CN109627032B - Preparation method of high-thermal-conductivity and electric-conductivity ceramic matrix composite containing three-dimensional ordered graphene - Google Patents

Preparation method of high-thermal-conductivity and electric-conductivity ceramic matrix composite containing three-dimensional ordered graphene Download PDF

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CN109627032B
CN109627032B CN201910083454.2A CN201910083454A CN109627032B CN 109627032 B CN109627032 B CN 109627032B CN 201910083454 A CN201910083454 A CN 201910083454A CN 109627032 B CN109627032 B CN 109627032B
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graphene
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CN109627032A (en
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刘永胜
张运海
王晶
曹立阳
李精鑫
成来飞
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Northwestern Polytechnical University
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Abstract

The invention relates to a preparation method of a high-thermal-conductivity and electric-conductivity ceramic matrix composite containing three-dimensional ordered graphene. According to the technical scheme provided by the invention, the graphene/fiber core-shell structure with better graphene coating can be prepared in a short time, so that interface assembly is realized; and processing an oriented channel on the semi-compact composite material, backfilling to finish graphene assembly in the thickness direction, and compacting to obtain the composite material. The method has the advantages of stable process, high repeatability, low cost and high yield, and can improve the final thermal conductivity of the composite material by 10-50 times and the final electrical conductivity by 50-300 times.

Description

Preparation method of high-thermal-conductivity and electric-conductivity ceramic matrix composite containing three-dimensional ordered graphene
Technical Field
The invention belongs to a preparation method of a ceramic matrix composite, and relates to a preparation method of a high-thermal-conductivity and electric-conductivity ceramic matrix composite containing three-dimensional ordered graphene.
Background
Carbon fiber toughened silicon carbide ceramic matrix composite (C)fSiC) overcomes the fatal weaknesses of single silicon carbide ceramic such as large brittleness, poor reliability and the like, has the characteristics of high temperature resistance, high strength, low density, small thermal expansion, good thermal conductivity, higher high temperature strength, corrosion resistance and the like, and can realize the integration of ablation, heat insulation, structural bearing and other functions, thereby realizing the purposes of structure simplification, weight reduction, repeated use and performance improvement of an aerospace structure, and achieving the final purposes of performance improvement and reliability improvement of an aerospace system. However, with the development of aerospace technology, the requirements on the performance and speed of airplanes are improved, and the requirements on the performance of materials are higher and higher, especially for the C applied to the fields of aircraft engines, rocket engines, thermal protection systems of aerospace vehicles and the likefthe/SiC composite material is not only required to have better performanceBesides mechanical properties, it is also required to integrate functional properties such as heat conduction, electric conduction, magnetic shielding and the like. Then, C is increased while strength and toughness are ensuredfThe functionality (high thermal conductivity, electric conductivity and the like) of the/SiC composite material is one of the key problems to be solved in the field at present.
