CN116178030A - Silicon nitride ceramic containing high-entropy nitride and preparation method and application thereof - Google Patents
Silicon nitride ceramic containing high-entropy nitride and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 60
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 59
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 53
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 37
- 238000000498 ball milling Methods 0.000 claims abstract description 31
- 239000011812 mixed powder Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 15
- 238000007731 hot pressing Methods 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000007873 sieving Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- 229910052723 transition metal Inorganic materials 0.000 claims description 14
- 239000004677 Nylon Substances 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 229920001778 nylon Polymers 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 229910014299 N-Si Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
The invention belongs to the technical field of ceramics, and discloses a silicon nitride ceramic containing high-entropy nitride, a preparation method and application thereof, wherein the silicon nitride ceramic is prepared by mixing high-entropy nitride powder and Si 3 N 4 Powder, sintering aid Al 2 O 3 ‑Y 2 O 3 Adding ethanol and Si 3 N 4 Ball milling and mixing, drying and sieving the balls to obtain mixed powder; the mixed powder is heated to 1600-1800 ℃ under the protection atmosphere by the axial pressure of 30-100 MPa, and then the powder is obtained by hot-pressing sintering. The silicon nitride ceramic has high hardness, high toughness and high wear resistance, and can be applied to the field of ceramic cutters.
Description
Technical Field
The invention belongs to the technical field of structural ceramics, and particularly relates to silicon nitride ceramics containing high-entropy nitride, and a preparation method and application thereof.
Background
The high-entropy nitride is composed of transition metal elements of IV (Ti, zr, hf), V (V, nb, ta) and VI (Cr, mo, W) according to an equal molar ratio. High entropy nitrides have higher than transition metal monobasic nitridesIs described (see scientific reports,2020, 10:19874). Si (Si) 3 N 4 The ceramic has high hardness, high strength, wear resistance, oxidation resistance, good thermal shock resistance and mechanical impact resistance, si 3 N 4 Ceramics are widely used in the field of ceramic tools. Si (Si) 3 N 4 When ceramic is used as a tool material, tiN is usually added as a reinforcing phase to improve toughness, wear resistance and the like. However, si containing TiN reinforcing phase 3 N 4 When the ceramic cutter is used for cutting difficult-to-machine materials such as high-temperature alloy, the cutting life is short, and the hardness, toughness and wear resistance of the silicon nitride ceramic are required to be further improved.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide silicon nitride ceramics containing high-entropy nitride.
The invention also aims to provide a preparation method of the silicon nitride ceramic containing the high-entropy nitride.
It is still another object of the present invention to provide an application of the above silicon nitride ceramic containing high entropy nitride.
The aim of the invention is achieved by the following technical scheme:
a silicon nitride ceramic containing high-entropy nitride is prepared from high-entropy nitride powder and Si 3 N 4 Powder, sintering aid Al 2 O 3 -Y 2 O 3 Adding ethanol and Si 3 N 4 Ball milling and mixing, drying and sieving the balls to obtain mixed powder; the mixed powder is heated to 1600-1800 ℃ under the protection atmosphere by the axial pressure of 30-100 MPa, and then the powder is obtained by hot-pressing sintering.
Preferably, the high-entropy nitride powder is a nitride composed of five or more elements of group iv transition metal elements, group v transition metal elements and group vi transition metal elements in equimolar ratio.
More preferably, the group VI transition metal element is Ti, zr, hf; the V group transition metal element is V, nb and Ta; the VI group transition metal elements are Cr, mo and W.
Preferably, the grain diameter of the high-entropy nitride powder is 0.05-2 mu m, and the purity is 97-100 wt%; the Si is 3 N 4 The grain diameter of the powder is 0.1-2 mu m, and the purity is 98-100 wt%; the Al is 2 O 3 The grain diameter of the powder is 0.1-2 mu m, and the purity is 98-100 wt%; the Y is 2 O 3 The grain diameter of the powder is 0.1-2 mu m, and the purity is 98-100 wt%.
