CN117510220A - High-density heat-dredging composite material and preparation method thereof - Google Patents
High-density heat-dredging composite material and preparation method thereof Download PDFInfo
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- 238000007598 dipping method Methods 0.000 claims description 26
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
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- C04B35/83—Carbon fibres in a carbon matrix
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
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Abstract
The invention relates to a high-density heat-dredging composite material and a preparation method thereof. The method comprises the following steps: preparing a high-heat-conductivity carbon fiber preform; placing the high-heat-conductivity carbon fiber preform in an atmosphere containing argon, hydrogen and methane gas, and depositing a carbon nano sheet interface layer on the fiber surface of the high-heat-conductivity carbon fiber preform by a chemical vapor deposition method to obtain an intermediate blank; the volume flow rate ratio of the argon gas, the hydrogen gas and the methane gas is (36-40): (1-2): (4-5), wherein the deposition temperature is 900-1000 ℃; the intermediate blank is modified by using a carbon precursor solution as an impregnating solution through a PIP process of impregnating/curing/cracking, and then graphitized to obtain a carbon/carbon blank; covering the carbon/carbon blank with zirconium hafnium tantalum silicon quaternary mixed powder, and preparing the high-density heat-dredging composite material through reaction infiltration. The high-density heat-dredging composite material prepared by the invention has the advantages of high density, high heat conductivity, high mechanical property and the like.
Description
Technical Field
The invention belongs to the technical field of composite materials and preparation, and particularly relates to a high-density heat-dredging composite material and a preparation method thereof.
Background
Due to the continuous rapid development of aerospace technology, the temperature of a high-temperature area of an aircraft reaches the upper limit of temperature resistance of part of materials, and the thermal structural materials used by the aircraft have higher and higher performance requirements on thermal management and heat conduction. Compared with the traditional metal heat dissipation material, the heat dissipation composite material has excellent performances of low density, high heat conduction, low thermal expansion coefficient, high strength, high modulus and the like, and becomes the best high heat conduction candidate material at present, and the current and future possible application fields comprise aerospace craft structural parts, aircraft heat exchangers, aircraft solar lenses, instrument cabin electronic components and the like.
The heat-conducting composite material needs to adopt high-heat-conductivity mesophase pitch-based carbon fiber as a reinforcing body, and generally adopts carbon or ceramic as a matrix. At present, the preparation period of the heat-dredging composite material is generally longer, and more holes are formed, so that a plurality of preparation processes are additionally added for filling the holes. Even so, although macropores can be filled, there are still more pores in the material, such as between fibers, which can increase phonon scattering, significantly reduce the thermal conductivity of the material, resulting in the problems of low thermal conductivity and insufficient compactness of the thermally conductive composite material in the prior art. In addition, the heat-dredging composite material in the prior art has the problem of poor mechanical properties and the like.
Therefore, it is highly desirable to provide a highly dense thermally-conductive composite material and method of making the same that provides material and technical support for later applications.
Disclosure of Invention
In order to solve one or more technical problems in the prior art, the invention provides a high-density heat-dredging composite material and a preparation method thereof.
The present invention provides in a first aspect a method of preparing a highly densified thermally-conductive composite, the method comprising the steps of:
(1) Preparing a high-heat-conductivity carbon fiber preform;
(2) Placing the high-heat-conductivity carbon fiber preform in an atmosphere containing argon, hydrogen and methane gas, and depositing a carbon nano sheet interface layer on the fiber surface of the high-heat-conductivity carbon fiber preform by a chemical vapor deposition method to obtain an intermediate blank; wherein the volume flow rate ratio of argon, hydrogen and methane gas is (36-40): (1-2): (4-5), wherein the deposition temperature is 900-1000 ℃;
(3) The intermediate blank is modified by using a carbon precursor solution as an impregnating solution through a PIP process of impregnating, solidifying and cracking, and then graphitizing is carried out to obtain a carbon/carbon blank; in the present invention, the cleavage is performed in an inert atmosphere such as an argon atmosphere;
(4) Covering the carbon/carbon blank with zirconium hafnium tantalum silicon quaternary mixed powder, and preparing the high-density heat-dredging composite material through reaction infiltration.
Preferably, in step (1): mixing and weaving high-heat-conductivity carbon fibers and polyacrylonitrile-based carbon fibers to form a high-heat-conductivity carbon fiber preform, wherein the high-heat-conductivity carbon fiber preform is of a three-way orthogonal structure; the high-heat-conductivity carbon fiber is a mesophase pitch-based carbon fiber, and the thermal conductivity of the adopted high-heat-conductivity carbon fiber after graphitization treatment is more than 850W/(m.K), the tensile strength is more than 2.4GPa, and the tensile modulus is more than 950GPa; the density of the high heat conduction carbon fiber preform is 0.8-1.1 g/cm 3 。
Preferably, in step (1), the preparation of the high thermal conductivity carbon fiber preform includes the following sub-steps:
(a) Dispersing the mesophase pitch-based carbon fiber bundles through mechanical vibration and/or ultrasonic vibration, and then fixing the mesophase pitch-based carbon fiber bundles by using a thermal fuse to obtain unidirectional pitch-based carbon fiber cloth;
(b) Laminating unidirectional asphalt-based carbon fiber cloth, and then sewing by adopting polyacrylonitrile-based carbon fibers to obtain a high-heat-conductivity carbon fiber preform;
preferably, the diameter of the mesophase pitch-based carbon fiber in the mesophase pitch-based carbon fiber bundle is 10-11 μm, the thermal conductivity after graphitization treatment is not lower than 850W/(m.K), the tensile strength is more than 2.4GPa, the tensile modulus is more than 950GPa, and/or the specification of the mesophase pitch-based carbon fiber bundle is 1K-4K;
Preferably, the width of the dispersed mesophase pitch-based carbon fiber bundles is 15-20 mm; the surface density of the unidirectional pitch-based carbon fiber cloth is 50-100 g/m 2 The thickness is 0.1-0.2 mm.
Preferably, in step (b): the unidirectional asphalt-based carbon fiber cloth is laminated according to one direction or two directions; the included angle between the fibers in each layer of unidirectional asphalt-based carbon fiber cloth is 0 degree or 90 degrees; when the included angle between the fibers is 90 degrees, the ratio of the fiber contents in two directions is (1-4): 1, a step of; and stitching is performed by adopting polyacrylonitrile-based carbon fibers in the direction perpendicular to the lamination direction, wherein the stitching interval is 1-2.5 mm.
Preferably, in step (2): the thickness of the carbon nano-sheet interface layer is 300-500 nm.