Graphene (Gr) is a polymer made of carbon atoms in sp2The hybrid orbitals form hexagonal honeycomb lattice two-dimensional carbon nanomaterials, which are one of the materials with the highest known strength. Due to the special structure, the graphene also has excellent functionality, such as the thermal conductivity coefficient of single-layer graphene is as high as 5300W/mK, and the room-temperature carrier mobility is as high as 15000cm2V · s is the best material for reinforcement of highly thermally and electrically conductive composite materials. However, due to the influence of the graphene structure, the surface energy is high, and the van der waals force between layers is strong, so that the defects of sheet curling, stacking and agglomeration, difficult dispersion and the like are easily generated. In document 1, Kinloch, I.A, et al, in the article, "Composites with carbon nanotubes and graphene: An outlook", show that the more the lamellar defects of graphene are, the more the number of stacked layers is, the more the graphene is agglomerated, the more the graphene is distributed, the more disordered the graphene is, the greater the influence on the performance of the graphene is, and thus the performance of the graphene is limited. In document 2, "the contamination of SiCtf-CNTs/SiC compositions with high thermal conductivity by vacuum filtration combined with CVI" reports the use of CNTs film and SiCfPreparation of SiC by fiber cloth interlayer assemblyfThe method of the-CNTs/SiC composite material finally improves the thermal conductivity of the composite material by 2.9 times, and the improvement is not obvious. This is because CNTs are only assembled between layers, and complete three-dimensional network channels are not constructed, thus making the final thermal conductivity improvement insignificant. In document 3, "Thermal and mechanical properties of SiC/SiC-CNTs composites bonded by CVI bonded with electro-phoretic deposition" reports a method of improving the Thermal conductivity of the composite material by introducing a CNTs interface on the surface of SiC by electrophoretic deposition, but the Thermal conductivity is improved by only 1.74 times. The same problem exists as that of document 2, that is, there is no effective heat conduction channel in the thickness direction, and heat flow cannot be conducted in all directions in the composite material, so that the thermal conductivity of the composite material is not obviously improved.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a preparation method of a high-thermal-conductivity and electric-conductivity ceramic matrix composite containing three-dimensional ordered graphene, which adopts a sizing process to complete graphene/fiber interface assembly, and then weaves to prepare fiber cloth and complete lamination assembly, or weaves into 2.5-dimensional and 3-dimensional preforms; after the prefabricated body is deposited with the interface layer and the matrix, the directional channel is prepared, and the graphene is backfilled, so that the three-dimensional heat conduction channel in the composite material can be constructed. And finally, further introducing a matrix for densification by adopting a CVI or RMI method to prepare the high-thermal-conductivity composite material.
Technical scheme
A preparation method of a high-thermal-conductivity and electric-conductivity ceramic matrix composite containing three-dimensional ordered graphene is characterized by comprising the following steps:
step 1: carrying out surface activation treatment on the graphene for 0.5-12 hours by adopting an acid reagent; the mass ratio of the graphene to the acid reagent is 1: 40-1: 120;
step 2: preparing 0.1-50 mg/mL solution from the pretreated graphene, a dispersant and a solvent, and adjusting the pH value to 5-10 to obtain slurry; the mass ratio of the dispersing agent to the graphene is 0.1-30;
step 3, interface assembly: orderly assembling graphene onto fibers by adopting a sizing process to form a one-dimensional graphene/fiber core-shell structure, and completing interface assembly after drying;
the assembly process parameters are as follows: the temperature of a drying box of a sizing machine is 25-120 ℃, the drying time is 1-60 minutes, the temperature of a stock chest is 25-100 ℃, and the yarn feeding speed is 5-30 m/min, so that the fiber after graphene interface assembly is obtained;
and 4, step 4: preparing a graphene solution with the concentration of 0.1-10 mg by using graphene and a solvent, and preparing a graphene film by using a vacuum filtration method, wherein the thickness of the graphene film is controlled to be 15-1000 mu m; the pressure of a vacuum pump is controlled to be-0.08-0.096 MPa during vacuum filtration;
step 5, preparing a prefabricated body: weaving the fibers obtained in the step 3 into two-dimensional fiber cloth or 2.5-dimensional and 3-dimensional prefabricated bodies; carrying out interlayer assembly with the graphene film obtained in the step 4 to obtain a prefabricated body; directly shaping the 2.5-dimensional and 3-dimensional fiber preforms by using a graphite mold;
the warp density and weft density of the woven two-dimensional fiber cloth are controlled to be 80-120 bundles/10 cm;
step 6, depositing an interface layer and a matrix: depositing an interface layer and a SiC matrix on the prefabricated body by adopting a chemical vapor infiltration method to prepare a semi-compact composite material, and controlling the density of the semi-compact composite material to be 1.2-1.8 g/cm3；
The process parameters for depositing the interface layer and the matrix are as follows:
the deposited PyC interface parameters were: with C3H6As a gas source, Ar is a diluent gas, H2As carrier gas, the deposition temperature is 670-;
the parameters of the deposited SiC matrix are as follows: using trichloromethylsilane as gas source, Ar as diluent gas, and using H in bubbling mode2Taking MTS as carrier gas to be brought into a reaction furnace, wherein the deposition temperature is about 1000-1300 ℃, the total pressure of the system is 5-6 kPa, and H2The molar ratio of the MTS to the MTS is 10: 1;
and 7: processing a micro directional channel with the diameter of 0.3-1 mm on the semi-compact composite material by adopting laser, wherein the distance between the channels is 2-30 mm; controlling the volume ratio of the channel to be 10-60%;
and 8, assembling in the thickness direction: dipping the material punched in the step 7 into the graphene solution prepared in the step 2 or the step 4, and backfilling by adopting a vacuum dipping or injection method, wherein the dipping pressure range is that the vacuum pump pressure is controlled at-0.08-0.096 MPa;
repeating the steps for multiple times, and backfilling the graphene until the directional channel is light-tight;
and step 9: further densifying the three-dimensionally assembled composite material by siliconizing by adopting a chemical vapor infiltration method or an RMI method, so that the final relative density of the composite material reaches 85-95%; the parameters are the same as those of the deposition substrate in step 6.