Preferably, the high-entropy nitride powder, si 3 N 4 Powder and Al 2 O 3 -Y 2 O 3 The mass ratio of (1-3) to (6-8) to 1, wherein Al 2 O 3 And Y 2 O 3 The mass ratio of (2-3) is (2-3).
Preferably, the high-entropy nitride powder, si 3 N 4 Powder, sintering aid Al 2 O 3 -Y 2 O 3 Total mass of (C) and Si 3 N 4 The mass ratio of the balls is (2-5): 1.
Preferably, the mesh size of the screen is 100-200 mesh; the rate of heating to 1600-1800 ℃ is 10-50 ℃/min, and the hot-pressing sintering time is 30-180 min.
Preferably, the protective atmosphere is nitrogen or argon; the density of the silicon nitride ceramic containing the high-entropy nitride is 95-100%.
The preparation method of the silicon nitride ceramic containing the high-entropy nitride comprises the following specific steps:
s1, high-entropy nitride powder and Si 3 N 4 Powder, al 2 O 3 -Y 2 O 3 Placing the powder in a nylon ball milling tank, adding ethanol and Si 3 N 4 Ball milling and mixing the balls, and drying to obtain mixed powder;
s2, filling the mixed powder into a graphite mold, and heating to 1600-1800 ℃ at a speed of 10-50 ℃/min under an axial pressure of 30-100 MPa in a nitrogen or argon atmosphere, and hot-pressing and sintering for 30-180 min to obtain the silicon nitride ceramic containing high-entropy nitride;
the silicon nitride ceramics containing high entropy nitride are applied to the field of cutters.
Compared with the prior art, the invention has the following beneficial effects:
1. the silicon nitride ceramic containing high-entropy nitride has higher hardness, higher toughness and better wear resistance than the traditional silicon nitride ceramic.
2. The silicon nitride ceramic containing high-entropy nitride has better cutting performance than the traditional TiN reinforced silicon nitride cutter, can be applied to the field of cutting cutters, and is used for cutting stone, steel materials, nonferrous metals, aluminum alloys, high-temperature alloys and the like.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
1.10wt% of high entropy nitride powder (Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) N (particle size 0.5 μm); 80wt% Si 3 N 4 (particle size 0.2 μm, purity 99 wt.%); 5wt% Al 2 O 3 (particle size 300nm, purity 99 wt.%); 5wt% Y 2 O 3 (particle size 500nm, purity 99 wt.%). Placing the mixed powder into a nylon ball milling tank, adding ethanol and Si 3 N 4 Ball is used as a ball milling medium, the mass ratio of ball materials is 4:1, the ball milling time is 12 hours, the rotating speed is 300r/min, and the ball milling rotary evaporation drying is carried out, and then a 100-mesh sieve is adopted to obtain mixed powder;
2. filling the mixed powder into a graphite mold, and placing the graphite mold in N 2 Under the atmosphere, the axial pressure of 50MPa is added, the temperature is increased to 1800 ℃ at the speed of 20 ℃/min, the heat is preserved for 60min, and the silicon nitride ceramics containing high-entropy nitride is prepared through hot-pressing sintering, and the molecular formula of the silicon nitride ceramics is (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 )N-Si 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the The density of the silicon nitride ceramic containing the high-entropy nitride is 97%, the hardness is 20.3GPa, and the silicon nitride ceramic containing the high-entropy nitride is brokenToughness of 7.9 MPa.m 1/2 。
Example 2
1.20wt% of high entropy nitride powder (Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) N (particle size 0.5 μm); 70wt% Si 3 N 4 (particle size 0.2 μm, purity 99 wt.%); 5wt% Al 2 O 3 (particle size 300nm, purity 99 wt.%); 5wt% Y 2 O 3 (particle size 500nm, purity 99 wt.%). Placing the mixed powder into a nylon ball milling tank, adding ethanol and Si 3 N 4 Ball is used as a ball milling medium, the mass ratio of ball materials is 4:1, the ball milling time is 12 hours, the rotating speed is 300r/min, and the ball milling rotary evaporation drying is carried out, and then a 100-mesh sieve is adopted to obtain mixed powder;
