CN115028465B - Carbon/carbon composite material and preparation method and application thereof - Google Patents

Carbon/carbon composite material and preparation method and application thereof Download PDF

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CN115028465B
CN115028465B CN202210618123.6A CN202210618123A CN115028465B CN 115028465 B CN115028465 B CN 115028465B CN 202210618123 A CN202210618123 A CN 202210618123A CN 115028465 B CN115028465 B CN 115028465B
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carbon
composite material
carbon composite
carbon fiber
fiber
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CN115028465A (en
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徐俊波
胡竹峰
杨超
王敏
李志坤
权维利
赵永忠
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Institute of Process Engineering of CAS
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    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • C04B35/6455—Hot isostatic pressing
    • 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
    • C04B2235/5252—Fibers having a specific pre-form
    • C04B2235/5256—Two-dimensional, e.g. woven structures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides a carbon/carbon composite material and a preparation method and application thereof, wherein the carbon/carbon composite material comprises a carbon fiber framework, a graphitized carbon matrix filled and coated with the carbon fiber framework and a zirconium oxide coating coated on the surface of the graphitized carbon matrix; the thickness of the zirconia coating is 0.1-1 μm. According to the carbon/carbon composite material provided by the invention, the graphitized carbon matrix is uniformly and firmly distributed in the framework carbon fiber and on the surface of the framework carbon fiber, and the zirconia coating is coated on the surface of the graphitized carbon matrix, so that the high temperature resistance and ablation resistance of the carbon/carbon composite material are effectively improved, the diffusion of an oxidizing atmosphere from the surface of the carbon/carbon composite material to the inside is limited, the preparation period is short, the cost is low, and the carbon/carbon composite material can be used in the field of aerospace structural materials.

Description

Carbon/carbon composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of carbon fiber composite materials, in particular to a carbon/carbon composite material and a preparation method and application thereof.
Background
The carbon/carbon composite material, i.e. carbon fiber reinforced carbon matrix composite material, is a novel structural material applied to high-temperature environment, and the matrix composition of the carbon/carbon composite material comprises a carbon fiber framework and a carbon-based reinforcement body and has the common characteristics of carbon fiber, common carbon materials and fiber composite materials.
The preparation process of the carbon/carbon composite material is mainly divided into four stages: the method comprises the following steps of selection of carbon fibers and a matrix precursor, a forming process of a preform, a densification process of the preform and the matrix and a post-treatment process of materials. The selection of the carbon fiber and the matrix precursor is the basis for preparing the carbon/carbon composite material, and the fabric weaving process of the preform has important influence on the mechanical property of the carbon/carbon composite material. The densification process directly determines the structural density and the interface strength of the composite material, and the post-treatment process of the composite material is an important link for improving the ablation resistance and the wear resistance of the composite material. At present, the densification process of carbon/carbon composite materials can be divided into: chemical Vapor Infiltration (CVI), liquid impregnation-pyrolysis (PIP), slurry, reactive infiltration, and the like.
CN 104311093A discloses a preparation method of a low-cost high-performance carbon/carbon composite material, which comprises the following 6 steps: 1) Preparing a prefabricated body; 2) Preparing a low-density preform and a pyrolytic carbon complex by adopting a chemical vapor infiltration process; 3) Preparing a medium-density carbon/carbon composite material by adopting a chemical liquid phase gasification infiltration process; 4) Intermediate high-temperature heat treatment is carried out to improve the porosity so as to be beneficial to further densification; 5) Performing final densification by adopting liquid-phase impregnation pyrolysis to obtain a high-density carbon/carbon composite material; 6) And carrying out final high-temperature heat treatment to obtain a finished product of the carbon/carbon composite material. However, the method has complex preparation process, overhigh production cost and longer process period, and the strength of the carbon fiber in the composite material can be obviously reduced by multiple high-temperature treatments, so that the microstructure of the material is difficult to regulate and control.
CN 111960842A discloses anti-electrolysis MnO 2 The preparation method of the carbon/carbon composite material for calcium-magnesium crystallization comprises the steps of impregnating a mixture of graphite-graphene powder and a carbon fiber woven felt in modified petroleum asphalt to obtain an impregnated blank, carrying out high-temperature carbonization under the protection of argon, and repeatedly impregnating and carbonizing until the pore space of the preform is densified; and (3) treating by adopting a chemical vapor surface deposition process to obtain the carbon/carbon composite material. The chemical vapor surface deposition method has higher reaction activation energy and longer preparation time of the material; micropores on the surface of the preform are easy to block in the carbon deposition process of the matrix, so that the density of the material is not uniform, and the repeated operation is required.