The graphene is as follows: one or more of liquid-phase stripping graphene, electric stripping graphene, oxidized graphene, reduced oxidized graphene, high-temperature expanded graphene and low-temperature expanded graphene.
The acid reagent is one or more of nitric acid, concentrated sulfuric acid, potassium permanganate and hydrogen peroxide.
The solvent is one or more of deionized water, N-dimethylformamide DMF, ethanol and isopropanol.
The dispersing agent is: one or more of polyvinyl alcohol, triton, a silane coupling agent, a titanate coupling agent, dodecyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, waterborne polyurethane, hexadecyl trimethyl ammonium bromide, polyvinylpyrrolidone, sodium carboxymethyl cellulose, methyl cellulose, sodium cholate, polyethylene oxide and Arabic gum.
The fibers are: carbon fibers, silicon carbide fibers, boron fibers, or oxides and other high temperature ceramic fibers.
The graphene film is prepared by adopting pretreated graphene or untreated graphene.
The shape of the micro directional channel is regular or irregular; the regular shape is circular or square
The micro directional channels are arranged orderly or disorderly; in a side-by-side arrangement, a ring arrangement or a staggered arrangement.
The micro directional channels are arranged at equal intervals or at unequal intervals.
Advantageous effects
According to the preparation method of the high-heat-conductivity and electric-conduction ceramic-based composite material containing the three-dimensional ordered graphene, a graphene/carbon fiber and shell structure is constructed on the surface of the carbon fiber by utilizing a sizing process, then a prefabricated body is prepared by weaving and other methods, a heat conduction channel is constructed on a two-dimensional plane, and meanwhile, the graphene heat conduction channel between a fiber layer and the fiber is communicated in an interlayer assembly manner to form a three-dimensional network structure; finally, the heat conduction network in the thickness direction is directly opened by processing the directional channel and backfilling graphene, so that a three-dimensional heat conduction channel in the composite material is further constructed and strengthened, the transmission in all directions in the heat flow composite material is greatly promoted, and the heat conductivity of the composite material is remarkably improved.
The invention has the following beneficial effects:
(1) after the graphene is pretreated, the surface property of the graphene can be changed, the structure of the graphene cannot be damaged too much, and the problem of graphene dispersibility can be obviously improved by combining the introduction of different dispersing agents.
(2) The graphene is orderly assembled by adopting a slashing process, so that the graphene is orderly combined with fibers, and prefabricated bodies with different dimensions can be prepared by a weaving process to construct a heat conduction network structure.
(3) The problem of graphene isolation between fiber cloth layers can be solved by carrying out interlayer assembly on the fiber cloth; processing an orientation channel on the semi-densified composite material, backfilling graphene, assembling the graphene in the thickness direction, and communicating the graphene between layers and an interface, thereby constructing a three-dimensional graphene network channel.
