CN113845368B - High-thermal-conductivity carbon-carbon composite material and preparation method thereof - Google Patents

High-thermal-conductivity carbon-carbon composite material and preparation method thereof Download PDF

Info

Publication number
CN113845368B
CN113845368B CN202111210369.1A CN202111210369A CN113845368B CN 113845368 B CN113845368 B CN 113845368B CN 202111210369 A CN202111210369 A CN 202111210369A CN 113845368 B CN113845368 B CN 113845368B
Authority
CN
China
Prior art keywords
carbon
composite material
carbon composite
temperature
carbon fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111210369.1A
Other languages
Chinese (zh)
Other versions
CN113845368A (en
Inventor
叶青
李益
杜钧
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Carbon Sheng Technology Co ltd
Original Assignee
Shanghai Carbon Sheng Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Carbon Sheng Technology Co ltd filed Critical Shanghai Carbon Sheng Technology Co ltd
Priority to CN202111210369.1A priority Critical patent/CN113845368B/en
Publication of CN113845368A publication Critical patent/CN113845368A/en
Application granted granted Critical
Publication of CN113845368B publication Critical patent/CN113845368B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • C04B35/83—Carbon fibres in a carbon matrix
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/522—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
    • C04B35/532—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

Abstract

The invention discloses a preparation method of a high-thermal-conductivity carbon-carbon composite material, which comprises the following steps: coating mesophase pitch matrix powder on the mesophase pitch carbon fiber reinforcement to form a carbon-carbon composite material precursor; carrying out hot press molding treatment on the carbon-carbon composite material precursor to obtain a carbon-carbon composite material; and carrying out high-temperature carbonization and graphitization treatment on the carbon-carbon composite material to obtain the high-thermal-conductivity carbon-carbon composite material. By adopting the technical scheme, in the process of preparing the carbon-carbon composite material precursor, the matrix powder is directly coated on the carbon fiber reinforcement and then hot-pressed, so that the matrix powder and the carbon fiber reinforcement can be fully infiltrated, the operation is simple, convenient and quick, the problems of long preparation period and high cost caused by the fact that the matrix is attached to the carbon fiber reinforcement to prepare the carbon-carbon composite material by adopting conventional liquid-phase impregnation and vapor-phase deposition in the prior art are solved, and the large-size complex structural member can be formed at one time. The invention also discloses a high-thermal-conductivity carbon composite material prepared by the preparation method.

