CN116178027B - High-entropy boride-based ceramic with high hardness, high toughness and high oxidation resistance, and preparation method and application thereof - Google Patents
High-entropy boride-based ceramic with high hardness, high toughness and high oxidation resistance, and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 62
- 230000003647 oxidation Effects 0.000 title claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 75
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 238000000498 ball milling Methods 0.000 claims abstract description 26
- 239000011812 mixed powder Substances 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 16
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 9
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000000280 densification Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011215 ultra-high-temperature ceramic Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention belongs to the technical field of ceramic materials, and discloses a high-entropy boride-based ceramic with high hardness, high toughness and strong oxidation resistance, and a preparation method and application thereof. The molecular formula of the boride ceramic is (Hf aMobTacCrdTie)B2 -FeCoNiAlCrBY, wherein a is more than or equal to 0.1 and less than or equal to 0.8,0< b <0.75,0< c <0.9,0< d <0.9,0< e <0.9, and a+b+c+d+e=1), the ceramic is prepared by heating a blank obtained after ball milling HfO 2、MoO3、Ta2O5、Cr2O3、TiO2 powder and boron powder and pressing to 1400-1700 ℃ for vacuum heat treatment, and HEB-HEA mixed powder obtained by mixing high-entropy boride powder and FeCoNiAlCrBY powder is prepared by spark plasma sintering at 1300-1700 ℃, and can be applied to preparing high-temperature structural member materials.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and in particular relates to a high-entropy boride-based ceramic with high hardness, high toughness and strong oxidation resistance, and a preparation method and application thereof.
Background
The high-entropy ceramic is an ultra-high temperature ceramic (UHTC) which has been recently developed, and is a single-phase solid solution ceramic composed of five or more metal elements. The unique performance and wide application prospect of the novel material are interesting to a plurality of scholars, and therefore the novel material is widely studied. The high-entropy boride ceramic is one of high-entropy ceramics, and has high hardness, high Young's modulus, good chemical stability and excellent mechanical properties under high-temperature conditions, so that the high-entropy boride ceramic becomes a candidate material in various fields, such as: structural members such as aerospace, nuclear, gas turbine, cutting tools, and the like. However, the existing high-entropy boride ceramic powder has poor sintering activity, and usually requires a sintering temperature of up to 2000 ℃ to realize densification, and the too high sintering temperature causes coarse grain size, so that the mechanical property of the powder is reduced.
In the reported prior art, if the high-entropy boride ceramic contains a metal element (such as Nb, mo, etc.) with a relatively low melting point of the corresponding oxide, the oxidation resistance of the high-entropy ceramic is also greatly reduced. Zhang Yan et al compared two kinds of high entropy ceramics (preparation and performance study of high entropy boride ceramics, university of Guangdong Industrial, 2021) containing Nb element (HEB-Nb) and not containing Nb element (HEB-Cr), found that the oxide layer thickness of the former was 4 times as large as that of the latter under the condition of 1400 ℃ oxidation for 1h, because the Nb 2O5 oxidation product in sample HEB-Nb has a lower melting point, is easy to form liquid phase and volatilize during the 1400 ℃ oxidation process, accelerates the oxidation rate of the whole material, and finally leads the mechanical property of the material to be more easily deteriorated under the high temperature condition.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the high-entropy boride-based ceramic with high hardness, high toughness and strong oxidation resistance is provided. The ceramic has the characteristics of low densification temperature, small grain size, high hardness and fracture toughness and strong oxidation resistance.
Another object of the present invention is to provide a method for preparing the above-mentioned high entropy boride-based ceramic.
It is a further object of the present invention to provide the use of the above high entropy boride-based ceramic.
The aim of the invention is achieved by the following technical scheme:
a high-entropy boride-based ceramic of high hardness, high toughness and strong oxidation resistance, having a molecular formula of (Hf aMobTacCrdTie)B2 -FeCoNiAlCrBY, wherein 0.ltoreq.a.ltoreq.0.8, 0< b <0.75,0< c <0.9,0< d <0.9,0< e <0.9, and a+b+c+d+e=1.
Preferably, the high entropy boride-based ceramic has the formula (Hf aMobTacCrdTie)B2 -FeCoNiAlCrBY, where a=b=c=d=e=0.2).