CN 110156485A discloses a method for preparing a high-performance carbon/carbon composite material with short period and low cost, which combines a chemical vapor infiltration process and a liquid impregnation process to prepare the carbon/carbon composite material, and a prefabricated body needs to be repeatedly impregnated in an impregnation liquid and carbonized in an inert atmosphere, so that the mechanical property of carbon fiber is easily damaged, and a resin carbon matrix can shrink in the process of multiple treatments to cause interlayer cracking of a product; in addition, the existing resin impregnation densification technology has low efficiency and long preparation period.
In view of the deficiencies of the prior art, it is desirable to provide a carbon/carbon composite material with high ablation, short preparation period and low production cost.
Disclosure of Invention
The invention aims to provide a carbon/carbon composite material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a carbon/carbon composite material, including a carbon fiber skeleton, a graphitized carbon matrix filling and coating the carbon fiber skeleton, and a zirconia coating the surface of the graphitized carbon matrix;
the thickness of the zirconia coating is 0.1 to 1 μm, and may be, for example, 0.1 μm, 0.3 μm, 0.5 μm, 0.8 μm or 1 μm, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.
According to the carbon/carbon composite material provided by the invention, the zirconia coating on the surface and the graphitized carbon matrix uniformly distributed on the surface and inside the carbon fiber framework can effectively limit the diffusion of the oxidizing atmosphere from the surface to the inside of the composite material, so that the ablation resistance of the composite material is improved.
In a second aspect, the present invention provides a method for preparing a carbon/carbon composite material as described in the first aspect, the method comprising the steps of:
(1) Sewing carbon/carbon prepreg by using carbon fiber to obtain a carbon/carbon composite material prefabricated body;
(2) Graphitizing the carbon/carbon composite material preform obtained in the step (1) at high temperature to obtain a carbon/carbon composite material precursor;
(3) Dipping and heat treating the carbon/carbon composite material precursor obtained in the step (2) to obtain a carbon/carbon composite material;
the carbon/carbon prepreg in the step (1) is obtained by sequentially impregnating and drying carbon fiber fabrics.
The carbon/carbon composite material provided by the invention is prepared by taking carbon/carbon prepreg as a raw material and performing carbon fiber sewing, high-temperature graphitization and zirconia sol coating, can obviously reduce the large-scale production cost of the carbon/carbon composite material by adopting reasonable preparation process parameters, obviously shortens the preparation period, and can realize integral molding and preparation of irregular and large-size devices according to self-designed and manufactured moulds.
Preferably, the carbon fiber in step (1) includes any one of or a combination of at least two of a T300 type carbon fiber, a T400 type carbon fiber, a T700 type carbon fiber, a T800 type carbon fiber or a T1000 type carbon fiber, and typical but non-limiting combinations include a combination of a T300 type carbon fiber and a T400 type carbon fiber, a combination of a T700 type carbon fiber and a T800 type carbon fiber, a combination of a T800 type carbon fiber and a T1000 type carbon fiber, a combination of a T300 type carbon fiber, a T400 type carbon fiber and a T700 type carbon fiber, a combination of a T700 type carbon fiber, a T800 type carbon fiber and a T1000 type carbon fiber, a combination of a T300 type carbon fiber, a T400 type carbon fiber, a T700 type carbon fiber and a T800 type carbon fiber, or a combination of a T300 type carbon fiber, a T400 type carbon fiber, a T700 type carbon fiber, a T800 type carbon fiber and a T1000 type carbon fiber.
Preferably, the density of the suture of the step (1) is 10-25 needles/cm 2 For example, it may be 10 needles/cm 2 12 needles/cm 2 15 needles/cm 2 18 needles/cm 2 20 needles/cm 2 22 needles/cm 2 Or 25 needles/cm 2 But are not limited to the recited values, and other values within the numerical range not recited are equally applicable.
Preferably, the suture needle adopted by the suture in the step (1) comprises a C2 type needle and/or a C3 type needle.
Preferably, the C2 needles have a needle diameter of 0.44 to 0.46mm, for example 0.44mm, 0.445mm, 0.45mm, 0.455mm or 0.46mm, but are not limited to the values listed, and other values not listed in the numerical range are equally suitable.
Preferably, the C3 needles have a needle diameter of 0.54 to 0.56mm, for example 0.54mm, 0.545mm, 0.55mm, 0.555mm or 0.56mm, but are not limited to the values listed, and other values not listed in the numerical range are equally suitable.
Preferably, the stitching of step (1) is performed using a lock and/or chain process.