Preferably, in step (3): carrying out a PIP process of 1-5 rounds of dipping/curing/cracking by taking a carbon precursor solution as a dipping liquid, wherein the dipping is carried out by vacuum dipping firstly, then pressure dipping is carried out, the pressure of the pressure dipping is 2-3 MPa, the time of each vacuum dipping is 1-2 h, the time of each pressure dipping is 1-2 h, the curing temperature is 280-400 ℃, the time of each curing is 2-4 h, the cracking is hot isostatic pressing cracking, the cracking temperature is 900-1000 ℃, the cracking pressure is 60-90 MPa, and the time of each cracking is 2-4 h; the carbon precursor in the carbon precursor solution is resin and/or asphalt; and/or the temperature of the graphitization treatment is 2700-3100 ℃, and the graphitization treatment time is 15-45 min.
Preferably, in step (4): the zirconium, hafnium, tantalum and silicon quaternary mixed powder comprises 10-20% of zirconium, 6-10% of hafnium, 4-10% of tantalum and 70-80% of silicon in mole fraction; and/or the temperature of the reaction infiltration is 1500-1700 ℃ and the time is 2-3 h.
Preferably, the high-density heat-dredging composite material prepared by the reaction infiltration method is provided with a ZrC-HfC-TaC-SiC-C complex phase coating with the thickness of 50-100 mu m, wherein the ceramic content in the complex phase coating is 95-100 wt%, the ceramic content gradually decreases from the ZrC-HfC-TaC-SiC-C complex phase coating to the inside of the material, and the ceramic content is 5-10 wt% when the ceramic content extends to 50-100 mu m below the surface of the material.
Preferably, the carbon precursor solution contains graphene nano sheets, and the preparation of the carbon precursor solution is as follows: adding a carbon precursor and graphene nano sheets into a solvent, and then stirring and performing ultrasonic treatment to obtain the graphene nano sheet; preferably, the carbon precursor solution contains carbon precursor and graphene nano-sheets in a mass ratio of (90-94): (6-10); preferably, the graphene nano-sheets have a sheet diameter of 5-10 μm and a thickness of 3-10 nm.
The present invention provides in a second aspect a highly densified thermally-conductive composite made by the method of the invention described in the first aspect.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The preparation method has the advantages that the period is short, the material is compact, even micro-nano level tiny pores among fibers can be filled by a matrix, the performances of the material such as heat conductivity and the like are obviously improved, and the material, especially the compactness near the outer surface of the material, can be further improved through the reaction infiltration of the zirconium hafnium tantalum silicon quaternary composite alloy powder; the invention adopts zirconium hafnium tantalum silicon quaternary composite alloy powder, forms ZrC-HfC-TaC-SiC-C composite coating near the outer surface of the composite material through one-time reaction infiltration, the ceramic content at the outer surface reaches 95-100%, the ceramic content gradually decreases to form component gradient, when the ceramic content extends to 50-100 mu m in the material, the ceramic content range is 5-10%, and the ZrC-HfC-TaC-SiC-C thermal protection coating which is coordinated with high temperature oxidation resistance and ablation resistance is formed.
(2) According to the invention, the carbon nano-sheet interface layer is formed on the fiber surface of the high-heat-conductivity carbon fiber preform instead of the common pyrolytic carbon interface layer by adjusting the chemical vapor deposition method for the first time, and compared with the pyrolytic carbon interface layer, the carbon nano-sheet interface layer can transfer heat more effectively, so that the heat conductivity of the whole material is increased, and the material is more suitable for heat dredging application; in addition, the invention discovers that the carbon nano-sheet interface layer can more effectively fill micropores and cracks on the surface of the fiber than the pyrolytic carbon interface layer, reduces the porosity of the material, and is beneficial to improving the compactness of the material.
(3) In some preferred technical schemes of the invention, the mole fraction of zirconium in the zirconium-hafnium-tantalum-silicon quaternary mixed powder is 10% -20%, the mole fraction of hafnium is 6% -10%, the mole fraction of tantalum is 4% -10%, the mole fraction of silicon is 70% -80%, the silicon content is high, the zirconium-hafnium-tantalum-silicon quaternary mixed powder can serve as a main component of a matrix in a reaction infiltration process, and is beneficial to filling original pores and microcracks, so that the compactness of the material is improved, and the existence of zirconium, hafnium and tantalum with proper content can enhance the chemical combination between a ceramic matrix and a carbon/carbon blank, so that the interface strength is improved, the mechanical property of the material is improved, and the existence of zirconium, hafnium, tantalum and silicon with proper content can improve the overall thermal conductivity of the material; the invention discovers that improper component ratio in zirconium, hafnium, tantalum and silicon quaternary mixed powder can influence the uniformity of reaction infiltration, so that pores or cracks exist in the material, the compactness, the heat conductivity and the mechanical property of the material can be reduced, and if the content of zirconium, hafnium and tantalum is too high, the brittleness of the material can be increased, the fracture toughness is reduced, and the material is easy to crack or fracture, so that the toughness and the impact resistance of the material are also unfavorable.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The present invention provides in a first aspect a method of preparing a highly densified thermally-conductive composite, the method comprising the steps of:
(1) Preparing a high-heat-conductivity carbon fiber preform;
(2) Placing the high-heat-conductivity carbon fiber preform in an atmosphere containing argon, hydrogen and methane gas, and depositing a carbon nano sheet interface layer on the fiber surface of the high-heat-conductivity carbon fiber preform by a chemical vapor deposition method to obtain an intermediate blank; wherein the volume flow rate ratio of argon, hydrogen and methane gas is (36-40): (1-2): (4-5), wherein the deposition temperature is 900-1000 ℃;
(3) The intermediate blank is modified by using a carbon precursor solution as an impregnating solution through a PIP process of impregnating, solidifying and cracking, and then graphitizing is carried out to obtain a carbon/carbon blank; the carbon precursor solution may be, for example, xylene as a solvent, and the carbon precursor solution has a solid content of, for example, 50 to 70wt%; in the invention, for example, a PIP process of 1-5 rounds of dipping, solidification and hot isostatic pressing cracking is carried out by adopting a carbon-containing precursor solution until the weight gain is less than 1%, graphitization treatment is carried out after the last round of cracking, a carbon matrix with high density and high heat conductivity is prepared, and a carbon/carbon blank body is obtained; the dosage of the carbon precursor solution and the intermediate blank is not particularly limited, so that the intermediate blank can be completely immersed in the carbon precursor solution;
(4) Covering the carbon/carbon blank with zirconium hafnium tantalum silicon quaternary mixed powder, and preparing a high-density heat-dredging composite material through a reaction infiltration method; according to the invention, a zirconium hafnium tantalum silicon quaternary mixed powder covered carbon/carbon blank is adopted, a single reaction infiltration method is adopted to obtain a high-density heat-dredging composite material, and a coating (ZrC-HfC-TaC-SiC-C complex phase coating) can be formed on the near surface (outer surface) of the material; the density range of the high-density heat-dredging composite material prepared by the invention is preferably 2.1-2.6 g/cm 3 The porosity is preferably less than 3%, more preferably not more than 2.2%, high-heat-conductivity carbon fibers are adopted in the material, the ceramic matrix is distributed in a gradient manner from the outer surface to the inside of the material, and the high-density heat-conducting composite material has the characteristics of low density, high heat conductivity, high mechanical property and the like.