Preferably, the high-entropy boride-based ceramic is prepared by adding HfO 2、MoO3、Ta2O5、Cr2O3、TiO2 powder and amorphous boron powder into a solvent for ball milling to obtain mixed powder, putting a blank obtained after compression molding into a graphite crucible, heating to 1400-1700 ℃, preserving heat, and performing vacuum heat treatment to obtain high-entropy boride powder; adding FeCoNiAlCrBY powder with 0.1-30wt% of the obtained high-entropy boride powder into the powder, adding a solvent, ball milling the powder to obtain (Hf aMobTacCrdTie)B2 -FeCoNiAlCrBY mixed powder, which is abbreviated as HEB-HEA (HEB stands for high-entropy boride and HEA stands for high-entropy alloy)), heating the HEB-HEA powder to 800-1000 ℃ by adopting spark plasma sintering, filling protective atmosphere, heating to 1300-1700 ℃, axially pressurizing and calcining to obtain the high-entropy boride powder.
Preferably, the grain size of the high-entropy boride-based ceramic is 0.3-0.9 mu m, and the relative density is more than 97%; the hardness is 30-40 GPa; the fracture toughness is 6.4-12.8 MPa.m 1/2, and the thickness of the oxide layer obtained by oxidizing for 1h at the high temperature of 1400 ℃ is 40-150 mu m.
Further, the grain size of the high-entropy boride-based ceramic is 0.7-0.86 mu m; the hardness is 35-37 GPa; the fracture toughness is 7.6-8.5 MPa.m 1/2, and the thickness of the oxide layer obtained by oxidizing for 1h at the high temperature of 1400 ℃ is 60-100 mu m.
Preferably, the purity of the HEB-HEA powder is 95 to 99.9 weight percent, and the particle size is 0.1 to 1 mu m; the oxygen content of the HEB-HEA powder is 0.01-5 wt%.
Preferably, the purity of the HfO 2、MoO3、Ta2O5、Cr2O3、TiO2 powder is 99.0-99.9 wt% and the particle size is 0.1-10 μm; the purity of the amorphous boron powder is 95.0-99.9 wt% and the grain diameter is 1-1.5 mu m.
Preferably, the solvent is ethanol, propanol, methanol or acetone; the protective atmosphere is N 2 or Ar.
The preparation method of the high-entropy boride-based ceramic with high hardness, high toughness and strong oxidation resistance comprises the following specific steps:
s1, adding HfO 2、MoO3、Ta2O5、Cr2O3、TiO2 powder and amorphous boron powder into a solvent and a ball milling medium for ball milling and mixing, and drying to obtain mixed powder;
S2, placing the green body obtained after the mixed powder is molded into a graphite crucible for vacuum heat treatment, heating to 1400-1700 ℃ and preserving heat to obtain (Hf aMobTacCrdTie)B2 high-entropy boride ceramic powder;
S3, adding the (Hf aMobTacCrdTie)B2 high-entropy boride ceramic powder and FeCoNiAlCrBY powder into a solvent and a ball milling medium for ball milling and mixing, and drying to obtain HEB-HEA powder;
S4, placing HEB-HEA powder into a graphite die, adopting spark plasma sintering to heat to 800-1000 ℃, filling a protective atmosphere, heating to 1300-1700 ℃ for heat preservation, pressurizing to 10-100 MPa, and calcining to obtain the high-entropy boride-based ceramic.
Preferably, the rate of temperature rise in the step S2 is 5-15 ℃/min; the heat preservation time is 0.5-2 h; the ball milling and mixing time in the step S1 and the step S3 is 20-40 h, the heating rate in the step S4 is 100-400 ℃/min, and the heat preservation time is 10-30 min.
Preferably, the FeCoNiAlCrBY powder in the step S3 is (0.1-30 wt% of Hf aMobTacCrdTie)B2 high entropy boride powder), and further, the FeCoNiAlCrBY powder is (5-15 wt% of Hf aMobTacCrdTie)B2 high entropy boride powder.
The high-entropy boride-based ceramic with high hardness, high toughness and high oxidation resistance is applied to the preparation of high-temperature structural member materials.
The high-entropy boride-based ceramic is prepared by taking HfO 2、MoO3、Ta2O5、Cr2O3、TiO2 powder and boron powder as raw materials and adopting a boron thermal reduction reaction (Hf aMobTacCrdTie)B2 high-entropy boride powder, adding FeCoNiAlCrBY high-entropy alloy powder into the obtained high-entropy boride powder, fully and uniformly mixing, and finally adopting SPS low-temperature sintering to prepare the dense, fine-grain, high-hardness, high-toughness and high-oxidation-resistance high-entropy boride-based ceramic.
