CN114774750A - Tungsten carbide material bonded by enhanced high-entropy alloy and preparation method thereof - Google Patents
Tungsten carbide material bonded by enhanced high-entropy alloy and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 132
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 129
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 35
- 239000010941 cobalt Substances 0.000 claims abstract description 35
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 33
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 33
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 23
- 239000011651 chromium Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims description 103
- 238000005245 sintering Methods 0.000 claims description 49
- 239000011812 mixed powder Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- VRKNSQQFHRIXPD-UHFFFAOYSA-N chromium cobalt iron nickel Chemical compound [Fe][Ni][Cr][Co] VRKNSQQFHRIXPD-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 18
- 238000002490 spark plasma sintering Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 description 8
- 238000000713 high-energy ball milling Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- LGRDPUAPARTXMG-UHFFFAOYSA-N bismuth nickel Chemical compound [Ni].[Bi] LGRDPUAPARTXMG-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- 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
- 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
- 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
-
- 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
-
- 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
- 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
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
-
- 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
Abstract
The invention discloses a tungsten carbide material bonded by enhanced high-entropy alloy and a preparation method thereof, wherein the tungsten carbide material comprises the enhanced high-entropy alloy and tungsten carbide; the reinforced high-entropy alloy is used as a binding phase, the high-entropy alloy used as the binding phase is selected to be 0.5-40 parts and the tungsten carbide is selected to be 60-99.5 parts according to 100 parts by weight of the total weight of the reinforced high-entropy alloy, the reinforced high-entropy alloy comprises the following components in parts by weight: 5-30 parts of cobalt, 5-30 parts of nickel, 5-30 parts of iron, 5-30 parts of chromium, 0.1-10 parts of aluminum and 0.1-10 parts of bismuth. The tungsten carbide material prepared by the invention has excellent hardness, toughness and high-temperature hardness; the invention not only can reduce the preparation cost of the tungsten carbide material, but also effectively expands the application range of the tungsten carbide material, and the tungsten carbide material is suitable for being used as a cutter, a die and a wear-resistant part.
Description
Technical Field
The invention relates to a tungsten carbide (WC) material and a preparation method thereof, in particular to a tungsten carbide material bonded by enhanced high-entropy alloy cobalt, nickel, iron and chromium and a preparation method thereof.
Background
Tungsten carbide cemented carbide is widely used as tools, dies and wear parts due to its high hardness and high wear resistance. The existing tungsten carbide hard alloy material mainly comprises matrix tungsten carbide, binder phase cobalt and the like, however, because cobalt resources are relatively scarce in China and the high-temperature strength, the high-temperature creep resistance and the corrosion resistance of the cobalt are relatively low, the application of the tungsten carbide hard alloy taking the cobalt as the binder phase is limited to a certain extent; and the main preparation method comprises the following steps: after preforming, sintering is carried out by adopting methods such as radiation heating sintering, hot isostatic pressing sintering and the like, and the sintering methods have longer sintering time and are easy to grow tungsten carbide grains, so that the performance of the alloy in a sintering state is weakened.
The first article on high-entropy alloy was published by the professor of the university of Qinghua in Taiwan, China on the international journal "Advanced Engineering Materials", and because the high-entropy alloy is a multi-principal-element alloy, the material system is rich, and the structure is special, and generally has more excellent performance than the same system alloy, the interest of researchers is aroused. In recent years, the research heat of high-entropy alloys is rising year by year, more and more high-entropy alloy systems are developed, and the alloys generally have excellent mechanical properties at room temperature, high temperature and low temperature and high wear resistance and corrosion resistance, so that the high-entropy alloys have great potential application value in multiple aspects.
