CN112830792B - High-hardness hafnium-based ternary solid solution boride ceramic and preparation method and application thereof - Google Patents

High-hardness hafnium-based ternary solid solution boride ceramic and preparation method and application thereof Download PDF

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CN112830792B
CN112830792B CN202110088777.8A CN202110088777A CN112830792B CN 112830792 B CN112830792 B CN 112830792B CN 202110088777 A CN202110088777 A CN 202110088777A CN 112830792 B CN112830792 B CN 112830792B
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solid solution
hafnium
powder
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CN112830792A (en
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黄梓键
郭伟明
张岩
许亮
林华泰
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Guangdong University of Technology
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Abstract

The invention belongs to the technical field of ceramic materials, and discloses a high-hardness hafnium-based ternary solid solution boride ceramic as well as a preparation method and application thereof. The boride ceramic has a molecular formula of (Hf) a Me1 b Me2 c )B 2 Wherein a is more than or equal to 0.1 and less than or equal to 0.9,0<b<0.9,0<c<0.9, and a + b + c =1; me1 and Me2 are Zr, ta or Ti, the ceramic is prepared by mixing HfO 2 Me1 and Me2 oxides, B 4 C. Adding carbon powder into a solvent, performing ball milling to obtain mixed powder, performing die pressing to obtain a blank, placing the blank into a graphite crucible, heating to 1400-1600 ℃, performing heat preservation, and performing vacuum heat treatment to obtain hafnium-based ternary solid solution boride powder; the ternary solid solution boride powder is heated to 1000-1400 ℃ by adopting spark plasma sintering, then is filled into protective atmosphere, and is heated to 1900-2100 ℃ and calcined under the pressure of 10-100 MP to obtain the ternary solid solution boride powder.

Description

High-hardness hafnium-based ternary solid solution boride ceramic and preparation method and application thereof
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a high-hardness hafnium-based ternary solid solution boride ceramic as well as a preparation method and application thereof.
Background
Hafnium diboride (HfB) 2 ) As ultra-high temperature ceramics (UHTC), attention has been paid to the ultra-high temperature ceramics (UHTC) because of its extremely high melting point (3380 ℃ C.), high Young's modulus (500 GPa), high hardness (18-21 GPa), excellent high temperature performance and chemical stability. HfB2 ceramics are expected to be useful in the supersonic aerospace industry and high temperature parts (>3000 ℃ C., etc. Compared with single-component materials, the preparation of the solid solution ceramic can effectively improve the sinterability of boride ceramic and overcome the challenge of densification. The solid solution material has better mechanical property and thermal stability. Solid solution of MeB2 (Me = Zr/Ta/Ti) greatly improves HfB 2 Densification, texture and mechanical properties of the ceramic. Therefore, the solid solution ceramic has wide application prospect in the high-temperature field. Very few reports have been made on the synthesis of ternary solid solution boride powders and sintered ceramics. The literature reports the preparation of single-phase (Ta) by the molten salt method 1/3 Nb 1/ 3 Ti 1/3 )B 2 The powder has a diameter of 20-40 nm and a length of 100-200 nm, and is in the shape of a nanorod. However, this method cannot synthesize a single phase (Hf) 1/3 Zr 1/3 Ti 1/3 )B 2 Powder of boride phase (TiB) 2 ) Still exist. In addition, the mechanical properties of the ternary boride and the influence of solid solution elements on the sintering properties thereof have not been determined.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, a hafnium-based ternary solid solution boride ceramic with high hardness is provided. The ceramic has the advantages of uniform solid solution phase, stable component and high hardness.
The invention also aims to provide a preparation method of the hafnium-based ternary solid solution boride ceramic.
The invention further aims to provide application of the hafnium-based ternary solid solution boride ceramic.
The purpose of the invention is realized by the following technical scheme:
the high-hardness hafnium-based ternary solid solution boride ceramic is characterized in that the molecular formula of the boride ceramic is (Hf) a Me1 b Me2 c )B 2 Wherein a is more than or equal to 0.1 and less than or equal to 0.9,0<b<0.9,0<c<0.9, and a + b + c =1; me1 and Me2 are Zr, ta or Ti, and the ceramic is prepared by mixing HfO 2 Me oxide ZrO 2 、Ta 2 O 5 、TiO 2 Any two of them, B 4 C. Adding carbon powder into a solvent, ball-milling and mixing to obtain mixed powder, pressing the mixed powder to obtain a blank, putting the blank into a graphite crucible, heating the blank to 1400-1600 ℃, preserving the temperature, and carrying out vacuum heat treatment to obtain (Hf) a Me1 b Me2 c )B 2 Hafnium-based ternary solid solution boride powder; the ternary solid solution boride powder is heated to 1000-1400 ℃ by spark plasma sintering, then filled into protective atmosphere, heated to 1900-2100 ℃ and calcined under the pressure of 10-100 MP to obtain the ternary solid solution boride powder.
