CN113582710A - High-thermal-conductivity carbon fiber rod for weaving and preparation method and application thereof - Google Patents
High-thermal-conductivity carbon fiber rod for weaving and preparation method and application thereof Download PDFInfo
- Publication number
- CN113582710A CN113582710A CN202110850960.7A CN202110850960A CN113582710A CN 113582710 A CN113582710 A CN 113582710A CN 202110850960 A CN202110850960 A CN 202110850960A CN 113582710 A CN113582710 A CN 113582710A
- Authority
- CN
- China
- Prior art keywords
- thermal
- temperature
- carbon fiber
- conductivity carbon
- dredging
- 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.)
- Granted
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
-
- 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62844—Coating fibres
- C04B35/62857—Coating fibres with non-oxide ceramics
- C04B35/62873—Carbon
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5062—Borides, Nitrides or Silicides
- C04B41/5071—Silicides
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
- C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5216—Inorganic
- C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
- C04B2235/5248—Carbon, e.g. 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
- 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 relates to a high-thermal-conductivity carbon fiber rod for weaving and a preparation method and application thereof. The method comprises the following steps: the intermediate phase pitch is taken as a raw material, and a high-thermal-conductivity carbon fiber intermediate product is prepared by sequentially carrying out melt spinning, drying, pre-oxidation and carbonization on the raw material; graphitizing the intermediate product of the high-thermal-conductivity carbon fiber in a vacuum environment or an inert atmosphere environment to prepare the high-thermal-conductivity carbon fiber; and (3) sequentially carrying out the processes of gum dipping, winding, curing and cutting on the high-thermal-conductivity carbon fiber to obtain the high-thermal-conductivity carbon fiber rod for weaving. The high-thermal-conductivity carbon fiber rod prepared by the invention has excellent weaving performance while keeping high strength, high modulus and high thermal conductivity, and the process is simple and controllable, so that the problem of high weaving difficulty of the high-thermal-conductivity carbon fiber in the using process is solved; the thermal dredging composite material prepared by the high-thermal-conductivity carbon fiber rod has the characteristics of high thermal conductivity, high density, excellent mechanical property, excellent high-temperature ablation resistance and the like.
Description
Technical Field
The invention belongs to the technical field of carbon fiber preparation, and particularly relates to a high-thermal-conductivity carbon fiber rod for weaving, and a preparation method and application thereof.
Background
The high-thermal-conductivity carbon fiber has the characteristics of ultrahigh thermal conductivity (500-. The high heat conduction carbon fiber has lower density (density of 2.0-2.2 g/cm)3) The material has high specific thermal conductivity, specific modulus and specific strength, and is one of excellent structure-function integrated materials. Compared with the traditional carbon fiber reinforced composite material, the heat dredging composite material prepared by the high-heat-conductivity carbon fiber has more excellent mechanical and heat-conducting properties, and can be used in the fields of aerospace, electronic equipment and the like.
However, the high thermal conductivity carbon fiber has low elongation at break (generally less than 0.6%, even less than 0.3%), high brittleness, low hooking strength, and is not suitable for bending at a small angle, broken filaments and the like are easy to occur in the using process, and the difficulty of weaving the carbon fiber preform is high. Chinese patent application CN201810136681.2 discloses an asphalt-based carbon fiber for weaving and a method for preparing the same, wherein asphalt-based carbon fiber for weaving is obtained by three-stage carbonization, and although the elongation at break of the obtained asphalt-based carbon fiber is improved to about 1.1%, the obtained asphalt-based carbon fiber can be used for weaving, the highest carbonization temperature in the patent application is only 1200 to 1800 ℃, which is much lower than the graphitization temperature, the asphalt-based carbon fiber in the patent application is not graphitized, the thermal conductivity is very low, and can only reach about 20 to 30W/(m · K), and once the asphalt-based carbon fiber is graphitized, the elongation at break of the obtained asphalt-based graphite fiber can be greatly reduced to 0.43%, and the problem that weaving is not easy exists. At present, the related technology that the graphitized high-thermal-conductivity carbon fiber can be used for weaving has not been reported.
Therefore, it is very necessary to provide a high thermal conductivity carbon fiber rod for weaving and a preparation method thereof, so as to provide material and technical support for the application of the high thermal conductivity carbon fiber in the later period.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a high-thermal-conductivity carbon fiber rod for weaving and a preparation method and application thereof. The high-thermal-conductivity carbon fiber rod for weaving, prepared by the invention, has excellent weaving performance while keeping high strength, high modulus and high thermal conductivity of the carbon fiber rod, and the process is simple and controllable, so that the problem of high weaving difficulty of the high-thermal-conductivity carbon fiber in the using process is solved; the high-thermal-conductivity carbon fiber rod for weaving prepared by the invention is suitable for preparing a thermal dredging composite material, and the extremely high-temperature ablation-resistant thermal dredging composite material prepared by the high-thermal-conductivity carbon fiber rod for weaving disclosed by the invention has the characteristics of high thermal conductivity, high density, excellent mechanical property, excellent high-temperature ablation resistance and the like.
In order to achieve the above object, the present invention provides in a first aspect a method for preparing a highly thermally conductive carbon fiber rod useful for weaving, the method comprising the steps of:
(1) the intermediate phase pitch is taken as a raw material, and a high-thermal-conductivity carbon fiber intermediate product is prepared by sequentially carrying out melt spinning, drying, pre-oxidation and carbonization on the raw material;
(2) graphitizing the high-thermal-conductivity carbon fiber intermediate product in a vacuum environment or an inert atmosphere environment to prepare high-thermal-conductivity carbon fibers;
(3) and sequentially carrying out the procedures of gum dipping, winding, curing and cutting on the high-thermal-conductivity carbon fiber to obtain the high-thermal-conductivity carbon fiber rod for weaving.
Preferably, in step (1): the melting temperature of the melt spinning is 200-300 ℃, and the spinning speed of the melt spinning is 0.05-0.5 m/min; the drying temperature is 150-250 ℃, and the drying time is 800-1000 s; the pre-oxidation temperature is 260-400 ℃, and the pre-oxidation time is 1500-2500 s; and/or the carbonization is carried out in an inert atmosphere environment, the carbonization temperature is 1500-2000 ℃, and the carbonization time is 300-500 s.
Preferably, in step (2): the temperature of the graphitization treatment is 2400-3200 ℃, and the time of the graphitization treatment is 0.5-2 h; the fiber diameter of the prepared high-thermal-conductivity carbon fiber is 8-20 microns.
Preferably, in step (3): the resin adopted by the gum dipping is epoxy resin or phenolic resin, and after gum dipping, the surface coverage rate of the resin on the high-thermal-conductivity carbon fiber is more than 90%; and/or the curing sequentially comprises room temperature curing and high temperature curing, wherein the room temperature curing time is 0.5-1 h, the high temperature curing temperature is 100-130 ℃, and the high temperature curing time is 3-5 h.
Preferably, the heat conductivity of the high-heat-conductivity carbon fiber rod for weaving is 500-1100W/(m.K), the tensile strength is 1.4-3.7 GPa, and the tensile modulus is 450-950 GPa; and/or the specification of the high-heat-conductivity carbon fiber rod capable of being woven is 0.5K, 1K or 2K.
The present invention provides, in a second aspect, a highly thermally conductive carbon fiber rod useful for weaving, which is produced by the production method according to the first aspect of the present invention.