201910775800.3 discloses an ultra-fine grain high-entropy metal ceramic composite material and a preparation method thereof, wherein the composite material is prepared by taking (MoTiWTaZr) C high-entropy ceramic as a hard phase and FeCoCrNiAl high-entropy alloy as a metal binding phase; the method specifically comprises the steps of performing high-energy ball milling on five carbide powders of molybdenum carbide, titanium carbide, tungsten carbide, tantalum carbide and zirconium carbide to form high-entropy ceramic powder, performing high-energy ball milling on five metal powders of iron, cobalt, chromium, nickel and aluminum to form single-phase solid solution high-entropy alloy powder, mechanically mixing the high-entropy ceramic powder and the high-entropy alloy powder, and performing discharge plasma sintering to obtain the ultrafine-crystal high-entropy metal ceramic composite material, wherein the comprehensive performance of the obtained composite material is obviously improved. Although it is improved to some extent, it still needs to be developed in the whole.
Disclosure of Invention
In order to solve the technical problems, the invention provides a tungsten carbide material bonded by an enhanced high-entropy alloy and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the tungsten carbide material bonded by the enhanced high-entropy alloy comprises the enhanced high-entropy alloy and tungsten carbide, wherein the enhanced high-entropy alloy is used as a bonding phase, the high-entropy alloy used as the bonding phase is selected to be 0.5-40 parts and the tungsten carbide is selected to be 60-99.5 parts according to 100 parts by weight of the sum of the parts by weight, and the enhanced high-entropy alloy comprises cobalt, nickel, iron, chromium, aluminum and bismuth.
The reinforced high-entropy alloy comprises the following components in parts by weight and 100 parts by weight: 5-30 parts of cobalt, 5-30 parts of nickel, 5-30 parts of iron, 5-30 parts of chromium, 0.1-10 parts of aluminum and 0.1-10 parts of bismuth.
A preparation method of a tungsten carbide material bonded by an enhanced high-entropy alloy comprises the following steps:
step one, designing components of the enhanced high-entropy alloy:
cobalt powder, nickel powder, iron powder, chromium powder, aluminum powder and bismuth powder are mixed according to the following weight portions: 5-30 parts of cobalt, 5-30 parts of nickel, 5-30 parts of iron, 5-30 parts of chromium, 0.1-10 parts of aluminum and 0.1-10 parts of bismuth;
step two, preparing the enhanced high-entropy alloy powder:
feeding the raw material powder, and performing ball milling treatment by using ball milling equipment until enhanced high-entropy alloy powder is obtained;
step three: preparing tungsten carbide powder and enhanced high-entropy alloy powder:
preparing tungsten carbide powder and the enhanced high-entropy alloy powder prepared in the first step according to the following parts by weight: 60-99.5 parts of tungsten carbide powder and 0.5-40 parts of enhanced high-entropy alloy powder;
step four: powder mixing and sieving:
mixing tungsten carbide powder and enhanced high-entropy alloy powder by a mixer, and then filtering and screening to obtain mixed powder;
step five: spark plasma sintering of mixed powder:
and performing discharge plasma sintering and molding on the mixed powder to obtain the tungsten carbide material which has tungsten carbide crystal grains with the size of 0.1-10 mu m, is uniformly distributed around WC crystal grains and is bonded by enhanced high-entropy alloy cobalt-nickel-iron-chromium.
In the fourth step, after filtering and screening, the particle size of the mixed powder is less than or equal to 250 mu m.
In the spark plasma sintering process, the sintering process conditions are as follows: type of sintering current: a direct current pulse current; sintering pressure: 30-50 Mpa; sintering heating rate: 50-300 ℃/min; sintering temperature: 1200-1400 ℃; sintering and heat preservation time: 1-20 min; sintering vacuum degree: less than or equal to 4Pa, and preserving heat after reaching the set sintering temperature.
The purity of the cobalt, nickel, aluminum and bismuth powder is more than or equal to 99.9 percent, the granularity is 1-3 mu m, and the purity of the iron and chromium powder is more than or equal to 99.0 percent, and the granularity is 0.6-3 mu m.
And the ball milling treatment in the second step is to perform ball milling in a planetary ball mill, wherein the material of the milling balls is WC hard alloy, and inert gas is used as protective atmosphere.
The inert gas is Ar gas.