Preferably, the high temperature graphitization in step (2) is performed in a protective atmosphere under hot isostatic pressing, with gases including any one or a combination of at least two of helium, argon, or nitrogen, with typical but non-limiting combinations including helium and argon, argon and nitrogen, helium and nitrogen, or helium, argon and nitrogen.
The high-temperature graphitization is carried out in a high-temperature hot-pressing sintering furnace or a vacuum hot-pressing sintering furnace.
Preferably, the hot isostatic pressing in step (2) is carried out at a pressure of 15-100MPa, such as 15MPa, 20MPa, 30MPa, 50MPa, 80MPa or 100MPa, but not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the high temperature graphitization in step (2) is at a temperature of 1800 to 2900 ℃, for example 1800 ℃, 2000 ℃, 2200 ℃, 2400 ℃, 2500 ℃, 2700 ℃ or 2900 ℃, but not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the high temperature graphitization time in step (2) is 0.5-6h, such as 0.5h, 1h, 2h, 3h, 4h, 5h or 6h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the impregnation liquid used in the impregnation in the step (3) comprises zirconia sol.
Preferably, the zirconia sol is obtained by mixing zirconium oxychloride, yttrium oxide and deionized water.
The zirconia sol keeps a 'nano-micron' two-state structure, and has lower thermal conductivity, higher linear expansion coefficient and good mechanical property; the carbon/carbon composite material ablation-resistant coating can effectively prevent high-temperature gas from cavitation erosion to the interior of the material and improve the ablation resistance of the composite material.
Preferably, the molar concentration of zirconium oxychloride in the zirconia sol is from 0.1 to 0.5mol/L, and can be, for example, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5mol/L, but is not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
The molar concentration of zirconium oxychloride in the zirconia sol is used for impregnating the carbon/carbon composite material with the impregnating solution
Preferably, the molar concentration of yttria in the zirconia sol is from 3 to 9mmol/L, and can be, for example, 3mmol/L, 4mmol/L, 5mmol/L, 6mmol/L, 7mmol/L, 8mmol/L, or 9mmol/L, but is not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the impregnation time in step (3) is 3 to 5 hours, for example 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the temperature of the heat treatment in step (3) is 240 to 300 ℃, for example, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃ or 300 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the heat treatment time in step (3) is 1-2h, such as 1h, 1.2h, 1.5h, 1.8h or 2h, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the carbon fiber fabric comprises a carbon fiber cloth made by a weaving process, and the carbon fiber cloth comprises any one of plain cloth, twill cloth, satin cloth or unidirectional cloth or a combination of at least two of the same, and typical but non-limiting combinations comprise a combination of plain cloth and twill cloth, a combination of satin cloth and unidirectional cloth, a combination of plain cloth, twill cloth and satin cloth, a combination of twill cloth, satin cloth and unidirectional cloth, or a combination of plain cloth, twill cloth, satin cloth and unidirectional cloth.
Preferably, the carbon fiber fabric is subjected to deionized water and ethanol cleaning treatment, drying and acid treatment in sequence.
The temperature of the oven is 40 to 80 ℃, for example 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃, but not limited to the recited values, and other values not recited within the numerical ranges are equally applicable.
The drying time is 2-4h, for example, 2h, 2.5h, 3h, 3.5h or 4h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
The acid treatment is to soak the carbon fiber fabric by using a nitric acid solution and then wash the carbon fiber fabric to be neutral by using deionized water.
The mass fraction of nitric acid in the nitric acid solution is 20 to 60 wt.%, and may be, for example, 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, or 60 wt.%, but is not limited to the recited values, and other values not recited within the numerical ranges are equally applicable.
The temperature of the soaking is 60 to 90 ℃, for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
The soaking time is 6-10h, for example 6h, 7h, 8h, 9h or 10h, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the impregnation is performed in a mixed solution of graphite powder, a sizing agent and deionized water.
Preferably, the graphite powder comprises high purity graphite and/or graphite derivatives.
Preferably, the sizing agent comprises any one or a combination of at least two of polyvinyl alcohol, polyvinylpyrrolidone or acrylamide, typical but non-limiting combinations include a combination of polyvinyl alcohol and polyvinylpyrrolidone, a combination of polyvinylpyrrolidone and acrylamide, a combination of polyvinyl alcohol and acrylamide, or a combination of polyvinyl alcohol, polyvinylpyrrolidone and acrylamide.
Preferably, the impregnation time is from 0.5 to 12h, for example 0.5h, 2h, 5h, 8h or 2h, but is not limited to the values listed, and other values not listed in the numerical ranges are equally applicable.