The preparation method has the advantages that the period is short, the material is compact, even micro-nano level tiny pores among fibers can be filled by a matrix, the performances of the material such as heat conductivity and the like are obviously improved, and the material, especially the compactness near the outer surface of the material, can be further improved through the reaction infiltration of the zirconium hafnium tantalum silicon quaternary composite alloy powder; the invention adopts zirconium hafnium tantalum silicon quaternary composite alloy powder, forms ZrC-HfC-TaC-SiC-C composite coating near the outer surface of the composite material through one-time reaction infiltration, the ceramic content at the outer surface reaches 95-100%, the ceramic content gradually decreases to form component gradient, when the ceramic content extends to 50-100 mu m in the material, the ceramic content range is 5-10%, and the ZrC-HfC-TaC-SiC-C thermal protection coating which is coordinated with high temperature oxidation resistance and ablation resistance is formed.
According to the invention, the carbon nano-sheet interface layer is formed on the fiber surface of the high-heat-conductivity carbon fiber preform instead of the common pyrolytic carbon interface layer by adjusting the chemical vapor deposition method for the first time, and compared with the pyrolytic carbon interface layer, the carbon nano-sheet interface layer can transfer heat more effectively, so that the heat conductivity of the whole material is increased, and the material is more suitable for heat dredging application; in addition, the invention discovers that the carbon nano-sheet interface layer can more effectively fill micropores and cracks on the surface of the fiber than the pyrolytic carbon interface layer, reduces the porosity of the material, and is beneficial to improving the compactness of the material.
According to some preferred embodiments, in step (1): mixing and weaving high-heat-conductivity carbon fibers (mesophase pitch-based carbon fibers) and polyacrylonitrile-based carbon fibers (PAN-based carbon fibers) to form a high-heat-conductivity carbon fiber preform, wherein the high-heat-conductivity carbon fiber preform is of a three-way orthogonal structure; specifically, for example, a three-way orthogonal structure is adopted, the thermal conduction direction (X direction) adopts high thermal conductivity carbon fibers, the other two directions (Y direction and Z direction) adopt high thermal conductivity carbon fibers or PAN-based carbon fibers for mixed knitting, or the thermal conduction direction (X direction and Y direction) adopts high thermal conductivity carbon fibers, and the thickness direction (Z direction) adopts PAN-based carbon fibers for mixed knitting; the invention does not limit the sources of the mesophase pitch-based carbon fiber and the polyacrylonitrile-based carbon fiber, and products which can be directly purchased in the market or synthesized by the prior method can be adopted; the high-heat-conductivity carbon fiber is a mesophase pitch-based carbon fiber, and the thermal conductivity of the adopted high-heat-conductivity carbon fiber after graphitization treatment is more than 850W/(m.K), the tensile strength is more than 2.4GPa, and the tensile modulus is more than 950GPa; The specification of the fiber bundle of the high heat conduction carbon fiber is 1K, 2K or 4K, and the diameter range of the fiber is 10-11 mu m; the high heat conduction carbon fiber accounts for 60-100% of the volume fraction of the carbon fiber in the high heat conduction carbon fiber preform; the density of the high heat conduction carbon fiber preform is 0.8-1.1 g/cm 3 。
According to some preferred embodiments, in step (1), the preparation of the high thermal conductivity carbon fiber preform comprises the following sub-steps:
(a) Dispersing the mesophase pitch-based carbon fiber bundles through mechanical vibration and/or ultrasonic vibration, and then fixing the mesophase pitch-based carbon fiber bundles by using a thermal fuse to obtain unidirectional pitch-based carbon fiber cloth; specifically, the mesophase pitch-based carbon fiber bundles are dispersed into a planar structure through mechanical vibration and/or ultrasonic vibration, so that the mesophase pitch-based carbon fiber bundles extend in the width direction and are thinned in the thickness direction, and are fixed by using a thermal fuse, for example, the two-way pitch-based carbon fiber bundles can be fixed in a thermal fuse sewing mode, and a unidirectional pitch-based carbon fiber cloth with low surface density is obtained; more specifically, the mesophase pitch-based carbon fiber bundles are dispersed into a planar structure mesophase pitch-based carbon fiber cloth by a transmission device (such as a vibration transmission device) through mechanical vibration and/or ultrasonic vibration, and the mesophase pitch-based carbon fiber cloth is directly sewn together by a linear thermal fuse, for example, the periphery of the mesophase pitch-based carbon fiber cloth is sewn together by the thermal fuse, so that the preliminary fixing effect can be achieved, the carbon residue ratio of the thermal fuse is low, the thermal fuse is basically disappeared after being subjected to high temperature in the subsequent preparation process of the thermal-dredging composite material, and the sewing interval can be 1-2.5 mm (for example, 1.0, 1.5, 2.0 or 2.5 mm); the type of the thermal fuse is not particularly limited, and the thermal fuse can be a product which can be directly purchased in the market, and in some specific embodiments, the thermal fuse can be a nylon thermal fuse; the conditions of mechanical vibration and ultrasonic vibration are not particularly limited, and the mesophase pitch-based carbon fiber bundles can be dispersed into a planar structure through mechanical vibration and/or ultrasonic vibration, wherein the frequency of the mechanical vibration can be 25-200 Hz, and the time of the mechanical vibration can be 1-5 min; the frequency of the ultrasonic vibration can be 20-40 kHz, and the time of the ultrasonic vibration can be 1-5 min;
(b) Laminating unidirectional asphalt-based carbon fiber cloth, and then sewing by adopting polyacrylonitrile-based carbon fibers to obtain a high-heat-conductivity carbon fiber preform; the unidirectional pitch-based carbon fiber cloth refers to that carbon fibers are arranged along one direction in the same piece (same layer) of pitch-based carbon fiber cloth; specifically, stacking unidirectional asphalt-based carbon fiber cloth, placing the stacked unidirectional asphalt-based carbon fiber cloth into a fixed mold for braiding, and sewing by adopting polyacrylonitrile-based carbon fibers in the direction (Z direction) perpendicular to the stacking direction to obtain a high-heat-conductivity carbon fiber preform; in the lamination, the included angle between the fibers in each layer of fiber cloth (two adjacent layers of fiber cloth) is 0 ° or 90 °, and the ratio of the fiber contents in two directions when the included angle is 90 ° is, for example, (1 to 4): 1, namely the fiber volume fraction ratio in two directions is (1-4) when the included angle is 90 degrees: 1, a step of; in the invention, when the unidirectional pitch-based carbon fiber cloth is laminated, the unidirectional pitch-based carbon fiber cloth can be laminated vertically according to one direction or alternatively laminated vertically according to two directions, namely, the directions of carbon fibers in two adjacent unidirectional pitch-based carbon fiber cloths are mutually perpendicular, so that the thermal-dredging composite material can be provided with mesophase pitch-based carbon fibers as heat conduction and reinforcement bodies in one direction (X) or two perpendicular directions (X, Y) in the plane.