In the discharge plasma sintering process, heating at a constant heating rate to raise the temperature; or heating and raising the temperature in a multi-stage way at a plurality of different heating rates.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the traditional tungsten carbide-cobalt hard alloy, the high-strength tungsten carbide-cobalt hard alloy has good strength, higher hardness and more excellent fracture toughness at room temperature, and particularly has more excellent red hardness, strength, creep resistance and the like at high temperature. The method can be widely applied to processing tools, in particular to manufacturing special cutters such as micro drill bits, shield machine cutter heads and the like with high requirements on the toughness and the high temperature resistance of materials.
2. The enhanced high-entropy alloy cobalt-nickel-iron-chromium is used for replacing the traditional cobalt as a binding phase, so that the comprehensive performance is excellent, and the cost of the tungsten carbide hard alloy material can be effectively reduced because the overall price of the raw materials used by the high-entropy alloy is lower than that of the cobalt, thereby improving the cost performance and having better popularization and application prospects.
3. The discharge plasma sintering technology adopted by the invention is simple and convenient in process, and can inhibit the growth of tungsten carbide grains due to the short sintering time, and simultaneously avoid the performance deterioration caused by the structural transformation of the high-entropy alloy, thereby improving the mechanical property of the sintered tungsten carbide material.
Detailed Description
The embodiments of the present invention will be described in detail below, it should be noted that the contents set forth in the following examples are not intended to limit the present invention, although the present invention is described in detail with reference to the examples. It will be understood and appreciated by those of ordinary skill in the art that changes may be made in accordance with the circumstances and where appropriate.
The tungsten carbide material bonded by the enhanced high-entropy alloy comprises the enhanced high-entropy alloy and tungsten carbide, wherein the enhanced high-entropy alloy is used as a bonding phase, the tungsten carbide is used as a hard phase, and according to the sum of 100 parts by weight, the high-entropy alloy used as the bonding phase is selected to be 0.5-40 parts, and the tungsten carbide is selected to be 60-99.5 parts. The enhanced high-entropy alloy comprises the components of cobalt, nickel, iron, chromium, aluminum and bismuth. In the enhanced high-entropy alloy, the total weight of the alloy is 100 parts, and the alloy comprises 5-30 parts of cobalt, 5-30 parts of nickel, 5-30 parts of iron, 5-30 parts of chromium, 0.1-10 parts of aluminum and 0.1-10 parts of bismuth. As bismuth and nickel can form a bismuth-nickel intermetallic compound, namely a new hard phase is formed in the high-entropy alloy matrix, and the hard phase has higher hardness and high-temperature hardness, the hardness and the high-temperature softening resistance of the high-entropy alloy are improved. Compared with the tungsten carbide material bonded by the high-entropy alloy cobalt, nickel, iron and chromium, the high-temperature hardness of the tungsten carbide material bonded by the enhanced high-entropy alloy can be improved by 5-30%.
The enhanced high-entropy alloy cobalt-nickel-iron-chromium replaces the traditional cobalt to serve as a binding phase, so that the overall performance is excellent, and the cost of the tungsten carbide hard alloy material can be effectively reduced because the overall price of the raw materials used by the high-entropy alloy is lower than that of the cobalt.
Room temperature hereinafter refers to a temperature of 20-30 degrees celsius and elevated temperatures are in the range of greater than 80 degrees celsius.
Example 1
The method comprises the following steps: designing the components of the enhanced high-entropy alloy:
mixing cobalt powder, nickel powder, iron powder, chromium powder, aluminum powder and bismuth powder according to the following weight parts: 25 parts of cobalt, 25 parts of nickel, 25 parts of iron, 23.9 parts of chromium, 1 part of aluminum and 0.1 part of bismuth; the purity of the cobalt, nickel, aluminum and bismuth powders was 99.9% with a particle size of 1 μm, and the purity of the iron and chromium powders was 99.5% with a particle size of 1 μm.
