CN108546130B - Ultrahigh-temperature ceramic and preparation method thereof - Google Patents
Ultrahigh-temperature ceramic and preparation method thereof Download PDFInfo
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Abstract
The application belongs to the technical field of ultra-high temperature ceramic materials, and particularly relates to an ultra-high temperature ceramic and a preparation method thereof. The ultrahigh-temperature ceramic is prepared by hot-pressing and sintering the following raw materials; wherein the raw material is a mixture of zirconium oxide powder, titanium oxide powder and boron powder. The application also discloses a preparation method of the ultrahigh-temperature ceramic, which comprises the following steps: step 1, mixing zirconium oxide powder, titanium oxide powder, boron powder and a solvent, and drying to obtain mixed powder; step 2, heating the mixed powder to 1450-1600 ℃, and then preserving heat to obtain an intermediate product; and 3, under the condition of protective gas, under the pressure of 20-50MPa, heating the intermediate product to 1900-2100 ℃, and then preserving heat to obtain the ultrahigh-temperature ceramic. The method is used for improving the ZrB prepared by the prior process2Densification of ceramics and improved ZrB2Mechanical properties of the ceramic.
Description
Technical Field
The application belongs to the technical field of ultra-high temperature ceramic materials, and particularly relates to an ultra-high temperature ceramic and a preparation method thereof.
Background
The ultra-high temperature ceramics generally refer to transition metal carbide, boride, nitride and their corresponding complex phase ceramics with melting point of more than 3000 deg.C, such as ZrB2、TiB2、TaB2ZrC, TiC, HfC, etc. The ultrahigh-temperature ceramic and the composite material thereof have excellent performances of high melting point, low density, high strength, high heat conductivity and the like. Has wide application prospect in the fields of aerospace, energy, weapons and the like, wherein ZrB2Ultrahigh temperature ceramics have received a high degree of attention from researchers.
But ZrB due to strong covalent bond and low diffusion coefficient2Sintering is difficult; meanwhile, due to the difference of chemical bond characteristics, crystal grains are arranged along the c-axis direction in the middle period of the sintering processThe growth speed of the crystal grain is obviously higher than that of other directions, so that the crystal grain grows abnormally, and ZrB is further grown2The relative density, hardness, fracture toughness and bending strength of the ceramic are low, and the grain size of the ceramic is large.
Content of application
In view of this, the application discloses an ultra-high temperature ceramic and a preparation method thereof, which can effectively solve the problem that ZrB prepared by the existing ultra-high temperature ceramic2The technical drawback of deterioration of the properties of the ceramic.
The application provides an ultrahigh-temperature ceramic which is prepared by hot-pressing and sintering the following raw materials;
wherein the raw material is a mixture of zirconium oxide powder, titanium oxide powder and boron powder.
Preferably, the zirconium oxide powder is zirconium dioxide powder.
Preferably, the oxide powder of titanium is titanium dioxide powder.
Preferably, the molar ratio of the zirconium dioxide powder to the titanium dioxide powder is (9-39): 1.
preferably, the ratio of the sum of the amounts of the substances of the zirconium dioxide powder and the titanium dioxide powder to the amount of the substance of the boron powder is 1: (3.3-4.5).
Preferably, the zirconium oxide powder has a particle size of 0 to 5 μm, and the titanium oxide powder and the boron powder have a particle size of 0 to 1 μm.
The application also discloses a preparation method of the ultrahigh-temperature ceramic, which comprises the following steps:
step 1, mixing zirconium oxide powder, titanium oxide powder, boron powder and a solvent, and drying to obtain mixed powder;
step 2, heating the mixed powder to 1450-1600 ℃, and then preserving heat to obtain an intermediate product;
and 3, under the condition of protective gas, under the pressure of 20-50MPa, heating the intermediate product to 1900-2100 ℃, and then preserving heat to obtain the ultrahigh-temperature ceramic.
Preferably, after step 1, step 2 further comprises: pretreating the mixed powder, wherein the pretreatment comprises the following steps: and heating the mixed powder to 950-1100 ℃, and then preserving heat.
Preferably, the zirconium oxide powder is zirconium dioxide powder, and the titanium oxide powder is titanium dioxide powder.
Preferably, the mixing is ball milling.