The invention provides a preparation method of an extremely high temperature ablation-resistant thermal dredging composite material in a third aspect, which comprises the following steps:
(a) weaving the high-thermal-conductivity carbon fiber rod which is prepared by the preparation method of the first aspect and can be used for weaving into a high-thermal-conductivity carbon fiber preform;
(b) preparing a carbon interface layer on the fiber surface of the high-thermal-conductivity carbon fiber preform by adopting a chemical vapor deposition method to obtain a high-thermal-conductivity carbon fiber preform with the carbon interface layer, and then carrying out high-temperature graphitization treatment on the high-thermal-conductivity carbon fiber preform with the carbon interface layer to obtain a thermal dredging composite material preform;
(c) impregnating the heat dredging composite material prefabricated body with a polycarbosilane ceramic precursor, and then sequentially carrying out curing and cracking on the impregnated heat dredging composite material prefabricated body;
(d) repeating the step (c) for 2-4 times to prepare the thermally-dredging ceramic matrix composite;
(e) dipping the thermal dredging ceramic matrix composite material by adopting a hafnium-tantalum ceramic precursor, and then sequentially carrying out curing and cracking on the dipped thermal dredging ceramic matrix composite material;
(f) repeating the step (e) for 20-25 times to prepare the heat-dredging ultra-high temperature ceramic matrix composite;
(g) and preparing an anti-ablation ceramic coating on the surface of the thermal dredging ultrahigh-temperature ceramic-based composite material to prepare the extremely-high-temperature anti-ablation thermal dredging composite material.
Preferably, the deposition temperature of the chemical vapor deposition method in the step (b) is 1000-1100 ℃, the deposition time is 300-500 h, and the deposition thickness is 1-5 μm; and/or the treatment temperature of the high-temperature graphitization treatment in the step (b) is 2800-3200 ℃, and the treatment time is 1-3 h; in the step (c), the cracking temperature is 900-1200 ℃, and the cracking time is 2-4 h; and/or in the step (e), the cracking temperature is 1400-1650 ℃, and the cracking time is 2-4 h.
Preferably, the prepared ablation-resistant ceramic coating is HfC-TaSi2Ultra-high temperature ceramic coating; the HfC-TaSi2The mass fraction of HfC contained in the ultrahigh-temperature ceramic coating is 65-75%, and the HfC-TaSi is2TaSi contained in ultrahigh-temperature ceramic coating2The mass fraction of (A) is 25-35%; the HfC-TaSi2The thickness of the ultrahigh-temperature ceramic coating is 150-300 mu m, and the porosity is less than 10%.
In a fourth aspect, the invention provides a very high temperature ablation-resistant thermally conductive composite material prepared by the preparation method of the third aspect of the invention.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the existing high-thermal-conductivity carbon fiber has low elongation at break, high brittleness, low hooking strength and low bending difficulty at a small angle, and broken filaments, broken filaments and the like are easy to appear in the using process and are difficult to weave into a carbon fiber preform; the high-thermal-conductivity carbon fiber rod provided and prepared by the invention is easy to weave, and can effectively avoid the phenomena of broken filaments, broken tows and the like in the use process, improve the structural integrity of the prefabricated body, and further improve the force, thermal performance and the like of the high-thermal-conductivity carbon fiber material.
(2) The high-thermal-conductivity carbon fiber rod for weaving and the high-thermal-conductivity carbon interface layer prepared by chemical vapor deposition and high-temperature graphitization treatment technologies are adopted in the heat-dredging composite material preform, so that the thermal conductivity of the composite material can be improved, the stagnation surface temperature during ablation is reduced, and the ablation resistance is further improved.
(3) The method adopts two ceramic precursors to prepare the ultrahigh-temperature ceramic matrix, firstly adopts a polycarbosilane ceramic precursor to prepare a silicon carbide matrix, and then adopts a hafnium tantalum ceramic precursor to prepare a hafnium carbide-tantalum carbide ceramic matrix (preferably, the mass ratio of HfC to TaC is (4-5): 1); the density and the thermal expansion coefficient of the silicon carbide substrate are between those of the carbon interface layer and the hafnium carbide-tantalum carbide substrate, and the silicon carbide substrate is used as a transition substrate; the HfC-TaC ultrahigh-temperature ceramic has the characteristics of high melting point, high thermal conductivity, excellent high-temperature oxidation and ablation resistance and the like, and is used as a main component in the composite material matrix; meanwhile, the HfC-TaC matrix has higher bonding strength and an integral structure, thereby having higher density and fewer defects.
(4) The invention adopts a plasma spraying method to prepare HfC-TaSi2Ultra-high temperature ceramic coating; the plasma spraying method is a fast integrated and low-cost coating preparation method, and the HfC-TaSi2The composition of the coating is close to that of an HfC-TaC matrix in the composite material, a chemical bond is easily formed between the coating and the composite material matrix, and the bonding strength is high; the thermal expansion coefficient is close, and the thermal stress generated in the high-temperature ablation process is small; furthermore, HfC-TaSi2The ultra-high temperature ceramic coating has excellent high temperature resistanceAblation performance.
Drawings
Fig. 1 is a macro-topography of a high thermal conductivity carbon fiber rod which can be used for weaving and is obtained 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 with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of a high-heat-conductivity carbon fiber rod for weaving in a first aspect, which comprises the following steps:
(1) the intermediate phase pitch is taken as a raw material, and a high-thermal-conductivity carbon fiber intermediate product is prepared by sequentially carrying out melt spinning, drying, pre-oxidation and carbonization on the raw material; in the present invention, the pre-oxidation is carried out in a tube furnace, the pre-oxidation being carried out in an air atmosphere; in the invention, the melting temperature of the melt spinning is preferably 200-300 ℃, and the spinning speed of the melt spinning is preferably 0.05-0.5 m/min; the drying temperature is 150-250 ℃, and the drying time is 800-1000 s; the pre-oxidation temperature is 260-400 ℃, and the pre-oxidation time is 1500-2500 s; and/or the carbonization is carried out in an inert atmosphere environment, the carbonization temperature is 1500-2000 ℃, and the carbonization time is 300-500 s.
(2) Graphitizing the high-thermal-conductivity carbon fiber intermediate product in a vacuum environment or an inert atmosphere environment to prepare high-thermal-conductivity carbon fibers; in the present invention, it is preferable that the temperature of the graphitization treatment in the step (2) is 2400 to 3200 ℃, and the time of the graphitization treatment is 0.5 to 2 hours.
(3) Sequentially carrying out the procedures of gum dipping, winding, curing and cutting on the high-thermal-conductivity carbon fiber to prepare a high-thermal-conductivity carbon fiber rod for weaving; in the invention, preferably, the impregnation process is to impregnate one or more bundles of high thermal conductivity carbon fibers into epoxy resin or phenolic resin, so that the outer layer of the high thermal conductivity carbon fibers is uniformly covered with a layer of resin, and the resin coverage rate is more than 90%; then, winding the impregnated high-thermal-conductivity carbon fiber on a frame-shaped or I-shaped tool mold; then, curing the tooling die wound with the high-thermal-conductivity carbon fibers at room temperature (for example, 20-30 ℃) for 0.5-1 h, and then curing at 100-130 ℃ for 3-5 h; and finally, cutting by using tools such as scissors and a foot knife according to the actual use size to obtain the high-heat-conductivity carbon fiber rod for weaving.
As is well known, the high-thermal-conductivity carbon fiber subjected to graphitization treatment has the advantages of low breaking elongation, high brittleness, low hooking strength, difficulty in small-angle bending, easiness in broken filaments, broken filaments and the like in the use process, and difficulty in weaving into a carbon fiber preform; compared with the conception that in the prior art CN201810136681.2, in order to realize weaving of asphalt-based carbon fibers, the conception that the weaving performance is realized by performing graphitization treatment but three-stage carbonization treatment is not adopted, the invention firstly thinks that the high-heat-conductivity carbon fibers after high-temperature graphitization treatment are protected by resin to prepare the high-heat-conductivity carbon fiber rod, and firstly realizes that the high-heat-conductivity carbon fibers after graphitization treatment can be used for weaving; according to the invention, the high-thermal-conductivity carbon fibers are protected by resin, so that the manufactured high-thermal-conductivity carbon fiber rod can keep various mechanical properties during weaving without damage in the weaving process, and is easy to weave and form, and the thermal conductivity of the high-thermal-conductivity carbon fiber rod is very high and can reach about 800W/(m.K); the invention discovers that after a composite device is prepared by weaving a high-thermal-conductivity carbon fiber preform with a unidirectional structure by using high-thermal-conductivity carbon fiber rods which can be used for weaving, the thermal conductivity of the prepared composite device can still reach about 700W/(m.K), while the thermal conductivity of a preform composite material obtained by high-temperature treatment of asphalt-based carbon fibers in CN201810136681.2 after weaving can only reach 570W/(m.K).