Step two: preparing enhanced high-entropy alloy powder:
feeding the raw material powder into a planetary ball mill for high-energy ball milling according to the set weight part dosage, wherein the grinding ball is made of WC hard alloy, and the ball-material ratio is 10: 1, ball milling at 266r/min, and adopting high-purity Ar gas as protective atmosphere; the ball milling time is 60 hours, and the powder is a single FCC phase and is in a high entropy state.
Step three: preparing tungsten carbide powder and enhanced high-entropy alloy powder:
preparing the tungsten carbide powder and the enhanced high-entropy alloy powder prepared in the second step according to the following weight parts: 80 parts of tungsten carbide and 20 parts of enhanced high-entropy alloy powder; the purity of WC powder is 99.0%, and the granularity is 800 nm.
Step four: powder mixing and sieving:
the prepared materials are mixed by a V-shaped mixer and then sieved to obtain mixed powder with the particle size of 250 mu m.
Step five: spark plasma sintering of mixed powder:
weighing 24g of the mixed powder, putting the weighed mixed powder into a graphite sintering mold with the diameter of phi 20mm, and performing spark plasma sintering, wherein the sintering pressure is 30MPa, the sintering temperature is 1200 ℃, the heating rate is 100 ℃/min, the heat preservation time is 5min, the vacuum degree is 4Pa, and the heat preservation is started after the temperature reaches 1200 ℃. The bulk tungsten carbide material bonded by the enhanced high-entropy alloy cobalt-nickel-iron-chromium is obtained by rapid sintering, the structure of the bulk tungsten carbide material is fine and uniform, the bulk tungsten carbide material contains 20% of the enhanced high-entropy alloy of the bonding phase, and the mass percentage of the enhanced high-entropy alloy is the proportion of the enhanced high-entropy alloy in the whole tungsten carbide material. The room temperature hardness and the high temperature hardness of the prepared bulk tungsten carbide material in a sintered state are HV 2135 and HV 1742 respectively, and the average size of WC crystal grains is 1 mu m.
Example 2
The method comprises the following steps: the composition design of the enhanced high-entropy alloy comprises the following steps:
mixing cobalt powder, nickel powder, iron powder, chromium powder, aluminum powder and bismuth powder according to the following weight parts: 5 parts of cobalt, 30 parts of nickel, 30 parts of iron, 15 parts of chromium, 10 parts of aluminum and 10 parts of bismuth; the purity of the cobalt, nickel, aluminum and bismuth powders was 99.93% with a particle size of 1.5 μm, and the purity of the iron and chromium powders was 99.6% with a particle size of 1.5 μm.
Step two: preparing enhanced high-entropy alloy cobalt-nickel-iron-chromium powder:
according to the weight parts of the raw material powder, the raw material powder is fed into a planetary ball mill for high-energy ball milling, the material of the grinding ball is WC hard alloy, and the ball-material ratio is 10: 1, ball milling at 266r/min, and adopting high-purity Ar gas as protective atmosphere; the ball milling time is 40 hours, and the powder is a single FCC phase and is in a high entropy state.
Step three: preparing tungsten carbide powder and enhanced high-entropy alloy cobalt-nickel-iron-chromium powder:
preparing the tungsten carbide powder and the enhanced high-entropy alloy powder prepared in the step two according to the following weight part ratio: 60 parts of tungsten carbide and 40 parts of enhanced high-entropy alloy powder; the purity of WC powder is 99.5%, and the granularity is 850 nm.
Step four: powder mixing and sieving:
the above prepared materials were mixed by a V-type blender mixer and then sieved to obtain a mixed powder having a particle size of 240 μm.
