CN114956842B - Boron carbide fiber/boron carbide ceramic composite material and preparation method thereof - Google Patents
Boron carbide fiber/boron carbide ceramic composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a boron carbide fiber/boron carbide ceramic composite material and a preparation method thereof. The method comprises the following steps: 1) Sequentially adding boron carbide powder, boron powder and ferric salt into deionized water, stirring, then adding ammonium salt, continuously stirring, filtering, and vacuum drying to obtain a boron carbide-boron-catalyst precursor; 2) Placing the precursor in a chemical vapor deposition furnace, and carrying out heat treatment reaction in methane atmosphere to obtain boron carbide fiber/boron carbide ceramic composite powder; 3) And placing the composite powder in an argon atmosphere for hot-pressing sintering, and then cooling to room temperature along with the furnace to obtain the boron carbide fiber/boron carbide ceramic composite material. In the obtained ceramic composite material, the boron carbide fiber is formed by in-situ reaction in the boron carbide ceramic powder body, is uniformly dispersed in the ceramic composite material, can fully play the strengthening and toughening effects of the one-dimensional boron carbide fiber, has good interface bonding characteristics with the boron carbide ceramic matrix, and effectively improves the mechanical properties and sintering properties of the boron carbide ceramic material.
Description
Technical Field
The invention belongs to the field of advanced structural ceramic materials, and particularly relates to a boron carbide fiber/boron carbide ceramic composite material and a preparation method thereof.
Background
The low-dimensional reinforced phase toughened boron carbide ceramic-based composite material has the excellent characteristics of high specific strength, high specific modulus, high hardness, low density, high fracture toughness, high fracture work and the like, is an important light ceramic armor material, and is one of important support materials for national defense construction and modern industry. With the continuous expansion of the application field and the service environment, higher requirements are provided for the strength, toughness and reliability of the boron carbide ceramic matrix composite material.
The one-dimensional inorganic non-metallic nano material (such as carbon nano tube, carbon fiber, silicon carbide fiber and boron nitride nano tube) has achieved a certain effect on reinforcing and toughening boron carbide ceramics, and the strengthening and toughening mechanism mainly comprises load transfer, bridging effect and pulling-out effect; or prestress is generated in the material matrix, and when the material bears longitudinal tensile load, the residual stress counteracts partial external stress.
In fact, the above inorganic nano-reinforcing phase faces the following problems in boron carbide ceramic composites: (1) The interface problem of the reinforcing phase and the boron carbide matrix easily causes the cracking of the boron carbide ceramic matrix; (2) In the sintering process of the ceramic material, the density of the ceramic material can be reduced due to the reinforcing phase with good high-temperature stability and chemical stability.
Therefore, how to design and prepare the inorganic nano reinforced phase-boron carbide ceramic composite material with excellent mechanical properties and good interface bonding characteristics and sintering properties is urgent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a boron carbide fiber/boron carbide ceramic composite material and a preparation method thereof. The boron carbide fiber is formed by in-situ reaction in the boron carbide ceramic powder and is uniformly dispersed in the ceramic composite material, the strengthening and toughening effects of the one-dimensional boron carbide fiber can be fully exerted, and the boron carbide ceramic powder has good interface bonding characteristics with the boron carbide ceramic matrix, so that the mechanical property and sintering property of the boron carbide ceramic material are effectively improved, and an important technical support is provided for the application field and the expansion of the service environment of the boron carbide ceramic.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the boron carbide fiber/boron carbide ceramic composite material comprises the following specific steps:
(1) Preparing a precursor of boron carbide-boron-catalyst: sequentially adding boron carbide powder, boron powder and ferric salt into deionized water, uniformly stirring, then adding ammonium salt, stirring at a certain temperature for reaction, filtering after the reaction is finished, and drying in vacuum to obtain a precursor of 'boron carbide-boron-catalyst'; the ammonium salt is ammonium carbonate or ammonium bicarbonate; the mass ratio of the boron carbide, the boron powder, the ferric salt and the ammonium salt is 1:0.02 to 0.1:0.01 to 0.05:0.05 to 0.1;
(2) Preparing boron carbide fiber/boron carbide ceramic composite powder: placing the precursor of the boron carbide-boron-catalyst obtained in the step (1) in a chemical vapor deposition furnace, heating to a certain temperature in methane atmosphere for heat treatment reaction, and then naturally cooling to room temperature to obtain boron carbide fiber/boron carbide ceramic composite powder; the heat treatment temperature is 1100-1300 ℃, and the heat treatment time is 1-3 h;
(3) Preparing the boron carbide fiber/boron carbide ceramic composite material: and (3) placing the boron carbide fiber/boron carbide ceramic composite powder obtained in the step (2) in an argon atmosphere for hot-pressing sintering, and then cooling to room temperature along with a furnace to obtain the boron carbide fiber/boron carbide ceramic composite material.