According to some preferred embodiments, in step (1): the melt spinning has a melt temperature of 200 to 300 ℃ (e.g., 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, or 300 ℃), and a spinning rate of 0.05 to 0.5m/min (e.g., 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, or 0.5m/min), wherein the unit "m/min" represents "m/min"; the drying temperature is 150-250 ℃ (such as 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃), and the drying time is 800-1000 s (such as 800, 850, 900, 950 or 1000 s); the pre-oxidation temperature is 260-400 ℃ (such as 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃ or 400 ℃), and the pre-oxidation time is 1500-2500 s (such as 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400 or 2500 s); and/or the carbonization is performed under an inert atmosphere, the carbonization temperature is 1500-2000 ℃ (such as 1500 ℃, 1550 ℃, 1600 ℃, 1650 ℃, 1700 ℃, 1750 ℃, 1800 ℃, 1850 ℃, 1900 ℃, 1950 ℃ or 2000 ℃), and the carbonization time is 300-500 s (such as 300, 350, 400, 450 or 500 s).
According to some preferred embodiments, in step (2): the graphitization treatment temperature is 2400-3200 ℃ (for example 2400 ℃, 2450 ℃, 2500 ℃, 2550 ℃, 2600 ℃, 2650 ℃, 2700 ℃, 2750 ℃, 2800 ℃, 2850 ℃, 2900 ℃, 2950 ℃, 3000 ℃, 3050 ℃, 3100 ℃ or 3200 ℃), and the graphitization treatment time is 0.5-2 h (for example 0.5, 1, 1.5 or 2 h); the fiber diameter of the prepared high-thermal-conductivity carbon fiber is 8-20 microns.
According to some preferred embodiments, in step (3): the resin adopted by the gum dipping is epoxy resin or phenolic resin, and after gum dipping, the surface coverage rate of the resin on the high-thermal-conductivity carbon fiber is more than 90%; and/or the curing comprises room temperature curing and high temperature curing in sequence, wherein the room temperature (such as 20-30 ℃) curing time is 0.5-1 h, the high temperature curing temperature is 100-130 ℃ (such as 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃), and the high temperature curing time is 3-5 h (such as 3, 3.5, 4, 4.5 or 5 h); the invention discovers that after gum dipping, the resin can effectively protect the high-heat-conductivity carbon fiber to prepare the high-heat-conductivity carbon fiber rod only by sequentially curing for 0.5-1 h at room temperature and curing for 3-5 h at 100-130 ℃.
According to some preferred embodiments, the heat conductivity of the high-heat-conductivity carbon fiber rod capable of being woven is 500-1100W/(m.K), the tensile strength is 1.4-3.7 GPa, and the tensile modulus is 450-950 GPa; and/or the specification of the high-heat-conductivity carbon fiber rod capable of being woven is 0.5K, 1K or 2K.
The present invention provides, in a second aspect, a highly thermally conductive carbon fiber rod useful for weaving, which is produced by the production method according to the first aspect of the present invention.
The invention provides a preparation method of an extremely high temperature ablation-resistant thermal dredging composite material in a third aspect, which comprises the following steps:
(a) weaving the high-thermal-conductivity carbon fiber rod which is prepared by the preparation method of the first aspect and can be used for weaving into a high-thermal-conductivity carbon fiber preform; the weave used may be, for example, a three-way, two-way or one-way weave, and more preferably a three-way weave.
(b) Preparing a carbon interface layer (pyrolytic carbon interface layer) on the fiber surface of the high-thermal-conductivity carbon fiber preform by adopting a chemical vapor deposition method to obtain the high-thermal-conductivity carbon fiber preform with the carbon interface layer, and then carrying out high-temperature graphitization treatment on the high-thermal-conductivity carbon fiber preform with the carbon interface layer to change the carbon interface layer into the high-thermal-conductivity carbon interface layer to obtain a thermal-dredging composite material preform; in the invention, the high-temperature graphitization treatment can increase the thermal conductivity of the carbon interface layer, thereby improving the thermal conductivity of the finally prepared extremely-high-temperature ablation-resistant thermal dredging composite material.
(c) Impregnating the heat dredging composite material prefabricated body with a polycarbosilane ceramic precursor, and then sequentially carrying out curing and cracking on the impregnated heat dredging composite material prefabricated body; in the invention, a polycarbosilane ceramic precursor is used as an impregnation liquid to prepare the silicon carbide transition matrix for the heat-dredging composite material preform through a PIP (impregnation-solidification-cracking) process, the PIP process conditions are not limited in any way, and the conventional conditions are adopted; preferably, in the PIP process, the dipping temperature is, for example, 10-100 ℃, the dipping pressure is 0.5-2 MPa, the dipping time is 0.5-2 h, the curing temperature is 100-350 ℃, the curing pressure is 0.5-2 MPa, the curing time is 0.5-2 h, the cracking temperature is 900-1200 ℃, and the cracking time is 2-4 h; in the invention, for example, a polycarbosilane ceramic precursor with a concentration of 40-60 wt.% is used as an impregnation liquid, the polycarbosilane ceramic precursor comprises a solute and a solvent, the solute is selected from one or more of solid Polycarbosilane (PCS), perhydropolycarbosilane (AHPCS) and Liquid Polycarbosilane (LPCS), and/or the solvent is selected from one or more of butanone, xylene and toluene; in the present invention, the liquid polycarbosilane may be, for example, a vinyl-containing Liquid Polycarbosilane (LPVCS). In the invention, when the polycarbosilane ceramic precursor is liquid polycarbosilane, the thermal dredging composite material preform can also be directly impregnated with the liquid polycarbosilane.