Step five: spark plasma sintering of mixed powder:
and weighing 24g of the mixed powder, putting the weighed mixed powder into a graphite sintering mold with the diameter phi of 20mm, and performing spark plasma sintering, wherein the sintering pressure is 50MPa, the sintering temperature is 1250 ℃, the temperature rise rate is 300 ℃/min, the heat preservation time is 1min, and the vacuum degree is 4 Pa. The bulk tungsten carbide material bonded by the enhanced high-entropy alloy cobalt-nickel-iron-chromium is obtained through rapid sintering, wherein the bulk tungsten carbide material has fine and uniform tissue, contains 40% of bonding phase enhanced high-entropy alloy cobalt-nickel-iron-chromium, and is the mass percentage, namely the proportion of the enhanced high-entropy alloy in the whole tungsten carbide material. The room temperature hardness and the high temperature hardness of the prepared bulk tungsten carbide material in a sintered state are HV 2036 and HV 1643 respectively, and the average size of WC crystal grains is 1.2 mu m.
Example 3
The method comprises the following steps: designing the components of the enhanced high-entropy alloy:
cobalt powder, nickel powder, iron powder, chromium powder, aluminum powder and bismuth powder are mixed according to the following weight parts: 30 parts of cobalt, 5 parts of nickel, 25 parts of iron, 30 parts of chromium, 0.1 part of aluminum and 9.9 parts of bismuth; the purity of the cobalt, nickel, aluminum and bismuth powders was 99.96% with a particle size of 2 μm, and the purity of the iron and chromium powders was 99.6% with a particle size of 1.5 μm.
Step two: preparing enhanced high-entropy alloy powder:
according to the weight parts of the raw material powder, feeding the raw material powder into a planetary ball mill for high-energy ball milling, wherein the grinding ball is made of WC hard alloy, and the ball-material ratio is 10: 1, ball milling at 266r/min, and adopting high-purity Ar gas as protective atmosphere; the ball milling time was 42 hours, at which point the powder was a single FCC phase in a high entropy state.
Step three: preparing tungsten carbide powder and enhanced high-entropy alloy powder:
preparing the tungsten carbide powder and the enhanced high-entropy alloy powder prepared in the second step according to the following weight parts: 90 parts of tungsten carbide and 10 parts of enhanced high-entropy alloy cobalt-nickel-iron-chromium powder; the purity of WC powder is 99.5%, and the granularity is 850 nm.
Step four: powder mixing and sieving:
the prepared materials are mixed by a V-shaped mixer and then sieved to obtain mixed powder with the particle size of 235 mu m.
Step five: spark plasma sintering of mixed powder:
and weighing 24g of the mixed powder, putting the weighed mixed powder into a graphite sintering mold with the diameter phi of 20mm, and performing spark plasma sintering, wherein the sintering pressure is 30MPa, the sintering temperature is 1300 ℃, the heating rate is 50 ℃/min, the heat preservation time is 20min, and the vacuum degree is 4 Pa. The bulk tungsten carbide material bonded by the enhanced high-entropy alloy cobalt-nickel-iron-chromium is obtained through rapid sintering, wherein the bulk tungsten carbide material has fine and uniform tissue, contains 10% of bonding phase enhanced high-entropy alloy cobalt-nickel-iron-chromium, and is the mass percentage, namely the proportion of the enhanced high-entropy alloy in the whole tungsten carbide material. The room temperature hardness and the high temperature hardness of the prepared sintered bulk tungsten carbide material are HV 2240 and HV 1798 respectively, and the average size of WC crystal grains is 1.2 mu m.
Example 4
The method comprises the following steps: designing the components of the enhanced high-entropy alloy:
cobalt powder, nickel powder, iron powder, chromium powder, aluminum powder and bismuth powder are mixed according to the following weight parts: 30 parts of cobalt, 25 parts of nickel, 20 parts of iron, 5 parts of chromium, 10 parts of aluminum and 10 parts of bismuth; the purity of the cobalt, nickel, aluminum and bismuth powders was 99.98% with a particle size of 3 μm, and the purity of the iron and chromium powders was 99.7% with a particle size of 3 μm.
Step two: preparing enhanced high-entropy alloy powder:
according to the weight parts of the raw material powder, the raw material powder is fed into a planetary ball mill for high-energy ball milling, the material of the grinding ball is WC hard alloy, and the ball-material ratio is 10: 1, ball milling at 266r/min, and adopting high-purity Ar gas as protective atmosphere; the ball milling time is 45 hours, and the powder is a single FCC phase and is in a high entropy state.