In the scheme, in the step (1), the ferric salt is ferric trichloride, ferric nitrate or ferric sulfate.
In the scheme, in the step (1), the stirring reaction temperature is 60-90 ℃, and the reaction time is 2-8 h.
In the scheme, in the step (1), the vacuum drying temperature is 80-120 ℃, and the drying time is 12-24 h.
In the scheme, in the step (2), the flow rate of the methane gas is 100-300 ml/min.
In the above scheme, in the step (2), the heating rate during the heat treatment is 4-10 ℃/min.
In the scheme, in the step (3), the hot-pressing sintering temperature is 1850-1950 ℃, the sintering pressure is 30-50 MPa, and the sintering time is 30-60 min.
Provides the boron carbide fiber/boron carbide ceramic composite material prepared by the preparation method.
The invention has the beneficial effects that:
1. the invention provides a preparation method of boron carbide fiber/boron carbide ceramic composite material, which comprises the steps of firstly preparing a precursor of boron carbide-boron-catalyst with a catalyst uniformly distributed on boron carbide-boron powder by utilizing chemical precipitation reaction; then carrying out high-temperature heat treatment reaction, cracking methane gas to provide a carbon source, providing a boron source by boron powder, and carrying out in-situ reaction on a boron carbide ceramic powder matrix to form boron carbide nanowires through the processes of dissolution, adsorption, diffusion and deposition by taking the boron carbide ceramic powder as nucleation sites under the action of an iron-based catalyst, thereby obtaining composite powder in which boron carbide fibers and the boron carbide ceramic powder are uniformly dispersed; finally, carrying out hot-pressing sintering to obtain the boron carbide fiber/boron carbide ceramic composite material; wherein: the boron carbide fiber is uniformly dispersed in the ceramic composite material, and the strengthening and toughening effects of the one-dimensional boron carbide fiber can be fully exerted; meanwhile, the reinforcing phase and the ceramic matrix in the composite material are both boron carbide, the reinforcing phase and the ceramic matrix have good interface bonding characteristics, and the composite material is stable in structure and not easy to crack; in addition, the boron carbide fiber reinforced phase and the boron carbide ceramic matrix can be effectively sintered, and a small amount of iron-based catalyst is favorable for sintering in the ceramic composite material, so that the compactness of the material can be improved.
2. The preparation method is simple, the obtained ceramic composite material has good compactness and excellent mechanical property and sintering property, and provides important technical support for the application field of boron carbide ceramic materials and the expansion of service environment.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A preparation method of boron carbide fiber/boron carbide ceramic composite material comprises the following specific steps:
(1) Preparing a precursor of boron carbide-boron-catalyst: sequentially adding 1mol of boron carbide powder, 0.02mol of boron powder and 0.01mol of ferric trichloride into 500ml of deionized water, stirring for 30min, then adding 0.05mol of ammonium carbonate, stirring for 8h in water bath at 60 ℃, filtering, and carrying out vacuum drying on the filtrate for 24h at 80 ℃ to obtain the precursor of the 'boron carbide-boron-catalyst'.