(4) The whole process is simple to operate, high in repeatability and low in cost, and the preparation of the composite material can be completed without upgrading and modifying the existing equipment.
Drawings
FIG. 1 is a flow chart of composite material preparation.
FIG. 2 SEM images of carbon fibers before assembly (a) and after assembly (b)
FIG. 3 is a schematic diagram of a three-dimensional assembled composite material.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
solution C of the present inventionfThe problem of poor function of the/SiC composite material and the problem of oriented and ordered assembly of graphene and fiber to prepare high-thermal-conductivity Gr-Cfa/SiC functional composite material. According to the method, a sizing process is adopted to complete graphene/fiber interface assembly, and then weaving is carried out to prepare fiber cloth and complete lamination assembly, or weaving is carried out to form 2.5-dimensional and 3-dimensional prefabricated bodies; after the prefabricated body is deposited with the interface layer and the matrix, the directional channel is processed, and the graphene is backfilled, so that the three-dimensional heat conduction channel in the composite material can be constructed. Finally, further introducing the matrix for densification by adopting a CVI or RMI method to finally prepare the composite materialA composite material having excellent functionality.
In order to achieve the purpose, the invention adopts the following technical scheme:
step 1, carrying out surface activation treatment on Graphene (Gr) for 0.5-12 hours;
wherein the treatment reagent and the treatment process are as follows: the reagent adopted by the pretreatment comprises one or more of concentrated nitric acid, concentrated sulfuric acid, potassium permanganate or hydrogen peroxide, phosphorus pentoxide and potassium thiosulfate, and one of liquid-phase exfoliated graphene, electric exfoliated graphene, reduced graphene oxide, high-temperature expanded graphene and low-temperature expanded graphene is pretreated for 0.5-24 hours at 35-100 ℃; the mass ratio of the graphene to the reagent is 1: 40-1: 120.
And 2, adding the pretreated graphene into a solvent, adding a dispersing agent to prepare a solution of 0.1-50 mg/mL, and adjusting the pH value to 5-10 to obtain slurry.
Step 3, interface assembly: and (3) orderly assembling the graphene slurry prepared in the step (1) onto fibers by adopting a sizing process to form a one-dimensional graphene/fiber core-shell structure, and drying to complete interface assembly.
The assembly process parameters are as follows: and (3) setting the temperature of a drying box of the sizing machine to be 25-120 ℃, the drying time to be 1-60 minutes, the temperature of a stock chest to be 25-100 ℃, and the yarn feeding speed to be 5-30 m/min, so as to obtain the fiber with the assembled graphene interface.
And 4, preparing the graphene solution with the concentration of 0.1-10 mg again, and preparing the graphene film by adopting a vacuum filtration method, wherein the thickness of the graphene film is controlled to be 15-1000 microns.
The graphene used in the step can be pretreated graphene or untreated graphene; the pressure of the vacuum pump is controlled to be-0.08-0.096 MPa.
Step 5, preparing a prefabricated body: weaving the fibers obtained in the step 3 into two-dimensional fiber cloth or 2.5-dimensional and 3-dimensional prefabricated bodies; cutting the fiber cloth into a certain size, and carrying out interlayer assembly on the fiber cloth and the graphene film obtained in the step 4 to obtain a prefabricated body; the 2.5-dimensional and 3-dimensional fiber preforms are directly shaped by a graphite mold.
The warp density and weft density of the woven two-dimensional fiber cloth in the step are controlled to be 80-120 bundles/10 cm.