Step three: preparing tungsten carbide powder and enhanced high-entropy alloy powder:
preparing the tungsten carbide powder and the enhanced high-entropy alloy powder prepared in the step two according to the following weight part ratio: 99.5 parts of tungsten carbide, 0.5 part of enhanced high-entropy alloy cobalt-nickel-iron-chromium powder and the balance of inevitable trace impurities; the purity of WC powder is 99.5%, and the granularity is 750 nm.
Step four: powder mixing and sieving:
the above prepared materials were mixed by a V-type mixer and then sieved to obtain a mixed powder having a particle size of 220 μm.
Step five: spark plasma sintering of mixed powder:
and weighing 24g of the mixed powder, putting the weighed mixed powder into a graphite sintering mold with the diameter phi of 20mm, and performing spark plasma sintering, wherein the sintering pressure is 30MPa, the sintering temperature is 1400 ℃, the temperature rise rate is 50 ℃/min, the heat preservation time is 15min, and the vacuum degree is 4 Pa. The bulk tungsten carbide material bonded by the enhanced high-entropy alloy cobalt-nickel-iron-chromium is obtained by rapid sintering, the structure of the bulk tungsten carbide material is fine and uniform, wherein the bulk tungsten carbide material contains 0.5% of bonding phase enhanced high-entropy alloy cobalt-nickel-iron-chromium, and the mass percentage is the proportion of the enhanced high-entropy alloy in the whole tungsten carbide material. The room temperature hardness and the high temperature hardness of the prepared bulk tungsten carbide material in a sintered state are HV 2356 and HV 1878 respectively, and the average size of WC crystal grains is 1.5 mu m.
Example 5
The method comprises the following steps: the composition design of the enhanced high-entropy alloy comprises the following steps:
mixing cobalt powder, nickel powder, iron powder, chromium powder, aluminum powder and bismuth powder according to the following weight parts: 23 parts of cobalt, 28 parts of nickel, 5 parts of iron, 26 parts of chromium, 9 parts of aluminum and 9 parts of bismuth; the purity of the cobalt, nickel, aluminum and bismuth powders was 99.99% with a particle size of 1 μm, and the purity of the iron and chromium powders was 99.8% with a particle size of 2 μm.
Step two: preparing enhanced high-entropy alloy powder:
according to the weight parts of the raw material powder, the raw material powder is fed into a planetary ball mill for high-energy ball milling, the material of the grinding ball is WC hard alloy, and the ball-material ratio is 10: 1, ball milling at 266r/min, and adopting high-purity Ar gas as protective atmosphere; the ball milling time is 40 hours, and the powder is a single FCC phase and is in a high entropy state;
step three: preparing tungsten carbide powder and enhanced high-entropy alloy powder:
preparing the tungsten carbide powder and the enhanced high-entropy alloy powder prepared in the step two according to the following weight percentage: 92 parts of tungsten carbide, 8 parts of enhanced high-entropy alloy cobalt-nickel-iron-chromium powder and the balance of inevitable trace impurities; the purity of WC powder is 99.5%, and the granularity is 800 nm.
Step four: powder mixing and sieving:
the prepared materials are mixed by a V-shaped mixer and then sieved to obtain mixed powder with the particle size of 210 mu m.
