CN116082053B - Rapid preparation method of ceramic modified carbon/carbon composite material - Google Patents

Rapid preparation method of ceramic modified carbon/carbon composite material Download PDF

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CN116082053B
CN116082053B CN202310159424.1A CN202310159424A CN116082053B CN 116082053 B CN116082053 B CN 116082053B CN 202310159424 A CN202310159424 A CN 202310159424A CN 116082053 B CN116082053 B CN 116082053B
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carbon
carbon fiber
composite material
mixed powder
powder
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CN116082053A (en
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张福勤
丰欣妍
丰雪帆
孙婷婷
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Central South University
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Abstract

The invention discloses a rapid preparation method of a ceramic modified carbon/carbon composite material, wherein mixed powder is introduced in the preparation process of a carbon fiber preform to obtain a carbon fiber preform containing the mixed powder, then the carbon fiber preform is subjected to pyrolytic carbon densification of a chemical vapor deposition coarse layer structure, and finally reaction and melt siliconizing are carried out to obtain the ceramic modified carbon/carbon composite material, wherein the mixed powder consists of hafnium boride powder and zirconium boride powder. According to the invention, hafnium boride/zirconium boride mixed powder is introduced during braiding of the carbon fiber preform, and the ceramic mixed powder is used for filling macropores in the mesh layer of the preform, so that the specific surface area of reaction infiltration is increased, and the content of free silicon in the composite material after the reaction infiltration is reduced; the rough layer structure is utilized to pyrolyze carbon and carbon fiber to form tight interface combination, the carbon fiber is protected from being corroded by silicon at high temperature, the mechanical property of the composite material is improved, the density of the obtained composite material is 2.10-2.40g/cm 3, and the compressive strength is 280-450MPa.

Description

Rapid preparation method of ceramic modified carbon/carbon composite material
Technical Field
The invention discloses a rapid preparation method of a ceramic modified carbon/carbon composite material, and belongs to the technical field of preparation of carbon/ceramic composite materials.
Background
The ceramic modified carbon/carbon composite material is an advanced composite material which takes carbon fiber as a reinforcement and high-temperature resistant ceramic as a main matrix, has the excellent performances of light weight, high specific strength, high-temperature oxidation resistance and the like, and has wide application prospect in the fields of aviation, aerospace, transportation and the like.
The precursor impregnation and pyrolysis is a common method for introducing a ceramic phase into a carbon fiber preform, and the prepared carbon/ceramic composite material has the advantages of high mechanical property and the like, but the method has two main defects: the densification efficiency is low, taking a composite material with the density of 2.00g/cm 3 as an example, about 15 process cycles are needed; the manufacturing cost is high, the hafnium ceramic precursor is taken as an example, the weight of the ceramic in the composite material is converted, the consumed raw material cost of the ceramic precursor is about 10 times of that of the ceramic powder, and the application expansion of the carbon/ceramic composite material is limited by the high cost. The reaction infiltration is an important method for preparing the carbon/ceramic composite material, and the carbon/ceramic composite material prepared by the method has the advantages of short process flow, low manufacturing cost, high density and the like, and is a preferred method for high-temperature structural materials such as automobiles, high-speed rail trains, aerospace and the like. The reaction infiltration utilizes capillary effect to infiltrate molten silicon into pores in the carbon/ceramic composite material, and the molten silicon reacts with carbon in the carbon/ceramic composite material at high temperature to generate silicon carbide to realize ceramization. In the reaction infiltration process, the interface between the carbon fiber and the pyrolytic carbon can become a channel for infiltration of molten silicon, the infiltrated silicon reacts with the carbon fiber to destroy the surface structure of the carbon fiber and seriously damage the mechanical property of the carbon fiber. In addition, due to the diffusion depth of silicon in the solid pyrolytic carbon, silicon carbide is only generated on the surface of the pyrolytic carbon, so that part of silicon which is permeated into the pores of the composite material is reacted without a carbon source, and remains in the composite material in a free silicon form, thereby damaging the mechanical property and the physical property of the composite material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a rapid preparation method of a ceramic modified carbon/carbon composite material. According to the preparation method, hafnium boride/zirconium boride mixed powder is introduced in the weaving process of the carbon fiber preform, and hafnium boride/zirconium boride ceramic is rapidly and efficiently introduced in the ceramic modified carbon/carbon composite material; the rough layer structure is utilized to pyrolyze carbon and carbon fiber to form tight interface combination, so that the carbon fiber is protected from being corroded by silicon at high temperature; and filling macropores in the prefabricated body net layer by using the ceramic mixed powder, increasing the specific surface area of reaction infiltration, and reducing the content of free silicon in the composite material after the reaction infiltration.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The invention relates to a rapid preparation method of a ceramic modified carbon/carbon composite material, which is characterized in that mixed powder is introduced in the preparation process of a carbon fiber preform to obtain a carbon fiber preform containing the mixed powder, then the carbon fiber preform is subjected to chemical vapor deposition pyrolysis carbon densification, and finally the ceramic modified carbon/carbon composite material is obtained by reaction and siliconizing, wherein the mixed powder consists of hafnium boride powder and zirconium boride powder.