Preferably, the drying temperature is 30-120 ℃, for example 30 ℃, 50 ℃, 80 ℃, 100 ℃ or 120 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the drying time is 6 to 10 hours, for example 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, but is not limited to the values listed, and other values not listed within the range of values are equally applicable.
Preferably, the mass fraction of carbon fibers in the carbon/carbon prepreg of step (1) is 30 to 90wt%, and may be, for example, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, or 90wt%, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
As a preferable embodiment of the production method according to the second aspect of the present invention, the production method includes the steps of:
(1) Stitching carbon/carbon prepreg with carbon fiber, wherein the stitching density is 10-25 stitches/cm 2 Obtaining a carbon/carbon composite material prefabricated body;
the carbon/carbon prepreg is prepared by sequentially dipping carbon fiber fabric in a mixed solution of graphite powder, a sizing agent and deionized water for 0.5-12h and drying at 30-120 ℃ for 6-10 h; the carbon fiber fabric is obtained by sequentially washing with deionized water and ethanol, drying at 40-80 ℃ for 2-4h, soaking in a nitric acid solution at 60-90 ℃ for 6-10h, and washing to neutrality;
(2) Graphitizing the carbon/carbon composite material preform obtained in the step (1) for 0.5-6h under the protection of inert gas at a high temperature of 15-100MPa and 1800-2900 ℃ to obtain a carbon/carbon composite material precursor;
(3) Soaking the precursor of the carbon/carbon composite material obtained in the step (2) in zirconia sol for 3-5h, and carrying out heat treatment at 240-300 ℃ for 1-2h to obtain the carbon/carbon composite material;
the molar concentration of zirconium oxychloride in the zirconia sol is 0.1-0.5mol/L, and the molar concentration of yttrium oxide is 3-9mmol/L.
In a third aspect, the present invention provides the use of a carbon/carbon composite material according to the first aspect in the field of aerospace structural materials.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the carbon/carbon composite material provided by the invention, the graphitized carbon matrix is uniformly and firmly distributed in the carbon fiber framework and on the surface of the carbon fiber framework, and the zirconia coating is coated on the surface of the graphitized carbon matrix, so that the high temperature resistance and the ablation resistance of the carbon/carbon composite material are effectively improved, the diffusion of an oxidizing atmosphere from the surface of the carbon/carbon composite material to the inside is limited, and the mass ablation rate of the carbon/carbon composite material is 0.138-0.290mg s -1 ；
(2) The carbon/carbon composite material provided by the invention takes the carbon/carbon prepreg as a raw material, can realize low-cost rapid molding through a carbon fiber laying sewing process and high-temperature graphitization, can obviously reduce the large-scale production cost of the carbon/carbon composite material by adopting reasonable parameters of the impregnation and high-temperature graphitization processes, obviously shortens the preparation period, and can realize integral molding and preparation of irregular and large-size devices according to self-design and manufacturing molds.
Drawings
FIG. 1 is a digital optical diagram of a carbon/carbon composite preform provided in example 1 of the present invention;
fig. 2 is a scanning electron microscope image of the carbon/carbon composite precursor provided in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
The embodiment provides a carbon/carbon composite material, which comprises a carbon fiber framework, a graphitized carbon matrix filled and coated with the carbon fiber framework, and a zirconia coating coated on the surface of the graphitized carbon matrix, wherein the thickness of the zirconia coating is 0.5 μm.
The carbon/carbon composite material is prepared by the following preparation method, and the preparation method comprises the following steps:
(1) Carbon/carbon prepreg stitched with carbon fiber, the stitch density being 17 stitches/cm 2 Obtaining a carbon/carbon composite material prefabricated body;
the carbon/carbon prepreg is prepared by sequentially soaking carbon fiber fabric in a mixed solution of high-purity graphite, polyvinyl alcohol and deionized water for 6 hours and drying at 80 ℃ for 8 hours; the carbon fiber fabric is obtained by sequentially washing with deionized water and ethanol, drying at 60 ℃ for 3h, soaking in 75 ℃ nitric acid solution for 8h, and washing to neutrality;
(2) Graphitizing the carbon/carbon composite material preform obtained in the step (1) for 3h at high temperature of 2400 ℃ under the protection of nitrogen to obtain a carbon/carbon composite material precursor;
(3) Soaking the precursor of the carbon/carbon composite material obtained in the step (2) in zirconia sol for 4h, and carrying out heat treatment at 265 ℃ for 1.5h to obtain the carbon/carbon composite material;
the molar concentration of zirconium oxychloride in the zirconia sol is 0.3mol/L, and the molar concentration of yttrium oxide is 5mmol/L.