2. filling the mixed powder into a graphite mold, and placing the graphite mold in N 2 Under the atmosphere, the axial pressure of 50MPa is added, the temperature is increased to 1800 ℃ at the speed of 20 ℃/min, the heat is preserved for 60min, and the silicon nitride ceramics containing high-entropy nitride is prepared through hot-pressing sintering, and the molecular formula of the silicon nitride ceramics is (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 )N-Si 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the The density of the silicon nitride ceramic containing the high-entropy nitride is 98%, the hardness is 21.5GPa, and the fracture toughness is 8.3 MPa.m 1/2 。
Example 3
1.30wt% of high entropy nitride powder (Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) N (particle size 0.5 μm); 60wt% Si 3 N 4 (particle size 0.2 μm, purity 99 wt.%); 5wt% Al 2 O 3 (particle size 300nm, purity 99 wt.%); 5wt% Y 2 O 3 (particle size 500nm, purity 99 wt.%). Placing the mixed powder into a nylon ball milling tank, adding ethanol and Si 3 N 4 Ball is used as a ball milling medium, the mass ratio of ball materials is 4:1, the ball milling time is 12 hours, the rotating speed is 300r/min, and the ball milling rotary evaporation drying is carried out, and then a 100-mesh sieve is adopted to obtain mixed powder;
2. filling the mixed powder into a graphite mold, and placing the graphite mold in N 2 Under the atmosphere, the axial pressure of 50MPa is added, the temperature is increased to 1800 ℃ at the speed of 20 ℃/min, the heat is preserved for 60min, and the product is prepared through hot-pressing sinteringObtaining silicon nitride ceramics containing high-entropy nitride, the molecular formula of which is (Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 )N-Si 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the The density of the silicon nitride ceramic containing the high-entropy nitride is 99%, the hardness is 22.4GPa, and the fracture toughness is 8.7 MPa.m 1/2 。
Example 4
1.30wt% of high entropy nitride powder (Ti 0.2 Zr 0.2 Nb 0.2 Ta 0.2 Mo 0.2 ) N (particle size 0.5 μm); 60wt% Si 3 N 4 (particle size 0.2 μm, purity 99 wt.%); 5wt% Al 2 O 3 (particle size 300nm, purity 99 wt.%); 5wt% Y 2 O 3 (particle size 500nm, purity 99 wt.%). Placing the mixed powder into a nylon ball milling tank, adding ethanol and Si 3 N 4 Ball is used as a ball milling medium, the mass ratio of ball materials is 4:1, the ball milling time is 12 hours, the rotating speed is 300r/min, and the ball milling rotary evaporation drying is carried out, and then a 100-mesh sieve is adopted to obtain mixed powder;
2. filling the mixed powder into a graphite mold, and placing the graphite mold in N 2 Under the atmosphere, the axial pressure of 50MPa is added, the temperature is increased to 1800 ℃ at the speed of 20 ℃/min, the heat is preserved for 60min, and the silicon nitride ceramics containing high-entropy nitride is prepared through hot-pressing sintering, and the molecular formula of the silicon nitride ceramics is (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 )N-Si 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the The density of the silicon nitride ceramic containing the high-entropy nitride is 99%, the hardness is 23.5GPa, and the fracture toughness is 9.3 MPa.m 1/2 。
Comparative example 1
1.90wt％Si 3 N 4 (particle size 0.2 μm, purity 99 wt.%); 5wt% Al 2 O 3 (particle size 300nm, purity 99 wt.%); 5wt% Y 2 O 3 (particle size 500nm, purity 99 wt.%). Placing the mixed powder into a nylon ball milling tank, adding ethanol and Si 3 N 4 Ball is used as a ball milling medium, the mass ratio of ball materials is 4:1, the ball milling time is 12 hours, the rotating speed is 300r/min, and the ball milling rotary evaporation drying is carried out, and then a 100-mesh sieve is adopted to obtain mixed powder;