Description

High-thermal-conductivity carbon-carbon composite material and preparation method thereof
Technical Field
The invention relates to the field of composite materials, in particular to a high-thermal-conductivity carbon composite material and a preparation method thereof.
Background
The mesophase pitch-based carbon fiber graphite flake layer is preferentially oriented along the height of a fiber axis, has excellent electric conduction, heat conduction and mechanical properties, is widely applied to the fields of advanced military industry, space flight and aviation and civil use, has the characteristics of high modulus of high-heat-conduction pitch-based carbon fiber filaments, brittleness and difficulty in weaving, causes the problems of overhigh cost, limited size, incapability of weaving special-shaped parts and the like of a weaving technology, can only adopt the conventional impregnation and vapor deposition method in the later densification process of a precursor, has long period (10-40 days) and high cost, and limits the application of the high-heat-conduction pitch-based carbon fiber filaments in composite materials, particularly special-shaped parts, in certain key parts and the improvement of the overall performance of military aircrafts.
Disclosure of Invention
The invention aims to solve the problems of long preparation period and high cost in the preparation of the high-thermal-conductivity carbon-carbon composite material in the prior art.
In order to solve the technical problem, the invention provides a preparation method of a high-thermal-conductivity carbon-carbon composite material, which comprises the steps of coating mesophase pitch matrix powder on a mesophase pitch carbon fiber reinforcement to form a carbon-carbon composite material precursor; carrying out hot press molding treatment on the carbon-carbon composite material precursor to obtain a carbon-carbon composite material; and carrying out high-temperature carbonization and graphitization treatment on the carbon-carbon composite material to obtain the high-thermal-conductivity carbon-carbon composite material.
By adopting the technical scheme, in the process of preparing the carbon-carbon composite material precursor, the matrix powder is directly coated on the carbon fiber reinforcement and then hot-press molding is carried out, so that the matrix powder and the carbon fiber reinforcement can be fully infiltrated, the operation is simple, convenient and quick, and the problems of long preparation period and high cost caused by the fact that the matrix is attached to the carbon fiber reinforcement to prepare the carbon-carbon composite material by adopting conventional liquid-phase impregnation and vapor-phase deposition in the prior art are solved.
Further, mesophase pitch is prepared into mesophase pitch carbon fiber non-woven fabrics, and then the carbon fiber non-woven fabrics are subjected to oxidation stabilization and low-temperature carbonization treatment to obtain the carbon fiber reinforcement.
Further, the oxidation stabilization treatment includes: pre-oxidizing the carbon fiber non-woven fabric in a continuous pre-oxidizing furnace, controlling the temperature of the continuous pre-oxidizing furnace to be 200-300 ℃, the running speed of a mesh belt to be 0.02-0.2 m/min, and the pre-oxidizing time to be 2-4 h.
Further, low-temperature carbonization treatment is carried out in a nitrogen atmosphere, and the temperature of the low-temperature carbonization treatment is 400-600 ℃.
Further, the mesophase pitch is mechanically crushed and sieved by a 100-300-mesh sieve to obtain mesophase pitch matrix powder.
Further, the matrix powder is placed in a volatile solvent, mixed uniformly and sprayed on the carbon fiber reinforcement.
Further, the mass fraction of the matrix powder is 20-60% of the carbon-carbon composite material precursor.
Furthermore, the temperature of the hot-press molding treatment is 400-500 ℃, the heating rate is 5-8 ℃/min, the heat preservation time is 3-10 h, and the pressure is 8-15 MPa.
Further, the temperature of the high-temperature carbonization is 1000 to 1500 ℃, wherein the temperature rise rate in the range of 400 to 700 ℃ is 0.1 to 0.3 ℃/min, and the temperature rise rate in other temperature ranges is 2 to 5 ℃/min.
Further, the temperature of the graphitization treatment is 2000 to 3000 ℃.
Further, the thickness of the nonwoven fabric is 2 to 10mm, and the area weight is 100 to 1000g/m 2 The volume density is 0.03-0.1 kg/m 3 。
On the other hand, the embodiment of the invention also discloses a high-thermal-conductivity carbon composite material which is prepared by any one of the preparation methods and has the density of 1.7-1.9 g/cm 3 The thermal conductivity is more than or equal to 200W/(m.K), and the bending strength is more than or equal to 12MPa.
The high-thermal-conductivity carbon composite material prepared by the technical scheme has excellent performance, and the density is 1.7-1.9 g/cm 3 The fabric has the advantages of high thermal conductivity, high bending strength, easiness in weaving, no limitation of shape and size in subsequent processing, easiness in processing into various models according to actual requirements and wide applicability.
Drawings
FIG. 1 shows a photograph of a carbon fiber nonwoven fabric of an embodiment of the invention;
fig. 2 shows a photograph of a highly thermally conductive carbon-carbon composite of an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure. While the invention will be described in conjunction with the preferred embodiments, it is not intended that features of the invention be limited to these embodiments. On the contrary, the invention has been described in connection with the embodiments for the purpose of covering alternatives or modifications as may be extended based on the claims of the invention. In the following description, numerous specific details are included to provide a thorough understanding of the invention. The invention may be practiced without these particulars. Moreover, some of the specific details have been left out of the description in order to avoid obscuring or obscuring the focus of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
It should be noted that in this specification, like reference numerals and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
In the description of the present embodiment, it should be noted that the terms "upper", "lower", "inner", "bottom", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings or orientations or positional relationships that are conventionally placed when the products of the present invention are used, and are only used for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the devices or elements indicated must have specific orientations, be configured in specific orientations, and operate, and thus, should not be construed as limiting the present invention.
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
The application provides a preparation method of a high-thermal-conductivity carbon-carbon composite material, which comprises the following steps: firstly, respectively obtaining a mesophase pitch carbon fiber reinforcement and mesophase pitch matrix powder, and then coating the matrix powder on the carbon fiber reinforcement to form a carbon-carbon composite material precursor; carrying out hot press molding treatment on the carbon-carbon composite material precursor to obtain a carbon-carbon composite material; and carrying out high-temperature carbonization and graphitization treatment on the carbon-carbon composite material to obtain the carbon-carbon composite material with high thermal conductivity.