Preferably, the (Hf) a Me1 b Me2 c )B 2 The hafnium-based ternary solid solution boride powder has a purity of 95.0 to 99.9wt% and a particle size of 0.1 to 1 μm.
Preferably, said (Hf) a Me1 b Me2 c )B 2 The hafnium-based ternary solid solution boride powder has an oxygen content of 0.01 to 5wt% and a carbon content of 0.01 to 5wt%.
Preferably, the HfO 2 、ZrO 2 、Ta 2 O 5 And TiO 2 The purity of the product is 99.0-99.9 wt%, and the grain diameter is 0.1-10 μm; b is 4 The purity of the C powder and the carbon powder is 97-99.99 wt.%, and the particle size is 1-1.5 μm.
Preferably, the grain size of the hafnium-based ternary solid solution boride ceramic is 2.45-6.62 μm, and the relative density is 94-98%; the hardness of the hafnium-based ternary solid solution boride ceramic is 28-35 GPa.
Preferably, the solvent is ethanol, propanol, methanol or acetone.
Preferably, the protective atmosphere is N 2 Or Ar.
Preferably, the heating rate of heating to 1400-1600 ℃ is 5-15 ℃/min; the heat preservation time is 0.5-2 h; the heating rate is 100-400 ℃/min when the temperature is increased to 1000-1400 ℃; the heating rate is 100-400 ℃/min when the temperature is raised to 1900-2100 ℃.
The preparation method of the high-hardness hafnium-based ternary solid solution boride ceramic comprises the following specific steps:
s1, mixing HfO 2 Me oxide ZrO 2 、Ta 2 O 5 、TiO 2 Any two of them, B 4 C. Adding a solvent and a ball milling medium into carbon powder, mixing for 20-40 h on a ball mill, and drying to obtain mixed powder;
s2, placing the blank after the mixed powder is molded into a graphite crucible for vacuum heat treatment, heating to 1400-1600 ℃ at the speed of 5-15 ℃/min, and preserving the heat for 0.5-2 h to obtain hafnium-based ternary solid solution boride powder;
s3, placing the hafnium-based ternary solid solution boride powder into a graphite mold, heating to 1000-1400 ℃ at the speed of 100-400 ℃/min by adopting spark plasma sintering, filling protective atmosphere, heating to 1900-2100 ℃ at the speed of 100-400 ℃/min, preserving heat for 10-30 min, and pressurizing to 10-100 MPa for calcination to obtain the hafnium-based ternary solid solution boride powder ceramic.
The high-hardness hafnium-based ternary solid solution boride ceramic is applied to the field of preparation of superhard grinding tool materials.
The hafnium-based ternary solid solution boride ceramic of the invention is prepared from three metal oxides B 4 C and C are taken as raw materials, and are subjected to boron thermal carbon thermal reduction reaction to prepare (Hf) a Me1 b Me2 c )B 2 The method for preparing the hafnium-based ternary solid solution boride powder through in-situ solid solution is easier to form a single phase, has small powder particle size, high purity and large sintering driving force, and is easier to prepare high-performance (Hf) a Me1 b Me2 c )B 2 Hafnium-based ternary solid solution boride ceramics. And can be regulated and controlled according to different solid solution elements (Hf) a Me1 b Me2 c )B 2 The performance of the hafnium-based ternary solid solution boride ceramic.
Compared with the prior art, the invention has the following beneficial effects:
1. prepared by the invention of (Hf) a Me1 b Me2 c )B 2 Hafnium-based ternary solid solution boride ceramic powder can be synthesized into single-phase solid solution powder in situ by a borothermic carbothermic reduction method; prepared (Hf) a Me1 b Me2 c )B 2 Hafnium-based ternary solid solution boride ceramic, which can be controlled by solid solution of different elements compared to single-phase boride ceramic or binary boride ceramic (Hf) a Me1 b Me2 c )B 2 The performance of the hafnium-based ternary solid solution boride ceramic.