The high-heat-conductivity carbon fiber preform is preferably obtained through the step (a) and the step (b), so that the method can be used for preparing a large-area dispersed high-density heat-conducting composite material through near net-size molding, the fiber proportion and the matrix composition can be regulated and controlled, and the heat-conducting composite material prepared by adopting the high-heat-conductivity carbon fiber preform is lower in density, thinner in thickness, higher in specific strength, more uniform and compact in internal tissue structure, rapid in-plane large-area heat conduction, and more excellent in mechanical property and heat conduction property.
The method adopts a mode that mesophase pitch-based carbon fiber bundles are dispersed through mechanical and/or ultrasonic vibration and then are fixed by a thermal fuse, the unidirectional pitch-based carbon fiber cloth has the characteristic of ultrathin thickness, the prepared thermal-dredging composite material can have thinner thickness under the condition of basically the same density by adopting the unidirectional pitch-based carbon fiber cloth, the mesophase pitch-based carbon fibers are immersed in an organic carbon solution (mesophase pitch) in the prior art, then are placed in a mould in parallel, and are dried at a low temperature to obtain unidirectional carbon fiber sheets, the carbon fibers can be saturated and absorbed by the method in the immersing process, a layer of pitch-based material is left among the fibers in the subsequent drying process, the thickness of the sheets is increased, and the stacking between the carbon fiber layers is involved in the process of being placed in the mould in parallel to obtain a unidirectional structure (unidirectional sheets), and the thickness of the final sheets is also increased; in addition, the invention discovers that the unidirectional pitch-based carbon fiber cloth obtained by dispersing through mechanical and/or ultrasonic vibration and then fixing by using a thermal fuse can obtain more consistent and uniform carbon fiber arrangement, the directionality of the carbon fibers is more uniform, the consistency is helpful for improving the strength and stability of the heat-dispersion composite material and is helpful for resisting bending stress, the thinner unidirectional pitch-based carbon fiber cloth obtained by the invention means that the overall performance of the material is better and more uniform, for example, for preparing the heat-dispersion composite material with the total thickness of 3mm, the carbon cloth with the thicker thickness is adopted, the stacking layer number is less, for example, the carbon cloth with the common thickness of 0.5-1 mm can only be stacked by 3-6 layers, and the thickness of the unidirectional pitch-based carbon fiber cloth dispersed in the invention can be as thin as 0.1-0.2 mm, the unidirectional asphalt-based carbon fiber cloth can be stacked into 15-30 layers, the number of layers is relatively large, the interval between the layers is smaller, the prepared thermal-dredging composite material is better in uniformity in the thickness direction, the overall difference of the material performance is small, the performance is more uniform, the material stability is better, particularly, the stability is better when the thermal-dredging composite material is applied for a long time, when the thermal-dredging composite material is used, the thermal-dredging composite material is peeled off by 6 layers of carbon cloth with the thickness of 0.5mm, the loss degree of the material reaches 16.67% when the thermal-dredging composite material is peeled off by the next layer, and the thermal-dredging composite material is formed by 20 layers of unidirectional asphalt-based carbon fiber cloth with the thickness of 0.15mm, and even if the thermal-dredging composite material is peeled off by one layer, the loss degree of the material is only 5%.
According to some preferred embodiments, the mesophase pitch-based carbon fiber bundles are of the mesophase pitch-basedThe diameter of the carbon fiber (high heat conduction carbon fiber) is 10-11 mu m, the heat conductivity after graphitization treatment is not lower than 850W/(m.K), the tensile strength is more than 2.4GPa, the tensile modulus is more than 950GPa, and/or the specification of the mesophase pitch-based carbon fiber bundle is 1K-4K (for example, 1K, 2K, 3K or 4K); the high heat conduction carbon fiber accounts for 60-100% of the volume fraction of the carbon fiber in the high heat conduction carbon fiber preform, and the volume density of the high heat conduction carbon fiber preform is 0.8-1.1 g/cm 3 。
According to some preferred embodiments, the width of the dispersed mesophase pitch-based carbon fiber bundles is 15 to 20mm (e.g. 15, 16, 17, 18, 19 or 20 mm); the surface density of the unidirectional pitch-based carbon fiber cloth is 50-100 g/m 2 (e.g., 50, 60, 70, 80, 90 or 100 g/m) 2 ) The thickness is 0.1 to 0.2mm (for example, 0.1, 0.15 or 0.2 mm).
According to some preferred embodiments, in step (b): the unidirectional asphalt-based carbon fiber cloth is laminated according to one direction or two directions; the included angle between the fibers in each layer of unidirectional asphalt-based carbon fiber cloth is 0 degree or 90 degrees, namely, the included angle between the fibers in two adjacent layers of unidirectional asphalt-based carbon fiber cloth is 0 degree or 90 degrees; in the invention, when the unidirectional pitch-based carbon fiber cloth is laminated according to one direction, a unidirectional high-heat-conductivity carbon fiber preform is formed, carbon fibers in each layer of unidirectional pitch-based carbon fiber cloth are distributed along one direction, and the included angle between the carbon fibers is 0 degree; when unidirectional pitch-based carbon fiber cloth is alternately laminated according to two directions, a bidirectional high-heat-conductivity carbon fiber preform is formed, carbon fibers in the pitch-based carbon fiber cloth are arranged along the two directions, and an included angle between the carbon fibers in two adjacent layers of unidirectional pitch-based carbon fiber cloth is 90 degrees; when the included angle between the fibers is 90 °, the ratio of the fiber contents in both directions (fiber volume fraction) is (1 to 4): 1 (e.g., 1:1, 2:1, 3:1, or 4:1); the stitching is performed with polyacrylonitrile-based carbon fibers in a direction perpendicular to the lamination direction at a stitching pitch of 1 to 2.5mm (e.g., 1.0, 1.5, 2.0, or 2.5 mm).
According to some preferred embodiments, in step (2): the thickness of the carbon nano sheet interface layer is 300-500 nm;
the invention does not limit the deposition time of the carbon nano-sheet interface layer, and the person skilled in the art can adjust the deposition time until reaching the preset thickness; in the present invention, the deposition pressure is, for example, 5 to 10kPa when chemical vapor deposition is performed, unless otherwise specified.