(d) Repeating the step (c) for 2-4 times (for example, 2, 3 or 4 times) to obtain the thermally-dredging ceramic matrix composite;
(e) dipping the thermal dredging ceramic matrix composite material by adopting a hafnium-tantalum ceramic precursor, and then sequentially carrying out curing and cracking on the dipped thermal dredging ceramic matrix composite material; in the invention, the hafnium-tantalum ceramic precursor comprises a hafnium-tantalum copolymer and an organic solvent, wherein the hafnium-tantalum copolymer is a copolymer prepared by using hafnate (such as ethyl hafnate and butyl hafnate) and tantalate (such as methyl tantalate, ethyl tantalate and butyl tantalate) as raw materials through hydrolysis reaction and polycondensation reaction; the organic solvent is selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol and glycerol, and is preferably ethylene glycol; in the present invention, it is preferable that the hafnium-tantalum copolymer isThe hafnium-tantalum ceramic precursor is obtained by hydrolyzing and polycondensing hafnate and tantalate, wherein hafnium and tantalum are in the same molecular chain in the copolymer, so that the proportion of hafnium and tantalum in the hafnium-tantalum ceramic precursor can be regulated and controlled; by changing the proportion of the usage amount of the raw materials of the hafnium acid ester and the tantalate, the proportion of hafnium and tantalum in the precursor of the hafnium-tantalum ceramic can be effectively regulated, so that the mass ratio of hafnium carbide to tantalum carbide contained in the hafnium carbide-tantalum carbide ceramic matrix contained in the prepared heat-dredging ultrahigh-temperature ceramic-based composite material can be effectively controlled; in the present invention, the hafnium-tantalum copolymer (hafnium-tantalum coordination copolymer resin) is prepared, for example, by: with Ta5+Inorganic salt of (1) and Hf4+The inorganic salt is used as a raw material and reacts with micromolecular alcohol under the action of a catalyst at the temperature of about 0 ℃ to generate a hafnate solution and a tantalate solution (which are collectively called as a hafnate-tantalate solution), wherein the hafnate-tantalate is easy to hydrolyze and can be hydrolyzed at the temperature of 50-60 ℃, and then a certain amount of organic micromolecular ligand is added for polymerization reaction to obtain the hafnate-tantalate-based catalyst; ta5+Inorganic salt of (1) and Hf4+The inorganic salt is chloride, the catalyst is amine, the small molecular alcohol is monohydric alcohol or polyhydric alcohol, the ligand is acetylacetone, the polymerization reaction temperature is 70-110 ℃ (70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃), the polymerization reaction temperature is 70-90 ℃, and the polymerization time is 3-5 hours generally; the ligand is an organic micromolecule and can easily form a coordination polymer with metal hafnium and tantalum, so that the hafnium and the tantalum can be connected on the same polymer molecular chain; in the present invention, the viscosity of the hafnium tantalum ceramic precursor is preferably 220 to 250mpa · s (e.g., 220, 225, 230, 235, 240, 245 or 250mpa · s), and the solid content of the hafnium tantalum ceramic precursor is preferably 55 to 70% (e.g., 55%, 58%, 60%, 62%, 65%, 68% or 70%). In the invention, the viscosity and the solid content of the solution within the range are beneficial to the hafnium tantalum ceramic precursor to be easily impregnated into the thermal dredging ceramic matrix composite material, so that the impregnation time can be effectively reduced, the impregnation efficiency of the hafnium tantalum ceramic precursor is high, and the mechanical property of the finally prepared extremely-high-temperature ablation-resistant thermal dredging composite material is ensured to be more excellent; in the present invention, the PIP process (impregnation-solidification-cracking process) using the hafnium-tantalum ceramic precursor as the impregnation liquid is not subjected to the conditionsMaking any specific limitation, and adopting the conventional conditions; in the PIP process, it is preferred that the impregnation comprises a first pressure stage impregnation (vacuum impregnation) and a second pressure stage impregnation (pressure impregnation); the pressure of the first pressure stage impregnation is vacuum-0.1-0 MPa (the vacuum degree is 0-0.1 MPa), and the time of the first pressure stage impregnation is 0.5-1 h; the pressure of the second pressure stage impregnation is 0.5-2 MPa, and the time of the second pressure stage impregnation is 1.5-3 h; preferably, the curing pressure is 0.5-2 MPa, the curing temperature is 100-350 ℃, and the curing time is 0.5-2 h; preferably the cracking is carried out in an inert atmosphere; the cracking temperature is 1400-1650 ℃, and the cracking time is 2-4 h; in the invention, the cracking temperature is preferably 1400-1650 ℃, if the cracking temperature is lower than 1400 ℃, the formation of hafnium carbide and tantalum carbide is not facilitated, and if the cracking temperature is too high, the thermal dredging ceramic matrix composite material is damaged.
In particular, the pressure in the present invention is relative pressure based on atmospheric pressure, for example, the pressure of the curing is 0.5 to 2MPa, that is, the actual pressure (absolute pressure) applied to the material during curing is higher than 0.5 to 2MPa, that is, the absolute pressure in the pressure tank is higher than 0.5 to 2 MPa; for example, the vacuum impregnation is performed in an environment with a vacuum degree of 0 to 0.1MPa, that is, the absolute pressure during the vacuum impregnation is 0 to 0.1MPa lower than the atmospheric pressure.
(f) Repeating the step (e) for 20-25 times (for example, 20, 21, 22, 23, 24 or 25 times) to prepare the heat-dredging ultra-high temperature ceramic matrix composite; in the invention, the step (e) is repeated for 20-25 times to ensure that the weight gain of the thermal dredging ultra-high temperature ceramic matrix composite material obtained by the last cracking is less than 0.5%.
(g) Preparing an anti-ablation ceramic coating on the surface of the thermal dredging ultrahigh-temperature ceramic-based composite material to prepare an extremely high-temperature anti-ablation thermal dredging composite material; in the invention, preferably, the HfC-TaSi is prepared on the surface of the thermal dredging ultrahigh-temperature ceramic-based composite material by adopting a plasma spraying method2Ultra-high temperature ceramic coating; in the present invention, the extreme highThe composite material with high thermal conductivity and high ablation resistance is HfC-TaSi2C of the coatingfa/HfC-TaC-SiC ceramic matrix composite; in the invention, the extremely-high-temperature ablation-resistant thermal dredging composite material comprises a silicon carbide ceramic matrix and a hafnium carbide-tantalum carbide ceramic matrix; preferably, the mass ratio of hafnium carbide to tantalum carbide contained in the hafnium carbide-tantalum carbide ceramic matrix is (4 to 5): 1.
the high-thermal-conductivity carbon fiber rod for weaving and the high-thermal-conductivity carbon interface layer prepared by chemical vapor deposition and high-temperature graphitization treatment technologies are adopted in the heat-dredging composite material preform, so that the thermal conductivity of the composite material can be improved, the stagnation surface temperature during ablation is reduced, and the ablation resistance is further improved; the method adopts two ceramic precursors to prepare the ultrahigh-temperature ceramic matrix, firstly adopts a polycarbosilane ceramic precursor to prepare a silicon carbide matrix, and then adopts a hafnium tantalum ceramic precursor to prepare a hafnium carbide-tantalum carbide ceramic matrix (preferably, the mass ratio of HfC to TaC is (4-5): 1); the density and the thermal expansion coefficient of the silicon carbide substrate are between those of the carbon interface layer and the hafnium carbide-tantalum carbide substrate, and the silicon carbide substrate is used as a transition substrate; the HfC-TaC ultrahigh-temperature ceramic has the characteristics of high melting point, high thermal conductivity, excellent high-temperature oxidation and ablation resistance and the like, and is used as a main component in the composite material matrix; meanwhile, the HfC-TaC matrix has higher bonding strength and an integral structure, so that the HfC-TaC matrix has higher density and fewer defects; the invention adopts a plasma spraying method to prepare HfC-TaSi2Ultra-high temperature ceramic coating; the plasma spraying method is a fast integrated and low-cost coating preparation method, and the HfC-TaSi2The composition of the coating is close to that of an HfC-TaC matrix in the composite material, a chemical bond is easily formed between the coating and the composite material matrix, and the bonding strength is high; the thermal expansion coefficient is close, and the thermal stress generated in the high-temperature ablation process is small; furthermore, HfC-TaSi2The ultrahigh-temperature ceramic coating has excellent high-temperature ablation resistance.
The invention discovers that the steps (a) and (g) in the invention are carried out in sequence, so that the extremely high temperature ablation-resistant thermal dredging composite material with the advantages of high thermal conductivity, high density, excellent mechanical property, excellent high temperature ablation resistance and the like can be effectively ensured to be prepared; and no matter the high-temperature graphitization treatment is lacked during the preparation of the carbon interface layer, the PIP process is carried out by singly adopting the hafnium-tantalum ceramic precursor as the dipping solution, or the PIP process is carried out by singly adopting the polycarbosilane ceramic precursor as the dipping solution, the extremely-high-temperature ablation-resistant thermal dredging composite material with high thermal conductivity, high density, excellent mechanical property and excellent high-temperature ablation resistance can not be obtained.
According to some preferred embodiments, the deposition temperature of the chemical vapor deposition method in the step (b) is 1000 to 1100 ℃ (e.g., 1000 ℃, 1050 ℃ or 1100 ℃), the deposition time is 300 to 500 hours, and the deposition thickness is 1 to 5 μm (e.g., 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5 μm), i.e., the thickness of the carbon interface layer deposited by the chemical vapor deposition method is 1 to 5 μm; the treatment temperature of the high-temperature graphitization treatment method in the step (b) is 2800-3200 ℃ (for example 2800 ℃, 2850 ℃, 2900 ℃, 2950 ℃, 3000 ℃, 3050 ℃, 3100 ℃, 3150 ℃ or 3200 ℃), and the treatment time is 1-3 h (for example 1, 1.5, 2, 2.5 or 3 h); in step (c), the temperature of the cracking is 900-1200 ℃ (such as 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ or 1200 ℃), and the time of the cracking is 2-4 h (such as 2, 2.5, 3, 3.5 or 4 h); and/or in step (e), the temperature of the cracking is 1400-1650 ℃ (such as 1400 ℃, 1450 ℃, 1500 ℃, 1550 ℃, 1600 ℃ or 1650 ℃), and the time of the cracking is 2-4 h (such as 2, 2.5, 3, 3.5 or 4 h).