The digital optical diagram of the carbon/carbon composite material preform is shown in fig. 1, and it can be known from the diagram that according to the shape surface characteristics of the carbon/carbon composite material, the carbon/carbon prepreg preform is obtained by sewing through a lock type or chain type process, and graphite and pores sewn by carbon fibers in the Z-axis direction are uniformly distributed on the surface;
as shown in fig. 2, it can be seen that the surface of carbon fiber in the carbon/carbon composite precursor is coated with a layer of graphitized carbon matrix, and the carbon coating of the matrix is uniformly distributed and firmly bonded with the carbon fiber, so that interfacial fusion and chemical conversion from graphite prepreg to matrix carbon are realized.
Example 2
The embodiment provides a carbon/carbon composite material, which comprises a carbon fiber skeleton, a graphitized carbon matrix filled with and coated with the carbon fiber skeleton, and a zirconia coating coated on the surface of the graphitized carbon matrix, wherein the thickness of the zirconia coating is 0.5 μm.
The carbon/carbon composite material is prepared by the following preparation method, and the preparation method comprises the following steps:
(1) Carbon/carbon prepreg stitched with carbon fiber, the stitch density being 13 stitches/cm 2 Obtaining a carbon/carbon composite material prefabricated body;
the carbon/carbon prepreg is prepared by sequentially soaking carbon fiber fabric in a mixed solution of high-purity graphite, polyvinyl alcohol and deionized water for 3 hours and drying at 50 ℃ for 9 hours; the carbon fiber fabric is obtained by sequentially washing with deionized water and ethanol, drying at 50 ℃ for 3.5h, soaking in 70 ℃ nitric acid solution for 9h, and washing to neutrality;
(2) Graphitizing the carbon/carbon composite material preform obtained in the step (1) for 4.5h at high temperature of 2100 ℃ under the protection of nitrogen at 30MPa to obtain a carbon/carbon composite material precursor;
(3) Dipping the precursor of the carbon/carbon composite material obtained in the step (2) in zirconia sol for 4 hours, and carrying out heat treatment at 250 ℃ for 1.8 hours to obtain the carbon/carbon composite material;
the molar concentration of zirconium oxychloride in the zirconia sol is 0.2mol/L, and the molar concentration of yttrium oxide is 4mmol/L.
Example 3
The embodiment provides a carbon/carbon composite material, which comprises a carbon fiber framework, a graphitized carbon matrix filled and coated with the carbon fiber framework, and a zirconia coating coated on the surface of the graphitized carbon matrix, wherein the thickness of the zirconia coating is 0.5 μm.
The carbon/carbon composite material is prepared by the following preparation method, and the preparation method comprises the following steps:
(1) Carbon/carbon prepreg stitched with carbon fiber, the stitch density being 21 stitches/cm 2 Obtaining a carbon/carbon composite material prefabricated body;
the carbon/carbon prepreg is prepared by sequentially dipping a carbon fiber fabric in a mixed solution of high-purity graphite, polyvinyl alcohol and deionized water for 9 hours and drying at 100 ℃ for 7 hours; the carbon fiber fabric is obtained by sequentially washing with deionized water and ethanol, drying at 70 ℃ for 2.5h, soaking in 80 ℃ nitric acid solution for 7h, and washing to neutrality;
(2) Graphitizing the carbon/carbon composite material preform obtained in the step (1) for 1.5h at high temperature of 75MPa and 2700 ℃ under the protection of nitrogen to obtain a carbon/carbon composite material precursor;
(3) Dipping the precursor of the carbon/carbon composite material obtained in the step (2) in zirconia sol for 4 hours, and carrying out heat treatment at 280 ℃ for 1.2 hours to obtain the carbon/carbon composite material;
the molar concentration of zirconium oxychloride in the zirconia sol is 0.4mol/L, and the molar concentration of yttrium oxide is 7mmol/L.
Example 4
The embodiment provides a carbon/carbon composite material, which comprises a carbon fiber skeleton, a graphitized carbon matrix filled with and coated with the carbon fiber skeleton, and a zirconia coating coated on the surface of the graphitized carbon matrix, wherein the thickness of the zirconia coating is 0.5 μm.