2. Prepared by the invention of (Hf) a Me1 b Me2 c )B 2 The hafnium-based ternary solid solution boride ceramic powder has small particle size (0.1-1 mu m), high purity and large sintering driving force, is easy to burn out single-phase solid solution ceramic, and improves the performance of the ceramic.
3. (Hf) prepared by the method of the present invention a Me1 b Me2 c )B 2 Hafnium-based ternary solid solution boride ceramic in which TaB is solid-solubilized 2 Although finer powders can be obtained, it is noteworthy that TaB in solid solution 2 The finer powder of (Hf) is not easy to sinter and compact but instead dissolves TiB2 in solid form a Me1 b Me2 c )B 2 Hafnium-based ternary solidThe solution boride ceramic is denser and has higher hardness.
4. Prepared by the invention of (Hf) a Me1 b Me2 c )B 2 Hafnium-based ternary solid solution boride ceramic due to TaB 2 Has a large atomic radius, so that the crystal lattice distortion is large when the TaB is dissolved in a solid solution, and the TaB is dissolved in a solid solution 2 Of (Hf) a Me1 b Me2 c )B 2 The hafnium-based ternary solid solution boride ceramic is less dense but due to TaB 2 And (Hf) a Me1 b Me2 c )B 2 The hafnium-based ternary solid solution boride ceramic powder has good compatibility and TaB solid solution 2 Of (Hf) a Me1 b Me2 c )B 2 The particle size of the hafnium-based ternary solid solution boride ceramic powder is finer.
5. Prepared by the invention of (Hf) a Me1 b Me2 c )B 2 Hafnium-based ternary solid solution boride ceramics due to TiB 2 Has higher hardness even if TiB is dissolved in solution 2 (Hf) a Me1 b Me2 c )B 2 The hafnium-based ternary solid solution boride ceramic powder is coarse, but solid solution TiB 2 Of (Hf) a Me1 b Me2 c )B 2 The density of the hafnium-based ternary solid solution boride ceramic is 94-98%, and the hardness is improved to 28-35 GPa.
Description of the drawings
FIG. 1 shows (Hf) obtained in example 1 1/3 Zr 1/3 Ti 1/3 )B 2 Fracture morphology of hafnium-based ternary solid solution boride ceramic;
FIG. 2 shows (Hf) obtained in example 1 1/3 Zr 1/3 Ti 1/3 )B 2 Corrosion photo of polished surface of hafnium-based ternary solid solution boride ceramic
FIG. 3 is (Hf) obtained in example 2 1/3 Ta 1/3 Ti 1/3 )B 2 Fracture morphology of hafnium-based ternary solid solution boride ceramic;
FIG. 4 is (Hf) obtained in example 2 1/3 Ta 1/3 Ti 1/3 )B 2 Corrosion photo of polished surface of hafnium-based ternary solid solution boride ceramic
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. With HfO 2 (purity of powder 99%, particle diameter 1 μm), zrO 2 (purity of powder 99.8%, particle size 1 μm), tiO 2 (purity of powder 99%, particle diameter 0.5 μm), and B 4 C (purity of powder 99.9%, particle size 0.5 μm), carbon powder (purity of powder 99%, particle size 0.8 μm) as raw material, ethanol as solvent, and Si 4 N 3 Mixing the mixture serving as a ball milling medium on a ball mill for 24 hours, and drying to obtain mixed powder;
2. putting the blank after the mixed powder mould pressing into a graphite crucible, heating to 1600 ℃ at the speed of 10 ℃/min, preserving the heat for 1h, and carrying out vacuum heat treatment to obtain (Hf) 1/3 Zr 1/3 Ti 1/3 )B 2 Hafnium-based ternary solid solution boride ceramic powder.
3. Will (Hf) 1/3 Zr 1/3 Ti 1/3 )B 2 Putting hafnium-based ternary solid solution boride ceramic powder into a graphite die, heating to 1000 ℃ at the speed of 150 ℃/min by adopting spark plasma sintering, filling Ar protective atmosphere, heating to 2000 ℃ at the speed of 150 ℃/min, keeping the temperature for 10min, pressurizing to 30MPa, and calcining to obtain (Hf) 1/3 Zr 1/3 Ti 1/3 )B 2 Hafnium-based ternary solid solution boride ceramics.