According to some preferred embodiments, the ablation-resistant ceramic coating produced is HfC (hafnium carbide) -TaSi2(tantalum disilicide) ultra high temperature ceramic coatings; in some specific embodiments, the HfC-TaSi is prepared by plasma spraying2Ultra high temperature ceramic coating, inventive pair preparation of said HfC-TaSi2The process conditions of the ultrahigh-temperature ceramic coating are not limited in any way, and the conventional technology is adopted; specifically, for example, it may be: mixing HfC powder and TaSi2Uniformly mixing the powder to obtain mixed powder, then filling the mixed powder into a powder feeder, heating the mixed powder to 60-70 ℃, drying for 2-4 h, and adopting vacuumPreparation of HfC-TaSi by plasma spraying method2The technological parameters of the ultrahigh-temperature ceramic coating and the vacuum plasma spraying method are as follows: spraying power is 30-80 kW, spraying voltage is 30-40V, spraying current is 1500-2000A, powder feeding rate is 15-30 g/min, spraying distance is 500-700 mm, main gas flow Ar gas is 30-60L/min, He gas is 8-15L/min, vacuum degree is 5 x 103～7×103Pa, the rotating speed of the thermal dredging ultrahigh-temperature ceramic matrix composite material (matrix) is 5-15 r/min, powder feeding is started when the matrix is preheated to 500-600 ℃, and deposition is carried out for 5-10 min to obtain HfC-TaSi with the thickness of 150-300 mu m2Ultra-high temperature ceramic coating.
According to some preferred embodiments, the HfC-TaSi is2The mass fraction of HfC contained in the ultrahigh-temperature ceramic coating is 65-75%, and the HfC-TaSi is2TaSi contained in ultrahigh-temperature ceramic coating2The mass fraction of (A) is 25-35%; the HfC-TaSi2During the process of oxidizing and ablating ultrahigh-temperature ceramic coating, HfC can be changed into hafnium oxide and TaSi2Can be changed into tantalum oxide and silicon oxide, wherein the melting point of the tantalum oxide and the silicon oxide is not higher than 2000 ℃, the melting point of the hafnium oxide is more than 2700 ℃, and the tantalum oxide and the silicon oxide can resist ablation at higher temperature, and the HfC-TaSi is preferred in the invention2The mass fraction of HfC contained in the ultrahigh-temperature ceramic coating is 65-75%, and the HfC-TaSi is2TaSi contained in ultrahigh-temperature ceramic coating2The mass fraction of (b) is 25-35%, so that not only can enough anti-ablation components be generated at a lower temperature, but also enough anti-ablation components can be generated at a high temperature, and the HfC-TaSi can be ensured2The ultrahigh-temperature ceramic coating has the best ablation resistance; and/or the HfC-TaSi2The thickness of the ultrahigh-temperature ceramic coating is 150-300 mu m, and the porosity is less than 10%; the invention preferably selects the HfC-TaSi2The thickness of the ultrahigh-temperature ceramic coating is 150-300 mu m, and the invention discovers that if the HfC-TaSi is adopted, the HfC-TaSi can be used2If the thickness of the ultrahigh-temperature ceramic coating is less than 150 mu m, the coating is too thin, the coating cannot play a good protection effect, the service cycle is short, and if the thickness of the coating is more than 300 mu m, the coating is too thick, the internal thermal stress is too large, extrusion and lifting can be caused, and the coating fails early。
According to some preferred embodiments, the very high temperature ablation-resistant thermal dredging composite material comprises a silicon carbide ceramic matrix and a hafnium carbide-tantalum carbide ceramic matrix (HfC-TaC ceramic matrix); the silicon carbide ceramic matrix mainly plays a transition role, the proportion of the silicon carbide ceramic matrix is not particularly required, and the polycarbosilane ceramic precursor is repeatedly used as impregnation liquid and is repeatedly subjected to PIP (poly-propylene-oxide-silane) process for 2-4 times; the mass ratio of hafnium carbide to tantalum carbide contained in the hafnium carbide-tantalum carbide ceramic matrix is (4-5): 1 (e.g., 4:1, 4.5:1, or 5: 1); in the invention, the mass ratio of hafnium carbide to tantalum carbide contained in the hafnium carbide-tantalum carbide ceramic matrix of the prepared very-high-temperature ablation-resistant thermal dredging composite material is preferably (4-5): the inventor finds that the HfC-TaC matrix has the highest bonding strength and the best integrity under the proportion, so that the finally prepared extremely-high-temperature ablation-resistant thermal dredging composite material has extremely high compactness and few defects.
In a fourth aspect, the invention provides a very high temperature ablation-resistant thermally conductive composite material prepared by the preparation method of the third aspect of the invention. In the invention, the density of the extremely-high-temperature ablation-resistant thermal dredging composite material is 3.0-3.6 g/cm3The extremely-high-temperature ablation-resistant heat-conducting composite material adopts the high-strength, high-modulus and high-heat-conductivity carbon fiber rod and the ultra-high-temperature ablation-resistant ceramic, and has the characteristics of high strength, high modulus, high heat conductivity, extremely-high-temperature ablation resistance and the like.
The present invention will be further described with reference to the following 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.
Example 1
A preparation method of a high-thermal-conductivity carbon fiber rod for weaving comprises the following specific steps:
preparing a high-thermal-conductivity carbon fiber intermediate product: the preparation method comprises the following steps of taking mesophase pitch as a raw material, and preparing a high-thermal-conductivity carbon fiber intermediate product through melt spinning, drying, pre-oxidation and carbonization (high-temperature carbonization), wherein the melt spinning temperature is 280 ℃, and the spinning speed is 0.1 m/min; the drying temperature is 180 ℃, and the drying time is 1000 s; the pre-oxidation temperature is 300 ℃, and the pre-oxidation time is 1500 s; the high-temperature carbonization is carried out in a nitrogen environment, the temperature is 1600 ℃, and the carbonization time is 300 s.
Preparing high-thermal-conductivity carbon fibers: graphitizing the high-thermal-conductivity carbon fiber intermediate product in a vacuum environment to prepare high-thermal-conductivity carbon fiber; the graphitization temperature is 2950 ℃, and the graphitization time is 0.5 h.
Preparing a high-heat-conductivity carbon fiber rod: immersing a bundle of the high-thermal-conductivity carbon fiber prepared in the second step into epoxy resin, and uniformly covering a layer of resin on the outer layer of the high-thermal-conductivity carbon fiber, wherein the resin coverage rate is more than 90%; then, winding the impregnated high-thermal-conductivity carbon fiber on a 1m × 1m frame-shaped tooling mold; then, the die of the tooling die wound with the high-thermal-conductivity carbon fibers is firstly placed in a room-temperature environment for curing for 0.5h and then cured for 3h in an atmospheric environment at the temperature of 120 ℃; and finally, cutting by using scissors to obtain the high-heat-conductivity carbon fiber rod for weaving.
The thermal conductivity of the high-thermal-conductivity carbon fiber rod which is prepared and obtained by the embodiment and can be used for weaving is 817W/(m.K) tensile strength of 2.4GPa and tensile modulus of 897GPa, the specification of the high-thermal-conductivity fiber rod is 2K, and the diameter of a single fiber is 13 μm.
Example 2
Example 2 is essentially the same as example 1, except that:
example 2 does not include step (c).
