CN117303926A - Dispersed heat-dredging ceramic matrix composite material and preparation method thereof - Google Patents
Dispersed heat-dredging ceramic matrix composite material and preparation method thereof Download PDFInfo
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- 239000004917 carbon fiber Substances 0.000 claims abstract description 175
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 152
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000007598 dipping method Methods 0.000 claims abstract description 47
- 230000008569 process Effects 0.000 claims abstract description 42
- 239000000835 fiber Substances 0.000 claims abstract description 41
- 239000011302 mesophase pitch Substances 0.000 claims abstract description 41
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- 238000005087 graphitization Methods 0.000 claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims abstract description 20
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- 238000009958 sewing Methods 0.000 claims abstract description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 8
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- 229910021389 graphene Inorganic materials 0.000 claims description 37
- 229910052582 BN Inorganic materials 0.000 claims description 34
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 34
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Abstract
The invention relates to a dispersion type heat-dredging ceramic matrix composite material and a preparation method thereof. The method comprises the following steps: 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; laminating unidirectional pitch-based carbon fiber cloth, and then sewing by adopting polyacrylonitrile-based carbon fibers to obtain a pitch-based carbon fiber preform; preparing a carbon interface layer on the fiber surface of the asphalt-based carbon fiber preform by a chemical vapor deposition method and carrying out graphitization treatment to obtain a carbon fiber intermediate blank; and (3) reacting the ceramic precursor solution with the carbon fiber intermediate blank by adopting a precursor dipping and cracking process to prepare the dispersed heat-conducting ceramic matrix composite material. The invention can prepare large-area heat-conducting ceramic matrix composite material by near net-size molding, the fiber proportion and matrix components can be regulated and controlled, and the prepared material has the characteristics of low density, thin thickness, high specific strength, uniform and compact internal tissue structure, rapid in-plane large-area heat conduction and the like.
Description
Technical Field
The invention belongs to the technical field of composite materials and preparation, and particularly relates to a dispersion type heat-dredging ceramic matrix composite material and a preparation method thereof.
Background
The high heat conduction carbon fiber and heat conduction composite material has the characteristics of high modulus, high heat conduction, low expansion, electric conduction, light weight, high strength and the like, has great application prospect in the military and civil fields, and is an excellent dual-purpose material for military and civil use.
In the civil field, the high modulus characteristic of the high heat conduction carbon fiber is an excellent high-precision bearing material, and can be used for manufacturing precision machine tools, mechanical arms of robots, large-scale high-speed rollers and the like, and can be used as a structural material of the robots due to the high modulus and light weight. Particularly in the civil aerospace field, the high-heat-conductivity carbon fiber composite material has higher modulus and better dimensional stability, and can meet the higher precision requirements of large space structures such as civil satellites on optical structural members and precision components in extreme environments. The special electric conductivity of the high heat conduction carbon fiber enables the prepared composite material to have good lightning-proof effect, and can be used for manufacturing aircraft skins. In the field of manufacturing of equipment, electronics, automobiles, etc., the need for heat dissipation has also been continually addressed. The high heat conduction characteristic can be used for large-scale integrated circuits, high-power lasers, LEDs, automobile brake discs and the like with high heat dissipation requirements. In a spacecraft thermal control system, a heat conducting material is widely used for instruments and equipment needing to strengthen heat conduction, and has the functions of device heat dissipation, equipment temperature equalization, waste heat transmission, contact thermal resistance reduction and the like. However, the current thermally-conductive ceramic-based materials, although having relatively high strength and thermal conductivity, have problems of thicker thickness at the same density, such as in certain fields of aerospace or electronic devices, having stricter volume and weight limitations, may not well satisfy applications in these fields due to thicker structures, or have problems of poor overall performance due to the thermally-conductive ceramic-based materials at the same thickness, and further, the thermally-conductive ceramic-based composite materials in the prior art have problems of further improvement in mechanical properties and thermal conductivity.
Therefore, there is an urgent need for a dispersion type heat-conducting ceramic matrix composite and a method for preparing the same.
Disclosure of Invention
In order to solve one or more technical problems in the prior art, the invention provides a dispersion type heat-conducting ceramic matrix composite material and a preparation method thereof.
The present invention provides in a first aspect a method of preparing a dispersed thermally-induced ceramic matrix composite, the method comprising the steps of:
(1) 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;
(2) Laminating unidirectional pitch-based carbon fiber cloth, and then sewing by adopting polyacrylonitrile-based carbon fibers to obtain a pitch-based carbon fiber preform;
(3) Preparing a carbon interface layer on the fiber surface of the asphalt-based carbon fiber preform by a chemical vapor deposition method and carrying out graphitization treatment to obtain a carbon fiber intermediate blank;
(4) And (3) reacting the ceramic precursor solution with the carbon fiber intermediate blank by adopting a precursor dipping and cracking process to prepare the dispersed heat-conducting ceramic matrix composite material.