2. filling the mixed powder into a graphite mold, and placing the graphite moldN 2 Under the atmosphere, the axial pressure of 50MPa is added, the temperature is increased to 1800 ℃ at the speed of 20 ℃/min, the heat is preserved for 60min, and the silicon nitride ceramic Si is prepared through hot-pressing sintering 3 N 4 . The compactness of the silicon nitride ceramic is 99%, the hardness is 14.5GPa, and the fracture toughness is 7.2MPa m 1/2 。
Comparative example 2
1.30wt% TiN (particle size 0.3 μm, purity 99 wt.%); 60wt% of Si 3 N 4 (particle size 0.2 μm, purity 99 wt.%); 5wt% Al 2 O 3 (particle size 300nm, purity 99 wt.%); 5wt% Y 2 O 3 (particle size 500nm, purity 99 wt.%). Placing the mixed powder into a nylon ball milling tank, adding ethanol and Si 3 N 4 Ball is used as a ball milling medium, the mass ratio of ball materials is 4:1, the ball milling time is 12 hours, the rotating speed is 300r/min, and the ball milling rotary evaporation drying is carried out, and then a 100-mesh sieve is adopted to obtain mixed powder;
3. filling the mixed powder into a graphite mold, and placing the graphite mold in N 2 Under the atmosphere, the axial pressure of 50MPa is added, the temperature is raised to 1800 ℃ at the speed of 20 ℃/min, the heat is preserved for 60min, and the silicon nitride ceramic containing TiN phase is prepared through hot-pressing sintering. The density of the silicon nitride ceramic containing TiN phase is 99%, the hardness is 16GPa, and the fracture toughness is 8.3 MPa.m 1/2 。
As is clear from the above, the high-entropy nitride-containing silicon nitride ceramic of the present invention has a density of 97% or more, a hardness of 20.3GPa or more, and a fracture toughness of 7.9MPa m 1/2 The above; the silicon nitride ceramics containing high-entropy nitride of the present invention have significantly improved hardness and toughness compared to the silicon nitride ceramics of comparative example 1, and the silicon nitride ceramics containing TiN phase of comparative example 2 has better fracture toughness, but has significantly lower hardness than the silicon nitride ceramics containing high-entropy nitride of the present invention.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A silicon nitride ceramic containing high-entropy nitride is characterized in that the silicon nitride ceramic is prepared by mixing high-entropy nitride powder and Si 3 N 4 Powder, sintering aid Al 2 O 3 -Y 2 O 3 Adding ethanol and Si 3 N 4 Ball milling and mixing, drying and sieving the balls to obtain mixed powder; the mixed powder is heated to 1600-1800 ℃ under the protection atmosphere by the axial pressure of 30-100 MPa, and then the powder is obtained by hot-pressing sintering.
2. The high-entropy nitride-containing silicon nitride ceramic according to claim 1, wherein the high-entropy nitride powder is a nitride composed of five or more elements of group iv transition metal element, group v transition metal element and group vi transition metal element in equimolar ratio.
3. The high-entropy nitride-containing silicon nitride ceramic according to claim 2, wherein the group vi transition metal element is Ti, zr, hf; the V group transition metal element is V, nb and Ta; the VI group transition metal elements are Cr, mo and W.
4. The silicon nitride ceramic containing high-entropy nitride according to claim 1, wherein the particle size of the high-entropy nitride powder is 0.05-2 μm and the purity is 97-100 wt.%; the Si is 3 N 4 The grain diameter of the powder is 0.1-2 mu m, and the purity is 98-100 wt%; the Al is 2 O 3 The grain diameter of the powder is 0.1-2 mu m, and the purity is 98-100 wt%; the Y is 2 O 3 The grain diameter of the powder is 0.1-2 mu m, and the purity is 98-100 wt%.
5. The silicon nitride ceramic containing high-entropy nitride according to claim 1, wherein the high-entropy nitride powder, si 3 N 4 Powder and Al 2 O 3 -Y 2 O 3 The mass ratio of (1-3) to (6-8) to 1, wherein Al 2 O 3 And Y 2 O 3 Mass ratio of (2)(2-3), namely (2-3); the high-entropy nitride powder and Si 3 N 4 Powder, sintering aid Al 2 O 3 -Y 2 O 3 Total mass of (C) and Si 3 N 4 The mass ratio of the balls is (2-5): 1.