(2) Preparing boron carbide fiber/boron carbide ceramic composite powder: and (2) placing the precursor of the boron carbide-boron-catalyst obtained in the step (1) in a chemical vapor deposition furnace, heating to 1300 ℃ at the speed of 4 ℃/min in the methane atmosphere with the flow rate of 100ml/min, preserving the temperature for 1h, and then naturally cooling to room temperature to obtain the boron carbide fiber/boron carbide ceramic composite powder.
(3) Preparing the boron carbide fiber/boron carbide ceramic composite material: and (3) placing the boron carbide fiber/boron carbide ceramic composite powder obtained in the step (2) into a cylindrical graphite mold, sintering the boron carbide fiber/boron carbide ceramic composite powder for 60min at 1950 ℃ under the axial pressure of 50MPa in a hot-pressing sintering furnace in an argon atmosphere, and cooling the graphite mold to room temperature along with the furnace to obtain the boron carbide fiber/boron carbide ceramic composite material with the diameter of 50mm and the thickness of 5 mm.
The bending strength of the obtained boron carbide fiber/boron carbide ceramic composite material is 551MPa by using a three-point bending method; the fracture toughness of the boron carbide fiber/boron carbide ceramic composite material measured by a single-side notched beam method is 4.82 MPa.m 1/2 (ii) a The relative density was 99.5% by archimedes drainage method.
The pure boron carbide ceramic material obtained under the same hot-pressing sintering conditions (50MPa, 1950 ℃ and 60 min) measured by the method has the bending strength of 398MPa and the fracture toughness of 3.30 MPa-m 1/2 The relative density was 98.2%. The comparison shows that the bending strength and the fracture toughness of the boron carbide fiber/boron carbide ceramic composite material are respectively improved by 38.4 percent and 46.1 percent, and the sintering performance is also improved.
Example 2
A preparation method of a boron carbide fiber/boron carbide ceramic composite material comprises the following specific steps:
(1) Preparing a precursor of boron carbide-boron-catalyst: sequentially adding 1mol of boron carbide powder, 0.1mol of boron powder and 0.01mol of ferric nitrate into 500ml of deionized water, stirring for 30min, then adding 0.1mol of ammonium bicarbonate, stirring for 2h in a water bath at 90 ℃, filtering, and carrying out vacuum drying on the filtrate for 12h at 120 ℃ to obtain a precursor of 'boron carbide-boron-catalyst'.
(2) Preparing boron carbide fiber/boron carbide ceramic composite powder: and (2) placing the precursor of the boron carbide-boron-catalyst obtained in the step (1) in a chemical vapor deposition furnace, heating to 1100 ℃ at the speed of 10 ℃/min in a methane atmosphere with the flow rate of 300ml/min, preserving the temperature for 3h, and then naturally cooling to room temperature to obtain the boron carbide fiber/boron carbide ceramic composite powder.
(3) Preparing the boron carbide fiber/boron carbide ceramic composite material: and (3) placing the boron carbide fiber/boron carbide ceramic composite powder obtained in the step (2) into a cylindrical graphite mold, sintering for 30min at 1950 ℃ under the axial pressure of 30MPa in a hot-pressing sintering furnace in an argon atmosphere, and cooling to room temperature along with the furnace to obtain the boron carbide fiber/boron carbide ceramic composite material with the diameter of 50mm and the thickness of 5 mm.
The products prepared in the examples of the present invention were tested in a similar manner to example 1, and the results showed that the bending strength and fracture toughness of the resulting boron carbide fiber/boron carbide ceramic composite material were 492MPa and 4.46 MPa-m, respectively 1/2 Compared with the pure boron carbide ceramic material without boron carbide fiber obtained under the same hot pressing sintering conditions (30MPa, 1950 ℃,30 min), the performance of the pure boron carbide ceramic material is improved by 34.8 percent and 42.5 percent; and the relative density of the boron carbide fiber/boron carbide ceramic composite material exceeds 99 percent.