Step 6, depositing an interface layer and a matrix: depositing an interface layer and a certain amount of SiC matrix on the preform obtained in the step 5 by adopting a chemical vapor infiltration method at a certain temperature to prepare a semi-compact composite material, and controlling the density of the semi-compact composite material to be 1.2-1.8 g/cm3。
Wherein the process parameters for depositing the interface layer and the substrate are as follows: wherein the deposited PyC interface parameters are: with C3H6As a gas source, Ar is a diluent gas, H2The deposition temperature is 670-: c3H6→PyC+CxHy(ii) a The parameters of the deposited SiC matrix are as follows: with trichloromethylsilane (CH)3SiCl3MTS) as gas source, Ar as diluent gas, and H in bubbling mode2Taking MTS as carrier gas to be brought into a reaction furnace, wherein the deposition temperature is about 1000-1300 ℃, the total pressure of the system is 5-6 kPa, and H2The mol ratio of the SiC to MTS is 10:1, and the chemical reaction for preparing SiC is as follows: CH (CH)3SiCl3+H2→SiC+HCl。
Step 7, processing the semi-compact composite material obtained in the step 6 by adopting laser to form a tiny directional channel, and controlling the diameter of the channel to be 0.3-1 mm;
the directional channel is characterized in that: the shape and the arrangement of the directional channels have designability, the shape can be regular shapes such as round, square and the like or irregular shapes, the arrangement can be equidistant, non-equidistant, ordered and disordered, and can also be arranged side by side, annularly arranged or staggered. Controlling the diameter of the directional channel to be 0.3-1 mm and the distance between the channels to be 2-30 mm; the volume of the control channel accounts for 10-60% of the volume of the sample.
And 8, assembling in the thickness direction: backfilling the graphene solution prepared in the step 2 or the step 4 by adopting a vacuum impregnation or injection method, wherein the backfilling of graphene can be carried out for multiple times to ensure the introduction amount of the graphene until the directional channel is light-tight; wherein the impregnation pressure is controlled in the range of-0.08 to 0.096MPa by the vacuum pump pressure.
And 9, adopting a chemical vapor infiltration method to further densify the composite material deposition matrix after three-dimensional assembly, so that the final relative density of the composite material reaches 85-95%. Wherein the chemical vapor infiltration method parameters are the same as the parameters of the deposition matrix in the step 6.
The specific embodiment is as follows:
example 1.
Step 1: and preparing graphene slurry.
2g of graphene is taken and added into a beaker containing 500mL of concentrated sulfuric acid and hydrogen peroxide, the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is 4:1 (note: the preparation process is dangerous and the use is careful!), and the graphene is treated at 35 ℃ for two hours, washed, ultrasonically treated for 30 minutes and dried. 2g of pretreated graphene and 4g of CMC are added into 500mL of deionized water, and ultrasonic dispersion is carried out.
Step 2: and (4) orderly assembling. The temperature of a drying box of a sizing machine is 80 ℃, the drying time is 2 minutes, the temperature of a size box is 80 ℃, and the yarn feeding speed is 5-30 m/min, so that the graphene assembled carbon fiber is obtained. And after drying, weaving the two-dimensional carbon fiber cloth, controlling the warp density and weft density of the carbon fiber cloth to be 80-120 bundles/10 cm, and cutting.
And step 3: adding 0.5g of graphene without surface treatment and 0.5g of CMC (carboxymethyl cellulose) into 500mL of deionized water, performing ultrasonic dispersion, performing suction filtration to form a film, and drying; and repeating the steps, preparing a plurality of graphene films, and laminating and assembling the graphene films with the fiber cloth prepared in the step three, wherein the number of the graphene films between every two layers of fibers is 1.
And 4, step 4: depositing pyrolytic carbon PyC on the assembled preform under a certain condition, and then depositing matrix SiC by adopting a CVI method until the density reaches 1.3g/cm3The deposition is stopped.
The process parameters for depositing the interface layer and the matrix are as follows:
the deposited PyC interface parameters were: with C3H6As a gas source, Ar is a diluent gas, H2As carrier gas, the deposition temperature is 670-;
the parameters of the deposited SiC matrix are as follows: using trichloromethylsilane as gas source, Ar as diluent gas, and using H in bubbling mode2Taking MTS as carrier gas to be brought into a reaction furnace, wherein the deposition temperature is about 1000-1300 ℃, the total pressure of the system is 5-6 kPa, and H2The molar ratio of the MTS to the MTS is 10: 1;
and 5: and (4) processing the semi-compact composite material in the step (4) into directional channels by adopting femtosecond laser, wherein the diameter of each channel is 0.3mm, the hole spacing is 10mm, the channels are arranged side by side, and the volume percentage of each channel is 15%.