Preferably, in step (1): the elongation at break of the mesophase pitch-based carbon fibers in the mesophase pitch-based carbon fiber bundles is not less than 0.75%, the fiber diameter is 9-11 μm, and/or the thermal conductivity after graphitization treatment is not less than 800W/(m.K); and/or the specification of the mesophase pitch-based carbon fiber bundles is 3K-6K.
Preferably, in step (1): the width of the dispersed mesophase pitch-based carbon fiber bundles is 15-20 mm; and/or 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 (2): the unidirectional pitch-based carbon fiber cloth is according to a squareStacking in one or both 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; stitching with polyacrylonitrile-based carbon fiber in the direction perpendicular to the lamination direction, wherein the stitching interval is 1-2.5 mm; and/or the density of the pitch-based carbon fiber preform is 0.5-1.0 g/cm 3 。
Preferably, in step (3): the thickness of the carbon interface layer is 50-200 nm; and/or the temperature of the graphitization treatment is 2800-3200 ℃, and the graphitization treatment time is 15-30 min.
Preferably, the precursor dip cracking process is performed with a ceramic precursor solution comprising one or more of the SiC, siCN, siBCN, siBCNZr ceramic precursors; the solid content of the ceramic precursor solution is 50% -70%; in the precursor dipping and cracking process, the dipping time is 2-3 h, and the dipping pressure is 1.5-3.0 MPa; in the precursor dipping and cracking process, the curing temperature is 250-400 ℃ and the curing time is 3-5 h; in the precursor dipping and cracking process, the cracking temperature is 1000-1600 ℃ and the cracking time is 3-5 h; and/or the precursor impregnation and cleavage is repeated for 7 to 10 times.
Preferably, the ceramic precursor solution further comprises graphene nanoplatelets and boron nitride nanoplatelets; the ceramic precursor solution contains a ceramic precursor, graphene nano sheets and boron nitride nano sheets in a mass ratio of (80-90): (8-12): (4-6).
Preferably, the preparation of the ceramic precursor solution is as follows: adding a ceramic precursor, graphene nano sheets and boron nitride nano sheets into a solvent, and then stirring and carrying out ultrasonic treatment to obtain the nano-composite material; the sheet diameter of the graphene nano sheet is 5-10 mu m, and the thickness is 3-10 nm; and/or the sheet diameter of the boron nitride nano sheet is 1-2 mu m, and the thickness is 60-120 nm.
The present invention provides in a second aspect a dispersed thermally-induced ceramic matrix composite material produced by the method of the invention described in the first aspect.
Preferably, the dispersed thermally-conductive ceramic matrix composite has one or more of the following properties:
the density is 2.0-2.5 g/cm 3 。
The in-plane dimensions are: the length direction is not less than 600mm, and the width direction is not less than 400mm;
the thickness is 1.5-2.5 mm;
the bending strength is 200-350 MPa;
when the unidirectional pitch-based carbon fiber cloth is laminated according to one direction, the unidirectional heat conduction direction heat conductivity is 350-650W/(m.K);
when the unidirectional pitch-based carbon fiber cloth is laminated in two directions and is bidirectional and perpendicular, the in-plane thermal conductivity is 150 to 380W/(m.K).
Compared with the prior art, the invention has at least the following beneficial effects:
(1) 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 unidirectional pitch-based carbon fiber cloth can enable the prepared thermal-dredging ceramic-based composite material to have thinner thickness under the condition of basically the same density, in the prior art, the mesophase pitch-based carbon fiber is put into an organic carbon solution (mesophase pitch) for impregnation, then is placed in a mould in parallel, and is dried at a low temperature to obtain unidirectional carbon fiber sheets, the carbon fibers can be saturated and absorbed by the method in the impregnation process, a layer of pitch-based material is left among fibers in the subsequent drying process, the thickness of the sheets is increased, and in the process of being placed in parallel in the mould to obtain a unidirectional structure (unidirectional sheets), stacking between carbon fiber layers is involved, and the thickness of a final sheet 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 uniform and even carbon fiber arrangement, the directionality of the carbon fibers is more uniform, the uniformity is helpful for improving the strength and the stability of the heat-dredging composite material and resisting bending stress, and the thinner unidirectional pitch-based carbon fiber cloth obtained by the invention means that the integrity of the material is better and more uniform.