Example 3
A preparation method of boron carbide fiber/boron carbide ceramic composite material comprises the following specific steps:
(1) Preparing a precursor of boron carbide-boron-catalyst: sequentially adding 1mol of boron carbide powder, 0.02mol of boron powder and 0.05mol of ferric sulfate into 500ml of deionized water, stirring for 30min, then adding 0.1mol of ammonium carbonate, stirring for 8h in water bath at 90 ℃, filtering, and carrying out vacuum drying on the filtrate for 24h at 120 ℃ to obtain the precursor of the boron carbide-boron-catalyst.
(2) Preparing boron carbide fiber/boron carbide ceramic composite powder: and (2) placing the precursor of the boron carbide-boron-catalyst obtained in the step (1) in a chemical vapor deposition furnace, heating to 1100 ℃ at a speed of 4 ℃/min in a methane atmosphere with a flow rate of 300ml/min, preserving heat for 1h, and naturally cooling to room temperature to obtain the boron carbide fiber/boron carbide ceramic composite powder.
(3) Preparing the boron carbide fiber/boron carbide ceramic composite material: and (3) placing the boron carbide fiber/boron carbide ceramic composite powder obtained in the step (2) into a cylindrical graphite die, axially applying 50MPa pressure to the graphite die in a hot-pressing sintering furnace in argon atmosphere, sintering at 1850 ℃ for 60min, and cooling to room temperature along with the furnace to obtain the boron carbide fiber/boron carbide ceramic composite material with the diameter of 50mm and the thickness of 5 mm.
The products prepared in the examples of the present invention were tested in a similar manner to example 1, and the results showed that the bending strength and fracture toughness of the resulting boron carbide fiber/boron carbide ceramic composite material were 467MPa and 4.13 MPa-m, respectively 1/2 Compared with the pure boron carbide ceramic material without boron carbide fiber obtained under the same hot-pressing sintering conditions (50MPa, 1850 ℃ and 60 min), the performance is improved by 30.4 percent and 36.8 percent; and the relative density of the boron carbide fiber/boron carbide ceramic composite material exceeds 99 percent.
Example 4
A preparation method of a boron carbide fiber/boron carbide ceramic composite material comprises the following specific steps:
(1) Preparing a precursor of boron carbide-boron-catalyst: sequentially adding 1mol of boron carbide powder, 0.1mol of boron powder and 0.05mol of ferric chloride into 500ml of deionized water, stirring for 30min, then adding 0.05mol of ammonium bicarbonate, stirring for 2h in a water bath at 60 ℃, filtering, and carrying out vacuum drying on the filtrate for 12h at 80 ℃ to obtain a precursor of 'boron carbide-boron-catalyst'.
(2) Preparing boron carbide fiber/boron carbide ceramic composite powder: and (2) placing the precursor of the boron carbide-boron-catalyst obtained in the step (1) in a chemical vapor deposition furnace, heating to 1300 ℃ at the speed of 10 ℃/min in the methane atmosphere with the flow rate of 100ml/min, preserving the heat for 3h, and then naturally cooling to room temperature to obtain the boron carbide fiber/boron carbide ceramic composite powder.
(3) Preparing the boron carbide fiber/boron carbide ceramic composite material: and (3) placing the boron carbide fiber/boron carbide ceramic composite powder obtained in the step (2) into a cylindrical graphite die, axially applying 30MPa pressure to the graphite die in a hot-pressing sintering furnace in argon atmosphere, sintering at 1850 ℃ for 30min, and cooling to room temperature along with the furnace to obtain the boron carbide fiber/boron carbide ceramic composite material with the diameter of 50mm and the thickness of 5 mm.