Step 6: dipping the material punched in the step 5 into the graphene solution prepared in the step 3, and backfilling by adopting a vacuum dipping or injection method, wherein the dipping pressure range is that the pressure of a vacuum pump is controlled at-0.08-0.096 MPa; repeating the steps for multiple times, and backfilling the graphene until the directional channel is light-tight;
and 7: the dense Gr-C is prepared by adopting a CVI method to carry out multiple deposition silicon carbide densificationfa/SiC composite material; the parameters are the same as those of the deposition substrate in step 4.
Example 2.
Step 1: and preparing graphene slurry.
And taking 2g of liquid-phase stripped graphene, 1g of sodium cholate and 1g of PAM, adding into 500mL of deionized water, and carrying out high-speed ball milling for 1 hour to obtain slurry with uniform dispersion.
Step 2: and (6) assembling an interface. And (3) setting the temperature of a drying box of a sizing machine to be 90 ℃, the drying time to be 1 minute, the temperature of a size box to be 70 ℃, and the yarn feeding speed to be 5-30 m/min, thus obtaining the graphene assembled carbon fiber. After drying, weaving the two-dimensional carbon fiber cloth, controlling the warp density and weft density of the carbon fiber cloth to be 80-120 bundles/10 cm, and cutting the carbon fiber cloth into a certain size.
And step 3: and (3) performing suction filtration on the pretreated graphene prepared in the step (1) to form a plurality of films, assembling the films with the fiber cloth layers obtained in the step (3), controlling the number of the graphene films between the layers, controlling the number of the graphene films between the two initial layers of carbon fibers to be 1 layer, controlling the number of the graphene films between the second layer of carbon fibers and the third layer of carbon fibers to be 2 layers of graphene films, and so on.
And 4, step 4: depositing pyrolytic carbon PyC on the assembled preform under a certain condition, and then depositing matrix SiC by adopting a CVI method until the density reaches 1.4g/cm3The deposition is stopped.
The process parameters for depositing the interface layer and the matrix are as follows:
the deposited PyC interface parameters were: with C3H6Is an air source and is used as a gas source,ar is a diluent gas, H2As carrier gas, the deposition temperature is 670-;
the parameters of the deposited SiC matrix are as follows: using trichloromethylsilane as gas source, Ar as diluent gas, and using H in bubbling mode2Taking MTS as carrier gas to be brought into a reaction furnace, wherein the deposition temperature is about 1000-1300 ℃, the total pressure of the system is 5-6 kPa, and H2The molar ratio of the MTS to the MTS is 10: 1;
and 5: and (4) processing the semi-compact composite material obtained in the step (4) by adopting femtosecond laser to process directional channels, wherein the diameter of each channel is 0.5mm, the hole spacing is 6mm, the channels are arranged in a staggered mode, and the volume of each channel accounts for 20%.
Step 6: backfilling the graphene slurry prepared in the step 2 by pinhole injection;
and 7: the dense Gr-C is prepared by adopting a CVI method to carry out multiple deposition silicon carbide densificationfa/SiC composite material; the parameters are the same as those of the deposition substrate in step 4.
Example 3.
Step 1: and preparing graphene slurry.
Taking 2g of electrically-stripped graphene and 4g of CTAB, adding into 500mL of deionized water, carrying out ultrasonic treatment for 30min, and carrying out high-speed ball milling for 1 hour to obtain slurry with uniform dispersion.
Step 2: and (4) orderly assembling. The temperature of a drying box of a sizing machine is 60 ℃, the drying time is 3 minutes, the temperature of a size box is 90 ℃, and the yarn feeding speed is 5-30 m/min, so that the graphene assembled carbon fiber is obtained. Drying and weaving into 3-dimensional carbon fiber preforms.