6. The high entropy nitride-containing silicon nitride ceramic according to claim 1, wherein the mesh size of the sieve is 100 to 200 mesh; the temperature rising rate to 1600-1800 ℃ is 10-50 ℃/min.
7. The high entropy nitride-containing silicon nitride ceramic according to claim 1, wherein the protective atmosphere is nitrogen or argon.
8. The high-entropy nitride-containing silicon nitride ceramic according to claim 1, wherein the density of the high-entropy nitride-containing silicon nitride ceramic is 95 to 100%.
9. The method for producing a silicon nitride ceramic containing a high-entropy nitride according to any one of claims 1 to 8, comprising the specific steps of:
s1, high-entropy nitride powder and Si 3 N 4 Powder, al 2 O 3 -Y 2 O 3 Placing the powder in a nylon ball milling tank, adding ethanol and Si 3 N 4 Ball milling and mixing the balls, and drying to obtain mixed powder;
s2, filling the mixed powder into a graphite mold, and heating to 1600-1800 ℃ at a speed of 10-50 ℃/min under an axial pressure of 30-100 MPa in a nitrogen or argon atmosphere, and hot-pressing and sintering for 30-180 min to obtain the silicon nitride ceramic containing the high-entropy nitride.
10. Use of a silicon nitride ceramic containing a high entropy nitride according to any one of claims 1 to 8 in the field of tools.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109987941A (en) * | 2019-03-11 | 2019-07-09 | 广东工业大学 | One kind having antioxidative high entropy ceramic composite and its preparation method and application |
| CN110606748A (en) * | 2019-09-04 | 2019-12-24 | 广东工业大学 | Alumina-enhanced high-entropy boride ceramic and preparation method and application thereof |
| CN110735076A (en) * | 2019-09-04 | 2020-01-31 | 广东工业大学 | high-entropy metal ceramics and preparation method and application thereof |
| CN113213945A (en) * | 2020-12-31 | 2021-08-06 | 兆山科技（北京）有限公司 | Method for preparing high-entropy boron ceramic by atmosphere sintering |
| CN114807849A (en) * | 2022-04-22 | 2022-07-29 | 广东工业大学 | Nano composite high-entropy nitride coating and composite deposition method thereof |
| CN115340387A (en) * | 2022-09-06 | 2022-11-15 | 中国有色桂林矿产地质研究院有限公司 | Boron nitride superhard material containing high-entropy ceramic phase and preparation method and application thereof |
-
2022
- 2022-12-16 CN CN202211625492.4A patent/CN116178030A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109987941A (en) * | 2019-03-11 | 2019-07-09 | 广东工业大学 | One kind having antioxidative high entropy ceramic composite and its preparation method and application |
| CN110606748A (en) * | 2019-09-04 | 2019-12-24 | 广东工业大学 | Alumina-enhanced high-entropy boride ceramic and preparation method and application thereof |
| CN110735076A (en) * | 2019-09-04 | 2020-01-31 | 广东工业大学 | high-entropy metal ceramics and preparation method and application thereof |
| CN113213945A (en) * | 2020-12-31 | 2021-08-06 | 兆山科技（北京）有限公司 | Method for preparing high-entropy boron ceramic by atmosphere sintering |
| CN114807849A (en) * | 2022-04-22 | 2022-07-29 | 广东工业大学 | Nano composite high-entropy nitride coating and composite deposition method thereof |
| CN115340387A (en) * | 2022-09-06 | 2022-11-15 | 中国有色桂林矿产地质研究院有限公司 | Boron nitride superhard material containing high-entropy ceramic phase and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 林锐霖等: "高熵硼化物含量对 Si3N4陶瓷显微结构与性能的影响", 《硅酸盐学报》, vol. 20, no. 6, pages 1499 - 1503 * |
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