According to some preferred embodiments, in step (3): carrying out a PIP process of 1-5 rounds of impregnation/curing/cracking by taking a carbon precursor solution as an impregnating solution, wherein the impregnation is carried out by vacuum impregnation, the pressure of the vacuum impregnation is, for example, -0.1 to-0.05 MPa, then the pressure impregnation is carried out, the pressure of the pressure impregnation is 2-3 MPa, the time of each vacuum impregnation is 1-2 h, the time of each pressure impregnation is 1-2 h, the curing temperature is 280-400 ℃ (for example 280 ℃, 300 ℃, 320 ℃, 350 ℃, 380 ℃ or 400 ℃), the time of each curing is 2-4 h (for example 2, 3 or 4 h), the cracking is carried out by hot isostatic pressing, the cracking temperature is 900-1000 ℃, the cracking pressure is 60-90 MPa (for example 60, 70, 80 or 90 MPa), and the time of each cracking is 2-4 h (for example 2, 3 or 4 h). The invention preferably carries out hot isostatic pressing cracking at the temperature of 900-1000 ℃ and the pressure of 60-90 MPa, and discovers that compared with normal pressure cracking, the hot isostatic pressing cracking can promote the carbon precursors to be more tightly combined together, is favorable for making the prepared carbon/carbon blank more compact, reducing structural defects, being favorable for improving the density and the heat conductivity of the material, can more effectively conduct heat, and can form stronger interface bonding when carrying out the hot isostatic pressing cracking under high pressure, thereby improving the mechanical properties of the material, such as tensile strength, bending strength, impact resistance and the like.
According to some preferred embodiments, the carbon precursor in the carbon precursor solution is a resin, such as a phenolic resin, and/or a pitch, such as one or more of a mesophase pitch, a pitch; and/or the graphitization treatment is at a temperature of 2700 to 3100 ℃ (e.g., 2700 ℃, 2800 ℃, 2900 ℃, 3000 ℃, or 3100 ℃), and the graphitization treatment is for a time of 15 to 45 minutes (e.g., 15, 20, 25, 30, 35, 40, or 45 minutes).
According to some preferred embodiments, in step (4): the zirconium, hafnium, tantalum and silicon quaternary mixed powder contains 10% -20% (for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%) of zirconium, 6% -10% (for example, 6%, 7%, 8%, 9% or 10%) of hafnium, 4% -10% (for example, 4%, 5%, 6%, 7%, 8%, 9% or 10%) of tantalum, and 70% -80% (for example, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79% or 80%) of silicon, and the sum of the mole fractions of zirconium, hafnium, tantalum and silicon is 100%; the invention preferably comprises 10% -20% of zirconium, 6% -10% of hafnium, 4% -10% of tantalum, 70% -80% of silicon and higher silicon content, wherein the zirconium, hafnium and tantalum can be used as main components of a matrix in a reaction infiltration process, so that original pores and microcracks can be filled, the compactness of the material is improved, the chemical combination between a ceramic matrix and a carbon/carbon blank can be enhanced by the existence of zirconium, hafnium and tantalum with proper content, the interfacial strength is improved, the mechanical property of the material is improved, and the overall thermal conductivity of the material can be improved by the existence of zirconium, hafnium, tantalum and silicon with proper content; the invention discovers that improper component ratio in zirconium, hafnium, tantalum and silicon quaternary mixed powder can influence the uniformity of reaction infiltration, so that pores or cracks exist in the material, the compactness, the heat conductivity and the mechanical property of the material can be reduced, and if the content of zirconium, hafnium and tantalum is too high, the brittleness of the material can be increased, the fracture toughness is reduced, and the material is easy to crack or fracture, so that the toughness and the impact resistance of the material are also unfavorable.
According to some preferred embodiments, the temperature of the reactive infusion is 1500-1700 ℃ (e.g. 1500 ℃, 1550 ℃, 1600 ℃, 1650 ℃ or 1700 ℃) for a period of 2-3 hours (e.g. 2, 2.5 or 3 hours).
According to some preferred embodiments, the high-density heat-dredging composite material prepared by reaction infiltration is formed with a ZrC-HfC-TaC-SiC-C complex phase coating with the thickness of 50-100 mu m on the surface of the material, wherein the ceramic content in the complex phase coating is 95-100 wt% and extends from the ZrC-HfC-TaC-SiC-C complex phase coating to the inside of the material, the ceramic content gradually decreases, and the ceramic content is 5-10 wt% when the ceramic content extends to 50-100 mu m inside the surface of the material; in the invention, after reaction infiltration, a ZrC-HfC-TaC-SiC-C complex phase coating with the thickness of 50-100 mu m is formed near the outer surface of the material, the ceramic content at the outer surface reaches 95-100%, the ceramic content gradually decreases to form a component gradient, and the ceramic content range is 5-10% when the ceramic content extends to 50-100 mu m; in the invention, the ceramic content can gradually decrease from the outer surface of the material to the inner part of the material due to reactive infiltration, and the high-density heat-dredging composite material can be also referred to as a high-density gradient heat-dredging composite material.
According to some preferred embodiments, the carbon precursor solution contains graphene nanoplatelets, and the carbon precursor solution is prepared by the following steps: adding a carbon precursor and graphene nano sheets into a solvent, and then stirring and performing ultrasonic treatment to obtain the graphene nano sheet; specifically, in the present invention, the rotational speed of the stirring is, for example, 400 to 800rpm, and the stirring time is, for example, 20 to 40 minutes; the frequency of the ultrasonic treatment is 20-40 kHz, and the time of the ultrasonic treatment is 20-40 min; according to the invention, the carbon precursor and the graphene nano-sheets are uniformly dispersed in the solvent in a stirring and ultrasonic treatment mode, so that the graphene nano-sheets are uniformly distributed in the whole carbon precursor solution as much as possible, thereby being beneficial to improving the uniformity of the high-density heat-dredging composite material and being beneficial to ensuring the performance of the material; in the present invention, the solvent may be, for example, xylene, and the sum of mass fractions of the carbon precursor and the graphene nanoplatelets contained in the carbon precursor solution may be, for example, 50 to 70%; preferably, the carbon precursor solution contains carbon precursor and graphene nano-sheets in a mass ratio of (90-94): (6-10) (e.g., 94:6, 92:8, or 90:10).
In the invention, preferably, during the PIP process of dipping/curing/cracking, the carbon precursor solution also contains a proper amount of graphene nano-sheets, and the invention discovers that the proper amount of graphene nano-sheets can serve as a filler in the carbon precursor solution, so that the potential pores and microcracks are filled, the porosity is reduced on the basis of not influencing the subsequent reaction infiltration, the addition of the graphene nano-sheets can effectively improve the thermal conductivity of the material, and in addition, the addition of the graphene nano-sheets can also effectively enhance the mechanical property of the material, thereby being beneficial to improving the overall performance of the material.
According to some preferred embodiments, the graphene nanoplatelets have a sheet diameter of 5 to 10 μm and a thickness of 3 to 10nm.
The present invention provides in a second aspect a highly densified thermally-conductive composite made by the method of the invention described in the first aspect.
The invention is further illustrated below with reference to examples. These examples are merely illustrative of preferred embodiments of the present invention and the scope of the present invention should not be construed as being limited to these examples only.