Example 3
Example 3 is essentially the same as example 1, except that:
the step III of preparing the high-heat-conductivity carbon fiber rod is as follows: immersing a bundle of the high-thermal-conductivity carbon fiber prepared in the second step into epoxy resin, and uniformly covering a layer of resin on the outer layer of the high-thermal-conductivity carbon fiber, wherein the resin coverage rate is more than 90%; then, winding the impregnated high-thermal-conductivity carbon fiber on a 1m × 1m frame-shaped tooling mold; then, curing the die of the tooling die wound with the high-thermal-conductivity carbon fibers for 3 hours at 70 ℃ in an atmospheric environment; and finally, cutting by using scissors to obtain the high-heat-conductivity carbon fiber rod.
The curing temperature of this embodiment is too low, and the epoxy curing is not sufficient, can't obtain the high heat conduction carbon fiber stick that can weave.
The performance ratio of the carbon fiber rods with high thermal conductivity obtained in examples 1 and 3 of the present invention and the carbon fibers with high thermal conductivity obtained in example 2 is shown in table 1.
Table 1: the performance indexes and weavability of the carbon fiber rods with high thermal conductivity prepared in examples 1 and 3 and the carbon fiber rods with high thermal conductivity prepared in example 2 were compared.
As can be seen from the results in table 1, the high thermal conductivity carbon fiber rod for weaving is prepared by sequentially performing the processes of dipping, winding, curing and cutting on the high thermal conductivity carbon fiber after the high temperature graphitization treatment, and although the tensile strength and the tensile modulus of the high thermal conductivity carbon fiber rod are not changed greatly, the high thermal conductivity carbon fiber rod prepared by effectively protecting the high thermal conductivity carbon fiber after the high temperature graphitization treatment by using a resin through a suitable process can be woven in a three-way, two-way or one-way manner.
Example 4
A preparation method of an extremely high temperature ablation-resistant thermal dredging composite material comprises the following specific steps:
weaving a high-thermal-conductivity carbon fiber preform: the high-thermal-conductivity carbon fiber preform with the three-way orthogonal structure is woven by using the high-thermal-conductivity carbon fiber rod for weaving prepared in the embodiment 1, and the volume density of the high-thermal-conductivity carbon fiber preform is 1.1g/cm3。
Preparing a carbon interface layer: firstly, preparing a pyrolytic carbon interface layer on the fiber surface of the high-thermal-conductivity carbon fiber preform by adopting a chemical vapor deposition method, wherein the deposition time is 400 hours, the deposition temperature is 1030 ℃, and the deposition thickness of the pyrolytic carbon interface layer is 2 microns; and then, carrying out high-temperature graphitization treatment at the temperature of 3100 ℃ for 1.5h to obtain the thermal dredging composite material preform.
Preparing a ceramic matrix: immersing the thermal dredging composite material prefabricated body into a ceramic precursor solution, and preparing a silicon carbide ceramic matrix and a hafnium carbide-tantalum carbide ceramic matrix through a dip-cure cracking process (PIP process); the process comprises the following steps: a. adopting a polycarbosilane ceramic precursor, and carrying out 3 times of dipping, curing and cracking to obtain the thermally-dredging ceramic matrix composite; b. performing 23 times of dipping, curing and cracking on a hafnium-tantalum ceramic precursor to obtain a heat-conducting ultrahigh-temperature ceramic-based composite material; in a single PIP process using a polycarbosilane ceramic precursor as an impregnation liquid, a dimethylbenzene solution of polycarbosilane with the concentration of 50 wt.% is used as the impregnation liquid, the impregnation temperature is 25 ℃, the impregnation pressure is 1MPa, the impregnation time is 1h, the curing temperature is 250 ℃, the curing pressure is 2MPa, the curing time is 2h, the cracking temperature is 1000 ℃, and the cracking time is 2 h; in a single PIP process with a hafnium-tantalum ceramic precursor as an impregnation liquid, the hafnium-tantalum ceramic precursor with the viscosity of 230MPa · s and the solid content of the solution of 60% is used as the impregnation liquid, and is impregnated for 1h under the vacuum degree of 0.05MPa (first pressure stage impregnation), then is impregnated for 1.5h under the pressure of 1MPa (second pressure stage impregnation), and finally, under the curing pressure of 2MPa and the temperature of 300 ℃, the hafnium-tantalum ceramic precursor is fully crosslinked and cured for 2h, and then is cracked for 2h under the protection of argon atmosphere and at the temperature of 1500 ℃; in the obtained thermal dredging ultrahigh-temperature ceramic matrix composite, the mass ratio of hafnium carbide to tantalum carbide contained in the hafnium carbide-tantalum carbide ceramic matrix is 4.5: 1.
④HfC-TaSi2Preparing an ultrahigh-temperature ceramic coating: preparing HfC-TaSi on the surface of the thermal dredging ultrahigh-temperature ceramic-based composite material by adopting a low-pressure plasma spraying method2Ultra-high temperature ceramic coating; the HfC-TaSi2The mass fraction of HfC contained in the ultrahigh-temperature ceramic coating is 65 percent, and the HfC-TaSi is2TaSi contained in ultrahigh-temperature ceramic coating2Is 35 percent, the HfC-TaSi2The thickness of the ultrahigh-temperature ceramic coating is 260 mu m, and the porosity is 6.7%.
The performance index of the very high temperature ablation resistant thermal dredging composite material prepared by the embodiment is shown in table 2.
Example 5
Example 5 is essentially the same as example 4, except that:
weaving a high-thermal-conductivity carbon fiber preform as follows: a three-way orthogonal structure is adopted, 2K mesophase pitch-based high-heat-conductivity carbon fibers are adopted in the heat conduction direction (marked as X direction), PAN-based T700 carbon fibers are adopted in the other two directions (Y direction and Z direction) for mixed weaving, the mesophase pitch-based high-heat-conductivity carbon fibers account for 82% of the volume fraction of the total carbon fibers in the high-heat-conductivity carbon fiber preform, and the volume density of the high-heat-conductivity carbon fiber preform is 1.1g/cm3。
The performance index of the very high temperature ablation resistant thermal dredging composite material prepared by the embodiment is shown in table 2.
Example 6
Example 6 is essentially the same as example 4, except that:
in the heat dredging ultrahigh-temperature ceramic-based composite material obtained in the step (iii), by adopting hafnium-tantalum ceramic precursors with different hafnium-tantalum ratios, the mass ratio of hafnium carbide to tantalum carbide contained in the hafnium carbide-tantalum carbide ceramic matrix in the obtained heat dredging ultrahigh-temperature ceramic-based composite material is 3: 1.
The performance index of the final material obtained in this example is shown in table 2.
Example 7
Example 7 is essentially the same as example 4, except that:
in the heat dredging ultrahigh-temperature ceramic-based composite material obtained in the step (iii), by adopting hafnium-tantalum ceramic precursors with different hafnium-tantalum ratios, the mass ratio of hafnium carbide to tantalum carbide contained in the hafnium carbide-tantalum carbide ceramic matrix in the obtained heat dredging ultrahigh-temperature ceramic-based composite material is 6: 1.
The performance index of the final material obtained in this example is shown in table 2.
Example 8
Example 8 is essentially the same as example 4, except that:
HfC-TaSi produced in step (iv)2The mass fraction of HfC contained in the ultrahigh-temperature ceramic coating is 60%, and the HfC-TaSi is2TaSi contained in ultrahigh-temperature ceramic coating2Is 40 percent, the HfC-TaSi2The thickness of the ultra-high temperature ceramic coating is 260 μm.
The performance index of the final material obtained in this example is shown in table 2.
Example 9
Example 9 is essentially the same as example 4, except that:
HfC-TaSi produced in step (iv)2The mass fraction of HfC contained in the ultrahigh-temperature ceramic coating is 80%, and the HfC-TaSi is2TaSi contained in ultrahigh-temperature ceramic coating2Is 20%, the HfC-TaSi2The thickness of the ultra-high temperature ceramic coating is 260 μm.
The performance index of the final material obtained in this example is shown in table 2.