The results of tests conducted on the products prepared in the examples of the present invention in a manner similar to that of example 1 revealed that the resulting boron carbide fiber/boron carbide ceramic composite had flexural strength and fracture toughness of 446MPa and 3.88MPa · m, respectively 1/2 Compared with the same hot-pressing sintering condition (30MPa, 1850 ℃,30 min) the performance of the pure boron carbide ceramic material without boron carbide fiber is improved by 33.1 percent and 32.0 percent; and the relative density of the boron carbide fiber/boron carbide ceramic composite material exceeds 99 percent.
Example 5
A preparation method of boron carbide fiber/boron carbide ceramic composite material comprises the following specific steps:
(1) Preparing a precursor of boron carbide-boron-catalyst: sequentially adding 1mol of boron carbide powder, 0.04mol of boron powder and 0.02mol of ferric nitrate into 500ml of deionized water, stirring for 30min, then adding 0.09mol of ammonium carbonate, stirring for 4h in a water bath at 70 ℃, filtering, and carrying out vacuum drying on the filtered substance for 24h at 90 ℃ to obtain a precursor of 'boron carbide-boron-catalyst'.
(2) Preparing boron carbide fiber/boron carbide ceramic composite powder: and (2) placing the precursor of the boron carbide-boron-catalyst obtained in the step (1) in a chemical vapor deposition furnace, heating to 1100 ℃ at the speed of 6 ℃/min in the methane atmosphere with the flow rate of 250ml/min, preserving the temperature for 2h, and naturally cooling to room temperature to obtain the boron carbide fiber/boron carbide ceramic composite powder.
(3) Preparing the boron carbide fiber/boron carbide ceramic composite material: and (3) placing the boron carbide fiber/boron carbide ceramic composite powder obtained in the step (2) into a cylindrical graphite mold, sintering for 60min at 1950 ℃ under the axial pressure of 30MPa in a hot-pressing sintering furnace in an argon atmosphere, and cooling to room temperature along with the furnace to obtain the boron carbide fiber/boron carbide ceramic composite material with the diameter of 50mm and the thickness of 5 mm.
The products prepared in the examples of the present invention were tested in a manner similar to that of example 1, and the results showed that the bending strength and fracture toughness of the resulting boron carbide fiber/boron carbide ceramic composite material were 525MPa and 4.79 MPa-m, respectively 1/2 Compared with the pure boron carbide ceramic material without boron carbide fiber obtained under the same hot pressing sintering conditions (30MPa, 1950 ℃,60 min), the performance is improved by 38.2 percent and 48.3 percent; and the relative density of the boron carbide fiber/boron carbide ceramic composite material exceeds 99 percent.
Example 6
A preparation method of a boron carbide fiber/boron carbide ceramic composite material comprises the following specific steps:
(1) Preparing a precursor of boron carbide-boron-catalyst: sequentially adding 1mol of boron carbide powder, 0.05mol of boron powder and 0.03mol of ferric sulfate into 500ml of deionized water, stirring for 30min, then adding 0.06mol of ammonium bicarbonate, stirring for 6h in water bath at 80 ℃, filtering, and carrying out vacuum drying on the filtrate for 20h at 100 ℃ to obtain the precursor of the 'boron carbide-boron-catalyst'.
(2) Preparing boron carbide fiber/boron carbide ceramic composite powder: and (2) placing the precursor of the boron carbide-boron-catalyst obtained in the step (1) in a chemical vapor deposition furnace, heating to 1300 ℃ at the speed of 8 ℃/min in the methane atmosphere with the flow rate of 200ml/min, preserving the temperature for 2h, and then naturally cooling to room temperature to obtain the boron carbide fiber/boron carbide ceramic composite powder.