(Hf) 0.76 μm in powder particle size of the solid solution powder of this example as determined by laser particle size analysis, 0.01wt% in oxygen content of the solid solution powder as determined by a carbon oxygen analyzer, and 0.03wt% in carbon content of the solid solution powder 1/ 3 Zr 1/3 Ti 1/3 )B 2 The hafnium-based ternary solid solution boride ceramic has a grain size of 6.62 μm, a relative density of 98%, and a hardness of 35GPa.
FIG. 1 shows (Hf) obtained in example 1 1/3 Zr 1/3 Ti 1/3 )B 2 Fracture morphology of hafnium-based ternary solid solution boride ceramic; as can be seen from FIG. 1 (Hf) 1/3 Zr 1/3 Ti 1/3 )B 2 The hafnium-based ternary solid solution boride ceramic is more compact in sintering, basically has no pores and has a relative density of 98%. FIG. 2 shows (Hf) obtained in example 1 1/3 Zr 1/3 Ti 1/3 )B 2 And (3) corrosion pictures of the polished surface of the hafnium-based ternary solid solution boride ceramic. As can be seen from FIG. 2, the crystal grain size was 6.62 μm, and the anisotropy of the crystal grains was improved in the form of long rod-like crystal grains (Hf) 1/3 Zr 1/3 Ti 1/3 )B 2 The hafnium-based ternary solid solution boride ceramic has the performance that the hardness is 35GPa.
Example 2
1. With HfO 2 (purity of powder 99%, particle diameter 1 μm), ta 2 O 5 (purity of powder 99.8%, particle diameter 1 μm), tiO 2 (purity of powder 99%, particle diameter 0.5 μm), and B 4 C (purity of powder 99.9%, particle size 0.5 μm), carbon powder (purity of powder 99%, particle size 0.8 μm) as raw material, ethanol as solvent, and Si 4 N 3 Mixing the mixture serving as a ball milling medium on a ball mill for 24 hours, and drying to obtain mixed powder;
2. putting the blank after the mixed powder mould pressing into a graphite crucible, heating to 1600 ℃ at the speed of 10 ℃/min, preserving the heat for 1h, and carrying out vacuum heat treatment to obtain (Hf) 1/3 Ta 1/3 Ti 1/3 )B 2 Hafnium-based ternary solid solution boride ceramic powder.
3. Will (Hf) 1/3 Ta 1/3 Ti 1/3 )B 2 Putting hafnium-based ternary solid solution boride ceramic powder into a graphite mold, heating to 1000 ℃ at the speed of 150 ℃/min by adopting spark plasma sintering, filling Ar protective atmosphere, heating to 2000 ℃ at the speed of 150 ℃/min, preserving heat for 10min, pressurizing to 30MPa, and calcining to obtain (Hf) (Hf is prepared 1/3 Ta 1/3 Ti 1/3 )B 2 Hafnium-based ternary solid solution boride ceramics.
The powder of the solid solution powder of the present example was measured by laser particle size analysis(Hf) having a particle size of 0.26 μm, an oxygen content of 0.01wt% in the solid solution powder as measured by a carbon oxygen analyzer, and a carbon content of 0.03wt% in the solid solution powder 1/ 3 Ta 1/3 Ti 1/3 )B 2 The hafnium-based ternary solid solution boride ceramic has a grain size of 2.45 μm, a relative density of 94% and a hardness of 28GPa.
FIG. 3 is (Hf) obtained in example 2 1/3 Ta 1/3 Ti 1/3 )B 2 Fracture morphology of hafnium-based ternary solid solution boride ceramic; as can be seen from FIG. 3 (Hf) 1/3 Ta 1/3 Ti 1/3 )B 2 The hafnium-based ternary solid solution boride ceramic has many pores and a relative density of 94%. FIG. 4 shows (Hf) obtained in example 2 1/3 Ta 1/3 Ti 1/3 )B 2 And (3) corrosion photos of the hafnium-based ternary solid solution boride ceramic polished surface. As can be seen from FIG. 4, the grain size is 2.45 μm, and although the ceramic grain size is finer, due to TaB 2 The hardness of (2) is low, the compactness is not high, and the hardness is 28GPa.