(2) The heat-conducting ceramic matrix composite material prepared by the invention has the advantages of low density, high specific strength, uniform and compact internal tissue structure, rapid in-plane large-area heat conduction, and excellent mechanical property and heat conduction property.
(3) The method can prepare the large-area heat-conducting ceramic matrix composite material by near net-size molding, has adjustable fiber proportion and matrix composition, and is suitable for samples with large in-plane size and thin thickness.
(4) The method has wide process window, can be molded in a near net size, and has low processing difficulty.
Drawings
FIG. 1 is a cross-sectional scanning electron microscope image of a dispersion type heat-conducting ceramic matrix composite material prepared in example 1 of the present invention.
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 dispersed thermally-induced ceramic matrix composite, the method comprising the steps of:
(1) 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, the mesophase pitch-based carbon fiber cloth is directly stitched together by a linear thermal fuse, for example, the periphery of the mesophase pitch-based carbon fiber cloth is stitched together by the thermal fuse, which has a low carbon residue rate and can play a primary role in fixation, and the thermal fuse is basically disappeared after being subjected to high temperature in the subsequent preparation process of the dispersed heat-conducting ceramic-based composite material, and the stitching 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;
(2) Laminating unidirectional pitch-based carbon fiber cloth, and then sewing by adopting polyacrylonitrile-based carbon fibers to obtain a pitch-based 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 pitch-based carbon fiber cloth, placing the stacked unidirectional pitch-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 pitch-based carbon fiber preform; when the fiber cloth is laminated, the included angle between the fibers in each layer of fiber cloth is 0 degree or 90 degrees, and when the included angle is 90 degrees, the ratio of the fiber content in two directions is (1-4): 1, namely the fiber volume fraction ratio in two directions is (1-4) when the included angle is 90 degrees: 1, a step of;
(3) Preparing a carbon interface layer on the fiber surface of the asphalt-based carbon fiber preform by a chemical vapor deposition method and carrying out graphitization treatment to obtain a carbon fiber intermediate blank; the invention does not limit the technological conditions of the chemical vapor deposition method, and is a conventional technology in the field;
(4) The precursor dipping and cracking process is adopted to enable the ceramic precursor solution to react with the carbon fiber intermediate blank, so that the dispersion type heat-conducting ceramic matrix composite material is prepared; in the invention, for example, a ceramic precursor solution containing one or more ceramic precursors is adopted to implement precursor dipping and cracking processes for carbon fiber intermediate blanks for a plurality of times to prepare a compact ceramic matrix, and a very thin ceramic coating layer is formed on the near surface of the material to obtain the dispersed heat-dredged ceramic matrix composite material.
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 vertical, so that the dispersed heat-conducting ceramic-based composite material can be provided with mesophase pitch-based carbon fibers serving as heat conducting and reinforcing bodies in one direction (X) or two vertical directions (X, Y) in the plane, and a ceramic matrix can be made of one, two or more ceramic materials (such as SiC, siCN, siBCN, siBCNZr and the like) for example.
The method can prepare the large-area dispersed heat-conducting ceramic matrix composite material by near net-size molding, and the fiber proportion and the matrix composition can be regulated and controlled, so that the prepared dispersed heat-conducting ceramic matrix composite material has the characteristics of low density, thin thickness, high specific strength, uniform and compact internal tissue structure, rapid in-plane large-area heat conduction, excellent mechanical property and heat conduction property and the like.
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 unidirectional pitch-based carbon fiber cloth can enable the prepared thermal-dredging ceramic-based composite material to have thinner thickness under the condition of basically the same density, in the prior art, the mesophase pitch-based carbon fiber is put into an organic carbon solution (mesophase pitch) for impregnation, then is placed in a mould in parallel, and is dried at a low temperature to obtain unidirectional carbon fiber sheets, the carbon fibers can be saturated and absorbed by the method in the impregnation process, a layer of pitch-based material is left among fibers in the subsequent drying process, the thickness of the sheets is increased, and in the process of being placed in parallel in the mould to obtain a unidirectional structure (unidirectional sheets), stacking between carbon fiber layers is involved, and the thickness of a final sheet 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 the 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 ceramic-based composite material with the total thickness of 3mm, the thicker carbon cloth 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 heat-conducting ceramic-based 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 unidirectional asphalt-based carbon fiber cloth is applied for a long time, when the unidirectional asphalt-based carbon fiber cloth is used, the peeling phenomenon occurs, when the unidirectional asphalt-based carbon fiber cloth is peeled off, the loss degree of the material reaches 16.67%, and when the unidirectional asphalt-based carbon fiber cloth is peeled off into 20 layers, the loss degree of the material is only 5%.