Compared with the prior art, the method has the following beneficial effects: the method comprises the steps of carrying out hot-pressing sintering on a mixture of zirconium oxide powder, titanium oxide powder and boron powder to generate the ultra-high-temperature ceramic, wherein the boron powder reacts with the zirconium oxide powder to generate ZrB2The oxide powder of titanium and boron powder react to produce TiB2Simultaneously sintering TiB in a hot pressing way2Is solutionized to ZrB2In (3), ZrB can be effectively reduced2The movement speed of the grain boundary in the sintering process can inhibit the growth of abnormal grains, refine the grains and improve the mechanical property of the grains. Meanwhile, during the reaction hot pressing sintering process, the densification of the ultrahigh-temperature ceramic is promoted, and the ZrB is further improved2As can be seen from the examples, the relative density of the ultrahigh-temperature ceramic prepared by the method is more than 95%, the hardness is 15-28 GPa, and the fracture toughness is 4-8 MPa.m1/2The bending strength is 450-950 MPa, and the grain size is 0.5-3 μm, so that the performance of the ultra-high temperature ceramic can be greatly improved.
Detailed Description
The application provides an ultrahigh-temperature ceramic and a preparation method thereof, which are used for improving ZrB prepared by the existing process2Densification of ceramics and improved ZrB2Mechanical properties of the ceramic.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application specifically provides a preparation method of ultrahigh-temperature ceramic, which comprises the following steps:
step (1), taking zirconium dioxide powder, boron powder and titanium dioxide powder as raw materials, and mixing the raw materials according to the weight ratio of zirconium dioxide powder: the molar ratio of the titanium dioxide powder is (9-9.95): (0.05-1), the ratio of the sum of the amounts of the substances of zirconium dioxide powder and titanium dioxide powder to the amount of the substance of boron powder is 1: (3.3-4.5), ball-milling and mixing zirconium dioxide powder, boron powder, titanium dioxide powder and a solvent, and drying to obtain mixed powder (the component of the mixed powder is ZrO)2-TiO2-B)；
And (2) sieving the mixed powder obtained in the step (1), and preparing the ultra-high temperature ceramic (the component of the ultra-high temperature ceramic is ZrB) by hot-pressing and sintering the sieved mixed powder2-TiB2Solid solution ceramic).
Specifically, in the step (1), the purity of the zirconium dioxide powder is 98-100%, and the particle size of the zirconium dioxide powder is 0-5 μm; the purity of the titanium dioxide powder is 98-100%, and the particle size of the titanium dioxide powder is 0-1 μm; the purity of the boron powder is 98-100%, and the particle size of the boron powder is 0-1 μm.
Preferably, in the step (1), the ratio of zirconium dioxide powder: the molar ratio of the titanium dioxide powder is 19:1, the molar ratio of the mixture of zirconium dioxide powder and titanium dioxide powder to the boron powder is 1: 4.
Specifically, in the step (2), the hot-pressing sintering step of the sieved mixed powder is as follows:
step a, mixing zirconium dioxide powder, boron powder, titanium dioxide powder and a solvent, and drying to obtain mixed powder;
b, heating the mixed powder to 1450-1600 ℃, and then preserving heat to obtain an intermediate product;
and c, under the condition of protective gas, under the pressure of 20-50MPa, heating the intermediate product to 1900-2100 ℃, and then preserving heat to obtain the ultrahigh-temperature ceramic.
More preferably, in the step c, under the condition of protective gas, the pressure is 30MPa, the temperature of the intermediate product is raised to 1900-2100 ℃, and then the temperature is preserved, so that the ultrahigh-temperature ceramic is obtained.
Preferably, in the step (2), the hot-pressing sintering is to prepare the ultra-high temperature ceramic by hot-pressing sintering with a three-step heat preservation method.
More preferably, in the step (2), the hot-pressing sintering by the three-step heat preservation method comprises the following steps:
step a1, heating the mixed powder to 950-1100 ℃ at a vacuum degree of 0-20Pa and a heating rate of 5-15 ℃/min, and then preserving heat for 1-4 h to obtain an intermediate product 1;
step b1, heating the intermediate product 1 to 1450-1600 ℃ at the vacuum degree of 0-20Pa and the heating rate of 5-15 ℃/min, and then preserving the heat for 0.5-2 h to obtain an intermediate product 2;
and c1, under the condition of protective gas, heating the intermediate product 2 to 1900-2100 ℃ at the heating rate of 10-40 ℃/min under the pressure of 30MPa, and then preserving the heat for 0.5-1.5 h to obtain the ultrahigh-temperature ceramic.