Compared with the prior art, the invention has the following beneficial effects:
1. The high-entropy boride-based ceramic (Hf aMobTacCrdTie)B2 -FeCoNiAlCrBY) prepared by the method has good wettability to the high-entropy boride phase because a liquid phase with a low melting point such as Co 2 B, niB is formed in the sintering process, so that the sintering performance is greatly improved, and the densification temperature is lower.
2. The high-entropy boride-based ceramic (Hf aMobTacCrdTie)B2 -FeCoNiAlCrBY) prepared by the invention has the advantage that the grain size is further refined (0.3-0.9 mu m) because of the lower sintering temperature required for densification, so that the hardness and fracture toughness are further improved.
3. Compared with single-phase high-entropy boride ceramic (HfaMobTacCrdTie)B2(GILD J,ZHANG Y,HARRINGTON T,et al.High-entropy metal diborides:a new class of high-entropy materials and a new type of ultrahigh temperature ceramics[J].Science Reports,2016,6:37946), the high-entropy boride ceramic prepared by the invention has higher hardness and fracture toughness.
4. The high-entropy boride ceramic prepared by the method can form a compact oxide layer under high-temperature oxidation conditions so as to prevent further oxidation diffusion, and is oxidized for 1h at 1400 ℃ to obtain an oxide layer with the thickness of 40-150 mu m. Therefore, even though Mo, which is a metal element having a relatively low melting point of the corresponding oxide, is contained in the element assembly, it has excellent oxidation resistance.
Detailed Description
The present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention. 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. Taking HfO 2 (purity of powder 99%, particle size 1 μm), moO 3 (purity of powder 99.8%, particle size 1 μm), ta 2O5 (purity of powder 99%, particle size 1 μm), cr 2O3 (purity of powder 99%, particle size 1 μm), tiO 2 (purity of powder 99%, particle size 0.5 μm) and amorphous boron powder (purity of powder 95%, particle size 1 μm) as raw materials, taking absolute ethyl alcohol as a solvent, taking WC as a ball milling medium, ball milling and mixing for 24 hours on a ball mill, and drying to obtain mixed powder;
2. and (3) placing the green body obtained after the mixed powder is molded into a graphite crucible, heating to 1650 ℃ at a speed of 10 ℃/min, and preserving heat for 1h, and carrying out vacuum heat treatment to obtain the (Hf 0.2Mo0.2Ta0.2Cr0.2Ti0.2)B2 high-entropy boride powder.
3. Adding the obtained (Hf 0.2Mo0.2Ta0.2Cr0.2Ti0.2)B2 high-entropy boride powder and 10wt% of FeCoNiAlCrBY powder into absolute ethyl alcohol and a ball milling medium, mixing for 24 hours on a ball mill, and drying to obtain HEB-HEA powder.
4. And (3) placing HEB-HEA powder into a graphite die, heating to 1000 ℃ at a speed of 150 ℃/min by adopting spark plasma sintering, filling a protective atmosphere, heating to 1700 ℃ at a speed of 100 ℃/min, preserving heat for 10min, and calcining under a pressure of 35MPa to obtain the high-entropy boride-based ceramic, wherein the molecular formula of the high-entropy boride-based ceramic is (Hf 0.2Mo0.2Ta0.2Cr0.2Ti0.2)B2 -FeCoNiAlCrBY.
The oxidation experiment was carried out in a box furnace (GSL-1600X, hefeijidae materials science and technology Co., ltd.) at 1400℃for 1h. The oxidized sample cross section was observed using a scanning electron microscope (SEM, novaNanoSEM, FEI) and an energy spectrometer (EDS, X-MarN, oxford) to determine the thickness of the oxidized layer to be 53-77 μm. The grain size of the prepared high-entropy boride-based ceramic is 0.86 mu m, the relative density is 98.6%, the hardness is 36GPa, and the fracture toughness is 8.5MPa m 1 /2.
Example 2
1. Taking HfO 2 (purity of powder 99%, particle size 1 μm), moO 3 (purity of powder 99.8%, particle size 1 μm), ta 2O5 (purity of powder 99%, particle size 1 μm), cr 2O3 (purity of powder 99%, particle size 1 μm), tiO 2 (purity of powder 99%, particle size 0.5 μm) and amorphous boron powder (purity of powder 95%, particle size 1 μm) as raw materials, taking ethanol as a solvent, taking WC as a ball milling medium, ball milling and mixing for 24 hours on a ball mill, and drying to obtain mixed powder;
2. and (3) placing the green body obtained after the mixed powder is molded into a graphite crucible, heating to 1650 ℃ at a speed of 10 ℃/min, and preserving heat for 1h, and carrying out vacuum heat treatment to obtain the (Hf 0.2Mo0.2Ta0.2Cr0.2Ti0.2)B2 high-entropy boride powder.