According to some preferred embodiments, in step (1): the elongation at break of the mesophase pitch-based carbon fibers in the mesophase pitch-based carbon fiber bundles is not lower than 0.75% (e.g., 0.75%, 0.77%, 0.8%, etc.), the fiber diameter is 9 to 11 μm (e.g., 9, 10, or 11 μm), and/or the thermal conductivity after graphitization is not lower than 800W/(m·k), the temperature of graphitization is 2800 to 3200 ℃, the time of graphitization is 15 to 30min, that is, the thermal conductivity of the mesophase pitch-based carbon fibers in the mesophase pitch-based carbon fiber bundles after graphitization in step (3) is not lower than 800W/(m·k); and/or the mesophase pitch-based carbon fiber bundles have a gauge of 3K to 6K (e.g., 3K, 4K, 5K, or 6K).
According to some preferred embodiments, in step (1): the width of the dispersed mesophase pitch-based carbon fiber bundles is 15-20 mm (for example 15, 16, 17, 18, 19 or 20 mm) and/or the areal 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 (2): 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; in the invention, when the unidirectional pitch-based carbon fiber cloth is laminated according to one direction, a unidirectional pitch-based carbon fiber preform is formed, carbon fibers in each layer of unidirectional pitch-based carbon fiber cloth are arranged along one direction, and an 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 vertical pitch-based 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); stitching 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); and/or the density of the pitch-based carbon fiber preform is 0.5-1.0 g/cm 3 (e.g., 0.5, 0.6, 0.7, 0.8, 0.9 or 1.0 g/cm) 3 )。
According to some preferred embodiments, in step (3): the thickness of the carbon interface layer is 50-200 nm (such as 50, 100, 150 or 200 nm); and/or the graphitization treatment is performed at a temperature of 2800 to 3200 ℃ (e.g., 2800, 2900, 3000, 3100, or 3200 ℃), and for a time of 15 to 30 minutes (e.g., 15, 20, 25, or 30 minutes).
According to some preferred embodiments, the precursor dip-cracking process is performed with a ceramic precursor solution comprising one or more of the SiC, siCN, siBCN, siBCNZr ceramic precursors; in some embodiments, the dispersed thermally-induced ceramic matrix composite may be produced, for example, of formula C f X, wherein X = C, CN, BCN, BCNZr one or more; the solid content of the ceramic precursor solution is 50% -70% (such as 50%, 55%, 60%, 65% or 70%), and the viscosity of the ceramic precursor solution is, for example, 100-260 mpa·s (such as 100, 150, 200 or 260mpa·s); in the precursor impregnation cracking process, the impregnation time is 2-3 h (e.g. 2, 2.5 or 3 h), and the impregnation pressure is 1.5-3.0 MPa (e.g. 1.5, 2, 2.5 or 3 MPa); in the precursor dipping and cracking process, the curing temperature is 250-400 ℃ (such as 250 ℃, 280 ℃, 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃ or 400 ℃), the curing pressure is 1.5-3.0 MPa (such as 1.5, 2, 2.5 or 3 MPa), and the curing time is 3-5 h (such as 3, 3.5, 4, 4.5 or 5 h); in the precursor impregnation cracking process, the cracking temperature is 1000-1600 ℃ (e.g. 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃ or 1600 ℃), and the cracking time is 3-5 h (e.g. 3, 35, 4, 4.5 or 5 h); and/or the precursor impregnating and cracking are repeated for 7-10 times; specifically, the three processes of precursor dipping-curing-cracking are repeatedly carried out for 7 to 10 rounds until the weight gain of the composite material after the last cracking is less than 0.5 percent, and the dispersion type heat-dredged ceramic matrix composite material is obtained.
According to some preferred embodiments, the ceramic precursor solution further comprises graphene nanoplatelets and boron nitride nanoplatelets; the sources of the graphene nano sheets and the boron nitride nano sheets are not particularly limited, and products which can be directly purchased in the market or synthesized by the existing method can be adopted; the ceramic precursor solution contains a ceramic precursor, graphene nano sheets and boron nitride nano sheets in a mass ratio of (80-90): (8-12): (4-6); the ceramic precursor solution takes dimethylbenzene as a solvent; the xylene of the present invention is not particularly limited, and may be one or more of ortho-xylene, para-xylene, and meta-xylene.