Specifically, the protective gas is 1atm argon.
Specifically, the pressure is the pressure of the graphite mold.
Preferably, the gas pressure in step a1 is 20 Pa.
Preferably, the gas pressure in step b1 is 20 Pa.
Preferably, the pressure in step c1 is 1 atm.
Preferably, in the step a1, the temperature of the mixed powder is raised to 1000 ℃ at a rate of 5 ℃/min, and the temperature is maintained for 2 hours.
Preferably, in step b1, the temperature of intermediate product 1 is raised to 1550 ℃ at a heating rate of 10 ℃/min and kept for 1 h.
Preferably, in step c1, the temperature of intermediate product 2 is raised to 2000 ℃ at a ramp rate of 30 ℃/min and maintained for 1 h.
Specifically, the relative density of the prepared ultrahigh-temperature ceramic is more than 95%, the hardness is 15-28 GPa, and the fracture toughness is 4-8 MPa.m1/2The bending strength is 450 to 950MPa, and the grain size is 0.5 to 3 μm.
Preferably, the relative density of the ultra-high temperature ceramic prepared by the method is more than 95 percent, the hardness is 25GPa, and the fracture toughness is 6.8 MPa.m1/2Bending strength800MPa, and the grain size is about 1 μm.
The raw materials of the following examples are all commercially available or self-made.
Example 1
The preparation method of the first ultrahigh-temperature ceramic provided by the embodiment of the application comprises the following steps:
(1) taking zirconium dioxide powder, boron powder and titanium dioxide powder as raw materials, and mixing the following raw materials in parts by weight: the molar ratio of the titanium dioxide powder is 19:1, the mixture of the zirconium dioxide powder and the titanium dioxide powder and the boron powder are mixed according to the molar ratio of 1:4, ethanol is used as a solvent, ZrB2The ball is used as a ball milling medium, ball milling and mixing are carried out on a planet ball mill for 24 hours at the rotating speed of 300r/min, and mixed materials and drying are carried out to obtain mixed powder.
(2) Sieving the mixed powder, putting the sieved mixed powder into a hot pressing furnace, heating the mixed powder to 1000 ℃ at the temperature rise rate of 5 ℃/min under the condition that the vacuum degree is lower than 20Pa, and preserving the heat for 2 hours; then, the temperature is increased to 1550 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 1 h; then 1atm argon is introduced, the pressure of the graphite mold is 30MPa, the temperature is raised to 2000 ℃ at the heating rate of 30 ℃/min, and the temperature is kept for 1 h. Obtaining the ultra-high temperature ceramic (namely ZrB) by reaction hot pressing sintering2-TiB2Solid solution ceramic).
The ultrahigh-temperature ceramic prepared in the example has the relative density of 98 percent, the hardness of 25.5GPa and the fracture toughness of 6.8 MPa-m1/2The flexural strength was 700MPa, and the crystal grain size was 1 μm.
Example 2
The second preparation method of the ultrahigh-temperature ceramic provided by the embodiment of the application comprises the following steps:
(1) taking zirconium dioxide powder, boron powder and titanium dioxide powder as raw materials, and mixing the following raw materials in parts by weight: the molar ratio of titanium dioxide powder is 39:1, mixing a mixture of zirconium dioxide powder and titanium dioxide powder and boron powder according to a molar ratio of 1:3.5, taking ethanol as a solvent, and ZrB2The ball is used as a ball milling medium, ball milling and mixing are carried out on a planet ball mill for 24 hours at the rotating speed of 300r/min, and mixed materials and dried to obtain mixed powder.