The high-thermal-conductivity carbon-carbon composite material is prepared by adopting the mesophase pitch as a raw material, and the high-thermal-conductivity carbon-carbon composite material is easy to obtain, low in cost and easy to graphitize. Compared with the prior art which needs to prepare the carbon-carbon composite material precursor through liquid phase impregnation and gas phase deposition, the method for coating can simply and quickly enable the matrix powder to be uniformly arranged on the surface of the carbon fiber reinforcement to form the carbon-carbon composite material precursor. In the application, in order to combine the matrix powder with the carbon fiber reinforcement, the carbon-carbon composite precursor needs to be subjected to hot press molding, i.e., certain temperature and pressure are applied to the carbon-carbon composite precursor, so that the mesophase pitch matrix powder is melted and can be tightly attached to the surface of the carbon fiber reinforcement, and the carbon-carbon composite can be obtained. And finally, carrying out high-temperature carbonization and graphitization treatment on the carbon-carbon composite material to obtain the target high-heat-conductivity carbon-carbon composite material.
In the present application, the step of preparing mesophase pitch carbon fiber reinforcement comprises: preparing the mesophase pitch into mesophase pitch carbon fiber non-woven fabrics, and then carrying out oxidation stabilization and low-temperature carbonization treatment on the carbon fiber non-woven fabrics to obtain the carbon fiber reinforcement. Specifically, high-purity spinnable mesophase pitch is prepared into mesophase pitch carbon fiber non-woven fabrics through pitch melt-blown spinning equipment. The carbon fiber non-woven fabric is prepared by adopting a spray spinning technology, the production process difficulty is small, the flow is simple, and the requirement on the quality of the mesophase pitch is not high. In the examples of the present application, the high purity spinnable mesophase pitch is preferably a naphthalene based/petroleum based/coal based mesophase pitch with an ash content of < 100 ppm. Referring to fig. 1, a sheet-like carbon fiber non-woven fabric is prepared through melt-blown spinning. In this application, can adjust the parameter of melt-blown spinning equipment, obtain the carbon fiber non-woven fabrics that thickness is different, area weight is different, bulk density is different through spouting the spinning to satisfy the demand of different use scenes.
In the application, after the carbon fiber non-woven fabric is obtained by the jet spinning technology, oxidation stabilization and low-temperature carbonization treatment need to be further performed on the carbon fiber non-woven fabric to enhance the mechanical property of the carbon fiber non-woven fabric, so that the morphology can be maintained in the subsequent treatment process.
Specifically, the oxidation stabilization treatment is carried out in a continuous pre-oxidation furnace, and air is used as an oxidation medium and internally circulated in the furnace to carry out pre-oxidation on the carbon fibers. In the process, the temperature of the continuous pre-oxidation furnace is controlled to be 200-300 ℃, the running speed of the mesh belt is 0.02-0.2 m/min, and the pre-oxidation time is 2-4 h. Thus, the homogeneous preoxidation of the fiber protofilament can be realized, the small molecules of the asphalt are changed into large molecules, the mechanical property is enhanced, and the fiber shape can be kept in the subsequent preparation process.
Then, the pre-oxidized fiber obtained after the oxidation stabilization treatment is subjected to a low-temperature carbonization treatment. The low-temperature carbonization treatment is carried out in the nitrogen atmosphere, and the carbonization temperature is 400-600 ℃. In the process, the preoxidized fiber is subjected to polycondensation and crosslinking to a certain degree, so that the mechanical property of the carbon fiber non-woven fabric can be further enhanced. However, the temperature for low-temperature carbonization is not suitable to be too high, otherwise, the preoxidized fiber is subjected to polycondensation more completely, so that the number of active functional groups on the surface of the fiber is not enough, and the bonding with the matrix powder in the subsequent preparation process is not facilitated.
The carbon fiber reinforcement required by the carbon-carbon composite material can be obtained by the oxidation stabilization treatment and the low-temperature carbonization treatment of the carbon fiber non-woven fabric.
In the present application, the step of preparing the mesophase pitch matrix powder comprises: and (4) crushing and screening the mesophase pitch. For the present invention, in order to be able to obtain a carbon-carbon composite with a uniform texture, the mesophase pitch matrix powder should be sized as fine as possible so that the matrix powder is distributed uniformly over the carbon fiber reinforcement. Considering the experimental operating conditions in general, in the examples of the present application, the size of the matrix powder is 100 to 300 mesh. In this step, the mesophase pitch is also preferably a naphthalene based/petroleum based/coal based mesophase pitch having an ash content of less than 100 ppm. In each specific example, when preparing the carbon-carbon composite material, the matrix powder prepared from the same mesophase pitch and the carbon fiber non-woven fabric are preferably used to ensure the uniformity of the final product, namely the high-thermal-conductivity carbon-carbon composite material.
Further, after the mesophase pitch carbon fiber reinforcement and the matrix powder are obtained, the matrix powder is placed in a volatile solvent, the mixture is uniformly mixed and then sprayed on the carbon fiber reinforcement to complete the coating process, and the solvent is volatilized to obtain the carbon-carbon composite material precursor. In embodiments of the present invention, the volatile solvent is preferably isopropyl alcohol, because the density of isopropyl alcohol and the density of the pitch matrix powder are similar, which helps to uniformly disperse the matrix powder in isopropyl alcohol to ensure that the matrix powder is uniformly applied to the surface of the carbon fiber reinforcement. In addition, the isopropanol is non-toxic and good in volatility, and can be quickly volatilized after being sprayed to the carbon fiber reinforcement, so that the preparation time is saved. In the process of dispersing the matrix powder into the isopropanol, the mass ratio of the mesophase pitch powder to the isopropanol is 1: (2-4), the magnetic stirring speed is 200-400 rad/min, and the stirring time is 12-24 h. Of course, dry powder spraying or dispersion of the matrix powder using other solvents such as ethanol or water may be used in other embodiments of the present application, and the method of applying the matrix powder to the carbon fiber reinforcement is not limited as long as the purpose of application, i.e., uniform distribution of the matrix powder on the surface of the carbon fiber reinforcement, can be achieved.