Step five: spark plasma sintering of mixed powder:
and weighing 24g of the mixed powder, filling the weighed mixed powder into a graphite sintering mold with the diameter phi of 20mm, and performing spark plasma sintering, wherein the sintering pressure is 30MPa, the sintering temperature is 1300 ℃, the heating rate is 80 ℃/min, 90 ℃/min and 100 ℃/min, heating is performed from room temperature to 500 ℃ at the heating rate of 80 ℃/min, then heating is performed to 800 ℃ at the heating rate of 90 ℃/min, then heating is performed to 1300 ℃ at the heating rate of 100 ℃/min, the heat preservation time is 10min, and the vacuum degree is 4 Pa. The bulk tungsten carbide material bonded by the enhanced high-entropy alloy cobalt nickel iron chromium with fine and uniform tissues is obtained by rapid sintering, wherein the bulk tungsten carbide material contains 8% of bonding phase enhanced high-entropy alloy cobalt nickel iron chromium, and the bonding phase enhanced high-entropy alloy cobalt nickel iron chromium is in mass percentage, namely the proportion of the enhanced high-entropy alloy in the whole tungsten carbide material. The room temperature hardness and the high temperature hardness of the prepared bulk tungsten carbide material in a sintered state are HV 2258 and HV 1814 respectively, and the average size of WC crystal grains is 1 mu m.
According to the invention, by adding the bismuth component material, as bismuth and nickel can form a bismuth-nickel intermetallic compound, a new hard phase is formed in the high-entropy alloy matrix, and the hard phase has higher hardness and high-temperature hardness, so that the hardness and high-temperature softening resistance of the high-entropy alloy are improved. Thus, for conventional tungsten carbide materials, the hardness of the hard phase formed without the addition of bismuth may not be as great as the overall hardness of the material with the addition of bismuth.
It should be noted that, although the present invention has been described in detail with reference to the embodiments, the technical solutions described in the foregoing embodiments or some of the technical features of the embodiments can be modified or replaced with equivalents by those skilled in the art, but any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The tungsten carbide material bonded by the enhanced high-entropy alloy is characterized by comprising the enhanced high-entropy alloy and tungsten carbide, wherein the enhanced high-entropy alloy is used as a bonding phase, the high-entropy alloy used as the bonding phase is selected from 0.5 to 40 parts and the tungsten carbide is selected from 60 to 99.5 parts according to 100 parts by weight of the enhanced high-entropy alloy, and the enhanced high-entropy alloy comprises cobalt, nickel, iron, chromium, aluminum and bismuth.
2. The tungsten carbide material bonded by the enhanced high-entropy alloy according to claim 1, wherein the components in the enhanced high-entropy alloy are as follows, and the sum of the components in parts by weight is 100: 5-30 parts of cobalt, 5-30 parts of nickel, 5-30 parts of iron, 5-30 parts of chromium, 0.1-10 parts of aluminum and 0.1-10 parts of bismuth.
3. A preparation method of a tungsten carbide material bonded by an enhanced high-entropy alloy is characterized by comprising the following steps:
step one, designing components of the enhanced high-entropy alloy:
cobalt, nickel, iron, chromium, aluminum and bismuth powder are mixed according to the following weight parts: 5-30 parts of cobalt, 5-30 parts of nickel, 5-30 parts of iron, 5-30 parts of chromium, 0.1-10 parts of aluminum and 0.1-10 parts of bismuth;
step two, preparing the enhanced high-entropy alloy powder:
feeding the raw material powder, and performing ball milling treatment by using ball milling equipment until enhanced high-entropy alloy powder is obtained;
step three: preparing tungsten carbide powder and enhanced high-entropy alloy powder:
preparing tungsten carbide powder and the enhanced high-entropy alloy powder prepared in the first step according to the following parts by weight: 60-99.5 parts of tungsten carbide powder and 0.5-40 parts of enhanced high-entropy alloy powder;
step four: powder mixing and sieving:
mixing tungsten carbide powder and enhanced high-entropy alloy powder by a mixer, and then filtering and screening to obtain mixed powder;
step five: spark plasma sintering of mixed powder:
and performing discharge plasma sintering and molding on the mixed powder to obtain the tungsten carbide material with tungsten carbide grains of 0.1-10 mu m size and high-entropy alloy binder uniformly distributed around the WC grains and bonded by enhanced high-entropy alloy cobalt-nickel-iron-chromium.
4. A method for preparing a tungsten carbide material bonded by an enhanced high-entropy alloy according to claim 3, wherein in the fourth step, after filtering and screening, the particle size of the mixed powder is less than or equal to 250 μm.