According to the preparation method, the hafnium boride/zirconium boride mixed powder is introduced in the preparation process of the carbon fiber preform, so that the reaction period is greatly shortened, meanwhile, the introduced hafnium boride/zirconium boride mixed powder can fill the macropores in the mesh tire layer of the preform, more reaction spaces with smaller size and more uniform distribution can be provided for molten silicon in the subsequent reaction infiltration process, and meanwhile, pyrolytic carbon is deposited on the surface of the hafnium boride/zirconium boride mixed powder in the chemical vapor deposition process, so that the specific surface area of the reaction is greatly increased, and the content of free silicon in the composite material is effectively reduced.
The invention relates to a rapid preparation method of a ceramic modified carbon/carbon composite material, wherein the particle size of mixed powder is 5-15 mu m. The inventor finds that the particle size of the mixed powder needs to be effectively controlled, and the particle size range is controlled within the range of the invention, so that macropores with the inner diameter of 50-200 mu m in the net layer of the preform can be well filled, the specific surface area of reaction infiltration is increased, and the content of free silicon in the composite material after the reaction infiltration is reduced. If the particle size is too large, the specific surface area of the composite material for reaction infiltration is reduced, the content of free silicon in the composite material after reaction infiltration is increased, and if the particle size is too small, the composite material is expensive, and meanwhile, the composite material is hardened and airtight, so that the performance of the composite material is reduced.
The invention relates to a rapid preparation method of a ceramic modified carbon/carbon composite material, which comprises the following steps of: zirconium boride powder=100:20-90, preferably 100:25-85, further preferably 100:60-85.
The inventor finds that the mechanical property and the high-temperature property of the finally obtained composite material are optimal by controlling the mass ratio of the hafnium boride powder to the zirconium boride powder within the range, and if the adding amount of the hafnium boride powder is too small, the high-temperature oxidation property of the ceramic modified carbon/carbon composite material below 2000 ℃ can be influenced.
The invention relates to a rapid preparation method of a ceramic modified carbon/carbon composite material, wherein mixed powder is obtained by ball milling and mixing hafnium boride powder and zirconium boride powder, the rotational speed of ball milling is controlled to be 25-30r/min in the ball milling and mixing process, and the ball milling time is 10-12h.
Preferably, the grain sizes of the hafnium boride powder and the zirconium boride powder are 5-15 mu m.
Preferably, in the ball milling mixing process, the grinding balls are silicon carbide balls.
The ball milling in the invention adopts dry ball milling.
The invention relates to a rapid preparation method of a ceramic modified carbon/carbon composite material, wherein the mass fraction of mixed powder in a carbon fiber preform is 30-60%, preferably 34-56%, and more preferably 45-56%.
The inventor finds that the quality fraction of the mixed powder is controlled within the range, the performance of the finally obtained carbon/ceramic composite material is optimal, and if the quality fraction of the mixed powder is too small, the specific surface area for reducing the reaction infiltration is reduced, so that the content of free silicon in the composite material after the reaction infiltration is increased.
The invention relates to a rapid preparation method of a ceramic modified carbon/carbon composite material, wherein the density of a carbon fiber preform is 0.45-0.70g/cm 3.