3. Adding the obtained (Hf 0.2Mo0.2Ta0.2Cr0.2Ti0.2)B2 high-entropy boride powder and FeCoNiAlCrBY powder with the weight percentage of 5 percent) into absolute ethyl alcohol and a ball milling medium, ball milling and mixing for 24 hours on a ball mill, and drying to obtain HEB-HEA powder.
4. And (3) placing HEB-HEA powder into a graphite die, heating to 1000 ℃ at a speed of 150 ℃/min by adopting spark plasma sintering, filling a protective atmosphere, heating to 1500 ℃ at a speed of 100 ℃/min, preserving heat for 10min, and calcining under a pressure of 35MPa to obtain the high-entropy boride-based ceramic, wherein the molecular formula of the high-entropy boride-based ceramic is (Hf 0.2Mo0.2Ta0.2Cr0.2Ti0.2)B2 -FeCoNiAlCrBY.
The grain size of the prepared high-entropy boride-based ceramic is 0.73 mu m, the relative density is 97.2%, the hardness is 36.9GPa, and the fracture toughness is 7.6MPa m 1/2. The oxidation experiment was carried out in a box furnace (GSL-1600X, hefeijidae materials science and technology Co., ltd.) at 1400℃for 1h. The oxidized sample cross section was observed using a scanning electron microscope (SEM, novaNanoSEM, FEI) and an energy spectrometer (EDS, X-MarN, oxford) to determine that the thickness of the oxide layer was 62-97. Mu.m.
Example 3
1. Taking HfO 2 (purity of powder 99%, particle size 1 μm), moO 3 (purity of powder 99.8%, particle size 1 μm), ta 2O5 (purity of powder 99%, particle size 1 μm), cr 2O3 (purity of powder 99%, particle size 1 μm), tiO 2 (purity of powder 99%, particle size 0.5 μm) and amorphous boron powder (purity of powder 95%, particle size 1 μm) as raw materials, taking ethanol as a solvent, taking WC as a ball milling medium, ball milling and mixing for 24 hours on a ball mill, and drying to obtain mixed powder;
2. and (3) placing the green body obtained after the mixed powder is molded into a graphite crucible, heating to 1650 ℃ at a speed of 10 ℃/min, and preserving heat for 1h, and carrying out vacuum heat treatment to obtain the (Hf 0.2Mo0.2Ta0.2Cr0.2Ti0.2)B2 high-entropy boride powder.
3. Adding the obtained (Hf 0.2Mo0.2Ta0.2Cr0.2Ti0.2)B2 high-entropy boride powder and 15wt% of FeCoNiAlCrBY powder into absolute ethyl alcohol and a ball milling medium, ball milling and mixing for 24 hours on a ball mill, and drying to obtain HEB-HEA powder.
4. And (3) placing HEB-HEA powder into a graphite die, heating to 1000 ℃ at a speed of 150 ℃/min by adopting spark plasma sintering, filling a protective atmosphere, heating to 1600 ℃ at a speed of 100 ℃/min, preserving heat for 10min, and calcining under a pressure of 35MPa to obtain the high-entropy boride-based ceramic, wherein the molecular formula of the high-entropy boride-based ceramic is (Hf 0.2Mo0.2Ta0.2Cr0.2Ti0.2)B2 -FeCoNiAlCrBY.
The grain size of the prepared high-entropy boride-based ceramic is 0.79 mu m, the relative density is 98.8%, the hardness is 35.4GPa, and the fracture toughness is 8.1 MPa.m 1/2. The oxidation experiment was carried out in a box furnace (GSL-1600X, hefeijidae materials science and technology Co., ltd.) at 1400℃for 1h. The oxidized sample cross section was observed using a scanning electron microscope (SEM, novaNanoSEM, FEI) and an energy spectrometer (EDS, X-MarN, oxford) to determine the thickness of the oxide layer to be 44-68 μm.
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 high-entropy boride-based ceramic with high hardness, high toughness and strong oxidation resistance, characterized in that the molecular formula of the high-entropy boride ceramic is (Hf aMobTacCrdTie)B2 -FeCoNiAlCrBY, wherein 0<a is less than or equal to 0.8,0< b <0.75,0< c <0.9,0< d <0.9,0< e <0.9, and a+b+c+d+e=1.