In the invention, the ceramic precursor solution preferably further comprises graphene nanoplatelets and boron nitride nanoplatelets, and comprises ceramic precursors, the graphene nanoplatelets and the boron nitride nanoplatelets in a mass ratio of (80-90): (8-12): (4-6), the invention discovers that the proper amount of graphene nano-sheets and boron nitride nano-sheets are added into the ceramic precursor solution for precursor dipping and cracking process, so that the remarkable improvement of the bending strength and the in-plane heat conductivity of the dispersion type heat-conducting ceramic matrix composite material can be realized, and the dispersion type heat-conducting ceramic matrix composite material has wide application prospect in the fields with high temperature, high strength and high heat conductivity requirements; the possible reasons are that the addition of the graphene nano-sheets and the boron nitride nano-sheets can form a good interface structure with ceramic particles, so that the overall strength and heat resistance of the material can be improved, the bending strength of the material is improved, the graphene nano-sheets and the boron nitride nano-sheets have excellent heat conducting performance, and the graphene nano-sheets and the boron nitride nano-sheets are distributed in the whole material to form effective heat conducting channels and heat conducting networks, thereby being beneficial to quickly transferring heat and improving the overall heat conductivity of the material.
According to some preferred embodiments, the formulation of the ceramic precursor solution is: adding a ceramic precursor, graphene nano sheets and boron nitride nano sheets into a solvent, and then stirring and carrying out ultrasonic treatment to obtain the nano-composite material; in the present invention, the stirring speed 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 40-60 min; in the invention, the ceramic precursor, the graphene nano-sheets and the boron nitride nano-sheets are uniformly dispersed in the solvent in a stirring and ultrasonic treatment mode, so that the graphene nano-sheets and the boron nitride nano-sheets are uniformly distributed in the whole ceramic precursor solution as far as possible, thereby being beneficial to improving the uniformity of the dispersion type heat-dredging ceramic matrix composite material and being beneficial to ensuring the performance of the material.
According to some preferred embodiments, the graphene nanoplatelets have a sheet diameter of 5-10 μm and a thickness of 3-10 nm; and/or the sheet diameter of the boron nitride nano sheet is 1-2 mu m, and the thickness is 60-120 nm; in the invention, the sheet diameter of the graphene nano sheet is preferably 5-10 mu m, the thickness is 3-10 nm, the sheet diameter of the boron nitride nano sheet is 1-2 mu m, the thickness is 60-120 nm, the graphene nano sheet with smaller thickness and larger sheet diameter and the boron nitride nano sheet with larger thickness and smaller sheet diameter are added, the proper size difference of the graphene nano sheet and the boron nitride nano sheet can enable the graphene nano sheet and the boron nitride nano sheet to be effectively dispersed in a composite material and form a proper interface with ceramic particles with a micro concave-convex structure, the proper concave-convex structure is beneficial to improving the compatibility of the interface, the interface matching property is better, the effective area of the interface is increased, the stress concentration is reduced, the strength of the reinforced material is facilitated, and the small thickness and the large sheet diameter of the graphene nano sheet enable the graphene nano sheet to be very effective heat conducting channels, the heat transfer is facilitated to be fast, and the synergistic effect between the graphene nano sheet and the boron nitride nano sheet can enable the overall heat conductivity and the strength of the material to be further improved.
The present invention provides in a second aspect a dispersed thermally-induced ceramic matrix composite material produced by the method of the invention described in the first aspect.
According to some preferred embodiments, the dispersed thermally-induced ceramic matrix composite has one or more of the following properties:
the density is 2.0-2.5 g/cm 3 ；
The in-plane dimensions are: the length direction is not less than 600mm, and the width direction is not less than 400mm; specifically, the in-plane dimension is not less than 400mm (width) ×600mm (length) (e.g., 400mm×600mm, 400mm×700mm, 400mm×800mm, or 500mm×600mm, etc.);
a thickness of 1.5 to 2.5mm (e.g., 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, or 2.5 mm);
the bending strength is 200-350 MPa;
when the unidirectional pitch-based carbon fiber cloth is laminated according to one direction, the unidirectional heat conduction direction heat conductivity is 350-650W/(m.K);
when the unidirectional pitch-based carbon fiber cloth is laminated in two directions and is bidirectional and perpendicular, the in-plane thermal conductivity is 150 to 380W/(m.K).
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) Preparing unidirectional pitch-based carbon fiber cloth: 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 elongation at break of the fibers in the adopted mesophase pitch-based carbon fiber bundles is 0.8%, the fiber diameter is 10 mu m, the thermal conductivity after graphitization treatment is 860W/(m.K), the fiber bundle specification is 3K, the width of the dispersed mesophase pitch-based carbon fiber bundles 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 pitch-based carbon fiber cloth is 0.15mm.