The invention relates to a rapid preparation method of a ceramic modified carbon/carbon composite material, wherein a carbon fiber preform is obtained by stacking a carbon fiber net tire layer, mixed powder and a carbon fiber non-woven layer and continuously needling, and the mixed powder is controlled to be uniformly spread on the surface of the carbon fiber net tire layer.
In the process of the carbon fiber preform, the mixed powder is uniformly paved on the surface of the carbon fiber net tyre layer, so that the mixed powder can fill the macropores of the carbon fiber net tyre layer, and meanwhile, carbon is enriched in the thin net felt layer in the chemical vapor deposition process, so that the carbon is better deposited on the surfaces of hafnium boride and zirconium boride powder, and the mixed powder is wrapped.
Preferably, the upper surface and the lower surface of the carbon fiber net tire layer positioned in the middle layer are paved with mixed powder. In the present invention, the intermediate layer refers to a layer other than the outermost layer.
Preferably, in the carbon fiber preform, the arrangement directions of adjacent carbon fiber laid cloths are 90 ° to each other. The inventor finds that the arrangement direction of adjacent carbon fiber laid fabrics in the carbon fiber preform is controlled to be 90 degrees, the performance of the finally obtained composite material is optimal, and a large amount of leftover materials can be avoided.
Preferably, the row spacing and the pitch of the needling are less than or equal to 2mm.
Preferably, the carbon fiber preform is divided into N layers of preform basic units, and any layer of preform basic unit is obtained by sequentially stacking carbon fiber net layers, mixed powder and carbon fiber laid cloth and continuously needling, wherein the preparation process of the carbon fiber preform is as follows: uniformly spreading mixed powder on the surface of a carbon fiber net bed-material layer, then spreading carbon fiber weft-free cloth above the mixed powder, continuously needling to obtain a first layer of prefabricated body basic unit, uniformly spreading mixed powder on the surface of the carbon fiber weft-free cloth of the first layer of prefabricated body basic unit, setting a second layer of prefabricated body basic unit on the surface of the carbon fiber weft-free cloth, uniformly spreading ceramic mixed powder on the surface of the carbon fiber weft-free cloth of the second layer of prefabricated body basic unit, and so on, and after the N layer of prefabricated body basic unit is obtained, needling and combining the N layer of prefabricated body basic units to obtain the carbon fiber prefabricated body.
By the preparation method, the ceramic mixed powder in the same preform basic unit can be uniformly distributed in the carbon fiber net tire, and the upper surface and the lower surface of the carbon fiber net tire layer are paved with the mixed powder.
The invention relates to a rapid preparation method of a ceramic modified carbon/carbon composite material, wherein when chemical vapor deposition pyrolytic carbon is densified, C 3H6 is used as carbon source gas, H 2 is used as diluent gas, the mass flow ratio of C 3H6 to H 2 is 40-50:1, the temperature is 940-950 ℃, and the pressure in a furnace is 10-12kPa.
In the invention, the obtained pyrolytic carbon is of a coarse layer structure by controlling the technological parameters in densification of the chemical vapor deposition pyrolytic carbon in the range, and the inventor finds that the pyrolytic carbon of the coarse layer structure not only can surround the surface of the carbon fiber to form tight interface combination with the carbon fiber, but also can be deposited on the surface of hafnium boride and zirconium boride powder to wrap the ceramic mixed powder.
The invention relates to a rapid preparation method of a ceramic modified carbon/carbon composite material, wherein the density of the composite material obtained after chemical vapor deposition pyrolysis carbon densification is 1.40-1.75g/cm 3.
The invention relates to a rapid preparation method of a ceramic modified carbon/carbon composite material, which comprises the following steps: vacuum degree less than or equal to 1000Pa, heating rate of 5-10 ℃/min, heat preservation temperature of 1500-1800 ℃ and heat preservation time of 30-60min;
preferably, the grain size of the silicon powder used for the reaction melt carburization silicon is 30-50 mu m, and the mass fraction of silicon in the silicon powder is more than or equal to 98%.