And step 3: depositing pyrolytic carbon PyC on the group of the prefabricated bodies under certain conditions, and then depositing matrix SiC by adopting a CVI method until the density reaches 1.6g/cm3The deposition is stopped.
And 4, step 4: and (3) processing the semi-compact composite material in the step (3) into an oriented channel by adopting femtosecond laser, wherein the diameter of the channel is 0.8mm, the oriented channel is arranged in a ring shape, the distance between channels is 3mm, and the volume percentage of the channel with the distance between channel rings of 5mm is 10%.
The process parameters for depositing the interface layer and the matrix are as follows:
PyC interface parameters for depositionComprises the following steps: with C3H6As a gas source, Ar is a diluent gas, H2As carrier gas, the deposition temperature is 670-;
the parameters of the deposited SiC matrix are as follows: using trichloromethylsilane as gas source, Ar as diluent gas, and using H in bubbling mode2Taking MTS as carrier gas to be brought into a reaction furnace, wherein the deposition temperature is about 1000-1300 ℃, the total pressure of the system is 5-6 kPa, and H2The molar ratio of the MTS to the MTS is 10: 1;
step 6: backfilling the graphene slurry prepared in the step 2 by pinhole injection;
and 7: the dense Gr-C is prepared by adopting a CVI method to carry out multiple deposition silicon carbide densificationfa/SiC composite material; the parameters are the same as those of the deposition substrate in step 4.
The preparation method of the invention can be mainly applied to the modification of the reinforcement of the ultra-high temperature functional ceramic matrix composite and the field of functional composites. The method is technically characterized by comprising the steps of graphene pretreatment preparation, slurry preparation, ordered graphene assembly, semi-densified composite material preparation, directional channel processing, backfilling and final densification again to obtain the composite material. According to the technical scheme provided by the invention, the graphene/fiber core-shell structure with better graphene coating can be prepared in a short time, so that interface assembly is realized; and processing an oriented channel on the semi-compact composite material, backfilling to finish graphene assembly in the thickness direction, and compacting to obtain the composite material. The method has the advantages of stable process, high repeatability, low cost and high yield, and can improve the final thermal conductivity of the composite material by 10-50 times and the final electrical conductivity by 50-300 times.

Claims (7)

1. A preparation method of a high-thermal-conductivity and electric-conductivity ceramic matrix composite containing three-dimensional ordered graphene is characterized by comprising the following steps:
step 1: carrying out surface activation treatment on the graphene for 0.5-12 hours by adopting an acid reagent; the mass ratio of the graphene to the acid reagent is 1: 40-1: 120;
step 2: preparing 0.1-50 mg/mL solution from the pretreated graphene, a dispersant and a solvent, and adjusting the pH value to 5-10 to obtain slurry; the mass ratio of the dispersing agent to the graphene is 0.1-30;
step 3, interface assembly: orderly assembling graphene onto fibers by adopting a sizing process to form a one-dimensional graphene/fiber core-shell structure, and completing interface assembly after drying;
the assembly process parameters are as follows: the temperature of a drying box of a sizing machine is 25-120 ℃, the drying time is 1-60 minutes, the temperature of a stock chest is 25-100 ℃, and the yarn feeding speed is 5-30 m/min, so that the fiber after graphene interface assembly is obtained;
and 4, step 4: preparing a graphene solution with the concentration of 0.1-10 mg by using graphene and a solvent, and preparing a graphene film by using a vacuum filtration method, wherein the thickness of the graphene film is controlled to be 15-1000 mu m; the pressure of a vacuum pump is controlled to be-0.08-0.096 MPa during vacuum filtration;
step 5, preparing a prefabricated body: weaving the fibers obtained in the step 3 into two-dimensional fiber cloth or 2.5-dimensional and 3-dimensional prefabricated bodies; carrying out interlayer assembly with the graphene film obtained in the step 4 to obtain a prefabricated body; directly shaping the 2.5-dimensional and 3-dimensional fiber preforms by using a graphite mold;