(2) Sieving the mixed powder, and hot pressingIn the furnace, the temperature is raised to 1000 ℃ at the temperature rise rate of 5 ℃/min under the condition that the vacuum degree is lower than 20Pa, and the temperature is kept for 2 h; then, the temperature is increased to 1550 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 1 h; then 1atm argon is introduced, the pressure of the graphite mold is 30MPa, the temperature is raised to 2000 ℃ at the heating rate of 30 ℃/min, and the temperature is kept for 1 h. Obtaining the ultra-high temperature ceramic (namely ZrB) by reaction hot pressing sintering2-TiB2Solid solution ceramic).
The relative density of the ultrahigh-temperature ceramic prepared by the embodiment is about 96 percent, the hardness is 23.5GPa, and the fracture toughness is 6.1 MPa.m1/2The flexural strength was 460MPa, and the grain size was about 2 μm.
Example 3
The preparation method of the third ultrahigh-temperature ceramic provided by the embodiment of the application comprises the following steps:
(1) taking zirconium dioxide powder, boron powder and titanium dioxide powder as raw materials, and mixing the following raw materials in parts by weight: the molar ratio of the titanium dioxide powder is 19:1, mixing a mixture of zirconium dioxide powder and titanium dioxide powder and boron powder according to a molar ratio of 1:4, taking ethanol as a solvent, and ZrB2The ball is used as a ball milling medium, ball milling and mixing are carried out on a planet ball mill for 24 hours at the rotating speed of 300r/min, and mixed materials and dried to obtain mixed powder.
(2) Sieving the mixed powder, heating to 1000 ℃ at a heating rate of 5 ℃/min in a hot pressing furnace under the air pressure of less than 20Pa, and keeping the temperature for 1 h; then, the temperature is increased to 1500 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 1 h; then 1atm argon is introduced, the pressure of the graphite mold is kept at 30MPa, the temperature is raised to 1900 ℃ at the heating rate of 20 ℃/min, and the temperature is kept for 1 h. Obtaining the ultra-high temperature ceramic (namely ZrB) by reaction hot pressing sintering2-TiB2Solid solution ceramic).
The relative density of the ultrahigh-temperature ceramic prepared by the embodiment is about 96 percent, the hardness is 24GPa, and the fracture toughness is 6.2 MPa.m1/2The flexural strength was 500MPa, and the grain size was about 1.6 μm.
Example 4
The preparation method of the fourth ultrahigh-temperature ceramic provided by the embodiment of the application comprises the following steps:
(1) taking zirconium dioxide powder, boron powder and titanium dioxide powder as raw materials, and mixing the following raw materials in parts by weight: the molar ratio of the titanium dioxide powder is 9:1, mixing a mixture of zirconium dioxide powder and titanium dioxide powder and boron powder according to a molar ratio of 1:4, taking ethanol as a solvent, and ZrB2The ball is used as a ball milling medium, ball milling and mixing are carried out on a planet ball mill for 24 hours at the rotating speed of 300r/min, and mixed materials and dried to obtain mixed powder.
(2) Sieving the mixed powder, putting the sieved mixed powder in a hot pressing furnace, heating the mixed powder to 1000 ℃ at the temperature rise rate of 5 ℃/min under the condition that the air pressure is lower than 20Pa, and keeping the temperature for 2 hours; then, the temperature is increased to 1550 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 1 h; then 1atm argon is introduced, the pressure of the graphite mold is kept at 30MPa, the temperature is raised to 2100 ℃ at the heating rate of 30 ℃/min, and the temperature is kept for 1 h. Obtaining the ultra-high temperature ceramic (namely ZrB) by reaction hot pressing sintering2-TiB2Solid solution ceramic).
The relative density of the ultrahigh-temperature ceramic prepared by the embodiment is about 97 percent, the hardness is 22.5GPa, and the fracture toughness is 5.2 MPa.m1/2The flexural strength was 520MPa, and the grain size was about 1.2 μm.
Example 5
The preparation method of the fifth ultrahigh-temperature ceramic provided by the embodiment of the application comprises the following steps:
(1) taking zirconium dioxide powder, boron powder and titanium dioxide powder as raw materials, and mixing the following raw materials in parts by weight: the molar ratio of the titanium dioxide powder is 3.7:0.3, the mixture of the zirconium dioxide powder and the titanium dioxide powder and the boron powder are mixed according to the molar ratio of 1:3.5, ethanol is used as a solvent, ZrB is adopted2The ball is used as a ball milling medium, ball milling and mixing are carried out on a planet ball mill for 24 hours at the rotating speed of 300r/min, and mixed materials and dried to obtain mixed powder.