The invention relates to a rapid preparation method of a ceramic modified carbon/carbon composite material, wherein the density of the carbon/ceramic composite material is 2.10-2.40g/cm 3, and the compressive strength is 280-450MPa.
Advantages and positive effects
According to the invention, the mixed powder of hafnium boride and zirconium boride is woven in the preform, so that the rapid and efficient introduction of hafnium boride and other ceramics in the carbon/ceramic composite material is realized; the rough layer structure is utilized to pyrolyze carbon and carbon fiber to form tight interface combination, so that the carbon fiber is protected from being corroded by silicon at high temperature, and the problem of corrosion of high-temperature silicon melt to the carbon fiber in the reaction infiltration process is solved; the ceramic mixed powder is used for filling the macropores in the net layer of the preform, the specific surface area of the reaction infiltration is increased, and the content of free silicon in the composite material after the reaction infiltration is reduced.
(1) Compared with precursor dipping and cracking, the mixed powder of hafnium boride and zirconium boride woven by the preform shortens the process period from about 15 to 1, and obviously reduces the consumption of electric energy.
(2) The mass fraction of the mixed powder of the hafnium boride and the zirconium boride woven by the preform is 30-60%, and the mass ratio of the mixed powder to the zirconium boride is 100:20-90, so that the mixed powder can be regulated and controlled in a wider range.
(3) The grain size of the hafnium boride/zirconium boride mixed powder is 5-15 mu m, and the surfaces of the hafnium boride and zirconium boride powder are wrapped by pyrolytic carbon in the subsequent process of pyrolyzing carbon by chemical vapor deposition, so that a carbon source can be provided for subsequent reaction infiltration, and the specific surface area of the reaction is increased.
(4) The chemical vapor deposition pyrolytic carbon has a rough layer structure, is tightly combined with the carbon fiber around the surface of the carbon fiber, prevents silicon-containing liquid from penetrating into the carbon fiber/pyrolytic carbon interface in the subsequent processes of precursor dipping and cracking and reaction infiltration, and effectively protects the carbon fiber from high-temperature corrosion of silicon. Compared with a common pyrolytic carbon protective layer with a smooth layer structure, the pyrolytic carbon protective layer with a rough layer structure improves the mechanical property of the composite material by 20-40%.
(5) The chemical vapor deposition pyrolytic carbon is deposited on the surface of mixed powder of hafnium boride and zirconium boride with the particle size of 5-15 mu m, and the powder fills the macropores in the prefabricated body net tyre layer, so that more reaction spaces with smaller size and more uniform distribution can be provided for molten silicon in the subsequent reaction infiltration process, the specific surface area of the reaction is increased, the content of free silicon in the composite material is effectively reduced, the mass percent of the free silicon in the composite material is reduced by 30-60%, and the strength is improved by 10-30%.
Drawings
FIG. 1 is a process technology roadmap of the invention.
Detailed Description
Example 1
Braiding hafnium boride/zirconium boride mixed powder with the grain size of 5-15 mu m into a carbon fiber preform, performing chemical vapor deposition to pyrolyze carbon, and finally performing reaction to melt carburized silicon to prepare the carbon/ceramic composite material. The hafnium boride/zirconium boride mixed powder is prepared by ball milling and mixing hafnium boride powder and zirconium boride powder, wherein the particle size of the 2 kinds of powder is 5-15 mu m, the mass ratio is 100:60, and the ball milling and mixing process comprises the following steps: dry ball milling at 25r/min for 11 hr. The carbon fiber preform is obtained by sequentially superposing basic units of the preform and needling; the basic unit of the preform is formed by sequentially superposing a carbon fiber net tire layer, hafnium carbide/hafnium boride/zirconium boride mixed powder and carbon fiber weft-free cloth, and the ceramic mixed powder is uniformly paved on the surface of the carbon fiber net tire layer; uniformly spreading ceramic mixed powder on the laid fabric on which the first layer of prefabricated body basic unit is continuously needled, then superposing the second layer of prefabricated body basic unit on the laid fabric and continuously needled to realize uniform distribution of the ceramic mixed powder in the carbon fiber net in the same prefabricated body basic unit, and the like to obtain a carbon fiber prefabricated body obtained by needling the prefabricated body basic unit; the needling density is: the distance between adjacent rows is 2mm, and the distance in the same row is 2mm; in the carbon fiber preform, the arrangement directions of adjacent laid fabrics are 90 degrees; the hafnium carbide/hafnium boride/zirconium boride mixed powder is uniformly paved on the upper surface and the lower surface of the carbon fiber net tire layer; the density of the preform is 0.58g/cm 3, and the mass fraction of the ceramic mixed powder is 45%. The process for pyrolyzing carbon by chemical vapor deposition comprises the following steps: c 3H6 is used as carbon source gas, H 2 is used as diluent gas, the flow ratio of C 3H6 to H 2 is 46:1, the temperature is 940-950 ℃, the pressure in the furnace is 10-12kPa, and the density of the obtained composite material is 1.56g/cm 3. The process of the reactive melt carburized silicon comprises the following steps: the vacuum degree is less than or equal to 1000Pa, the heating rate is 6 ℃/min, the heat preservation temperature is 1700 ℃, the heat preservation time is 45min, and the density of the obtained ceramic modified carbon/carbon composite material is 2.29g/cm 3 and the compressive strength is 439MPa.