the warp density and weft density of the two-dimensional fiber cloth are controlled to be 80-120 bundles/10 cm;
step 6, depositing an interface layer and a matrix: depositing an interface layer and a SiC matrix on the prefabricated body by adopting a chemical vapor infiltration method to prepare a semi-compact composite material, and controlling the density of the semi-compact composite material to be 1.2-1.8 g/cm3；
The process parameters for depositing the interface layer and the matrix are as follows:
the deposited PyC interface parameters were: with C3H6As a gas source, Ar is a diluent gas, H2As carrier gas, the deposition temperature is 670-;
the parameters of the deposited SiC matrix are as follows: using trichloromethylsilane as gas source, Ar as diluent gas, and using H in bubbling mode2Taking MTS as carrier gas to be brought into a reaction furnace, wherein the deposition temperature is 1000-1300 ℃, the total pressure of the system is 5-6 kPa, and H2The molar ratio of the MTS to the MTS is 10: 1;
and 7: processing a micro directional channel with the diameter of 0.3-1 mm on the semi-compact composite material by adopting laser, wherein the distance between the channels is 2-30 mm; controlling the volume ratio of the channel to be 10-60%;
and 8, assembling in the thickness direction: dipping the material punched in the step 7 into the graphene solution prepared in the step 2 or the step 4, and backfilling by adopting a vacuum dipping or injection method, wherein the dipping pressure range is that the vacuum pump pressure is controlled at-0.08-0.096 MPa;
repeating the steps for multiple times, and backfilling the graphene until the directional channel is light-tight;
and step 9: further densifying the three-dimensionally assembled composite material by siliconizing by adopting a chemical vapor infiltration method or an RMI method, so that the final relative density of the composite material reaches 85-95%; the parameters are the same as those of the deposition matrix in the step 6;
the graphene film is prepared by adopting pretreated graphene or untreated graphene.
2. The preparation method of the high-thermal-conductivity and electric-conductivity ceramic matrix composite material containing the three-dimensional ordered graphene according to claim 1, characterized by comprising the following steps: the graphene is as follows: one or more of liquid-phase stripping graphene, electric stripping graphene, oxidized graphene and reduced oxidized graphene.
3. The preparation method of the high-thermal-conductivity and electric-conductivity ceramic matrix composite material containing the three-dimensional ordered graphene according to claim 1, characterized by comprising the following steps: the acid reagent is one or more of nitric acid, concentrated sulfuric acid, potassium permanganate and hydrogen peroxide.
4. The preparation method of the high-thermal-conductivity and electric-conductivity ceramic matrix composite material containing the three-dimensional ordered graphene according to claim 1, characterized by comprising the following steps: the solvent is one or more of deionized water, N-dimethylformamide DMF, ethanol and isopropanol.
5. The preparation method of the high-thermal-conductivity and electric-conductivity ceramic matrix composite material containing the three-dimensional ordered graphene according to claim 1, characterized by comprising the following steps: the dispersing agent is: one or more of polyvinyl alcohol, triton, a silane coupling agent, a titanate coupling agent, dodecyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, waterborne polyurethane, hexadecyl trimethyl ammonium bromide, polyvinylpyrrolidone, sodium carboxymethyl cellulose, methyl cellulose, sodium cholate, polyethylene oxide and Arabic gum.
6. The preparation method of the high-thermal-conductivity and electric-conductivity ceramic matrix composite material containing the three-dimensional ordered graphene according to claim 1, characterized by comprising the following steps: the shape of the micro directional channel is regular or irregular; the regular shape is a circle or a square.
7. The preparation method of the high-thermal-conductivity and electric-conductivity ceramic matrix composite material containing the three-dimensional ordered graphene according to claim 1 or 6, characterized by comprising the following steps: the micro directional channels are arranged at equal intervals or at unequal intervals.
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