(2) Sieving the mixed powder, putting the sieved mixed powder in a hot pressing furnace, heating the mixed powder to 1000 ℃ at the temperature rise rate of 10 ℃/min under the condition that the air pressure is lower than 20Pa, and keeping the temperature for 2 hours; then, the temperature is increased to 1550 ℃ at the heating rate of 15 ℃/min, and the temperature is kept for 1 h; then 1atm argon is introduced, the pressure of the graphite mould is kept at 30MPa, the temperature is raised to 2000 ℃ at the heating rate of 20 ℃/min, and the temperature is kept for 1 h. Tong (Chinese character of 'tong')Obtaining the ultra-high temperature ceramic (namely ZrB) by over-reaction hot-pressing sintering2-TiB2Solid solution ceramic).
The relative density of the ultrahigh-temperature ceramic prepared by the embodiment is about 96 percent, the hardness is 22GPa, and the fracture toughness is 6.0 MPa.m1/2The flexural strength was 450MPa, and the grain size was about 1.5 μm.
Example 6
The sixth preparation method of the ultrahigh-temperature ceramic provided by the embodiment of the application comprises the following steps:
(1) taking zirconium dioxide powder, boron powder and titanium dioxide powder as raw materials, and mixing the following raw materials in parts by weight: the molar ratio of titanium dioxide powder is 39:1, the mixture of zirconium dioxide powder and titanium dioxide powder and boron powder are mixed according to the molar ratio of 1:4, ethanol is used as solvent, ZrB2The ball is used as a ball milling medium, ball milling and mixing are carried out on a planet ball mill for 24 hours at the rotating speed of 300r/min, and mixed materials and dried to obtain mixed powder.
(2) Sieving the mixed powder, putting the sieved mixed powder in a hot pressing furnace, heating the mixed powder to 1100 ℃ at a heating rate of 15 ℃/min under the condition that the air pressure is lower than 20Pa, and keeping the temperature for 2 hours; then, the temperature is increased to 1550 ℃ at the heating rate of 15 ℃/min, and the temperature is kept for 1 h; then introducing argon gas of 1atm, keeping the pressure of a graphite die at 30MPa, heating the graphite die to 2100 ℃ at the heating rate of 40 ℃/min, preserving the heat for 1h, and obtaining the ultra-high temperature ceramic (namely ZrB) by reaction, hot pressing and sintering2-TiB2Solid solution ceramic).
The relative density of the ultrahigh-temperature ceramic prepared by the embodiment is about 97 percent, the hardness is 24GPa, and the fracture toughness is 5.2 MPa.m1/2The flexural strength was 640MPa, and the grain size was about 1.2 μm.
Comparative example 1
The present application provides undissolved TiB2The comparative example of (1), comprising the steps of:
(1) zirconium dioxide powder and boron powder are used as raw materials, the zirconium dioxide powder and the boron powder are mixed according to the molar ratio of 1:4, ethanol is used as a solvent, ZrB2Ball milling and mixing the mixture for 24 hours on a planetary ball mill at the rotating speed of 300r/min by taking the ball as a ball milling medium, and mixing and drying the mixture to obtain uniformly mixed ZrO2-B mixingAnd (3) powder.
(2) ZrO 2 is mixed with2Sieving the mixed powder B, heating to 1100 ℃ at a heating rate of 15 ℃/min in a hot-pressing furnace under the air pressure of less than 20Pa, and keeping the temperature for 2 h; then, the temperature is increased to 1550 ℃ at the heating rate of 15 ℃/min, and the temperature is kept for 1 h; then 1atm argon gas is introduced, the pressure of the graphite mold is kept at 30MPa, the temperature is raised to 2100 ℃ at the heating rate of 40 ℃/min, and the temperature is kept for 1 h. ZrB is obtained by reaction hot pressing sintering2A ceramic.
ZrB prepared in this comparative example2The relative density of the ceramic was 96%, the hardness was 20GPa, and the fracture toughness was 3.2 MPa.m1/2The flexural strength was 380MPa, and the grain size was about 7.4 μm.