Example 1
(1) Braiding of a high-heat-conductivity carbon fiber preform: adopting a three-way orthogonal structure, adopting mesophase pitch-based carbon fibers (high-heat-conductivity carbon fibers) in the X direction and the Y direction of the heat conduction direction, and adopting polyacrylonitrile-based carbon fibers (PAN-based carbon fibers) in the thickness direction (Z direction) for mixed braiding; the adopted mesophase pitch-based carbon fiber has the thermal conductivity of 860W/(m.K), the tensile strength of 2.5GPa, the tensile modulus of 960GPa, the fiber bundle specification of 2K, the fiber diameter of 10.5+/-0.2 mu m, the high heat conduction carbon fiber accounts for 80 percent of the volume fraction of the carbon fiber in the high heat conduction carbon fiber preform, and the volume density of the high heat conduction carbon fiber preform is 0.9g/cm 3 。
(2) Preparing a carbon nano sheet interface layer: placing the high-heat-conductivity carbon fiber preform obtained in the step (1) in an atmosphere containing argon, hydrogen and methane gas, and depositing a carbon nano sheet interface layer with the thickness of 400nm on the fiber surface of the high-heat-conductivity carbon fiber preform by a chemical vapor deposition method under the conditions of 950 ℃ and 6kPa to obtain an intermediate blank; wherein, the volume flow rate ratio of argon, hydrogen and methane gas is 40:1.5:4.5.
(3) preparing a carbon/carbon blank: completely immersing the intermediate blank body obtained in the step (2) into a carbon precursor solution, carrying out modification treatment on the intermediate blank body by taking the carbon precursor solution as an immersion liquid through a PIP (particle-in-particle) process of immersion/solidification/cracking, and carrying out graphitization treatment at 3000 ℃ for 30min to obtain a carbon/carbon blank body; the preparation of the carbon precursor solution comprises the following steps: uniformly mixing a carbon precursor (petroleum asphalt) by using dimethylbenzene to obtain a carbon precursor solution, wherein the carbon precursor solution contains 60% of petroleum asphalt by mass percent; the PIP process of 4 rounds of dipping/solidifying/cracking is carried out by taking the carbon precursor solution as the dipping liquid, and the specific PIP process is as follows: the impregnation is that vacuum impregnation is firstly carried out, the pressure of the vacuum impregnation is-0.05 MPa, the time of each vacuum impregnation is 1.5h, then the pressure impregnation is carried out, the pressure of each pressure impregnation is 3MPa, the time of each pressure impregnation is 2h, the curing temperature is 300 ℃, the time of each curing is 3h, and the cracking is hot isostatic pressing cracking carried out under the conditions of 1000 ℃ and 70MPa, and the time of each cracking is 2h.
(4) Reacting and infiltrating zirconium hafnium tantalum silicon quaternary mixed powder: covering the carbon/carbon blank obtained in the step (3) with zirconium hafnium tantalum silicon quaternary mixed powder, and adopting a one-time reaction infiltration method to obtain a high-density heat-dredging composite material; wherein, the mole fraction of zirconium in the zirconium hafnium tantalum silicon quaternary mixed powder is 10%, the mole fraction of hafnium is 6%, the mole fraction of tantalum is 4%, the mole fraction of silicon powder is 80%, the temperature of reaction infiltration is 1600 ℃, and the time of reaction infiltration is 2h.
After infiltration, a ZrC-HfC-TaC-SiC-C complex-phase coating with the thickness of 75 mu m is formed near the outer surface of the material, the ceramic content at the outer surface reaches 98% through element energy spectrum analysis, the ceramic content gradually decreases to the inside of the material, a component gradient is formed, and when the ceramic content extends to 75 mu m below the surface of the material, the ceramic content is reduced to 6% through element energy spectrum analysis.
Example 2
Example 2 is substantially the same as example 1 except that:
(3) preparing a carbon/carbon blank: completely immersing the intermediate blank body obtained in the step (2) into a carbon precursor solution, carrying out modification treatment on the intermediate blank body by taking the carbon precursor solution as an immersion liquid through a PIP (particle-in-particle) process of immersion/solidification/cracking, and carrying out graphitization treatment at 3000 ℃ for 30min to obtain a carbon/carbon blank body; the preparation of the carbon precursor solution comprises the following steps: uniformly mixing a carbon precursor (petroleum asphalt) by using dimethylbenzene to obtain a carbon precursor solution, wherein the carbon precursor solution contains 60% of petroleum asphalt by mass percent; the PIP process of 4 rounds of dipping/solidifying/cracking is carried out by taking the carbon precursor solution as the dipping liquid, and the specific PIP process is as follows: the impregnation is that vacuum impregnation is firstly carried out, the pressure of the vacuum impregnation is-0.05 MPa, the time of each vacuum impregnation is 1.5h, then the pressure impregnation is carried out, the pressure of the pressure impregnation is 3MPa, the time of each pressure impregnation is 2h, the curing temperature is 300 ℃, the time of each curing is 3h, the cracking is carried out under the normal pressure at the temperature of 1000 ℃, and the time of each cracking is 2h.
Example 3
Example 3 is substantially the same as example 1 except that:
(4) reacting and infiltrating zirconium hafnium tantalum silicon quaternary mixed powder: covering the carbon/carbon blank obtained in the step (3) with zirconium hafnium tantalum silicon quaternary mixed powder, and adopting a one-time reaction infiltration method to obtain a high-density heat-dredging composite material; the zirconium-hafnium-tantalum-silicon quaternary mixed powder comprises 25% of zirconium, 25% of hafnium, 25% of tantalum and 25% of silicon powder, wherein the temperature of reaction infiltration is 1600 ℃, and the time of reaction infiltration is 2 hours.
Example 4
Example 4 is substantially the same as example 1 except that:
(4) reacting and infiltrating zirconium hafnium tantalum silicon quaternary mixed powder: covering the carbon/carbon blank obtained in the step (3) with zirconium hafnium tantalum silicon quaternary mixed powder, and adopting a one-time reaction infiltration method to obtain a high-density heat-dredging composite material; the zirconium-hafnium-tantalum-silicon quaternary mixed powder comprises 25% of zirconium, 15% of hafnium, 15% of tantalum and 45% of silicon powder, wherein the reaction infiltration temperature is 1600 ℃, and the reaction infiltration time is 2 hours.