Example 2
Braiding hafnium boride/zirconium boride mixed powder with the grain size of 5-15 mu m into a carbon fiber preform, performing chemical vapor deposition to pyrolyze carbon, and finally performing reaction to melt carburized silicon to prepare the carbon/ceramic composite material. The hafnium boride/zirconium boride mixed powder is prepared by ball milling and mixing hafnium boride powder and zirconium boride powder, wherein the particle size of the 2 kinds of powder is 5-15 mu m, the mass ratio is 100:25, and the ball milling and mixing process comprises the following steps: dry ball milling at a rotation speed of 28r/min for 12 hours. The carbon fiber preform is obtained by sequentially superposing basic units of the preform and needling; the basic unit of the preform is formed by sequentially superposing a carbon fiber net tire layer, hafnium carbide/hafnium boride/zirconium boride mixed powder and carbon fiber weft-free cloth, and the ceramic mixed powder is uniformly paved on the surface of the carbon fiber net tire layer; uniformly spreading ceramic mixed powder on the laid fabric on which the first layer of prefabricated body basic unit is continuously needled, then superposing the second layer of prefabricated body basic unit on the laid fabric and continuously needled to realize uniform distribution of the ceramic mixed powder in the carbon fiber net in the same prefabricated body basic unit, and the like to obtain a carbon fiber prefabricated body obtained by needling the prefabricated body basic unit; the needling density is: the distance between adjacent rows is 1mm, and the distance in the same row is 1mm; in the carbon fiber preform, the arrangement directions of adjacent laid fabrics are 90 degrees; the hafnium carbide/hafnium boride/zirconium boride mixed powder is uniformly paved on the upper surface and the lower surface of the carbon fiber net tire layer; the density of the preform is 0.47g/cm 3, and the mass fraction of the ceramic mixed powder is 34%. The process for pyrolyzing carbon by chemical vapor deposition comprises the following steps: c 3H6 is used as carbon source gas, H 2 is used as diluent gas, the flow ratio of C 3H6 to H 2 is 42:1, the temperature is 940-950 ℃, the pressure in the furnace is 10-12kPa, and the density of the obtained composite material is 1.43g/cm 3. The process of the reactive melt carburized silicon comprises the following steps: the vacuum degree is less than or equal to 1000Pa, the heating rate is 5 ℃/min, the heat preservation temperature is 1580 ℃, the heat preservation time is 60min, and the density of the obtained ceramic modified carbon/carbon composite material is 2.15g/cm 3 and the compressive strength is 292MPa.