The carbon/carbon composite material is prepared by the following preparation method, and the preparation method comprises the following steps:
(1) Carbon/carbon prepreg stitched with carbon fibres, the stitch density being 10 stitches/cm 2 Obtaining a carbon/carbon composite material prefabricated body;
the carbon/carbon prepreg is prepared by sequentially soaking carbon fiber fabric in a mixed solution of high-purity graphite, polyvinyl alcohol and deionized water for 0.5h and drying at 30 ℃ for 10 h; the carbon fiber fabric is obtained by sequentially washing with deionized water and ethanol, drying at 40 ℃ for 4h, soaking in a nitric acid solution at 60 ℃ for 10h, and washing to neutrality;
(2) Graphitizing the carbon/carbon composite material preform obtained in the step (1) for 6h at high temperature of 1800 ℃ under the protection of nitrogen at 15MPa to obtain a carbon/carbon composite material precursor;
(3) Soaking the precursor of the carbon/carbon composite material obtained in the step (2) in zirconia sol for 4h, and carrying out heat treatment at 240 ℃ for 2h to obtain the carbon/carbon composite material;
the molar concentration of zirconium oxychloride in the zirconia sol is 0.1mol/L, and the molar concentration of yttrium oxide is 3mmol/L.
Example 5
The embodiment provides a carbon/carbon composite material, which comprises a carbon fiber skeleton, a graphitized carbon matrix filled with and coated with the carbon fiber skeleton, and a zirconia coating coated on the surface of the graphitized carbon matrix, wherein the thickness of the zirconia coating is 0.5 μm.
The carbon/carbon composite material is prepared by the following preparation method, and the preparation method comprises the following steps:
(1) Carbon/carbon prepreg stitched with carbon fiber, the stitch density being 25 stitches/cm 2 Obtaining a carbon/carbon composite material prefabricated body;
the carbon/carbon prepreg is prepared by sequentially soaking carbon fiber fabric in a mixed solution of high-purity graphite, polyvinyl alcohol and deionized water for 12 hours and drying at 120 ℃ for 6 hours; the carbon fiber fabric is obtained by sequentially washing with deionized water and ethanol, drying at 80 ℃ for 2h, soaking in 90 ℃ nitric acid solution for 6h, and washing to neutrality;
(2) Graphitizing the carbon/carbon composite material preform obtained in the step (1) for 0.5h at the high temperature of 2900 ℃ under the protection of nitrogen and under the pressure of 100MPa to obtain a carbon/carbon composite material precursor;
(3) Soaking the precursor of the carbon/carbon composite material obtained in the step (2) in zirconia sol for 4h, and carrying out heat treatment at 300 ℃ for 1h to obtain the carbon/carbon composite material;
the molar concentration of zirconium oxychloride in the zirconia sol is 0.5mol/L, and the molar concentration of yttrium oxide is 9mmol/L.
Example 6
This example provides a carbon/carbon composite material, which is different from example 1 in that the thickness of the zirconia coating is adjusted to 0.1 μm, and the time for impregnating the zirconia sol with the carbon/carbon composite material precursor in the method for preparing the carbon/carbon composite material is adaptively adjusted to 3 hours, but the rest is the same as example 1.
Example 7
This example provides a carbon/carbon composite material, which is different from example 1 in that the thickness of the zirconia coating is adjusted to 1 μm, and the time for impregnating the zirconia sol with the carbon/carbon composite material precursor in the method for preparing the carbon/carbon composite material is adaptively adjusted to 5 hours, but the rest is the same as example 1.
Example 8
This example provides a carbon/carbon composite material, which is different from example 1 in that the same as example 1 was used except that the molar concentration of zirconium oxychloride in the zirconia sol was adjusted to 0.01mol/L in the preparation method of the carbon/carbon composite material.
Example 9
This example provides a carbon/carbon composite material, which is different from example 1 in that the same as example 1 was used except that the molar concentration of zirconium oxychloride in the zirconia sol was adjusted to 0.7mol/L in the preparation method of the carbon/carbon composite material.
Comparative example 1
This comparative example provides a carbon/carbon composite material, which is the same as example 1 except that the thickness of the zirconia coating layer was adjusted to 0.05 μm and the time for impregnating the zirconia sol with the carbon/carbon composite precursor in the method for preparing the carbon/carbon composite material was adaptively adjusted to 2.9 hours, unlike example 1.
Comparative example 2
This comparative example provides a carbon/carbon composite, which is the same as example 1 except that the thickness of the zirconia coating layer was adjusted to 1.5 μm and the time for impregnating the zirconia sol with the carbon/carbon composite precursor in the method for preparing the carbon/carbon composite was adjusted to 5.5 hours, unlike example 1.
Comparative example 3
This comparative example provides a carbon/carbon composite material, which is different from example 1 in that the carbon/carbon composite material comprises a carbon fiber skeleton, a graphitized carbon matrix filling and coating the carbon fiber skeleton, step (3) of the preparation method of the carbon/carbon composite material is adaptively removed, and the rest is the same as example 1.