Example 10
Example 10 is essentially the same as example 4, except that:
step three, preparing the ceramic matrix as follows: immersing the thermal dredging composite material prefabricated body into a ceramic precursor solution, and preparing a silicon carbide ceramic matrix by using a dipping curing cracking process (PIP process); the process comprises the following steps: carrying out 8 times of dipping, curing and cracking on a polycarbosilane ceramic precursor to obtain a thermally-dredging ceramic matrix composite; in a single PIP process using a polycarbosilane ceramic precursor as an impregnation liquid, a dimethylbenzene solution of polycarbosilane with the concentration of 50 wt.% is used as the impregnation liquid, the impregnation temperature is 25 ℃, the impregnation pressure is 1MPa, the impregnation time is 1h, the curing temperature is 250 ℃, the curing pressure is 2MPa, the curing time is 2h, the cracking temperature is 1000 ℃, and the cracking time is 2 h.
Step (r) HfC-TaSi2The ultra-high temperature ceramic coating is prepared by the following steps: applying a low pressure plasma spray process to the thermally conductive ceramic matrixHfC-TaSi prepared on surface of composite material2Ultra-high temperature ceramic coating; the HfC-TaSi2The mass fraction of HfC contained in the ultrahigh-temperature ceramic coating is 65 percent, and the HfC-TaSi is2TaSi contained in ultrahigh-temperature ceramic coating2Is 35 percent, the HfC-TaSi2The thickness of the ultra-high temperature ceramic coating is 260 μm.
The performance index of the final material obtained in this example is shown in table 2.
Example 11
Example 11 is essentially the same as example 4, except that: step three, preparing the ceramic matrix as follows: immersing the thermal dredging composite material preform into a ceramic precursor solution, and preparing a hafnium carbide-tantalum carbide ceramic matrix through a dipping, curing and cracking process (PIP process); the process comprises the following steps: performing 23 times of dipping, curing and cracking on a hafnium-tantalum ceramic precursor to obtain a heat-conducting ultrahigh-temperature ceramic-based composite material; the single PIP process of the hafnium-tantalum ceramic precursor comprises the steps of taking a hafnium-tantalum ceramic precursor solution with the viscosity of 230MPa · s and the solid content of the solution of 60% as an impregnation solution, impregnating for 1h under the vacuum degree of 0.05MPa (first pressure stage impregnation), then impregnating for 1.5h under the pressure of 2MPa (second pressure stage impregnation), finally, fully crosslinking and curing the hafnium-tantalum ceramic precursor for 2h under the conditions of 2MPa (curing pressure) and temperature rise to 300 ℃, and then cracking for 2h under the protection of argon atmosphere at the temperature of 1500 ℃; in the obtained thermally-dredging ultrahigh-temperature ceramic-based composite material, the mass ratio of hafnium carbide to tantalum carbide contained in the hafnium carbide-tantalum carbide ceramic matrix is 4.5: 1.
④HfC-TaSi2Preparing an ultrahigh-temperature ceramic coating: preparing HfC-TaSi on the surface of the thermal dredging ultrahigh-temperature ceramic-based composite material by adopting a low-pressure plasma spraying method2Ultra-high temperature ceramic coating; the HfC-TaSi2The mass fraction of HfC contained in the ultrahigh-temperature ceramic coating is 65 percent, and the HfC-TaSi is2TaSi contained in ultrahigh-temperature ceramic coating2Is 35 percent, the HfC-TaSi2The thickness of the ultra-high temperature ceramic coating is 260 μm.
The performance index of the final material obtained in this example is shown in table 2.
The performance indexes of the ablation-resistant thermal dredging composite material prepared in the embodiments 4-11 of the invention are shown in the following table 2.
Table 2: the performance indexes of the ablation-resistant thermal dredging composite material prepared in the embodiment 4-11.
Finally, the description is as follows: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; 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 solutions described in the embodiments can still be modified, or some technical features can be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the present invention in its spirit and scope.
Claims (10)
1. A preparation method of a high-thermal-conductivity carbon fiber rod for weaving is characterized by comprising the following steps:
(1) the intermediate phase pitch is taken as a raw material, and a high-thermal-conductivity carbon fiber intermediate product is prepared by sequentially carrying out melt spinning, drying, pre-oxidation and carbonization on the raw material;
(2) graphitizing the high-thermal-conductivity carbon fiber intermediate product in a vacuum environment or an inert atmosphere environment to prepare high-thermal-conductivity carbon fibers;
(3) and sequentially carrying out the procedures of gum dipping, winding, curing and cutting on the high-thermal-conductivity carbon fiber to obtain the high-thermal-conductivity carbon fiber rod for weaving.
2. The production method according to claim 1, wherein in step (1):
the melting temperature of the melt spinning is 200-300 ℃, and the spinning speed of the melt spinning is 0.05-0.5 m/min;
the drying temperature is 150-250 ℃, and the drying time is 800-1000 s;
the pre-oxidation temperature is 260-400 ℃, and the pre-oxidation time is 1500-2500 s; and/or
And the carbonization is carried out in an inert atmosphere environment, the carbonization temperature is 1500-2000 ℃, and the carbonization time is 300-500 s.
3. The production method according to claim 1, wherein in step (2):
the temperature of the graphitization treatment is 2400-3200 ℃, and the time of the graphitization treatment is 0.5-2 h;
the fiber diameter of the prepared high-thermal-conductivity carbon fiber is 8-20 microns.
4. The production method according to claim 1, wherein in step (3):
the resin adopted by the gum dipping is epoxy resin or phenolic resin, and after gum dipping, the surface coverage rate of the resin on the high-thermal-conductivity carbon fiber is more than 90%; and/or
The curing sequentially comprises room temperature curing and high temperature curing, wherein the room temperature curing time is 0.5-1 h, the high temperature curing temperature is 100-130 ℃, and the high temperature curing time is 3-5 h.
5. The production method according to any one of claims 1 to 4, characterized in that:
the heat conductivity of the high-heat-conductivity carbon fiber rod capable of being woven is 500-1100W/(m.K), the tensile strength is 1.4-3.7 GPa, and the tensile modulus is 450-950 GPa; and/or
The specification of the high-thermal-conductivity carbon fiber rod capable of being used for weaving is 0.5K, 1K or 2K.
6. A high thermal conductive carbon fiber rod for weaving, which is prepared by the preparation method of any one of claims 1 to 5.
7. A preparation method of an extremely high temperature ablation-resistant thermal dredging composite material is characterized by comprising the following steps:
(a) weaving a high-thermal-conductivity carbon fiber preform by using the high-thermal-conductivity carbon fiber rod for weaving prepared by the preparation method of any one of claims 1 to 5;
(b) preparing a carbon interface layer on the fiber surface of the high-thermal-conductivity carbon fiber preform by adopting a chemical vapor deposition method to obtain a high-thermal-conductivity carbon fiber preform with the carbon interface layer, and then carrying out high-temperature graphitization treatment on the high-thermal-conductivity carbon fiber preform with the carbon interface layer to obtain a thermal dredging composite material preform;
(c) impregnating the heat dredging composite material prefabricated body with a polycarbosilane ceramic precursor, and then sequentially carrying out curing and cracking on the impregnated heat dredging composite material prefabricated body;
(d) repeating the step (c) for 2-4 times to prepare the thermally-dredging ceramic matrix composite;
(e) dipping the thermal dredging ceramic matrix composite material by adopting a hafnium-tantalum ceramic precursor, and then sequentially carrying out curing and cracking on the dipped thermal dredging ceramic matrix composite material;
(f) repeating the step (e) for 20-25 times to prepare the heat-dredging ultra-high temperature ceramic matrix composite;
(g) and preparing an anti-ablation ceramic coating on the surface of the thermal dredging ultrahigh-temperature ceramic-based composite material to prepare the extremely-high-temperature anti-ablation thermal dredging composite material.