(2) Preparing an asphalt-based carbon fiber preform: 10 layers of unidirectional pitch-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 the pitch-based carbon fiber preform with the thickness of 1.5mm is obtained by sewing with polyacrylonitrile-based carbon fibers in the vertical direction (Z); the pitch-based carbon fiber preform is a bidirectional vertical pitch-based carbon fiber preform, an included angle between fibers in two adjacent layers of unidirectional pitch-based carbon fiber cloth is 90 degrees, the ratio of fiber contents 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 pitch-based carbon fiber preform is 0.9g/cm 3 。
(3) Preparing a carbon fiber intermediate blank: and uniformly depositing a carbon interface layer on the fiber surface of the asphalt-based carbon fiber preform by adopting a chemical vapor deposition method and carrying out graphitization treatment to obtain a carbon fiber intermediate blank, wherein the thickness of the carbon interface layer is 100nm, the graphitization treatment temperature is 3000 ℃, and the graphitization treatment time is 20min.
(4) Preparing a dispersion type heat-conducting ceramic matrix composite: a precursor dipping and cracking process is adopted to enable a ceramic precursor solution containing a silicon carbide ceramic precursor (polycarbosilane) to react with a carbon fiber intermediate blank, so that a dispersion type heat-dredging ceramic matrix composite material is prepared; the preparation of the ceramic precursor solution comprises the following steps: uniformly mixing polycarbosilane by using dimethylbenzene to obtain a ceramic precursor solution, wherein the ceramic precursor solution contains 60 mass percent of polycarbosilane; in the precursor dipping and cracking process, dipping is carried out at room temperature for 2 hours, the dipping pressure is 1.5MPa, the curing temperature is 250 ℃, the curing time is 3 hours, the curing pressure is 2MPa, the cracking temperature is 1000 ℃, the cracking time is 3 hours, and the precursor dipping and cracking process is repeated for 10 times.
Example 2
Example 2 is substantially the same as example 1 except that:
(4) preparing a dispersion type heat-conducting ceramic matrix composite: adopting a precursor dipping and cracking process to enable a ceramic precursor solution containing a silicon carbide ceramic precursor (polycarbosilane), graphene nano sheets and boron nitride nano sheets to react with a carbon fiber intermediate blank to prepare a dispersed heat-conducting ceramic matrix composite material; the preparation of the ceramic precursor solution comprises the following steps: adding polycarbosilane, graphene nano sheets with the sheet diameter distribution range of 5-10 mu m and the thickness distribution range of 3-10 nm and boron nitride nano sheets with the sheet diameter distribution range of 1-2 mu m and the thickness distribution range of 60-120 nm into dimethylbenzene, stirring and carrying out ultrasonic treatment to obtain the material, wherein the material is firstly stirred for 40min under the condition of the stirring rotating speed of 400rpm, and then carrying out ultrasonic treatment for 50min under the condition of the frequency of 20 kHz; the ceramic precursor solution contains 60 percent of the sum of the mass percentages of the polycarbosilane, the graphene nano-sheets and the boron nitride nano-sheets, and the mass ratio of the polycarbosilane to the graphene nano-sheets to the boron nitride nano-sheets is 88:8:4; in the precursor dipping and cracking process, dipping is carried out at room temperature for 2 hours, the dipping pressure is 1.5MPa, the curing temperature is 250 ℃, the curing time is 3 hours, the curing pressure is 2MPa, the cracking temperature is 1000 ℃, the cracking time is 3 hours, and the precursor dipping and cracking process is repeated for 10 times.
Example 3
Example 3 is substantially the same as example 2 except that:
(4) preparing a dispersion type heat-conducting ceramic matrix composite: adopting a precursor dipping and cracking process to enable a ceramic precursor solution containing a silicon carbide ceramic precursor (polycarbosilane) and graphene nano sheets to react with a carbon fiber intermediate blank to prepare a dispersion type heat-dredging ceramic matrix composite material; the preparation of the ceramic precursor solution comprises the following steps: adding polycarbosilane 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, stirring and performing ultrasonic treatment to obtain the graphene nano sheets, stirring for 40min under the condition that the stirring rotation speed is 400rpm, and performing ultrasonic treatment for 50min under the condition that the frequency is 20 kHz; the ceramic precursor solution contains 60 percent of the sum of the mass percentages of the polycarbosilane and the graphene nano-sheets, and the mass ratio of the polycarbosilane to the graphene nano-sheets is 88:12; in the precursor dipping and cracking process, dipping is carried out at room temperature for 2 hours, the dipping pressure is 1.5MPa, the curing temperature is 250 ℃, the curing time is 3 hours, the curing pressure is 2MPa, the cracking temperature is 1000 ℃, the cracking time is 3 hours, and the precursor dipping and cracking process is repeated for 10 times.