Example 3
1. With HfO 2 (purity of powder 99%, particle diameter 2 μm), zrO 2 (purity of powder 99.8%, particle diameter 2 μm), ta 2 O 5 (purity of powder 99%, particle diameter 2 μm), and B 4 C (purity of powder 99.9%, particle size 2 μm), carbon powder (purity of powder 99%, particle size 2 μm) as raw material, ethanol as solvent, and Si 4 N 3 Mixing the materials serving as a ball milling medium on a ball mill for 24 hours, and drying to obtain mixed powder;
2. putting the blank after the mixed powder mould pressing into a graphite crucible, heating to 1600 ℃ at the speed of 10 ℃/min, preserving the heat for 1h, and carrying out vacuum heat treatment to obtain (Hf) 1/3 Zr 1/3 Ta 1/3 )B 2 Hafnium-based ternary solid solution boride ceramic powder.
3. Will (Hf) 1/3 Zr 1/3 Ta 1/3 )B 2 Putting hafnium-based ternary solid solution boride ceramic powder into a graphite mold, heating to 1000 ℃ at the speed of 150 ℃/min by adopting discharge plasma sintering, filling Ar protective atmosphere, and heating to 2000 ℃ at the speed of 150 ℃/minCalcining at 30MPa and keeping the temperature for 10min to obtain (Hf) 1/3 Zr 1/3 Ta 1/3 )B 2 Hafnium-based ternary solid solution boride ceramics.
(Hf) (0.02 wt% of carbon content in solid solution powder, 0.02wt% of oxygen content in solid solution powder, and 0.46 μm of powder particle size in solid solution powder according to the example measured by laser particle size analysis 1/3 Zr 1/ 3 Ta 1/3 )B 2 The hafnium-based ternary solid solution boride ceramic has a grain size of 3.23 μm, a relative density of 95%, and a hardness of 30GPa.
Example 4
1. With HfO 2 (purity of powder 99%, particle size 1 μm), zrO 2 (purity of powder 99.8%, particle diameter 1 μm), tiO 2 (purity of powder 99%, particle diameter 0.5 μm), and B 4 C (purity of powder 99.9%, particle size 0.5 μm), carbon powder (purity of powder 99%, particle size 0.8 μm) as raw material, ethanol as solvent, and Si 4 N 3 Mixing the mixture serving as a ball milling medium on a ball mill for 24 hours, and drying to obtain mixed powder;
2. putting the blank after the mixed powder mould pressing into a graphite crucible, heating to 1600 ℃ at the speed of 10 ℃/min, preserving the heat for 1h, and carrying out vacuum heat treatment to obtain (Hf) 1/10 Zr 0.45 Ti 0.45 )B 2 Hafnium-based ternary solid solution boride ceramic powder.
3. Will (Hf) 1/10 Zr 0.45 Ti 0.45 )B 2 Putting hafnium-based ternary solid solution boride ceramic powder into a graphite mold, heating to 1000 ℃ at the speed of 150 ℃/min by adopting spark plasma sintering, filling Ar protective atmosphere, heating to 2000 ℃ at the speed of 150 ℃/min, preserving heat for 20min, pressurizing to 40MPa, and calcining to obtain (Hf) (Hf is prepared 1/10 Zr 0.45 Ti 0.45 )B 2 Hafnium-based ternary solid solution boride ceramics.
(Hf, 0.03wt% in terms of the particle diameter of the solid solution powder in this example measured by laser particle size analysis, 0.45 μm in terms of the oxygen content of the solid solution powder measured by a carbon-oxygen analyzer, and 0.1wt% in terms of the carbon content of the solid solution powder 1/ 10 Zr 0.45 Ti 0.45 )B 2 The hafnium-based ternary solid solution boride ceramic has a grain size of 4.67 μm, a relative density of 97%, and a hardness of 34GPa.
Example 5
1. With HfO 2 (purity of powder 99%, particle diameter 4 μm), ta 2 O 5 (purity of powder 99.8%, particle size 4 μm), tiO 2 (purity of powder 99%, particle diameter 4 μm), and B 4 C (purity of powder 99.9%, particle size 4 μm), carbon powder (purity of powder 99%, particle size 4 μm) as raw material, ethanol as solvent, and Si 4 N 3 Mixing the materials serving as a ball milling medium on a ball mill for 24 hours, and drying to obtain mixed powder;
2. putting the mixed powder molded blank into a graphite crucible, heating to 1600 ℃ at the speed of 10 ℃/min, preserving heat for 2h, and carrying out vacuum heat treatment to obtain (Hf) 1/4 Ta 1/4 Ti 1/2 )B 2 Hafnium-based ternary solid solution boride ceramic powder.