In addition, in the embodiment of the application, the ratio of the matrix powder to the carbon fiber reinforcement can be adjusted by changing the spraying times of the matrix powder, that is, the total spraying amount, so as to adjust the comprehensive performance of the carbon-carbon composite material obtained after the graphitization treatment. In the present application, the mass fraction of the matrix powder is 20% to 60% of the carbon-carbon composite precursor.
In the application, after the carbon-carbon composite material precursor is obtained, the carbon-carbon composite material precursor is subjected to hot press molding treatment to obtain the carbon-carbon composite material. As described above, the purpose of the hot press molding is to adhere the matrix powder closely to the surface of the carbon fiber reinforcement. Specifically, in the embodiment of the application, the temperature of the hot-press molding treatment is 400-500 ℃, the temperature rise rate is 5-8 ℃/min, the heat preservation time is 3-10 h, and the hot-press pressure is 8-15 MPa. The hot-press molding treatment is carried out within the process parameter range, so that the matrix powder and the carbon fiber reinforcement are fully infiltrated and mixed. Of course, the above parameters can be continuously adjusted according to actual conditions in the hot press molding process, for example, when the selected carbon fiber non-woven fabric is thick, higher temperature or higher pressure can be adopted, so that the matrix powder is fully melted to enter the non-woven fabric with a certain thickness, and the tissue uniformity of the obtained carbon-carbon composite material is ensured. In addition, some small particles may be generated during the hot press molding processSub-substances, e.g. low-molecular tars, CH 4 CO, and the like.
The carbon fiber non-woven fabric adopted in the application has the thickness of 2-10 mm and the area weight of 100-1000 g/m 2 The volume density is 0.03-0.1 kg/m 3 So as to meet the requirements of different use scenes. For example, if the thickness of the carbon fiber nonwoven fabric to be used is small and a high thermal conductivity carbon composite material having a large thickness is to be obtained, it is necessary to use a plurality of carbon fiber reinforcements for the hot press molding treatment. In the preparation process of the carbon-carbon composite material in the embodiment of the application, a plurality of layers of carbon fiber reinforcements are adopted. Specifically, when the carbon-carbon composite material is prepared, the surface of each layer of carbon fiber reinforcement is coated with matrix powder, then the carbon fiber reinforcements coated with the matrix powder are superposed to obtain a multilayer carbon-carbon composite material precursor, and then the whole multilayer carbon-carbon composite material precursor is subjected to hot press molding treatment. Because the hot-press molding temperature is higher, the pressure is higher and the heat preservation time is longer, the sufficient infiltration of the matrix powder and the carbon fiber reinforcement can be ensured during the hot-press molding treatment, and the carbon-carbon composite material with uniform internal tissues can be obtained after the hot-press molding treatment.
In the application, after the carbon-carbon composite material is obtained, high-temperature carbonization and graphitization treatment are carried out on the carbon-carbon composite material to obtain the high-thermal-conductivity carbon-carbon composite material.
In the present application, the graphitization treatment is performed for the purpose of crystallizing the carbon-carbon composite material using a high temperature to form a regular graphite state. In the examples of the present application, the graphitization temperature is 2000 to 3000 ℃. The higher the graphitization temperature is, the higher the graphitization degree of the finally obtained carbon-carbon composite material is, and the higher the thermal conductivity is.
If direct carbon-carbon composite after to hot briquetting carries out graphitization, carbon-carbon composite can volatilize some light components at this in-process, and these light components can be shown as smog, influence common graphitizing furnace's infrared temperature measurement, lead to the temperature measurement inaccurate to unable accurate control graphitization's temperature leads to the adverse effect to high heat conduction carbon-carbon composite performance. On the other hand, because the temperature rise rate in the graphitization furnace cannot be accurately controlled, light components may rapidly volatilize in a large amount at a high temperature, so that the carbon-carbon composite material becomes fragile and cracked, and cannot maintain a complete morphology. Therefore, before the graphitization treatment, the carbon-carbon composite material needs to be subjected to high-temperature carbonization treatment, so that the light components are slowly released in the high-temperature carbonization process, and the quality of the product can be accurately controlled in the subsequent graphitization process.
Specifically, in the embodiment of the invention, the temperature of the high-temperature carbonization treatment is 1000-1500 ℃, the matrix powder and the carbon fiber reinforcement are carbonized at the temperature, and the macroscopic morphology of the carbon-carbon composite material cannot be changed in the high-temperature carbonization process due to the pretreatment of the carbon fiber non-woven fabric in the early preparation stage. Wherein the heating rate in the range of 400-700 ℃ is 0.1-0.3 ℃/min, and the heating rate in other temperature ranges is 2-5 ℃/min. The slow temperature rise in the range of 400-700 ℃ is to slowly release the light components and avoid cracking of the carbon-carbon composite material, and the termination temperature of the high-temperature carbonization is set to 1000-1500 ℃ to ensure the complete volatilization of the light components.
Referring to fig. 2, the carbon-carbon composite material of the present application, after high-temperature carbonization and graphitization treatment, obtains a graphitized bulk high thermal conductivity carbon-carbon composite material with uniform tissue.
On the other hand, the invention also discloses a high-thermal-conductivity carbon-carbon composite material which is prepared by adopting the preparation method and has the density of 1.7-1.9 g/cm 3 The thermal conductivity is more than or equal to 200W/(m.K), and the bending strength is more than or equal to 12MPa.
Further, the density of the high thermal conductivity carbon composite material is preferably 1.80 to 1.85g/cm 3 。
Compared with the carbon-carbon composite material obtained by liquid phase deposition, the carbon-carbon composite material obtained by the hot press molding treatment has higher density, and naturally, the high-thermal-conductivity carbon-carbon composite material with high density can be obtained after subsequent high-temperature carbonization and graphitization treatment. The high-thermal-conductivity carbon composite material with higher density has better mechanical property and electrical conductivity and longer service life.
Further, the thermal conductivity of the high thermal conductivity carbon composite material is preferably 240 to 280W/(mK).
Further, the flexural strength of the high thermal conductive carbon composite material is preferably 12 to 25MPa.
The technical solution of the present application is illustrated below with reference to specific examples.