Example 4
Example 4 is substantially the same as example 2 except that:
(4) preparing a dispersion type heat-conducting ceramic matrix composite: adopting a precursor dipping and cracking process to enable a ceramic precursor solution containing a silicon carbide ceramic precursor (polycarbosilane) and boron nitride nanosheets to react with a carbon fiber intermediate blank to prepare a dispersion type heat-dredging ceramic matrix composite material; the preparation of the ceramic precursor solution comprises the following steps: adding polycarbosilane and boron nitride nano-sheets with the sheet diameter distribution range of 1-2 mu m and the thickness distribution range of 60-120 nm into dimethylbenzene, stirring and carrying out ultrasonic treatment to obtain the finished product, wherein the stirring is carried out for 40min under the condition that the stirring rotating speed is 400rpm, and then the ultrasonic treatment is carried out for 50min under the condition that the frequency is 20 kHz; the ceramic precursor solution contains 60 percent of polycarbosilane and boron nitride nano-sheets in percentage by mass, and the mass ratio of the polycarbosilane to the boron nitride nano-sheets is 88:12; in the precursor dipping and cracking process, dipping is carried out at room temperature for 2 hours, the dipping pressure is 1.5MPa, the curing temperature is 250 ℃, the curing time is 3 hours, the curing pressure is 2MPa, the cracking temperature is 1000 ℃, the cracking time is 3 hours, and the precursor dipping and cracking process is repeated for 10 times.
Comparative example 1
(1) Preparing an asphalt-based carbon fiber preform: immersing mesophase pitch-based carbon fibers in mesophase pitch, then placing in a mold in parallel, and drying at a low temperature of 100 ℃ to obtain unidirectional fiber sheets, wherein the thickness of the unidirectional fiber sheets is 0.3mm; 10 unidirectional fiber sheets were alternately laminated in two directions of 0/90℃and then subjected to hot press molding at 1000℃and 10MPa to obtain a bidirectional vertical carbon fiber preform (pitch-based carbon fiber preform) having a thickness of 3mm, the pitch-based carbon fiber preform having a density of 0.9g/cm 3 。
(2) Preparing a carbon fiber intermediate blank: and uniformly depositing a carbon interface layer on the fiber surface of the asphalt-based carbon fiber preform by adopting a chemical vapor deposition method and carrying out graphitization treatment to obtain a carbon fiber intermediate blank, wherein the thickness of the carbon interface layer is 100nm, the graphitization treatment temperature is 3000 ℃, and the graphitization treatment time is 20min.
(3) Preparing a heat-conducting ceramic matrix composite: a precursor dipping and cracking process is adopted to enable a ceramic precursor solution containing a silicon carbide ceramic precursor (polycarbosilane) to react with a carbon fiber intermediate blank, so that a thermally-induced ceramic matrix composite material is prepared; the preparation of the ceramic precursor solution comprises the following steps: uniformly mixing polycarbosilane by using dimethylbenzene to obtain a ceramic precursor solution, wherein the ceramic precursor solution contains 60 mass percent of polycarbosilane; in the precursor dipping and cracking process, dipping is carried out at room temperature for 2 hours, the dipping pressure is 1.5MPa, the curing temperature is 250 ℃, the curing time is 3 hours, the curing pressure is 2MPa, the cracking temperature is 1000 ℃, the cracking time is 3 hours, and the precursor dipping and cracking process is repeated for 10 times.
Comparative example 2
(1) Preparing a carbon fiber preform: 10 pieces of polyacrylonitrile-based carbon fiber cloth with the thickness of 0.5mm are alternately laminated according to two directions of 0 degree/90 degree and then put into a fixed mould for braiding, and the polyacrylonitrile-based carbon fiber cloth is adopted for suturing in the vertical direction (Z) to obtain the fiber with the density of 0.9g/cm 3 A carbon fiber preform having a thickness of 5mm.
(2) Preparing a carbon fiber intermediate blank: and uniformly depositing a carbon interface layer on the fiber surface of the carbon fiber preform by adopting a chemical vapor deposition method and carrying out graphitization treatment to obtain a carbon fiber intermediate blank, wherein the thickness of the carbon interface layer is 100nm, the graphitization treatment temperature is 3000 ℃, and the graphitization treatment time is 20min.
(3) Preparing a heat-conducting ceramic matrix composite: a precursor dipping and cracking process is adopted to enable a ceramic precursor solution containing a silicon carbide ceramic precursor (polycarbosilane) to react with a carbon fiber intermediate blank, so that a thermally-induced ceramic matrix composite material is prepared; the preparation of the ceramic precursor solution comprises the following steps: uniformly mixing polycarbosilane by using dimethylbenzene to obtain a ceramic precursor solution, wherein the ceramic precursor solution contains 60 mass percent of polycarbosilane; in the precursor dipping and cracking process, dipping is carried out at room temperature for 2 hours, the dipping pressure is 1.5MPa, the curing temperature is 250 ℃, the curing time is 3 hours, the curing pressure is 2MPa, the cracking temperature is 1000 ℃, the cracking time is 3 hours, and the precursor dipping and cracking process is repeated for 10 times.