3. Will (Hf) 1/4 Ta 1/4 Ti 1/2 )B 2 Putting hafnium-based ternary solid solution boride ceramic powder into a graphite mold, heating to 1000 ℃ at the speed of 200 ℃/min by adopting spark plasma sintering, filling Ar protective atmosphere, heating to 2000 ℃ at the speed of 150 ℃/min, preserving heat for 30min, pressurizing to 50MPa, and calcining to obtain (Hf) (Hf is prepared 1/4 Ta 1/4 Ti 1/2 )B 2 Hafnium-based ternary solid solution boride ceramics.
(Hf, 0.03wt% in terms of the particle diameter of the solid solution powder in this example measured by laser particle size analysis, 0.33 μm in terms of the oxygen content of the solid solution powder measured by a carbon-oxygen analyzer, and 0.1wt% in terms of the carbon content of the solid solution powder 1/ 4 Ta 1/4 Ti 1/2 )B 2 The hafnium-based ternary solid solution boride ceramic has a grain size of 3.64 μm, a relative density of 96%, and a hardness of 31GPa.
Prepared by the invention of (Hf) a Me1 b Me2 c )B 2 Hafnium-based ternary solid solution boride ceramic powder can be synthesized into single-phase solid solution powder in situ by a borothermic carbothermic reduction method; prepared (Hf) a Me1 b Me2 c )B 2 Hafnium-based ternary solid solution boride ceramic, which can be controlled by solid solution of different elements compared to single-phase boride ceramic or binary boride ceramic (Hf) a Me1 b Me2 c )B 2 The performance of the hafnium-based ternary solid solution boride ceramic. The grain size of the hafnium-based ternary solid solution boride ceramic is 2.45-6.62 mu m, and the relative density is 94-98%; the hafnium-based ternary solid solution boride ceramic has a hardness of 28 to 35GPa.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.

Claims (5)

1. A preparation method of high-hardness hafnium-based ternary solid solution boride ceramic is characterized by comprising the following specific steps of:
s1, mixing HfO 2 、ZrO 2 、TiO 2 、B 4 C, adding a solvent and a ball milling medium into the carbon powder, mixing for 20 to 40h on a ball mill, and drying to obtain mixed powder;
s2, putting the blank after the mixed powder is molded into a graphite crucible for vacuum heat treatment, heating to 1400-1600 ℃ at the speed of 5-15 ℃/min, and preserving the heat for 0.5-2h to obtain hafnium-based ternary solid solution boride powder;
s3, putting the hafnium-based ternary solid solution boride powder into a graphite mold, heating to 1000-1400 ℃ at the speed of 100-400 ℃/min by adopting spark plasma sintering, filling into a protective atmosphere, heating to 1900-2100 ℃ at the speed of 100-400 ℃/min, preserving heat for 10-30min, and calcining under the pressure of 10-100MPa to obtain the hafnium-based ternary solid solution boride powder ceramic; the molecular formula of the boride ceramic is (Hf) a Zr b Ti c )B 2 Wherein a is more than or equal to 0.1 and less than or equal to 0.9,0<b<0.9,0<c<0.9, and a + b + c =1; the purity of the hafnium-based ternary solid solution boride powder is 95.0 to 99.9wt%, and the particle size is 0.1 to 1 mu m; the hafnium-based ternary solid solution borideThe oxygen content of the powder is 0.01 to 5wt%, and the carbon content is 0.01 to 5wt%; the HfO 2 、ZrO 2 And TiO 2 2 The purity of the particles is 99.0 to 99.9wt%, and the particle size is 0.1 to 10 mu m; b is described 4 The purity of C and carbon powder is 97 to 99.99wt.%, and the particle size is 1 to 1.5 mu m; the grain size of the hafnium-based ternary solid solution boride ceramic is 4.67 to 6.62 mu m, and the relative density is 97 to 98 percent; the hardness of the hafnium-based ternary solid solution boride ceramic is 34-35GPa.
2. The method for preparing a high-hardness hafnium-based ternary solid solution boride ceramic according to claim 1, wherein the solvent in step S1 is ethanol, propanol, methanol or acetone.
3. The method for preparing the high-hardness hafnium-based ternary solid solution boride ceramic according to claim 1, wherein the protective atmosphere in step S3 is N 2 Or Ar.
4. A high hardness hafnium based ternary solid solution boride ceramic, characterized in that it is prepared by the method of any one of claims 1 to 3.
5. The use of the high hardness hafnium-based ternary solid solution boride ceramic of claim 4 in the field of making superabrasive tool materials.
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