Example 3
Braiding hafnium boride/zirconium boride mixed powder with the grain size of 5-15 mu m into a carbon fiber preform, performing chemical vapor deposition to pyrolyze carbon, and finally performing reaction to melt carburized silicon to prepare the carbon/ceramic composite material. The hafnium boride/zirconium boride mixed powder is prepared by ball milling and mixing hafnium boride powder and zirconium boride powder, wherein the particle size of the 2 kinds of powder is 5-15 mu m, the mass ratio is 100:85, and the ball milling and mixing process comprises the following steps: dry ball milling at 30r/min for 10 hr. The carbon fiber preform is obtained by sequentially superposing basic units of the preform and needling; the basic unit of the preform is formed by sequentially superposing a carbon fiber net tire layer, hafnium carbide/hafnium boride/zirconium boride mixed powder and carbon fiber weft-free cloth, and the ceramic mixed powder is uniformly paved on the surface of the carbon fiber net tire layer; uniformly spreading ceramic mixed powder on the laid fabric on which the first layer of prefabricated body basic unit is continuously needled, then superposing the second layer of prefabricated body basic unit on the laid fabric and continuously needled to realize uniform distribution of the ceramic mixed powder in the carbon fiber net in the same prefabricated body basic unit, and the like to obtain a carbon fiber prefabricated body obtained by needling the prefabricated body basic unit; the needling density is: the distance between adjacent rows is 1.5mm, and the distance in the same row is 1.5mm; in the carbon fiber preform, the arrangement directions of adjacent laid fabrics are 90 degrees; the hafnium carbide/hafnium boride/zirconium boride mixed powder is uniformly paved on the upper surface and the lower surface of the carbon fiber net tire layer; the density of the preform is 0.68g/cm 3, and the mass fraction of the ceramic mixed powder is 56%. The process for pyrolyzing carbon by chemical vapor deposition comprises the following steps: c 3H6 is used as carbon source gas, H 2 is used as diluent gas, the flow ratio of C 3H6 to H 2 is 42:1, the temperature is 940-950 ℃, the pressure in the furnace is 10-12kPa, and the density of the obtained composite material is 1.72g/cm 3. The process of the reactive melt carburized silicon comprises the following steps: the vacuum degree is less than or equal to 1000Pa, the heating rate is 10 ℃/min, the heat preservation temperature is 1800 ℃, the heat preservation time is 30min, and the density of the obtained ceramic modified carbon/carbon composite material is 2.39g/cm 3 and the compressive strength is 365MPa.
Comparative example 1
Other conditions were the same as in example 2 except that the process of chemical vapor deposition of pyrolytic carbon was changed to: c 3H6 is used as carbon source gas, N 2 is used as diluent gas, the flow ratio of C 3H6 to H 2 is 100:1, the temperature is 980-1020 ℃, the pressure in the furnace is 5-6kPa, and the structure of pyrolytic carbon is changed from a rough layer to a smooth layer. Because gaps exist at the interface of the pyrolytic carbon with the carbon fiber with the smooth layer structure, the pyrolytic carbon becomes an erosion channel of molten silicon in the subsequent reaction infiltration process, the structure of the carbon fiber is damaged, and the compressive strength of the obtained ceramic modified carbon/carbon composite material is reduced from 292MPa to 197MPa.
Comparative example 2
Other conditions were the same as in example 2, except that the mass fraction of the hafnium boride/zirconium boride mixed powder in the preform was reduced from 34% to 10%, the content of free silicon in the composite material was increased by 41%, and the compressive strength of the ceramic modified carbon/carbon composite material was reduced from 292MPa to 226MPa.
Comparative example 3
Otherwise, the conditions are the same as those in example 2, except that the grain size of the hafnium boride/zirconium boride mixed powder in the preform is changed from 5-15 μm to 20-50 μm, the specific surface area of the composite material for reaction infiltration is reduced, the content of free silicon is increased by 32%, and the compressive strength of the ceramic modified carbon/carbon composite material is reduced from 292MPa to 263MPa.
Comparative example 4
Otherwise, the same conditions as in example 2 were applied, except that only hafnium boride powder was added to the mixed powder, and the ceramic modified carbon/carbon composite material was reduced in oxidation resistance at a high temperature of 2000 ℃.