Example 1
The mesophase pitch carbon fiber non-woven fabric is prepared by adopting self-made petroleum mesophase pitch with ash content of 70ppm through melt-blown spinning equipment, the thickness of the non-woven fabric is 5mm, and the area weight is 230g/m 2 Bulk density of 0.05kg/m 3 . And arranging the prepared carbon fiber non-woven fabric in a continuous mesh belt type pre-oxidation furnace for oxidation stabilization treatment, wherein the oxidation medium is air, the temperature of the continuous pre-oxidation furnace is set to be 200-280 ℃, the running speed of a mesh belt is 0.02m/min, and the pre-oxidation time is 2h, 3h and 4h respectively. And then placing the carbon fiber non-woven fabric subjected to oxidation stabilization in a carbonization furnace for low-temperature carbonization treatment to obtain a carbon fiber reinforcement, wherein the temperature of the low-temperature carbonization treatment is 500 ℃.
Putting the screened matrix powder of the mesophase pitch into volatile isopropanol, uniformly mixing by magnetic stirring, and pouring into a spraying tank, wherein the mass ratio of the mesophase pitch powder to the isopropanol is 1:2, the magnetic stirring speed is 200rad/min, and the stirring time is 24h. And uniformly spraying an isopropanol solution mixed with matrix powder on the carbon fiber reinforcement, and volatilizing the isopropanol after spraying to obtain the carbon-carbon composite material precursor, wherein the mass fraction of the matrix powder is 20%.
And (3) placing the carbon-carbon composite material precursor into a stainless steel mold for hot press molding treatment, wherein the hot press temperature is 450 ℃, the heating rate is 5 ℃/min, the heat preservation time is 5h, and the hot press pressure is 10MPa, so as to prepare the carbon-carbon composite material.
Then the carbon-carbon composite material is carbonized at the high temperature of 1000 ℃ and graphitized at the temperature of 3000 ℃. Wherein, the temperature rise rate in the range of 400-700 ℃ in the high-temperature carbonization process is 0.1 ℃/min, and the temperature rise rate of other temperatures is 3 ℃/min. Finally obtaining the density of 1.80 to 1.85g/cm 3 High heat conduction carbon-carbon compositeA material. The thermal conductivity of the graphitized high thermal conductivity carbon-carbon composite material is 260-280W/(m.K) through a laser scintillation method, and the bending strength is 20-25 MPa.
Table 1 shows the properties of the high thermal conductivity carbon composite material obtained through different pre-oxidation times.
Table 1.
Preoxidation time/h Density/g.cm -3 Thermal conductivity/W/(m. K) Flexural strength/MPa
2 1.80 260 20
3 1.85 280 25
4 1.83 272 24.5
Example 2
The mesophase pitch carbon fiber is prepared by adopting self-made petroleum mesophase pitch with ash content of 70ppm through melt-blown spinning equipmentThe nonwoven fabric has a thickness of 8mm and an area weight of 450g/m 2 The bulk density is 0.06kg/m 3 . And arranging the prepared carbon fiber non-woven fabric in a continuous mesh belt type pre-oxidation furnace for oxidation stabilization treatment, wherein the oxidation medium is air, the temperature of the continuous pre-oxidation furnace is set to be 200-280 ℃, the running speed of a mesh belt is 0.04m/min, and the pre-oxidation time is 3h. The oxidation-stabilized carbon fiber nonwoven fabric is then placed in a carbonization furnace for low-temperature carbonization treatment to obtain a carbon fiber reinforcement, wherein the low-temperature carbonization treatment temperature is 400 ℃, 500 ℃ and 600 ℃ in the embodiment.
Putting the screened matrix powder of the mesophase pitch into volatile isopropanol, uniformly mixing by magnetic stirring, and pouring into a spraying tank, wherein the mass ratio of the mesophase pitch powder to the isopropanol is 1:3, the magnetic stirring speed is 200rad/min, and the stirring time is 20h. And uniformly spraying an isopropanol solution mixed with matrix powder on the carbon fiber reinforcement, and volatilizing the isopropanol after spraying to obtain the carbon-carbon composite material precursor, wherein the mass fraction of the matrix powder is 60%.
And (3) placing the carbon-carbon composite material precursor into a stainless steel mold for hot press molding treatment, wherein the hot press temperature is 480 ℃, the heating rate is 8 ℃/min, the heat preservation time is 3h, and the hot press pressure is 12MPa, so as to prepare the carbon-carbon composite material.
Then the carbon-carbon composite material is carbonized at 1300 ℃ and graphitized at 2800 ℃. Wherein, the heating rate in the high-temperature carbonization process is 0.2 ℃/min within the range of 400-700 ℃, and the heating rate of other temperatures is 4 ℃/min. Finally obtaining the density of 1.80 to 1.85g/cm 3 The high heat conduction carbon-carbon composite material. The heat conductivity of the graphitized high-heat-conductivity carbon-carbon composite material is 260-278W/(m.K) through a laser scintillation method, and the bending strength is 20-25 MPa.
Table 2 shows the properties of the highly thermally conductive carbon-carbon composite materials obtained with different low-temperature carbonization temperatures.
Table 2.
Low temperature carbonization temperature/. Degree.C Density/g.cm -3 Thermal conductivity/W/(m.K) Flexural strength/MPa
400 1.80 260 20
500 1.85 278 25
600 1.84 274 23
Example 3
The mesophase pitch carbon fiber non-woven fabric is prepared by adopting self-made petroleum mesophase pitch with ash content of 70ppm through melt-blown spinning equipment, the thickness of the non-woven fabric is 3mm, and the area weight is 150g/m 2 The bulk density is 0.03kg/m 3 . And arranging the prepared carbon fiber non-woven fabric in a continuous mesh belt type pre-oxidation furnace for oxidation stabilization treatment, wherein the oxidation medium is air, the temperature of the continuous pre-oxidation furnace is set to be 200-280 ℃, the running speed of a mesh belt is 0.06m/min, and the pre-oxidation time is 2.5h. Then placing the oxidation-stabilized carbon fiber non-woven fabric in a carbonization furnace for low-temperature carbonization treatment to obtain a carbon fiber reinforcement, wherein the temperature of the low-temperature carbonization treatment is 5 DEG00℃。
Putting the screened matrix powder of the mesophase pitch into volatile isopropanol, uniformly mixing by magnetic stirring, and pouring into a spraying tank, wherein the mass ratio of the mesophase pitch powder to the isopropanol is 1:2, the magnetic stirring speed is 300rad/min, and the stirring time is 16h. And uniformly spraying an isopropanol solution mixed with matrix powder on the carbon fiber reinforcement, and volatilizing the isopropanol after spraying to obtain the carbon-carbon composite material precursor, wherein the mass fraction of the matrix powder is 30%.
And (3) placing the carbon-carbon composite material precursor into a stainless steel mold for hot-press molding treatment, wherein the hot-press temperature is 400 ℃, the heating rate is 6 ℃/min, the heat preservation time is 7h, and the pressure is 8MPa, 10MPa or 15MPa, so as to prepare the carbon-carbon composite material.