Example 5
Example 5 is substantially the same as example 1 except that:
(1) Braiding of a high-heat-conductivity carbon fiber preform: dispersing the mesophase pitch-based carbon fiber bundles into a planar structure through mechanical vibration, and sewing and fixing the planar structure by using a thermal fuse, wherein the sewing distance is 1.5mm, so as to obtain unidirectional pitch-based carbon fiber cloth; the frequency of the mechanical vibration is 100Hz, and the time of the mechanical vibration is 3min; the fiber diameter of the adopted mesophase pitch-based carbon fiber bundle is 10.5+/-0.2 mu m, the thermal conductivity after graphitization treatment is 860W/(m.K), the fiber bundle specification is 2K, the tensile strength is 2.5GPa, the tensile modulus is 960GPa, the width of the dispersed mesophase pitch-based carbon fiber bundle is 20mm, and the surface density of the prepared unidirectional pitch-based carbon fiber cloth is 80g/m 2 The thickness of the single-layer unidirectional asphalt-based carbon fiber cloth is 0.15mm; 10 layers of unidirectional asphalt-based carbon fiber cloth are alternately laminated in two directions (alternately laminated in two directions of 0 degree/90 degree) and then put into a fixed mould for braiding, and polyacrylonitrile-based carbon fibers are adopted for suturing in the vertical direction (Z), so that a high-heat-conductivity carbon fiber preform with the thickness of 1.5mm is obtained; the high-heat-conductivity carbon fiber preform is a bidirectional vertical high-heat-conductivity carbon fiber preform, an included angle between fibers in two adjacent layers of unidirectional asphalt-based carbon fiber cloth is 90 degrees, the ratio of fiber content in two directions (fiber volume fraction ratio) is 1:1, the distance between Z-direction fibers (sewing distance) is 1.5mm, and the density of the high-heat-conductivity carbon fiber preform is 0.9g/cm 3 。
Example 6
Example 6 is substantially the same as example 1 except that:
(3) preparing a carbon/carbon blank: completely immersing the intermediate blank body obtained in the step (2) into a carbon precursor solution, carrying out modification treatment on the intermediate blank body by taking the carbon precursor solution as an immersion liquid through a PIP (particle-in-particle) process of immersion/solidification/cracking, and carrying out graphitization treatment at 3000 ℃ for 30min to obtain a carbon/carbon blank body; the preparation of the carbon precursor solution comprises the following steps: adding a carbon precursor (petroleum asphalt) and graphene nano sheets with the sheet diameter distribution range of 5-10 mu m and the thickness distribution range of 3-10 nm into dimethylbenzene, then stirring for 40min under the condition of a stirring rotating speed of 400rpm, and then performing ultrasonic treatment for 40min under the condition of a frequency of 20kHz to obtain a carbon precursor solution, wherein the carbon precursor solution contains 60 percent of the sum of the mass percentages of the petroleum asphalt and the graphene nano sheets, and the mass ratio of the carbon precursor to the graphene nano sheets is 92:8; the PIP process of 4 rounds of dipping/solidifying/cracking is carried out by taking the carbon precursor solution as the dipping liquid, and the specific PIP process is as follows: the impregnation is that vacuum impregnation is firstly carried out, the pressure of the vacuum impregnation is-0.05 MPa, the time of each vacuum impregnation is 1.5h, then the pressure impregnation is carried out, the pressure of each pressure impregnation is 3MPa, the time of each pressure impregnation is 2h, the curing temperature is 300 ℃, the time of each curing is 3h, and the cracking is hot isostatic pressing cracking carried out under the conditions of 1000 ℃ and 70MPa, and the time of each cracking is 2h.
Example 7
Example 7 is substantially the same as example 1 except that:
(1) braiding of a high-heat-conductivity carbon fiber preform: dispersing the mesophase pitch-based carbon fiber bundles into a planar structure through mechanical vibration, and sewing and fixing the planar structure by using a thermal fuse, wherein the sewing distance is 1.5mm, so as to obtain unidirectional pitch-based carbon fiber cloth; the frequency of the mechanical vibration is 100Hz, and the time of the mechanical vibration is 3min; the fiber diameter of the adopted mesophase pitch-based carbon fiber bundle is 10.5+/-0.2 mu m, the thermal conductivity after graphitization treatment is 860W/(m.K), the fiber bundle specification is 2K, the tensile strength is 2.5GPa, the tensile modulus is 960GPa, the width of the dispersed mesophase pitch-based carbon fiber bundle is 20mm, and the surface density of the prepared unidirectional pitch-based carbon fiber cloth is 80g/m 2 The thickness of the single-layer unidirectional asphalt-based carbon fiber cloth is 0.15mm; 10 layers of unidirectional asphalt-based carbon fiber cloth are alternately laminated in two directions (alternately laminated in two directions of 0 degree/90 degree) and then put into a fixed mould for braiding, and polyacrylonitrile-based carbon fibers are adopted for suturing in the vertical direction (Z), so that a high-heat-conductivity carbon fiber preform with the thickness of 1.5mm is obtained; the high-heat-conductivity carbon fiber preform is a bidirectional vertical high-heat-conductivity carbon fiber preform, an included angle between fibers in two adjacent layers of unidirectional asphalt-based carbon fiber cloth is 90 degrees, the ratio of fiber content in two directions (fiber volume fraction ratio) is 1:1, the interval between Z-direction fibers (sewing interval) is 1.5mm, and the high-heat-conductivity carbon fiber preform Has a density of 0.9g/cm 3 。
(3) Preparing a carbon/carbon blank: completely immersing the intermediate blank body obtained in the step (2) into a carbon precursor solution, carrying out modification treatment on the intermediate blank body by taking the carbon precursor solution as an immersion liquid through a PIP (particle-in-particle) process of immersion/solidification/cracking, and carrying out graphitization treatment at 3000 ℃ for 30min to obtain a carbon/carbon blank body; the preparation of the carbon precursor solution comprises the following steps: adding a carbon precursor (petroleum asphalt) and graphene nano sheets with the sheet diameter distribution range of 5-10 mu m and the thickness distribution range of 3-10 nm into dimethylbenzene, then stirring for 40min under the condition of a stirring rotating speed of 400rpm, and then performing ultrasonic treatment for 40min under the condition of a frequency of 20kHz to obtain a carbon precursor solution, wherein the carbon precursor solution contains 60 percent of the sum of the mass percentages of the petroleum asphalt and the graphene nano sheets, and the mass ratio of the carbon precursor to the graphene nano sheets is 92:8; the PIP process of 4 rounds of dipping/solidifying/cracking is carried out by taking the carbon precursor solution as the dipping liquid, and the specific PIP process is as follows: the impregnation is that vacuum impregnation is firstly carried out, the pressure of the vacuum impregnation is-0.05 MPa, the time of each vacuum impregnation is 1.5h, then the pressure impregnation is carried out, the pressure of each pressure impregnation is 3MPa, the time of each pressure impregnation is 2h, the curing temperature is 300 ℃, the time of each curing is 3h, and the cracking is hot isostatic pressing cracking carried out under the conditions of 1000 ℃ and 70MPa, and the time of each cracking is 2h.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that:
after the carbon/carbon blank is obtained in step (3), step (4) is not performed.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that:
(2) preparing a pyrolytic carbon interface layer: placing the high-heat-conductivity carbon fiber preform obtained in the step (1) in an atmosphere containing argon and methane gas, and depositing a pyrolytic carbon interface layer (carbon interface layer) with the thickness of 400nm on the fiber surface of the high-heat-conductivity carbon fiber preform by a chemical vapor deposition method under the conditions of 1050 ℃ and 6kPa to obtain an intermediate blank; wherein the volume flow rate ratio of the argon gas to the methane gas is 1:1.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that:
(4) and (3) reacting and infiltrating silicon powder: covering the carbon/carbon blank obtained in the step (3) with silicon powder, and obtaining a heat-dredging composite material by adopting a one-time reaction infiltration method; wherein, the temperature of the reaction infiltration is 1600 ℃, and the time of the reaction infiltration is 2 hours.