Claims (9)

1. A rapid preparation method of a ceramic modified carbon/carbon composite material is characterized by comprising the following steps: introducing mixed powder into the preparation process of the carbon fiber preform to obtain a carbon fiber preform containing the mixed powder, performing chemical vapor deposition pyrolysis carbon densification on the carbon fiber preform, and finally performing reactive fusion siliconizing to obtain a ceramic modified carbon/carbon composite material, wherein the mixed powder consists of hafnium boride powder and zirconium boride powder;
The particle size of the mixed powder is 5-15 mu m;
In the mixed powder, the hafnium boride powder is prepared by the following components in percentage by mass: zirconium boride powder = 100:20-90;
In the carbon fiber preform, the arrangement directions of adjacent carbon fiber laid cloths are 90 degrees;
When the chemical vapor deposition pyrolytic carbon is densified, C 3H6 is used as carbon source gas, H 2 is used as diluent gas, the mass flow ratio of C 3H6 to H 2 is 40-50:1, the temperature is 940-950 ℃, and the furnace pressure is 10-12kPa.
2. The method for rapidly preparing a ceramic modified carbon/carbon composite material according to claim 1, wherein: the mixed powder is obtained by ball milling and mixing hafnium boride powder and zirconium boride powder, the rotation speed of ball milling is controlled to be 25-30r/min in the ball milling and mixing process, and the ball milling time is 10-12h;
The grain size of the hafnium boride powder and the zirconium boride powder is 5-15 mu m;
In the ball milling and mixing process, the grinding balls are silicon carbide balls.
3. The method for rapid preparation of a ceramic modified carbon/carbon composite material according to claim 1 or 2, characterized in that: in the carbon fiber preform, the mass fraction of the mixed powder is 30-60%;
the density of the carbon fiber preform is 0.45-0.70g/cm 3.
4. The method for rapid preparation of a ceramic modified carbon/carbon composite material according to claim 1 or 2, characterized in that: the carbon fiber preform is obtained by continuously needling a carbon fiber net tire layer, mixed powder and a carbon fiber non-woven layer stack, and the mixed powder is controlled to be uniformly spread on the surface of the carbon fiber net tire layer.
5. The method for rapidly preparing a ceramic modified carbon/carbon composite material according to claim 4, wherein: the upper surface and the lower surface of the carbon fiber net tire layer positioned in the middle layer are paved with mixed powder;
the row spacing and the interval of the needling are all less than or equal to 2mm.
6. The method for rapidly preparing a ceramic modified carbon/carbon composite material according to claim 5, wherein: the carbon fiber preform is divided into N layers of preform basic units, any one layer of preform basic unit is obtained by sequentially layering carbon fiber net layers, mixed powder and carbon fiber laid cloth and continuously needling, and the preparation process of the carbon fiber preform is as follows: uniformly spreading mixed powder on the surface of a carbon fiber net bed-material layer, then spreading carbon fiber weft-free cloth above the mixed powder, continuously needling to obtain a first layer of prefabricated body basic unit, uniformly spreading mixed powder on the surface of the carbon fiber weft-free cloth of the first layer of prefabricated body basic unit, setting a second layer of prefabricated body basic unit on the surface of the carbon fiber weft-free cloth, uniformly spreading ceramic mixed powder on the surface of the carbon fiber weft-free cloth of the second layer of prefabricated body basic unit, and so on, and after the N layer of prefabricated body basic unit is obtained, needling and combining the N layer of prefabricated body basic units to obtain the carbon fiber prefabricated body.
7. The method for rapid preparation of a ceramic modified carbon/carbon composite material according to claim 1 or 2, characterized in that: the density of the composite material obtained after the chemical vapor deposition pyrolysis carbon densification is 1.40-1.75g/cm 3.
8. The method for rapid preparation of a ceramic modified carbon/carbon composite material according to claim 1 or 2, characterized in that: the process of the reactive melt siliconizing comprises the following steps: vacuum degree is less than or equal to 1000Pa, heating rate is 5-10 ℃/min, heat preservation temperature is 1500-1800 ℃ and heat preservation time is 30-60min;
The grain diameter of the silicon powder used by the reaction melt carburized silicon is 30-50 mu m, and the mass fraction of silicon in the silicon powder is more than or equal to 98%.
9. The method for rapid preparation of a ceramic modified carbon/carbon composite material according to claim 1 or 2, characterized in that: the density of the carbon/ceramic composite material is 2.10-2.40g/cm 3, and the compressive strength is 280-450MPa.
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