Then the carbon-carbon composite material is carbonized at 1500 ℃ and graphitized at 2500 ℃. Wherein, the temperature rise rate in the range of 400-700 ℃ in the high-temperature carbonization process is 0.3 ℃/min, and the temperature rise rate of other temperatures is 5 ℃/min. Finally obtaining the density of 1.81-1.84 g/cm 3 The high heat conduction carbon-carbon composite material. The heat conductivity of the graphitized high-heat-conductivity carbon composite material is 262-280W/(m.K) through a laser scintillation method, and the bending strength is 18-25 MPa.
Table 3 shows the properties of the highly thermally conductive carbon-carbon composite obtained using different thermoforming pressures.
Table 3.
Hot press forming pressure/MPa Density/g.cm -3 Thermal conductivity/W/(m.K) Flexural strength/MPa
8 1.81 262 18
10 1.84 280 25
15 1.82 275 19
The pressure in the hot-press molding treatment can destroy the tissue structure of the carbon fiber reinforcement, so that the performance of the finally obtained high-heat-conductivity carbon-carbon composite material is reduced.
Example 4
The mesophase pitch carbon fiber non-woven fabric is prepared by adopting self-made petroleum mesophase pitch with ash content of 70ppm through melt-blown spinning equipment, the thickness of the non-woven fabric is 10mm, and the area weight is 600g/m 2 The bulk density is 0.07kg/m 3 . And arranging the prepared carbon fiber non-woven fabric in a continuous mesh belt type pre-oxidation furnace for oxidation stabilization treatment, wherein the oxidation medium is air, the temperature of the continuous pre-oxidation furnace is set to be 200-280 ℃, the running speed of a mesh belt is 0.1m/min, and the pre-oxidation time is 4h. And then placing the carbon fiber non-woven fabric subjected to oxidation stabilization in a carbonization furnace for low-temperature carbonization treatment to obtain a carbon fiber reinforcement, wherein the temperature of the low-temperature carbonization treatment is 500 ℃.
Putting the screened matrix powder of the mesophase pitch into volatile isopropanol, uniformly mixing by magnetic stirring, and pouring into a spraying tank, wherein the mass ratio of the mesophase pitch powder to the isopropanol is 1:4, the magnetic stirring speed is 200rad/min, and the stirring time is 12h. And uniformly spraying an isopropanol solution mixed with matrix powder on the carbon fiber reinforcement, and volatilizing the isopropanol after spraying to obtain the carbon-carbon composite material precursor, wherein the mass fraction of the matrix powder is 40%.
And (3) placing the carbon-carbon composite material precursor into a stainless steel mold for hot press molding treatment, wherein the hot press temperature is 500 ℃, the heating rate is 8 ℃/min, the heat preservation time is 10h, and the pressure is 15MPa, so as to prepare the carbon-carbon composite material.
Then the carbon-carbon composite material is carbonized at the high temperature of 1100 ℃ and graphitized at the temperature of 2000 ℃. Wherein, the heating rate in the high temperature carbonization process is 0.1 ℃/min, 0.3 ℃/min and 1 ℃/min within the range of 400-700 ℃, and the heating rate of other temperatures is 3 ℃/min. Finally obtaining the density of 1.81-1.85 g/cm 3 The high heat conduction carbon-carbon composite material. The heat conductivity of the graphitized high-heat-conductivity carbon composite material is 240-280W/(m.K) through a laser scintillation method, and the bending strength is 18-25 MPa.
Table 4 shows the properties of the highly thermally conductive carbon-carbon composite materials obtained using different high temperature carbonization ramp rates.
Table 4.
Temperature rise rate/DEG C.min for high-temperature carbonization -1 Density/g.cm -3 Thermal conductivity/W/(m.K) Flexural strength/MPa
0.1 1.81 280 25
0.3 1.85 273 23
1 1.82 240 18
During high-temperature carbonization treatment, the light components are not sufficiently released due to too fast heating rate, and in the subsequent graphitization process, volatilized light component smoke can influence the infrared temperature measurement of the graphitization furnace, so that the temperature measurement is inaccurate, the temperature cannot be accurately controlled in the graphitization process, and the performance of the final high-thermal-conductivity carbon-carbon composite material is influenced.
Example 5
The mesophase pitch carbon fiber non-woven fabric is prepared by adopting self-made petroleum mesophase pitch with ash content of 70ppm through melt-blown spinning equipment, the thickness of the non-woven fabric is 2mm, 10mm and 15mm, and the area weight is 100g/m 2 The bulk density is 0.03kg/m 3 . And arranging the prepared carbon fiber non-woven fabric in a continuous mesh belt type pre-oxidation furnace for oxidation stabilization treatment, wherein the oxidation medium is air, the temperature of the continuous pre-oxidation furnace is set to be 200-280 ℃, the running speed of a mesh belt is 0.2m/min, and the pre-oxidation time is 2 hours. And then placing the carbon fiber non-woven fabric subjected to oxidation stabilization in a carbonization furnace for low-temperature carbonization treatment to obtain a carbon fiber reinforcement, wherein the temperature of the low-temperature carbonization treatment is 500 ℃.
Putting the screened matrix powder of the mesophase pitch into volatile isopropanol, uniformly mixing by magnetic stirring, and pouring into a spraying tank, wherein the mass ratio of the mesophase pitch powder to the isopropanol is 1:2, the magnetic stirring speed is 400rad/min, and the stirring time is 24h. And uniformly spraying an isopropanol solution mixed with matrix powder on the carbon fiber reinforcement, and volatilizing the isopropanol after spraying to obtain the carbon-carbon composite material precursor, wherein the mass fraction of the matrix powder is 50%.
And (3) placing the carbon-carbon composite material precursor into a stainless steel mold for hot press molding treatment, wherein the hot press temperature is 500 ℃, the heating rate is 5 ℃/min, the heat preservation time is 3h, and the pressure is 8MPa, so as to prepare the carbon-carbon composite material.
Then the carbon-carbon composite material is carbonized at the high temperature of 1400 ℃ and graphitized at the temperature of 2300 ℃. Wherein, the temperature rise rate in the range of 400-700 ℃ in the high-temperature carbonization process is 0.2 ℃/min, and the temperature rise rate of other temperatures is 2 ℃/min. Finally obtaining the density of 1.80-1.85 g/cm 3 The high heat conduction carbon-carbon composite material. The thermal conductivity of the graphitized high thermal conductivity carbon-carbon composite material is 240-280W/(m.K) through a laser scintillation method, and the bending strength is 18-23 MPa.
Table 5 shows the properties of the highly thermally conductive carbon-carbon composite obtained with different nonwoven thicknesses.
Table 5.
Thickness/mm of nonwoven fabric Density/g.cm -3 Thermal conductivity/W/(m. K) Flexural strength/MPa
2 1.82 265 19
10 1.85 280 23
15 1.80 240 18
When the non-woven fabric is too thick, the matrix powder cannot fully enter the carbon fiber non-woven fabric in the hot press molding treatment process, so that the carbon-carbon composite material has uneven tissue, and the finally obtained high-thermal-conductivity carbon-carbon composite material has poor performance.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a more detailed description of the invention, taken in conjunction with the specific embodiments thereof, and that no limitation of the invention is intended thereby. Various changes in form and detail, including simple deductions or substitutions, may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (9)