2. The high hardness, high toughness, and strong oxidation resistant high entropy boride based ceramic according to claim 1, having a molecular formula of (Hf aMobTacCrdTie)B2 -FeCoNiAlCrBY, where a = b = c = d = e = 0.2.
3. The high-entropy boride-based ceramic with high hardness, high toughness and high oxidation resistance according to claim 1 or 2, wherein the high-entropy boride-based ceramic is prepared by adding HfO 2、MoO3、Ta2O5、Cr2O3、TiO2 powder and amorphous boron powder into a solvent for ball milling to obtain mixed powder, putting a blank obtained after compression molding into a graphite crucible, heating to 1400-1700 ℃, preserving heat, and carrying out vacuum heat treatment to obtain high-entropy boride powder; adding FeCoNiAlCrBY powder accounting for 0.1 to 30 weight percent of the high-entropy boride powder into the obtained high-entropy boride powder, and adding a solvent for ball milling to obtain HEB-HEA mixed powder; and (3) heating the HEB-HEA mixed powder to 800-1000 ℃ by adopting spark plasma sintering, filling a protective atmosphere, heating to 1300-1700 ℃, and calcining under the axial pressure of 10-100 MPa.
4. The high-entropy boride-based ceramic of high hardness, high toughness and strong oxidation resistance according to claim 3, wherein the grain size of the high-entropy boride-based ceramic is 0.3 to 0.9 μm, and the relative density is 97% or more; the hardness is 30-40 GPa; the fracture toughness is 6.4-12.8 MPa.m 1/2, and the thickness of the oxide layer obtained by oxidizing for 1h at the high temperature of 1400 ℃ is 40-150 mu m.
5. The high-entropy boride-based ceramic with high hardness, high toughness and strong oxidation resistance according to claim 3, wherein the purity of the HEB-HEA mixed powder is 95-99.9 wt%, and the particle size is 0.1-1 μm; the oxygen content of the HEB-HEA mixed powder is 0.01-5 wt%.
6. The high-entropy boride-based ceramic with high hardness, high toughness and strong oxidation resistance according to claim 3, wherein the purity of the HfO 2、MoO3、Ta2O5、Cr2O3、TiO2 powder is 99.0-99.9 wt%, and the particle size is 0.1-10 μm; the purity of the amorphous boron powder is 95.0-99.9 wt% and the grain diameter is 1-1.5 mu m.
7. The high-entropy boride-based ceramic of claim 3, wherein the solvent is ethanol, propanol, methanol or acetone; the protective atmosphere is N 2 or Ar.
8. The method for producing a high-entropy boride-based ceramic having high hardness, high toughness and strong oxidation resistance according to any one of claims 1 to 7, comprising the specific steps of:
s1, adding HfO 2、MoO3、Ta2O5、Cr2O3、TiO2 powder and amorphous boron powder into a solvent and a ball milling medium for ball milling and mixing, and drying to obtain mixed powder;
S2, placing the green body obtained after the mixed powder is molded into a graphite crucible for vacuum heat treatment, heating to 1400-1700 ℃ and preserving heat to obtain (Hf aMobTacCrdTie)B2 high-entropy boride ceramic powder;
S3, adding the (Hf aMobTacCrdTie)B2 high-entropy boride ceramic powder and FeCoNiAlCrBY powder into a solvent and a ball milling medium for ball milling and mixing, and drying to obtain HEB-HEA powder;
s4, placing HEB-HEA powder into a graphite die, adopting spark plasma sintering to heat to 800-1000 ℃, filling a protective atmosphere, heating to 1300-1700 ℃ for heat preservation, pressurizing to 10-100 MPa, and calcining to obtain the high-entropy boride-based ceramic (Hf aMobTacCrdTie)B2 -FeCoNiAlCrBY).
9. The method for producing a high-entropy boride-based ceramic with high hardness, high toughness and strong oxidation resistance according to claim 8, wherein the rate of temperature rise in step S2 is 5 to 15 ℃/min; the heat preservation time is 0.5-2 h; the ball milling and mixing time in the step S1 and the step S3 is 20-40 h, the heating rate in the step S4 is 100-400 ℃/min, and the heat preservation time is 10-30 min.
10. Use of a high-entropy boride-based ceramic of high hardness, high toughness and strong oxidation resistance according to any one of claims 1-7 for the preparation of high temperature structural member materials.
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