speed of the ball milling is 300 r/min; after the ball milling process is finished, putting the mixed powder into a vacuum drying oven for drying, sieving by a 100# sample sieve, and granulating to obtain mixed powder;
3) weighing 25g of the mixed powder in the step 2), and filling the mixed powder into a die cavity with the diameter of 20mm of a graphite die to preliminarily press the mixed powder into a sample; putting the sample into a discharge plasma sintering furnace, pumping to vacuum of less than 10Pa, adjusting the sintering pressure to 40MPa, heating to 1080 ℃ at a heating rate of 100 ℃/min, keeping the temperature for 3 minutes to facilitate the release of gas adsorbed in the powder, heating to 1450 ℃ (heating rate of 100 ℃/min), keeping the temperature for 6 minutes, and finally cooling to 100 ℃ along with the furnace to obtain the product with the WC average grain size of 201nm, the Vickers hardness of 2610HV30 and the fracture toughness of 9.94 MPa.m 1/2 The superfine tungsten carbide hard alloy based on the refractory high-entropy alloy binding phase.
Comparative example
A preparation method of tungsten carbide hard alloy comprises the following steps:
1) weighing 15g and 135g of Co powder with the purity of more than 99.9 percent and the average grain diameter of less than 45 mu m and the purity of more than 99.5 percent,
placing WC powder with the average particle size of 0.8 μm into a tank, mixing on a powder mixer for 5 hours, then carrying out dry grinding for 30 hours under the protection of argon gas, and then carrying out wet grinding for 2 hours; wherein the ball-material ratio is 5:1, the wet grinding medium is ethanol, and the rotation speed of ball milling is 300 r/min; after the ball milling process is finished, putting the mixed powder into a vacuum drying oven for drying, sieving by a 100# sample sieve, and granulating to obtain mixed powder;
2) weighing 25g of the mixed powder obtained in the step 1), and filling the mixed powder into a mold cavity with the diameter of 20mm of a graphite mold for preliminary pressing to obtain a sample. Putting the sample into a discharge plasma sintering furnace, pumping to vacuum of less than 10Pa, adjusting sintering pressure to 40MPa, heating to 1080 ℃ at a heating rate of 100 ℃/min, keeping the temperature for 2 minutes, facilitating the release of gas adsorbed in the powder, heating to 1450 ℃ (heating rate of 100 ℃/min), keeping the temperature for 6 minutes, cooling to 100 ℃ along with the furnace to obtain WC average grain size of 443nm,
the Vickers hardness is 2490HV30, and the fracture toughness is 10.88MPa m 1/2 WC-Co cemented carbide of (1).
Under the same technological parameters, the WC average grain size of the WC-Co hard alloy is obviously larger than that of the superfine tungsten carbide hard alloy of the refractory high-entropy alloy binding phase, the Vickers hardness HV30 of the WC-Co hard alloy is obviously lower than that of the superfine tungsten carbide hard alloy of the refractory high-entropy alloy binding phase, and the fracture toughness of the WC-Co hard alloy is higher than that of the superfine tungsten carbide hard alloy of the refractory high-entropy alloy binding phase. Meanwhile, the comprehensive mechanical property of the superfine tungsten carbide hard alloy of the refractory high-entropy alloy binding phase is superior to that of commercial WC-Co hard alloy with the same granularity, for example, the WC-Co hard alloy with the report mark of Chen et al, EF05, has the Vickers hardness and the fracture toughness of 1900HV30 and 9.1 MPa.m 1/2 。
Claims (5)
1. A preparation method of refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy is characterized by comprising the following steps: the method comprises the following steps:
mixing refractory high-entropy alloy powder and WC powder, and then performing discharge plasma sintering molding to obtain refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy; the sintering specifically comprises vacuumizing, adjusting sintering pressure, heating to 1050-1100 ℃, preserving heat, and continuously heating to 1450-1550 ℃ for heat preservation sintering; the sintering pressure is more than or equal to 40 MPa; the heat preservation time is 2-3 min; the time of the heat preservation sintering at 1450-1550 ℃ is 4-7 min;
the refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy takes the refractory high-entropy alloy as a binding phase and takes tungsten carbide as a hard phase;
the refractory high-entropy alloy comprises at least five elements of Nb, Re, Mo, Sc, Ta and Y, and the atomic percent of each element is 5-30%.
2. The preparation method of the refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy according to claim 1, is characterized in that:
and heating to 1050-1100 ℃ and preserving heat, namely heating to 1080 ℃.
3. The preparation method of the refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy according to claim 1, is characterized in that:
the mass percentage of the refractory high-entropy alloy in the refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy is 5-20%.
4. The preparation method of the refractory high-entropy alloy binder phase superfine tungsten carbide hard alloy according to any one of claims 1 to 3, characterized by comprising the following steps: the method specifically comprises the following steps:
(1) preparing refractory high-entropy alloy powder by ball milling, uniformly mixing Nb, Re, Mo, Sc, Ta and Y powder according to a ratio, and carrying out ball milling to obtain refractory high-entropy alloy powder; the ball milling is carried out in an inert atmosphere;
(2) ball milling mixing material
Mixing refractory high-entropy alloy powder and WC powder uniformly, ball-milling and sieving to obtain a mixture; the ball milling is carried out in an inert atmosphere;
(3) spark plasma sintering forming
Prepressing the mixture obtained in the step (2), then placing the mixture in a spark plasma sintering furnace for spark plasma sintering, and cooling
But, obtaining the refractory high-entropy alloy binding phase superfine tungsten carbide hard alloy.
5. The preparation method of the refractory high-entropy alloy bonding phase superfine tungsten carbide hard alloy according to claim 4, is characterized in that:
the inert atmosphere in the step (1) is argon; the ball milling refers to dry milling and then wet milling, and drying is needed after wet milling;
the inert atmosphere in the step (2) is argon; the ball milling means dry milling and then wet milling, and drying is needed after wet milling.
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