The carbon/carbon composite materials provided in examples 1 to 9 and comparative examples 1 to 3 were subjected to ablation resistance tests, and the mass loss per unit time of ablation was recorded using a self-heating protective material ablation test platform, the parameters of which are shown in table 1, and the results of which are shown in table 2.
TABLE 1
Device information Related parameter Device information Related parameter
Ablative gas Butane Temperature of central flame >1500℃
Diameter of nozzle 2.0mm Gas working pressure 0.4MPa
Ablation distance 60mm Flow rate of gas 558L/h
Ablation angle 90° Density of heat flow 1038±103.8KW/m 2
Temperature measurement optris CT 3M Ablation time 120s
TABLE 2
Figure BDA0003674093410000141
Figure BDA0003674093410000151
As can be seen from table 2, as shown by comparing example 1 with examples 2 to 5, the carbon/carbon composite material provided by the present invention includes carbon fibers, a graphitized carbon matrix, and a zirconia coating coated on the surface of the carbon/carbon composite material, and the ablation resistance of the carbon/carbon composite material can be effectively improved by adjusting and controlling reasonable parameters of the impregnation and high-temperature graphitization processes;
as can be seen from the comparison of examples 1, 6 and 7, the change in the thickness of the zirconia coating has an effect on the ablation resistance of the carbon/carbon composite; as is clear from the comparison between examples 1, 8 and 9, the molar concentration of zirconium oxychloride in the zirconia sol affects the impregnation effect of the carbon/carbon composite precursor, and an excessively high concentration affects the effective coating of the zirconia sol; at too low a concentration, the zirconia coating applied to the surface of the carbon/carbon composite precursor does not significantly inhibit diffusion of the oxidizing atmosphere into the carbon/carbon composite, resulting in a decrease in ablation resistance. Therefore, the molar concentration of zirconium oxychloride in the zirconia sol is within the reasonable range provided by the invention, and the impregnation effect is better;
as can be seen from the comparison of example 1 with comparative example 1 and comparative example 2, the ablation resistance of the carbon/carbon composite material is obviously reduced when the thickness of the zirconia coating is too small or too large; as is clear from comparison between example 1 and comparative example 3, the carbon/carbon composite material is not coated with the zirconia coating, and the oxidation atmosphere diffuses into the carbon/carbon composite material under a high-temperature environment, so that the ablation resistance is greatly reduced.
In summary, the carbon/carbon composite material provided by the present invention uniformly and firmly distributes the graphitized carbon matrix in and on the carbon fiber framework, and the zirconium oxide coating is coated on the surface of the graphitized carbon matrix, so as to effectively improve the high temperature resistance and ablation resistance of the carbon/carbon composite material, and limit the diffusion of the oxidizing atmosphere from the surface of the carbon/carbon composite material to the inside, wherein the mass ablation rate of the carbon/carbon composite material is 0.138-0.290mg · s -1 (ii) a The carbon/carbon composite material provided by the invention takes the carbon/carbon prepreg as a raw material, can realize low-cost and rapid molding through a carbon fiber sewing process and high-temperature graphitization, can obviously reduce the large-scale production cost of the carbon/carbon composite material by adopting reasonable preparation process parameters, obviously shortens the preparation period, and can realize integral molding and preparation of irregular and large-size devices according to self-designed and manufactured moulds.
The above description is only for the specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.

Claims (23)

1. The carbon/carbon composite material is characterized by comprising a carbon fiber framework, a graphitized carbon matrix filled with and coated on the carbon fiber framework and a zirconium oxide coating coated on the surface of the graphitized carbon matrix;
the thickness of the zirconia coating is 0.1-1 μm;
the carbon/carbon composite material is prepared by the following preparation method, and the preparation method comprises the following steps:
(1) Sewing carbon/carbon prepreg by using carbon fiber to obtain a carbon/carbon composite material prefabricated body;
(2) Graphitizing the carbon/carbon composite material preform obtained in the step (1) at high temperature to obtain a carbon/carbon composite material precursor;
(3) Dipping and heat treating the carbon/carbon composite material precursor obtained in the step (2) to obtain a carbon/carbon composite material;
the carbon/carbon prepreg in the step (1) is obtained by sequentially dipping and drying carbon fiber fabrics;
the impregnation is carried out in a mixed solution of graphite powder, a sizing agent and deionized water;
the impregnation liquid used in the impregnation in the step (3) comprises zirconia sol;
the molar concentration of zirconium oxychloride in the zirconia sol is 0.1-0.5mol/L.