Comparative example 2
The present application provides ZrB2The comparative example of hot press sintering of (1), comprising the steps of:
(1) with ZrB2Powder as raw material ZrB2The balls are used as ball milling media and are ball milled and mixed for 24 hours on a planet ball mill at the rotating speed of 300 r/min.
(2) Mixing the ZrB2After the powder is sieved, the powder is put in a hot pressing furnace, the temperature is raised to 2000 ℃ at the temperature rise rate of 20 ℃/min under the conditions that the air pressure is lower than 20Pa and the graphite mold is pressurized to 30MPa, and the temperature is kept for 1 h. The prepared TiB is hot pressed and sintered and does not dissolve in solid2Pure ZrB of2A ceramic.
ZrB prepared in this comparative example2The relative density of the ceramic was about 93%, the hardness was 17GPa, and the fracture toughness was 2.2 MPa.m1/2The flexural strength was 340MPa, and the grain size was about 7.6 μm.
In summary, it can be seen from the above examples and comparative examples that the relative density, hardness, fracture toughness, bending strength and grain size of the ultra-high temperature ceramics prepared in the examples are better than those prepared in the comparative examples. Experiments show that the densification of the ultrahigh-temperature ceramic is realized by applying a pressure of 20-50MPa and a high temperature of more than 2000 ℃ to zirconium oxide powder, titanium oxide powder and boron powder through hot-pressing sintering. The hot-pressing sintering can simultaneously lead the zirconium oxide powder and the titanium oxide powderReaction of the body with boron powder to form ZrB2And TiB2，TiB2Can be dissolved in ZrB2In (2), since the solid solution reaction occurs at the grain boundary, ZrB can be effectively reduced2The movement speed of the grain boundary in the sintering process can inhibit the growth of abnormal grains, refine the grains and improve the mechanical property of the grains.
The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.
Claims (5)
1. An ultra-high temperature ceramic, characterized by comprising the following steps:
step 1, mixing zirconium dioxide powder, titanium dioxide powder, boron powder and a solvent, and drying to obtain mixed powder; the molar ratio of the zirconium dioxide powder to the titanium dioxide powder is (9-39): 1; the ratio of the sum of the amounts of the substances of the zirconium dioxide powder and the titanium dioxide powder to the amount of the substance of the boron powder is 1: (3.3-4.5);
step 2, heating the mixed powder to 1450-1600 ℃, and then preserving heat to obtain an intermediate product;
step 3, under the condition of protective gas, under the pressure of 20-50MPa, heating the intermediate product to 1900-2100 ℃, and then preserving heat to obtain ultrahigh-temperature ceramic;
the relative density of the ultrahigh-temperature ceramic is more than 95%, the hardness is 15-28 GPa, and the fracture toughness is 4-8 MPa.m1/2The bending strength is 450 to 950MPa, and the grain size is 0.5 to 3 μm.
2. The ultrahigh-temperature ceramic of claim 1, wherein the zirconia powder has a particle size of 0 to 5 μm, and the titania powder and the boron powder have a particle size of 0 to 1 μm.
3. The preparation method of the ultrahigh-temperature ceramic according to any one of claims 1 to 2, characterized by comprising the following steps:
step 1, mixing zirconium dioxide powder, titanium dioxide powder, boron powder and a solvent, and drying to obtain mixed powder;
step 2, heating the mixed powder to 1450-1600 ℃, and then preserving heat to obtain an intermediate product;
step 3, under the condition of protective gas, under the pressure of 20-50MPa, heating the intermediate product to 1900-2100 ℃, and then preserving heat to obtain ultrahigh-temperature ceramic; the relative density of the ultrahigh-temperature ceramic is more than 95%, the hardness is 15-28 GPa, and the fracture toughness is 4-8 MPa.m1/2The bending strength is 450 to 950MPa, and the grain size is 0.5 to 3 μm.
4. The method for preparing ultra-high temperature ceramic according to claim 3, wherein after the step 1, before the step 2, further comprising: pretreating the mixed powder, wherein the pretreatment comprises the following steps: and heating the mixed powder to 950-1100 ℃, and then preserving heat.
5. The method for preparing ultra-high temperature ceramic according to claim 3, wherein the mixing is ball milling.
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