5. A method for preparing an enhanced high-entropy alloy-bonded tungsten carbide material according to claim 4, wherein in the spark plasma sintering process, the sintering process conditions are as follows: type of sintering current: direct current pulse current; sintering pressure: 30-50 Mpa; sintering heating rate: 50-300 ℃/min; sintering temperature: 1200-1400 ℃; sintering and heat preservation time: 1-20 min; sintering vacuum degree: not more than 4Pa, and preserving heat after reaching the set sintering temperature.
6. The preparation method of the tungsten carbide material bonded by the enhanced high-entropy alloy as claimed in claim 5, wherein the purity of the cobalt, nickel, aluminum and bismuth powder is not less than 99.9% and the particle size is 1-3 μm, and the purity of the iron and chromium powder is not less than 99.0% and the particle size is 0.6-3 μm.
7. The method for preparing the enhanced high-entropy alloy bonded tungsten carbide material according to claim 6, wherein the ball milling treatment in the second step is ball milling in a planetary ball mill, the material of the milling balls is WC hard alloy, and inert gas is used as protective atmosphere.
8. A method of producing an enhanced high entropy alloy bonded tungsten carbide material according to claim 7, wherein the inert gas is Ar gas.
9. A method of producing an enhanced high-entropy alloy-bonded tungsten carbide material according to any one of claims 3 to 8, wherein during the spark plasma sintering process, the temperature is raised at a constant heating rate.
10. A method for preparing an enhanced high-entropy alloy-bonded tungsten carbide material according to any one of claims 3-8, wherein the discharge plasma sintering process is performed by performing multi-stage heating at a plurality of different heating rates.
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| CN115383111A (en) * | 2022-08-26 | 2022-11-25 | 山东滨州华创金属有限公司 | Preparation process of multi-component energetic alloy material and multi-component energetic alloy material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020159914A1 (en) * | 2000-11-07 | 2002-10-31 | Jien-Wei Yeh | High-entropy multielement alloys |
| CN109161774A (en) * | 2018-11-23 | 2019-01-08 | 西安工业大学 | Haystellite and preparation method thereof by high-entropy alloy as binder |
| CN110499481A (en) * | 2019-09-30 | 2019-11-26 | 广东省智能制造研究所 | Alloy components and preparation method thereof |
| CN110964965A (en) * | 2019-12-25 | 2020-04-07 | 华南理工大学 | High-entropy alloy binding phase tungsten carbide hard alloy for water jet cutter and preparation method thereof |
| CN113396233A (en) * | 2019-01-04 | 2021-09-14 | 天纳克股份有限公司 | Hard powder particles with improved compressibility and green strength |
-
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- 2022-05-10 CN CN202210504377.5A patent/CN114774750A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020159914A1 (en) * | 2000-11-07 | 2002-10-31 | Jien-Wei Yeh | High-entropy multielement alloys |
| CN109161774A (en) * | 2018-11-23 | 2019-01-08 | 西安工业大学 | Haystellite and preparation method thereof by high-entropy alloy as binder |
| CN113396233A (en) * | 2019-01-04 | 2021-09-14 | 天纳克股份有限公司 | Hard powder particles with improved compressibility and green strength |
| CN110499481A (en) * | 2019-09-30 | 2019-11-26 | 广东省智能制造研究所 | Alloy components and preparation method thereof |
| CN110964965A (en) * | 2019-12-25 | 2020-04-07 | 华南理工大学 | High-entropy alloy binding phase tungsten carbide hard alloy for water jet cutter and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115383111A (en) * | 2022-08-26 | 2022-11-25 | 山东滨州华创金属有限公司 | Preparation process of multi-component energetic alloy material and multi-component energetic alloy material |
| CN115383111B (en) * | 2022-08-26 | 2023-12-19 | 山东滨州华创金属有限公司 | Preparation process of multi-component energy-containing alloy material and multi-component energy-containing alloy material |
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