2. A method for preparing the carbon/carbon composite material according to claim 1, comprising the steps of:
(1) Sewing carbon/carbon prepreg by using carbon fiber to obtain a carbon/carbon composite material prefabricated body;
(2) Graphitizing the carbon/carbon composite material preform obtained in the step (1) at high temperature to obtain a carbon/carbon composite material precursor;
(3) Dipping and heat treating the carbon/carbon composite material precursor obtained in the step (2) to obtain a carbon/carbon composite material;
the carbon/carbon prepreg in the step (1) is obtained by sequentially impregnating and drying carbon fiber fabrics;
the impregnation is carried out in a mixed solution of graphite powder, a sizing agent and deionized water;
the impregnation liquid used in the impregnation in the step (3) comprises zirconia sol;
the molar concentration of zirconium oxychloride in the zirconia sol is 0.1-0.5mol/L.
3. The method according to claim 2, wherein the carbon fiber in the step (1) comprises any one of or a combination of at least two of a T300 type carbon fiber, a T400 type carbon fiber, a T700 type carbon fiber, a T800 type carbon fiber and a T1000 type carbon fiber.
4. The method of claim 2, wherein the seam of step (1)The density of the blend is 10-25 needles/cm 2 。
5. The method for preparing a soft tissue patch according to claim 2, wherein the suture needle used in the step (1) comprises a C2 type needle and/or a C3 type needle.
6. The method of claim 5, wherein the C2 needle has a needle diameter of 0.44-0.46mm.
7. The method of claim 5, wherein the C3 needle has a needle diameter of 0.54-0.56mm.
8. The method of claim 2, wherein the high temperature graphitization of step (2) is performed in a protective atmosphere under hot isostatic pressing, and the gas used in the protective atmosphere comprises any one or a combination of at least two of helium, argon, or nitrogen.
9. The method of claim 8, wherein the hot isostatic pressing is at a pressure of 15-100MPa.
10. The method according to claim 2, wherein the high temperature graphitization temperature in the step (2) is 1800-2900 ℃.
11. The method according to claim 2, wherein the high-temperature graphitization in the step (2) is performed for 0.5-6h.
12. The method according to claim 2, wherein the zirconia sol is prepared by mixing zirconium oxychloride, yttrium oxide and deionized water.
13. The method according to claim 2, wherein the molar concentration of yttrium oxide in the zirconia sol is 3 to 9mmol/L.
14. The method according to claim 2, wherein the time for the impregnation in step (3) is 3 to 5 hours.
15. The method according to claim 2, wherein the temperature of the heat treatment in the step (3) is 240 to 300 ℃.
16. The method of claim 2, wherein the heat treatment of step (3) is carried out for a period of 1 to 2 hours.
17. The preparation method according to claim 2, wherein the carbon fiber fabric comprises carbon fiber cloth produced by a weaving process, and the carbon fiber cloth comprises any one of plain cloth, twill cloth, satin cloth or unidirectional cloth or a combination of at least two of the plain cloth, the twill cloth, the satin cloth and the unidirectional cloth.
18. The method of claim 2, wherein the time for the immersion is 0.5 to 12 hours.
19. The method according to claim 2, wherein the drying temperature is 30 to 120 ℃.
20. The method of claim 2, wherein the drying time is 6 to 10 hours.
21. The production method according to claim 2, wherein the mass fraction of carbon fibers in the carbon/carbon prepreg of step (1) is 30 to 90wt%.
22. The method of claim 2, comprising the steps of:
(1) Carbon/carbon prepregs using carbon fibres stitched at a density of 10-25 needles/cm 2 To obtain a carbon/carbon composite preformA body;
the carbon/carbon prepreg is prepared by sequentially dipping carbon fiber fabric in a mixed solution of graphite powder, a sizing agent and deionized water for 0.5-12h and drying at 30-120 ℃ for 6-10 h;
(2) Graphitizing the carbon/carbon composite material preform obtained in the step (1) for 0.5-6h under the protection of inert gas at a high temperature of 15-100MPa and 1800-2900 ℃ to obtain a carbon/carbon composite material precursor;
(3) Soaking the precursor of the carbon/carbon composite material obtained in the step (2) in zirconia sol for 3-5h, and carrying out heat treatment at 240-300 ℃ for 1-2h to obtain the carbon/carbon composite material;
the molar concentration of zirconium oxychloride in the zirconia sol is 0.1-0.5mol/L, and the molar concentration of yttrium oxide is 3-9mmol/L.
23. Use of the carbon/carbon composite material according to claim 1 in the field of aerospace structural materials.
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