1. A preparation method of a high-thermal-conductivity carbon-carbon composite material is characterized by comprising the following steps:
preparing mesophase pitch into mesophase pitch carbon fiber non-woven fabric, and then carrying out oxidation stabilization and low-temperature carbonization treatment on the carbon fiber non-woven fabric to obtain the carbon fiber reinforcement, wherein the temperature of the low-temperature carbonization treatment is 400-600 ℃;
putting the mesophase pitch matrix powder into a volatile solvent, uniformly mixing, spraying onto the mesophase pitch carbon fiber reinforcement, and volatilizing the solvent to form a carbon-carbon composite material precursor;
carrying out hot-press molding treatment on the carbon-carbon composite material precursor to obtain a carbon-carbon composite material;
and carrying out high-temperature carbonization and graphitization treatment on the carbon-carbon composite material to obtain the high-thermal-conductivity carbon-carbon composite material.
2. The preparation method according to claim 1, wherein the hot press molding treatment temperature is 400-500 ℃, the heating rate is 5-8 ℃/min, the holding time is 3-10 h, and the pressure is 8-15 MPa.
3. The method according to claim 1, wherein the high-temperature carbonization temperature is 1000 to 1500 ℃, and wherein the temperature increase rate in the range of 400 to 700 ℃ is 0.1 to 0.3 ℃/min, and the temperature increase rate in the other temperature ranges is 2 to 5 ℃/min.
4. The method according to claim 1, wherein the temperature of the graphitization treatment is 2000 to 3000 ℃.
5. The preparation method according to claim 1, wherein the mass fraction of the matrix powder is 20 to 60% of the carbon-carbon composite precursor.
6. The production method according to claim 1, wherein the carbon fiber nonwoven fabric has a thickness of 2 to 10mm and an areal weight of 100 to 1000g/m 2 The volume density is 0.03-0.1 kg/m 3 。
7. The production method according to claim 1, wherein the oxidation stabilization treatment includes: pre-oxidizing the carbon fiber non-woven fabric in a continuous pre-oxidizing furnace, controlling the temperature of the continuous pre-oxidizing furnace to be 200-300 ℃, controlling the running speed of a mesh belt to be 0.02-0.2 m/min, and controlling the pre-oxidizing time to be 2-4 h.
8. The production method according to claim 1, wherein the low-temperature carbonization treatment is performed in a nitrogen atmosphere.
9. A highly heat conductive carbon-carbon composite material, characterized in that, the preparation method of any one of claims 1 to 8 is usedThe density of the high-thermal-conductivity carbon composite material is 1.7-1.9 g/cm 3 The thermal conductivity is more than or equal to 200W/(m.K), and the bending strength is more than or equal to 12MPa.
CN202111210369.1A 2021-10-18 2021-10-18 High-thermal-conductivity carbon-carbon composite material and preparation method thereof Active CN113845368B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111210369.1A CN113845368B (en) 2021-10-18 2021-10-18 High-thermal-conductivity carbon-carbon composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111210369.1A CN113845368B (en) 2021-10-18 2021-10-18 High-thermal-conductivity carbon-carbon composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113845368A CN113845368A (en) 2021-12-28
CN113845368B true CN113845368B (en) 2023-02-28