(3) Preparing the boron carbide fiber/boron carbide ceramic composite material: and (3) placing the boron carbide fiber/boron carbide ceramic composite powder obtained in the step (2) into a cylindrical graphite mold, axially applying 40MPa pressure to the graphite mold in a hot-pressing sintering furnace in an argon atmosphere, sintering for 30min at 1900 ℃, and cooling to room temperature along with the furnace to obtain the boron carbide fiber/boron carbide ceramic composite material with the diameter of 50mm and the thickness of 5 mm.
The results of tests conducted on the products prepared in the examples of the present invention in a manner similar to that of example 1 revealed that the resulting boron carbide fiber/boron carbide ceramic composite had flexural strength and fracture toughness of 475MPa and 4.34MPa · m, respectively 1/2 Compared with the pure boron carbide ceramic material without boron carbide fiber obtained under the same hot-pressing sintering conditions (40MPa, 1900 ℃ and 30 min), the performance of the pure boron carbide ceramic material is improved by 31.6 percent and 40.9 percent; and the relative density of the boron carbide fiber/boron carbide ceramic composite material exceeds 99 percent.
Example 7
A preparation method of boron carbide fiber/boron carbide ceramic composite material comprises the following specific steps:
(1) Preparing a precursor of boron carbide-boron-catalyst: sequentially adding 1mol of boron carbide powder, 0.06mol of boron powder and 0.04mol of ferric chloride into 500ml of deionized water, stirring for 30min, then adding 0.07mol of ammonium carbonate, stirring for 6h in a water bath at 60 ℃, filtering, and carrying out vacuum drying on the filtered substance for 18h at 110 ℃ to obtain a precursor of 'boron carbide-boron-catalyst'.
(2) Preparing boron carbide fiber/boron carbide ceramic composite powder: and (2) placing the precursor of the boron carbide-boron-catalyst obtained in the step (1) in a chemical vapor deposition furnace, heating to 1200 ℃ at the speed of 8 ℃/min in a methane atmosphere with the flow rate of 150ml/min, preserving the temperature for 1h, and then naturally cooling to room temperature to obtain the boron carbide fiber/boron carbide ceramic composite powder.
(3) Preparing the boron carbide fiber/boron carbide ceramic composite material: and (3) placing the boron carbide fiber/boron carbide ceramic composite powder obtained in the step (2) into a cylindrical graphite mold, sintering the boron carbide fiber/boron carbide ceramic composite powder for 60min at 1900 ℃ under the axial pressure of the graphite mold in a hot-pressing sintering furnace in an argon atmosphere, and cooling the sintered powder to room temperature along with the furnace to obtain the boron carbide fiber/boron carbide ceramic composite material with the diameter of 50mm and the thickness of 5 mm.
The products prepared in the examples of the present invention were tested in a similar manner to example 1, and the results showed that the resulting boron carbide fiber/boron carbide ceramic composite had flexural strength and fracture toughness of 526MPa and 4.42 MPa-m, respectively 1/2 Compared with the pure boron carbide ceramic material without boron carbide fiber obtained under the same hot-pressing sintering conditions (50MPa, 1900 ℃ and 60 min), the performance of the pure boron carbide ceramic material is improved by 42.2 percent and 37.3 percent; and the relative density of the boron carbide fiber/boron carbide ceramic composite material exceeds 99 percent.
Example 8
A preparation method of a boron carbide fiber/boron carbide ceramic composite material comprises the following specific steps:
(1) Preparing a precursor of boron carbide-boron-catalyst: sequentially adding 1mol of boron carbide powder, 0.08mol of boron powder and 0.03mol of ferric nitrate into 500ml of deionized water, stirring for 30min, then adding 0.08mol of ammonium bicarbonate, stirring for 4h in water bath at 90 ℃, filtering, and carrying out vacuum drying on the filtrate for 24h at 110 ℃ to obtain the precursor of 'boron carbide-boron-catalyst'.