8. The method of claim 7, wherein:
the deposition temperature of the chemical vapor deposition method in the step (b) is 1000-1100 ℃, the deposition time is 300-500 h, and the deposition thickness is 1-5 mu m; and/or
The treatment temperature of the high-temperature graphitization treatment in the step (b) is 2800-3200 ℃, and the treatment time is 1-3 h;
in the step (c), the cracking temperature is 900-1200 ℃, and the cracking time is 2-4 h; and/or
In the step (e), the cracking temperature is 1400-1650 ℃, and the cracking time is 2-4 h.
9. The method of claim 7, wherein:
the prepared ablation-resistant ceramic coating is HfC-TaSi2Ultra-high temperature ceramic coating;
the HfC-TaSi2The mass fraction of HfC contained in the ultrahigh-temperature ceramic coating is 65-75%, and the HfC-TaSi is2TaSi contained in ultrahigh-temperature ceramic coating2The mass fraction of (A) is 25-35%; the HfC-TaSi2The thickness of the ultrahigh-temperature ceramic coating is 150-300 mu m, and the porosity is less than 10%.
10. The very high temperature ablation resistant thermal dredging composite material prepared by the preparation method of any one of claims 7-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110850960.7A CN113582710B (en) | 2021-07-27 | 2021-07-27 | High-thermal-conductivity carbon fiber rod for weaving and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110850960.7A CN113582710B (en) | 2021-07-27 | 2021-07-27 | High-thermal-conductivity carbon fiber rod for weaving and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113582710A true CN113582710A (en) | 2021-11-02 |
| CN113582710B CN113582710B (en) | 2022-07-22 |
Family
ID=78250478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110850960.7A Active CN113582710B (en) | 2021-07-27 | 2021-07-27 | High-thermal-conductivity carbon fiber rod for weaving and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113582710B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340397A (en) * | 2022-07-15 | 2022-11-15 | 航天特种材料及工艺技术研究所 | One-way high-temperature-resistant ablation-resistant ceramic matrix composite and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63243329A (en) * | 1987-03-27 | 1988-10-11 | Shozo Watabe | Industrial production of knit and fabric made of high-tenacity and high-modulus carbon fiber |
| US20050158590A1 (en) * | 2004-01-16 | 2005-07-21 | Honeywell International Inc. | Atomic layer deposition for turbine components |
| US20100028634A1 (en) * | 2006-07-31 | 2010-02-04 | Turevskaya Evgeniya P | Metal oxide coatings for electrically conductive carbon nanotube films |
| CN108911760A (en) * | 2018-08-08 | 2018-11-30 | 航天材料及工艺研究所 | The non-ablative type thermally protective materials of carbon fiber-reinforced resin gradient carbonization and preparation method |
| CN110776339A (en) * | 2019-11-29 | 2020-02-11 | 航天特种材料及工艺技术研究所 | Antioxidant coating for C/ZrC-SiC composite material and preparation method thereof |
| CN110904674A (en) * | 2019-12-10 | 2020-03-24 | 陕西天策新材料科技有限公司 | High-surface-activity asphalt-based graphite fiber, preparation method thereof and resin-based composite material prepared based on high-surface-activity asphalt-based graphite fiber |
| CN112898023A (en) * | 2021-01-29 | 2021-06-04 | 中国科学院上海硅酸盐研究所 | Cf/Ta4HfC5-SiC superhigh temperature ceramic matrix composite material and preparation method thereof |
-
2021
- 2021-07-27 CN CN202110850960.7A patent/CN113582710B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63243329A (en) * | 1987-03-27 | 1988-10-11 | Shozo Watabe | Industrial production of knit and fabric made of high-tenacity and high-modulus carbon fiber |
| US20050158590A1 (en) * | 2004-01-16 | 2005-07-21 | Honeywell International Inc. | Atomic layer deposition for turbine components |
| US20100028634A1 (en) * | 2006-07-31 | 2010-02-04 | Turevskaya Evgeniya P | Metal oxide coatings for electrically conductive carbon nanotube films |
| CN108911760A (en) * | 2018-08-08 | 2018-11-30 | 航天材料及工艺研究所 | The non-ablative type thermally protective materials of carbon fiber-reinforced resin gradient carbonization and preparation method |
| CN110776339A (en) * | 2019-11-29 | 2020-02-11 | 航天特种材料及工艺技术研究所 | Antioxidant coating for C/ZrC-SiC composite material and preparation method thereof |
| CN110904674A (en) * | 2019-12-10 | 2020-03-24 | 陕西天策新材料科技有限公司 | High-surface-activity asphalt-based graphite fiber, preparation method thereof and resin-based composite material prepared based on high-surface-activity asphalt-based graphite fiber |
| CN112898023A (en) * | 2021-01-29 | 2021-06-04 | 中国科学院上海硅酸盐研究所 | Cf/Ta4HfC5-SiC superhigh temperature ceramic matrix composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 侯发亮: "《建筑结构粘结加固的理论与实践》", 31 March 2006, 武汉大学出版社 * |
| 周瑞发 等: "《高温结构材料》", 30 April 2006, 国防工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340397A (en) * | 2022-07-15 | 2022-11-15 | 航天特种材料及工艺技术研究所 | One-way high-temperature-resistant ablation-resistant ceramic matrix composite and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113582710B (en) | 2022-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113563091B (en) | Extreme-high-temperature ablation-resistant thermal dredging composite material and preparation method thereof | |
| CN110028330B (en) | Ceramic matrix composite and preparation method thereof | |
| CN107353025A (en) | A kind of preparation method of resistance to 1200 DEG C of oxidation resistant ceramic matric composites | |
| EP2543650A1 (en) | Method for manufacturing high-density fiber reinforced ceramic composite materials | |
| CN107311682B (en) | SiC nanowire reinforced Cf/SiC ceramic matrix composite and preparation method thereof | |
| CN103332943B (en) | Microstructure design and the Properties Control method of carbon pottery based composites is prepared based on liquid silicon infiltration method | |
| CN110655414B (en) | Carbon fiber reinforced carbon-hafnium tantalum carbon solid solution composite material and preparation method thereof | |
| CN112010653B (en) | Fiber-reinforced silicon-boron-nitrogen composite material and preparation method thereof | |
| CN114573357A (en) | SiC nanowire reinforced SiC ceramic matrix composite and preparation method thereof | |
| CN1868971A (en) | Carbon-silicon carbide base composite material toughened by carbon fiber and its preparation method | |
| CN113582710B (en) | High-thermal-conductivity carbon fiber rod for weaving and preparation method and application thereof | |
| CN102808240A (en) | Preparation method of high-temperature-resistant silicon carbide fiber | |
| CN114702328B (en) | SiC nanowire network reinforced layered porous SiC ceramic and preparation method thereof | |
| CN113526973A (en) | Wave-transparent ceramic matrix composite with double interface phases and preparation method thereof | |
| CN113121253B (en) | Ultrahigh-temperature C/SiHfBCN ceramic matrix composite material and preparation method thereof | |
| CN114436669A (en) | Preparation method of one-dimensional high-thermal-conductivity C/C composite material | |
| CN112374901B (en) | Ablation-resistant modified C/SiC composite material and preparation method thereof | |
| CN113896558A (en) | High-performance thermal dredging composite material and preparation method thereof | |
| CN114057501A (en) | High-density anti-scouring ceramic matrix composite material and preparation method thereof | |
| CN105503229A (en) | Preparation method of Al2O3f/SiOC radar wave-absorbing composite material | |
| CN112521156A (en) | Hybrid matrix SiCf/SiC composite material and preparation method thereof | |
| CN113912407B (en) | C/HfC ultrahigh-temperature ceramic matrix composite and preparation method thereof | |
| CN113896557B (en) | C/ZrC-SiC composite material and preparation method and application thereof | |
| CN113461433B (en) | Prestressed fiber reinforced C/SiBCN ceramic composite material and preparation method thereof | |
| CN115231923A (en) | Structure function integrated ceramic matrix composite and preparation method thereof |
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 |