The high-density heat-dredged composite material prepared in each example and the material finally prepared in each comparative example are subjected to performance test according to the invention, and the test results are shown in table 1.
TABLE 1
In table 1, the symbol "-" indicates that the performance index was not tested.
The invention is not described in detail in a manner known to those skilled in the art.
The last explanation is: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in each embodiment can be modified or part of technical features in the technical scheme can be replaced equivalently; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing a highly dense thermally-conductive composite material, the method comprising the steps of:
(1) Preparing a high-heat-conductivity carbon fiber preform;
(2) Placing the high-heat-conductivity carbon fiber preform in an atmosphere containing argon, hydrogen and methane gas, and depositing a carbon nano sheet interface layer on the fiber surface of the high-heat-conductivity carbon fiber preform by a chemical vapor deposition method to obtain an intermediate blank; wherein the volume flow rate ratio of argon, hydrogen and methane gas is (36-40): (1-2): (4-5), wherein the deposition temperature is 900-1000 ℃;
(3) The intermediate blank is modified by using a carbon precursor solution as an impregnating solution through a PIP process of impregnating, solidifying and cracking, and then graphitizing is carried out to obtain a carbon/carbon blank;
(4) Covering the carbon/carbon blank with zirconium hafnium tantalum silicon quaternary mixed powder, and preparing the high-density heat-dredging composite material through reaction infiltration.
2. The method of claim 1, wherein in step (1):
mixing and weaving high-heat-conductivity carbon fibers and polyacrylonitrile-based carbon fibers to form a high-heat-conductivity carbon fiber preform, wherein the high-heat-conductivity carbon fiber preform is of a three-way orthogonal structure;
the high-heat-conductivity carbon fiber is a mesophase pitch-based carbon fiber, and the thermal conductivity of the adopted high-heat-conductivity carbon fiber after graphitization treatment is more than 850W/(m.K), the tensile strength is more than 2.4GPa, and the tensile modulus is more than 950GPa;
the density of the high heat conduction carbon fiber preform is 0.8-1.1 g/cm 3 。
3. The method of producing according to claim 1, wherein in step (1), the production of the high thermal conductive carbon fiber preform comprises the sub-steps of:
(a) Dispersing the mesophase pitch-based carbon fiber bundles through mechanical vibration and/or ultrasonic vibration, and then fixing the mesophase pitch-based carbon fiber bundles by using a thermal fuse to obtain unidirectional pitch-based carbon fiber cloth;
(b) Laminating unidirectional asphalt-based carbon fiber cloth, and then sewing by adopting polyacrylonitrile-based carbon fibers to obtain a high-heat-conductivity carbon fiber preform;
preferably, the diameter of the mesophase pitch-based carbon fiber in the mesophase pitch-based carbon fiber bundle is 10-11 μm, the thermal conductivity after graphitization treatment is not lower than 850W/(m.K), the tensile strength is more than 2.4GPa, the tensile modulus is more than 950GPa, and/or the specification of the mesophase pitch-based carbon fiber bundle is 1K-4K;
Preferably, the width of the dispersed mesophase pitch-based carbon fiber bundles is 15-20 mm; the surface density of the unidirectional pitch-based carbon fiber cloth is 50-100 g/m 2 The thickness is 0.1-0.2 mm.
4. A method of preparation according to claim 3, characterized in that: in step (b):
the unidirectional asphalt-based carbon fiber cloth is laminated according to one direction or two directions;
the included angle between the fibers in each layer of unidirectional asphalt-based carbon fiber cloth is 0 degree or 90 degrees;
when the included angle between the fibers is 90 degrees, the ratio of the fiber contents in two directions is (1-4): 1, a step of;
and stitching is performed by adopting polyacrylonitrile-based carbon fibers in the direction perpendicular to the lamination direction, wherein the stitching interval is 1-2.5 mm.
5. The method of claim 1, wherein in step (2):
the thickness of the carbon nano-sheet interface layer is 300-500 nm.
6. The method of claim 1, wherein in step (3):
carrying out a PIP process of 1-5 rounds of dipping/curing/cracking by taking a carbon precursor solution as a dipping liquid, wherein the dipping is carried out by vacuum dipping firstly, then pressure dipping is carried out, the pressure of the pressure dipping is 2-3 MPa, the time of each vacuum dipping is 1-2 h, the time of each pressure dipping is 1-2 h, the curing temperature is 280-400 ℃, the time of each curing is 2-4 h, the cracking is hot isostatic pressing cracking, the cracking temperature is 900-1000 ℃, the cracking pressure is 60-90 MPa, and the time of each cracking is 2-4 h;
The carbon precursor in the carbon precursor solution is resin and/or asphalt; and/or
The temperature of the graphitization treatment is 2700-3100 ℃, and the time of the graphitization treatment is 15-45 min.
7. The method of claim 1, wherein in step (4):
the zirconium, hafnium, tantalum and silicon quaternary mixed powder comprises 10-20% of zirconium, 6-10% of hafnium, 4-10% of tantalum and 70-80% of silicon in mole fraction; and/or
The temperature of the reaction infiltration is 1500-1700 ℃ and the time is 2-3 h.
8. The method of manufacturing according to claim 1, characterized in that:
a ZrC-HfC-TaC-SiC-C composite coating with the thickness of 50-100 mu m is formed on the surface of the material, wherein the ceramic content in the composite coating is 95-100 wt%, the ceramic content gradually decreases from the ZrC-HfC-TaC-SiC-C composite coating to the inside of the material, and the ceramic content is 5-10 wt% when the ceramic content extends to 50-100 mu m below the surface of the material.
9. The production method according to any one of claims 1 to 8, characterized in that:
the carbon precursor solution contains graphene nano sheets, and the preparation of the carbon precursor solution comprises the following steps: adding a carbon precursor and graphene nano sheets into a solvent, and then stirring and performing ultrasonic treatment to obtain the graphene nano sheet;
Preferably, the carbon precursor solution contains carbon precursor and graphene nano-sheets in a mass ratio of (90-94): (6-10);
preferably, the graphene nano-sheets have a sheet diameter of 5-10 μm and a thickness of 3-10 nm.
10. A highly dense thermally-conductive composite material produced by the production process of any one of claims 1 to 9.
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