The present invention conducted performance tests on the thermally-conductive ceramic matrix composites prepared in each example and each comparative example, 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 dispersion type heat-dredged ceramic matrix composite, which is characterized by comprising the following steps:
(1) 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;
(2) Laminating unidirectional pitch-based carbon fiber cloth, and then sewing by adopting polyacrylonitrile-based carbon fibers to obtain a pitch-based carbon fiber preform;
(3) Preparing a carbon interface layer on the fiber surface of the asphalt-based carbon fiber preform by a chemical vapor deposition method and carrying out graphitization treatment to obtain a carbon fiber intermediate blank;
(4) And (3) reacting the ceramic precursor solution with the carbon fiber intermediate blank by adopting a precursor dipping and cracking process to prepare the dispersed heat-conducting ceramic matrix composite material.
2. The method of claim 1, wherein in step (1):
the elongation at break of the mesophase pitch-based carbon fibers in the mesophase pitch-based carbon fiber bundles is not less than 0.75%, the fiber diameter is 9-11 μm, and/or the thermal conductivity after graphitization treatment is not less than 800W/(m.K); and/or
The specification of the mesophase pitch-based carbon fiber bundles is 3K-6K.
3. The method of claim 1, wherein in step (1):
the width of the dispersed mesophase pitch-based carbon fiber bundles is 15-20 mm; and/or
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. The method of claim 1, wherein in step (2):
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;
stitching with polyacrylonitrile-based carbon fiber in the direction perpendicular to the lamination direction, wherein the stitching interval is 1-2.5 mm; and/or
The density of the asphalt-based carbon fiber preform is 0.5-1.0 g/cm 3 。
5. The method of claim 1, wherein in step (3):
the thickness of the carbon interface layer is 50-200 nm; and/or
The temperature of the graphitization treatment is 2800-3200 ℃, and the time of the graphitization treatment is 15-30 min.
6. The method of manufacturing according to claim 1, characterized in that:
performing a precursor dip cracking process with a ceramic precursor solution comprising one or more of the ceramic precursors in SiC, siCN, siBCN, siBCNZr;
the solid content of the ceramic precursor solution is 50% -70%;
in the precursor dipping and cracking process, the dipping time is 2-3 h, and the dipping pressure is 1.5-3.0 MPa;
in the precursor dipping and cracking process, the curing temperature is 250-400 ℃ and the curing time is 3-5 h;
in the precursor dipping and cracking process, the cracking temperature is 1000-1600 ℃ and the cracking time is 3-5 h; and/or
The precursor impregnation and cracking are repeated for 7-10 times.
7. The method of manufacturing according to claim 6, wherein:
the ceramic precursor solution also comprises graphene nano sheets and boron nitride nano sheets;
the ceramic precursor solution contains a ceramic precursor, graphene nano sheets and boron nitride nano sheets in a mass ratio of (80-90): (8-12): (4-6).
8. The method of manufacturing according to claim 7, wherein:
the preparation of the ceramic precursor solution comprises the following steps: adding a ceramic precursor, graphene nano sheets and boron nitride nano sheets into a solvent, and then stirring and carrying out ultrasonic treatment to obtain the nano-composite material;
the sheet diameter of the graphene nano sheet is 5-10 mu m, and the thickness is 3-10 nm; and/or
The sheet diameter of the boron nitride nano sheet is 1-2 mu m, and the thickness is 60-120 nm.
9. A dispersed thermally-induced ceramic matrix composite produced by the production process of any one of claims 1 to 8.
10. The dispersed thermally-induced ceramic matrix composite of claim 9, wherein the dispersed thermally-induced ceramic matrix composite has one or more of the following properties:
the density is 2.0-2.5 g/cm 3 ；
The in-plane dimensions are: the length direction is not less than 600mm, and the width direction is not less than 400mm;
the thickness is 1.5-2.5 mm;
the bending strength is 200-350 MPa;
when the unidirectional pitch-based carbon fiber cloth is laminated according to one direction, the unidirectional heat conduction direction heat conductivity is 350-650W/(m.K);
when the unidirectional pitch-based carbon fiber cloth is laminated in two directions and is bidirectional and perpendicular, the in-plane thermal conductivity is 150 to 380W/(m.K).
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