(2) Preparing boron carbide fiber/boron carbide ceramic composite powder: and (2) placing the precursor of the boron carbide-boron-catalyst obtained in the step (1) in a chemical vapor deposition furnace, heating to 1200 ℃ at the speed of 6 ℃/min in the methane atmosphere with the flow rate of 100ml/min, preserving the heat for 3h, and naturally cooling to room temperature to obtain the boron carbide fiber/boron carbide ceramic composite powder.
(3) Preparing the boron carbide fiber/boron carbide ceramic composite material: and (3) placing the boron carbide fiber/boron carbide ceramic composite powder obtained in the step (2) into a cylindrical graphite mold, sintering for 45min at 1950 ℃ under the axial pressure of 40MPa in a hot-pressing sintering furnace in an argon atmosphere, and cooling to room temperature along with the furnace to obtain the boron carbide fiber/boron carbide ceramic composite material with the diameter of 50mm and the thickness of 5 mm.
The results of tests conducted on the products prepared in the examples of the present invention in a manner similar to that of example 1 revealed that the bending strength and fracture toughness of the resulting boron carbide fiber/boron carbide ceramic composite material were 531MPa and 4.77MPa · m, respectively 1/2 The performance of the pure boron carbide ceramic material without boron carbide fiber is improved by 39.0 percent and 46.8 percent compared with the pure boron carbide ceramic material without boron carbide fiber obtained under the same hot-pressing sintering conditions (40MPa, 1950 ℃ and 45 min); and the relative density of the boron carbide fiber/boron carbide ceramic composite material exceeds 99 percent.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious changes and modifications can be made without departing from the scope of the invention.
Claims (8)
1. A preparation method of boron carbide fiber/boron carbide ceramic composite material is characterized by comprising the following steps:
(1) Preparing a precursor of boron carbide-boron-catalyst: sequentially adding boron carbide powder, boron powder and ferric salt into deionized water, uniformly stirring, then adding ammonium salt, stirring at a certain temperature for reaction, filtering after the reaction is finished, and drying in vacuum to obtain a precursor of boron carbide-boron-catalyst; the ammonium salt is ammonium carbonate or ammonium bicarbonate; the mass ratio of the boron carbide, the boron powder, the ferric salt and the ammonium salt is 1:0.02 to 0.1:0.01 to 0.05:0.05 to 0.1;
(2) Preparing boron carbide fiber/boron carbide ceramic composite powder: placing the precursor of the boron carbide-boron-catalyst obtained in the step (1) in a chemical vapor deposition furnace, heating to a certain temperature in methane atmosphere for heat treatment reaction, and then naturally cooling to room temperature to obtain boron carbide fiber/boron carbide ceramic composite powder; the heat treatment temperature is 1100-1300 ℃, and the heat treatment time is 1-3 h;
(3) Preparing the boron carbide fiber/boron carbide ceramic composite material: and (3) placing the boron carbide fiber/boron carbide ceramic composite powder obtained in the step (2) in an argon atmosphere for hot-pressing sintering, and then cooling to room temperature along with a furnace to obtain the boron carbide fiber/boron carbide ceramic composite material.
2. The method according to claim 1, wherein in the step (1), the iron salt is ferric trichloride, ferric nitrate or ferric sulfate.
3. The method according to claim 1, wherein in the step (1), the stirring reaction temperature is 60 to 90 ℃ and the reaction time is 2 to 8 hours.
4. The preparation method according to claim 1, wherein in the step (1), the vacuum drying temperature is 80-120 ℃ and the drying time is 12-24 h.
5. The production method according to claim 1, wherein in the step (2), the flow rate of the methane gas is 100 to 300ml/min.
6. The production method according to claim 1, wherein in the step (2), the temperature increase rate at the time of the heat treatment is 4 to 10 ℃/min.
7. The method according to claim 1, wherein in the step (3), the hot press sintering temperature is 1850 to 1950 ℃, the sintering pressure is 30 to 50MPa, and the sintering time is 30 to 60min.
8. A boron carbide fiber/boron carbide ceramic composite material prepared by the preparation method according to any one of claims 1 to 7.
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