Family

ID=78978678

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111210369.1A Active CN113845368B (en) 2021-10-18 2021-10-18 High-thermal-conductivity carbon-carbon composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113845368B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115073198A (en) * 2022-02-18 2022-09-20 武汉科技大学 High-thermal-conductivity graphitized porous carbon/carbon composite material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2103832A1 (en) * 2008-03-18 2009-09-23 Honeywell International Inc. Densification of c-c composites with pitches followed by cvi/cvd
CN102504770A (en) * 2011-10-08 2012-06-20 中国科学院山西煤炭化学研究所 Preparation method of carbon-carbon composite material with high thermal conductivity
CN103936452A (en) * 2014-04-09 2014-07-23 中国科学院山西煤炭化学研究所 Preparation method of unidirectional carbon/carbon composite material with high heat conductivity
CN108314458A (en) * 2018-02-09 2018-07-24 西安天运新材料科技有限公司 A kind of preparation method of high heat conduction carbon/carbon compound material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060177663A1 (en) * 2005-02-08 2006-08-10 Honeywell International Inc. Carbon-carbon composite article manufactured with needled fibers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2103832A1 (en) * 2008-03-18 2009-09-23 Honeywell International Inc. Densification of c-c composites with pitches followed by cvi/cvd
CN102504770A (en) * 2011-10-08 2012-06-20 中国科学院山西煤炭化学研究所 Preparation method of carbon-carbon composite material with high thermal conductivity
CN103936452A (en) * 2014-04-09 2014-07-23 中国科学院山西煤炭化学研究所 Preparation method of unidirectional carbon/carbon composite material with high heat conductivity
CN108314458A (en) * 2018-02-09 2018-07-24 西安天运新材料科技有限公司 A kind of preparation method of high heat conduction carbon/carbon compound material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
中间相沥青纤维制备高导热炭材料的研究;马兆昆等;《无机材料学报》;20061030(第05期);第1167-1172页 *

Also Published As

Publication number Publication date
CN113845368A (en) 2021-12-28

Similar Documents

Publication Publication Date Title
CN111099911B (en) Carbon fiber reinforced carbon-silicon carbide-zirconium carbide composite material and preparation method thereof
US7384663B2 (en) Method of making a three-dimensional fiber structure of refractory fibers
KR100850657B1 (en) Method for manufacturing carbon fiber reinforced carbon composite material suitable for semiconductor heat sink
US20060177663A1 (en) Carbon-carbon composite article manufactured with needled fibers
CN113845368B (en) High-thermal-conductivity carbon-carbon composite material and preparation method thereof
US7927523B2 (en) Densification of C-C composites with pitches followed by CVI/CVD
RU2337083C2 (en) Method of production of fiber-reinforced carbon-silicon carbide composite material
WO2015183369A2 (en) Process for fabricating carbon-carbon composites
CN109056186B (en) Preparation method of low-density multi-angle woven carbon fiber hard heat-insulation cylinder
CN103332943A (en) Microstructure design and performance control method for preparing carbon-ceramic-based composite materials based on liquid silicon melt infiltration method
CN112500184B (en) Aluminum oxide doped modified carbon-based composite material and preparation method thereof
CN112538233A (en) Surface anti-scouring low-density ablation heat-proof material and preparation method thereof
CN102976782B (en) Carbon-to-carbon composite preform is formed using molten asphalt and carbon mono-filaments
EP3225871B1 (en) High density carbon-carbon friction materials
CN109228546A (en) A kind of preparation method of high density multi-angle establishment carbon fiber carbon carbon cylinder
EP1518016B1 (en) Isotropic pitch-based materials for thermal insulation
CN106044742B (en) A kind of preparation method of asphalt base carbon fiber self-adhesive network material
CN116693311A (en) Preparation and application of high-heat-conductivity matrix and coating integrated design and ablation-resistant composite material
CN115557800B (en) Method for preparing silicon carbide-based composite material by uniformly ceramifying porous carbon
JPH069270A (en) Preparation of carbon/carbon composite material part using mesophase powder
CN113292352B (en) Preparation method of unidirectional high-thermal-conductivity carbon/carbon composite material
KR102150325B1 (en) Method for manufacturing patterned artificial graphite heat dissipation sheet
RU2569385C1 (en) Method of making articles from heat-resistant composite materials
CN112110748A (en) Preparation method of two-dimensional high-thermal-conductivity C/C-ZrC-SiC composite material
TWI705934B (en) Manufacturing method of pitch-based carbon/carbon composite material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant