CN108947557B - Carbon/carbon composite material and preparation method thereof - Google Patents

Carbon/carbon composite material and preparation method thereof Download PDF

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CN108947557B
CN108947557B CN201811117812.9A CN201811117812A CN108947557B CN 108947557 B CN108947557 B CN 108947557B CN 201811117812 A CN201811117812 A CN 201811117812A CN 108947557 B CN108947557 B CN 108947557B
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carbon
coating
composite material
carbon composite
graphene
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CN108947557A (en
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于艺
宋环君
刘伟
王鹏
李晓东
金鑫
杨冰洋
张宝鹏
于新民
刘俊鹏
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Aerospace Research Institute of Materials and Processing Technology
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • C04B35/83—Carbon fibres in a carbon matrix
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • 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
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
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Abstract

The invention relates to a carbon/carbon composite material and a preparation method thereof. Specifically, the carbon/carbon composite material comprises a carbon/carbon composite material body, and a composite transition coating is formed on the surface of the carbon/carbon composite material body; the composite transition coating comprises a buffer coating formed on the surface of the carbon/carbon composite material body and a silicon carbide coating formed on the surface of the buffer coating; wherein the buffer coating is a graphene film. The carbon/carbon composite material has better oxidation ablation resistance, strength and toughness.

Description

Carbon/carbon composite material and preparation method thereof
Technical Field
The invention relates to the technical field of carbon/carbon composite materials, in particular to a carbon/carbon composite material and a preparation method thereof.
Background
The carbon/carbon composite material is a carbon-based composite material reinforced by carbon fibers, has a series of advantages of low density, high strength, high thermal conductivity, low expansion coefficient and the like, can keep higher mechanical property along with temperature rise, and has been successfully applied to aerospace craft nose cones, rocket engine throat liners and high thrust-weight ratio engine hot end parts. However, the oxidation resistance and ablation resistance of the carbon/carbon composite material in a high-temperature environment are poor, and the high-temperature easy oxidation is the most difficult bottleneck to break through in the practical application of the carbon/carbon composite material. In order to meet the development requirements of future spacecrafts, the ablation resistance and oxidation resistance of the carbon/carbon composite material must be further enhanced. The method is a necessary choice for realizing the high-temperature long-life oxidation resistance and ablation resistance of the carbon/carbon composite material by preparing a coating on the surface of the carbon/carbon composite material to prevent the oxygen-containing gas from contacting with a matrix.
The introduction of the coating introduces a new interface inside the composite material, and therefore a transition layer is needed to relieve the problem that the thermal expansion coefficient of the coating is not matched with that of the carbon/carbon composite material matrix. Silicon carbide (SiC) coatings are widely used as transition layers due to their good physical and chemical compatibility with carbon/carbon composites. However, the inventors have found in their studies that defects such as cracks occur on the surface of the coating layer due to the difference between the thermal expansion coefficients of SiC and carbon/carbon composites. When the overcoat is formed, the defects are completely filled if they cannot be effectively controlled. When the outer layer is oxidized and damaged at high temperature, an oxygen channel is formed, so that the carbon/carbon composite material body is rapidly oxidized, and the oxidation resistance of the coating is reduced.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
Technical problem to be solved
The technical problem to be solved by the invention is as follows: how to improve the oxidation resistance and ablation resistance of the existing carbon/carbon composite material.
(II) technical scheme
In order to solve the technical problems, the invention provides the following technical scheme:
a carbon/carbon composite comprising a carbon/carbon composite body having a composite transition coating formed on a surface thereof; the composite transition coating comprises a buffer coating formed on the surface of the carbon/carbon composite material body and a silicon carbide coating formed on the surface of the buffer coating; wherein the buffer coating is a graphene film.
Preferably, the composite transition coating also has a multilayer structure formed by sequentially repeating the buffer coating and the silicon carbide coating on the silicon carbide coating; wherein, in the multilayer structure, the number of layers of the buffer coating and the silicon carbide coating is the same.
Preferably, the graphene film has a thickness of 1 to 5 μm.
Preferably, the graphene used to form the graphene film is single-layer graphene and/or multi-layer graphene.
Preferably, the composite transition layer has a thickness of 1-100 μm.
Preferably, the carbon/carbon composite material body has 1.70-1.85 g/cm3The density of (c).
Preferably, an outer coating is also formed on the surface of the composite transition coating; preferably, the outer coating is a Zr-Si-O coating, a Y-Si-O coating, a Yb-Si-O coating, a ZrB coating2Any of the coatings.
The invention also provides a preparation method of the carbon/carbon composite material, which comprises the following steps:
(1) providing a carbon/carbon composite body;
(2) forming a graphene film with the thickness meeting the requirement on the surface of the carbon/carbon composite material body to serve as a buffer coating;
(3) forming a silicon carbide coating on the surface of the buffer coating, thereby compositely forming a composite transition coating comprising the buffer coating and the silicon carbide coating on the surface of the carbon/carbon composite material body;
preferably, when the composite transition coating layer further has a multilayer structure formed by repeating the buffer coating layer and the silicon carbide coating layer in this order on the silicon carbide coating layer, the production method further includes the step (4):
and (3) repeating the step (2) and the step (3) in sequence until a composite transition coating with the thickness meeting the requirement is formed on the surface of the carbon/carbon composite material body in a composite mode.
Preferably, the step (2) is performed as follows:
(21) preparing graphene into a graphene solution;
(22) compounding the graphene solution with a carbon/carbon composite material body by a dipping, brushing or spraying method;
(23) carbonizing;
(24) sequentially repeating the steps (22) and (23) until the thickness of the graphene film meets the requirement;
preferably, the concentration of the graphene solution is 1-10 wt%;
preferably, the graphene solution is prepared by using any one or more of water, methanol, ethanol, isopropanol, chloroform, carbon tetrachloride, acetone, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethyl sulfoxide, chlorobenzene, dichlorobenzene or trichlorobenzene as a solvent;
preferably, the carbonization is performed by a sintering method, and preferably, the sintering is performed at 500-1500 ℃.
Preferably, the step (3) is performed as follows:
(31) preparing silicon powder, graphite powder, boron powder and alumina powder into mixed powder;
(32) embedding the carbon/carbon composite material body treated in the step (2) by using the mixed powder, and then sintering in an oxygen-free atmosphere to enable the surface of the buffer coating to be provided with a silicon carbide coating;
preferably, in the mixed powder, the mass fraction of the silicon powder is 40-60%, the mass fraction of the graphite powder is 20-30%, the mass fraction of the boron powder is 10-15%, and the mass fraction of the alumina powder is 5-10%;
preferably, the sintering is carried out at 1600-1800 ℃, and the heat preservation time is 4-6 hours;
more preferably, the sintering is carried out at an elevated temperature as follows:
raising the temperature to 1200-1300 ℃ at a temperature raising speed of 2-3 ℃/min, and then raising the temperature to 1600-1800 ℃ at a temperature raising speed of 1-2 ℃/min.
(III) advantageous effects
The technical scheme of the invention has the following advantages:
(1) according to the carbon/carbon composite material provided by the invention, the buffer layer is formed between the SiC coating and the composite material body, and the buffer layer adopts the graphene film with good compatibility with the composite material body, so that the strength and toughness of the material are improved, and meanwhile, the oxidation and ablation resistance performance is obviously improved;
(2) the invention provides a preparation method of a carbon/carbon composite material graphene composite coating, which can be used for preparing a multi-cycle composite coating to a required thickness according to the requirements of a use environment, and is simple and feasible;
(3) according to the invention, the graphite thin solution is coated on the surface of the carbon/carbon composite material body, the continuous graphite thin film is formed by sintering and is attached to the surface of the carbon/carbon composite material body, the pit defects on the surface of the carbon/carbon composite material body are effectively coated, the number and the size of the holes are reduced, the inward diffusion of oxygen is effectively prevented, and the oxidation resistance is improved;
(4) the invention ensures the high efficiency, compactness and stability of the composite coating through the process design of the steps of preparing the graphene film, carbonizing the film, preparing the SiC coating by an embedding method and the like.
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 present invention provides in a first aspect a carbon/carbon composite having the structure:
the carbon/carbon composite material comprises a carbon/carbon composite material body, and a composite transition coating is formed on the surface of the carbon/carbon composite material body; the composite transition coating comprises a buffer coating formed on the surface of the carbon/carbon composite material body and a silicon carbide coating formed on the surface of the buffer coating; wherein the buffer coating is a graphene film.
The inventor finds in research that although the silicon carbide coating has good physical and chemical compatibility with the carbon/carbon composite material and a similar linear expansion coefficient, the difference in the linear expansion coefficient between the two materials still causes the surface of the coating to have defects such as cracks, and when the outer coating is formed on the silicon carbide coating, the defects are completely filled if the defects cannot be effectively controlled. When the outer layer is oxidized and damaged at high temperature, an oxygen channel is formed, so that the carbon/carbon composite material body is rapidly oxidized, and the oxidation resistance of the coating is reduced.
Based on the above findings, the inventors have provided a buffer coating between the silicon carbide coating and the carbon/carbon composite body, and employed a graphene film as the buffer coating. Experiments prove that the graphene film and the composite material body have better compatibility, cracks in the coating are effectively overcome, the continuous graphene film is attached to the surface of the composite material body, pit defects on the surface of the composite material body are effectively coated, inward diffusion of oxygen is effectively prevented by reducing the number and the size of holes, and the oxidation and ablation resistance of the material is improved.
In addition, the better toughness and strength of the graphene can also greatly improve the mechanical property of the material and improve the strength and toughness of the composite material.
The inventors have found that the thickness of the graphene film has an effect on the resistance to oxidative ablation, toughness and strength of the carbon/carbon composite. Under the same other conditions, the thicker graphene film can more effectively coat the pit defects on the surface of the carbon/carbon composite material body, so that the penetration of external oxygen can be better blocked, and the improvement degree of the toughness and the strength of the material is more remarkable. However, too much thickness can also result in a graphene film that has a reduced compatibility with the carbon/carbon composite body and the silicon carbide coating. The graphene film has a better thickness of 1-5 μm. The graphene used to form the graphene film may be single-layer graphene and/or multi-layer graphene.
A graphene film with the thickness meeting the requirement and a silicon carbide coating with the thickness meeting the requirement can be formed on the carbon/carbon composite material body. However, in the research, the inventor finds that the number of layers of the graphene film and the silicon carbide coating layer is increased under the condition that the bulk density of the carbon/carbon composite material is the same, so that the thickness of the composite transition coating layer is increased, and the influence on the performance of the final composite material is larger. Therefore, the carbon/carbon composite material provided by the invention can also form a multilayer structure formed by sequentially repeating the buffer coating and the silicon carbide coating on the silicon carbide coating; wherein, in the multilayer structure, the number of layers of the buffer coating and the silicon carbide coating is the same. The design can properly increase the thickness of the composite transition coating on the premise of not exceeding the optimal thickness of the graphene film, so that the oxidation ablation resistance and the mechanical property of the composite material are improved. The thickness of the composite transition coating layer is preferably 1 to 100 μm, for example, the thickness of the composite transition coating layer may be all values or sub-ranges within the range, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, and the sub-ranges may be 1 to 10 μm, 5 to 15 μm, 20 to 30 μm, 25 to 40 μm, 45 to 60 μm, 50 to 70 μm, 40 to 80 μm, 60 to 90 μm, 65 to 100 μm, or 80 to 100 μm. On the basis, the number of layers of the multilayer structure can be determined according to the thickness of the composite transitional coating.
It should be noted that, the preparation method of the carbon/carbon composite material body is not limited in the present invention, and the carbon/carbon composite material body can be prepared by the existing method, such as a chemical vapor deposition method, a precursor carbonization treatment process, and the like, but the density of the carbon/carbon composite material body is required to be high, and the density is preferably 1.70 to 1.85g/cm3May be all values or subranges within this range, e.g., may be 1.70g/cm3、1.71g/cm3、1.72g/cm3、1.73g/cm3、1.74g/cm3、1.75g/cm3、1.76g/cm3、1.77g/cm3、1.78g/cm3、1.79g/cm3、1.80g/cm3、1.81g/cm3、1.82g/cm3、1.83g/cm3、1.84g/cm3Or 1.85g/cm3。
The inventor finds in research that the density of the carbon/carbon composite material body is too low, the carbon/carbon composite material structure is loose, and although sufficient reaction infiltration space is provided for preparation of a subsequent coating, the mechanical property of the finally obtained composite material is poor, mainly because fibers are easily damaged when the density of the carbon/carbon material is too low and infiltration is carried out. When the density of the carbon/carbon composite material is changed within the range, the influence on the mechanical property and the oxidation resistance of the final product material is not obvious.
The carbon/carbon composite material provided by the invention can form a composite transition coating on the surface of the carbon/carbon composite material body, and can also form an outer coating on the surface of the composite transition coating. The outer coating can be a coating with high temperature resistance grade, low oxygen diffusion coefficient and high thermal emissivity, so that the service performance and the service life of the carbon/carbon composite material in an ultrahigh-temperature aerobic environment are improved. The outer coating can be a Zr-Si-O coating, a Y-Si-O coating, a Yb-Si-O coating and a ZrB2Any of the coatings. Of course, other existing coatings with high temperature resistance, low oxygen diffusion coefficient and high thermal emissivity can also be used as the outer coating of the invention. The preparation methods of the above coatings can be prepared by adopting the existing methods, and the details of the invention are not described.
The present invention provides, in a second aspect, a method for preparing any one of the above-described carbon/carbon composites, comprising the steps of:
(1) providing a carbon/carbon composite body;
as mentioned above, the carbon/carbon composite body can be prepared by using the existing preparation method, such as chemical vapor deposition, precursor carbonization treatment process, etc. The structure of the carbon/carbon composite body is also prior art and may be a structure consisting of carbon fibers and a matrix. However. In order to obtain better effect, the density of the carbon/carbon composite material body can be controlled to be 1.70-1.85 g/cm3。
(2) Forming a graphene film with the thickness meeting the requirement on the surface of the carbon/carbon composite material body to serve as a buffer coating;
in some embodiments, the graphene film may be prepared as follows:
(21) preparing graphene into a graphene solution; preferably, the concentration of the graphene solution is 1 to 10 wt%, may be all values or subranges within this range, for example, may be 1 to 5 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, and the subranges may be 1 to 5 wt%, 3 to 8 wt%, 5 to 10 wt%, or 6 to 10 wt%.
The graphene solution with the concentration has proper proportion of graphene and solvent, has proper concentration and adhesive force, can be easily adhered to the surface of a member, and does not flow.
In some embodiments, the graphene solution may be prepared using any one or more of water, methanol, ethanol, isopropanol, chloroform, carbon tetrachloride, acetone, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethyl sulfoxide, chlorobenzene, dichlorobenzene, or trichlorobenzene as a solvent.
(22) Compounding the graphene solution with a carbon/carbon composite material body by a dipping, brushing or spraying method;
in this step, the graphene solution can be compounded with the carbon/carbon composite material body by adopting a dipping, brushing or spraying method. The dipping time is not particularly limited, and the inventor finds in research that, as long as the concentration of the graphene solution is determined to be within the above-mentioned appropriate range, the factors such as dipping time and spraying uniformity have no obvious influence on the thickness of the formed graphene film and the subsequent embedding reaction, so that the specific process parameters (such as dipping time) of the compounding process are not particularly limited, and can be determined according to actual conditions in actual operation.
(23) Carbonizing;
in this step, the carbonization is performed by sintering, and the graphene is carbonized to form a graphene film with a dense structure on the surface of the carbon/carbon composite material body. Preferably, the sintering temperature is controlled to be 500-1500 ℃, and the sintering temperature can be all values in the range or any sub-range within the range, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃, or 1500 ℃, and the sub-range can be 500-600 ℃, 700-900 ℃, 900-1200 ℃, 1000-1300 ℃, or 1200-1500 ℃.
The sintering time is not particularly limited in the present invention, and the required sintering time can be determined according to actual conditions.
(24) Sequentially repeating the steps (22) and (23) until the thickness of the graphene film meets the requirement;
(3) forming a silicon carbide coating on the surface of the buffer coating, thereby compositely forming a composite transition coating comprising the buffer coating and the silicon carbide coating on the surface of the carbon/carbon composite material body;
the silicon carbide coating is prepared by an embedding method, and specifically, the silicon carbide coating can be prepared by the following steps:
(31) preparing silicon powder, graphite powder, boron powder and alumina powder into mixed powder;
preferably, in the powder mixture,
the mass fraction of the silicon powder is 40-60%, for example, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, or 60%;
the graphite powder is 20-30% by mass, for example, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%;
the mass fraction of the boron powder is 10-15%, for example, 10%, 11%, 12%, 13%, 14% or 15%;
the mass fraction of the alumina powder is 5 to 10%, and for example, may be 5%, 6%, 7%, 8%, 9%, or 10%.
When preparing the mixed powder, in order to obtain the mixed powder with a better particle size, the silicon powder, the graphite powder, the boron powder and the alumina powder can be put into a planetary ball mill using agate balls as a grinding medium to be ball-milled for a period of time (for example, 2 to 4 hours), so as to obtain the mixed powder for embedding the carbon/carbon composite material body.
(32) Embedding the carbon/carbon composite material body treated in the step (2) by using the mixed powder, and then sintering in an oxygen-free atmosphere to enable the surface of the buffer coating to be provided with a silicon carbide coating;
preferably, the sintering is carried out at 1600-1800 ℃, for example, 1600 ℃, 1650 ℃, 1700 ℃, 1750 ℃ or 1800 ℃, and the holding time is 4-6 hours, for example, 4 hours, 5 hours or 6 hours;
more preferably, the sintering is carried out at an elevated temperature as follows:
the temperature is raised to 1200 to 1300 ℃ at a raising rate of 2 to 3 ℃/min (e.g., 2 ℃/min, 2.1 ℃/min, 2.2 ℃/min, 2.3 ℃/min, 2.4 ℃/min, 2.5 ℃/min, 2.6 ℃/min, 2.7 ℃/min, 2.8 ℃/min, 2.9 ℃/min or 3 ℃/min) (e.g., 1200 ℃, 1210 ℃, 1220 ℃, 1230 ℃, 1240 ℃, 1250 ℃, 1260 ℃, 1270 ℃, 1280 ℃, 1290 ℃ or 1300 ℃), and further raised to 1600 to 1800 ℃ at a raising rate of 1 to 2 ℃/min (e.g., 1 ℃/min, 1.1 ℃/min, 1.2 ℃/min, 1.3 ℃/min, 1.4 ℃/min, 1.5 ℃/min, 1.6 ℃/min, 1.7 ℃/min, 1.8 ℃/min, 1.9 ℃/min or 2 ℃/min).
When the composite transition coating further has a multilayer structure formed by repeating the buffer coating and the silicon carbide coating in this order on the silicon carbide coating, the production method further includes the step (4):
and (3) repeating the step (2) and the step (3) in sequence until a composite transition coating with the thickness meeting the requirement is formed on the surface of the carbon/carbon composite material body in a composite mode.
The following are examples of the present invention.
Example 1
(1) Preparation of carbon/carbon composite bodies
Loading the carbon fiber preform into a CVI-C furnace, and introducing C under vacuum condition and at 1020 DEG C3H8And the mixed gas of the carbon dioxide and the Ar,depositing for 600 hours and discharging to obtain the density of 1.70g/cm3The carbon/carbon composite body of (a).
(2) Composition of buffer layer
(21) And adding 1g of monolayer graphene into 100g of aqueous solution, and carrying out ultrasonic treatment for 30min to obtain a graphene solution.
(22) And (3) soaking the carbon/carbon composite material body in the graphene solution for 2 hours.
(23) And (5) taking out the carbon/carbon composite material body in the step (22), drying and sintering, wherein the sintering temperature is 500 ℃, and the sintering time is 6 hours, so that a graphene film with the thickness of 1 mu m is formed on the carbon/carbon composite material body to serve as a buffer layer.
(3) Compounding of silicon carbide coatings
(31) Mixing and stirring silicon powder, graphite powder, boron powder and alumina powder uniformly; in the mixed material, the mass fraction content of the silicon powder is 55%, the mass fraction content of the graphite powder is 25%, the mass fraction content of the boron powder is 15%, and the mass fraction content of the alumina powder is 5%; and (3) placing the mixed material in a planetary ball mill using agate balls as grinding media to perform ball milling for 2 hours to obtain mixed powder required by embedding.
(32) Placing half of the mixed powder into a graphite crucible, then placing a carbon/carbon composite material body with a graphene film, and then placing the other half of the embedded powder to cover the body; putting the graphite crucible into a high-temperature atmosphere sintering furnace, vacuumizing to ensure that the vacuum degree reaches-0.1 MPa, maintaining the vacuum for 30min, introducing argon to normal pressure after the indication of a vacuum gauge is stable, vacuumizing again, repeating the process for 3 times, and introducing argon for protection in the whole process, thereby ensuring that the interior of the furnace is in an oxygen-free atmosphere. And (3) heating the furnace to 1700 ℃ from the room temperature, preserving the heat for 4 hours, and finally turning off the power supply to naturally cool to the room temperature, thereby forming the silicon carbide coating on the surface of the graphene film.
(4) And (4) repeating the step (2) and the step (3) in sequence for 2 times to obtain the carbon/carbon composite material with the composite transition coating with the thickness of 10 microns.
After the carbon/carbon composite material prepared in the example 1 is put in the air at 1500 ℃ for oxidizing for 100 hours, the mass loss rate of the sample is 0.8 percent.
Example 2
Example 2 was prepared substantially the same as example 1, except that:
and (4) circulating for multiple times to obtain the carbon/carbon composite material with the composite transition coating with the thickness of 20 mu m.
After the carbon/carbon composite material prepared in the example 2 is put in the air at 1500 ℃ for oxidation for 100 hours, the mass loss rate of the sample is 0.5 percent.
Example 3
Example 3 was prepared essentially as in example 1, except that:
and (4) circulating for multiple times to obtain the carbon/carbon composite material with the composite transition coating with the thickness of 100 mu m.
After the carbon/carbon composite material prepared in the example 3 is put in the air at 1500 ℃ for oxidizing for 100 hours, the mass loss rate of the sample is 0.4 percent.
Example 4
Example 4 was prepared essentially as in example 1, except that:
in step (2), steps (22) and (23) are repeated in sequence a plurality of times until a graphene film having a thickness of 5 μm is formed on the carbon/carbon composite body.
After the carbon/carbon composite material prepared in the example 4 is put in the air at 1500 ℃ for oxidizing for 100 hours, the mass loss rate of the sample is 0.6 percent.
Example 5
Example 5 was prepared essentially as in example 1, except that:
the density of the carbon/carbon composite material body is 1.85g/cm3。
After the carbon/carbon composite material prepared in the example 5 is put in the air at 1500 ℃ for oxidizing for 100 hours, the mass loss rate of the sample is 0.8 percent.
Comparative example 1
Comparative example 1 was prepared substantially the same as example 1, except that:
and (4) circulating for multiple times in the step to obtain the carbon/carbon composite material with the composite transition coating layer with the thickness of 130 mu m.
After the carbon/carbon composite material prepared in the comparative example 1 is put in 1500 ℃ air to be oxidized for 100 hours, the mass loss rate of the sample is 0.9 percent.
Comparative example 2
Comparative example 2 was prepared substantially the same as example 1, except that:
in step (2), steps (22) and (23) are repeated in sequence a plurality of times until a graphene film having a thickness of 8 μm is formed on the carbon/carbon composite body.
After the carbon/carbon composite material prepared in the comparative example 2 is put in 1500 ℃ air to be oxidized for 100 hours, the mass loss rate of the sample is 1.0 percent.
Comparative example 3
Comparative example 3 was prepared substantially the same as example 1, except that:
the density of the carbon/carbon composite material body is 1.9g/cm3。
After the carbon/carbon composite material prepared in the comparative example 3 is put in 1500 ℃ air to be oxidized for 100 hours, the mass loss rate of the sample is 1.0 percent.
In addition, the present invention also examined the fracture toughness and bending strength of the carbon/carbon composite materials prepared in the above examples and comparative examples, and the examination results are shown in table 1.
As can be seen from table 1, the composite of example 2 has better resistance to oxidative ablation, as well as flexural strength and fracture toughness than example 1, indicating that an increase in the thickness of the composite transition coating can improve the oxidation resistance, ablation resistance, and strength and toughness of the carbon/carbon composite. The results of the property measurements of the material of example 3 also further confirm this conclusion. However, the composite transition coating in comparative example 1 has a thickness of 130 μm, and from the detection result, the thickness of the composite transition coating is not as large as possible, and if the thickness is too thick, the bonding capability between the coatings is reduced, and the stripping speed of the coatings is increased under the oxygen-immersed environment. Based on the consideration, the thickness of the composite transition coating is preferably selected to be 1-100 mu m, and the coating with the thickness can be used as a transition layer to improve the oxidation ablation resistance, the bending strength and the fracture toughness of the composite material.
The difference between example 4 and example 1 in the preparation process is that the graphene film thickness is different, and the graphene film thickness of example 4 is greater than that of the graphene film in the examples. From the results of the tests, the composite material of example 4 has better resistance to oxidative ablation, as well as flexural strength and fracture toughness than example 1, which indicates that the increased graphene film thickness can improve the oxidation resistance, ablation resistance, and strength and toughness of the carbon/carbon composite material. However, the graphene film in comparative example 2 has a thickness of 8 μm, which is larger than that of the graphene film in example 1, but from the detection results thereof, it is shown that the larger the thickness of the graphene film, the better, the larger the thickness of the graphene film, the larger the contact area after oxygen permeation, the lower the oxidation resistance, and the lower the interaction force between graphene layers at the time of fracture, the lower the fracture toughness. In view of this, the thickness of the graphene film of the present invention is preferably selected to be 1 to 5 μm, and more preferably 3 μm.
The difference between example 5 and example 1 in the preparation process is that the density of the carbon/carbon composite bulk used is different, with example 5 having a slightly greater density than example 1. From the results of both tests, the flexural strength and fracture toughness of the composite material of example 5 were superior to those of example 1. If the carbon/carbon composite material body has lower density and loose structure, enough reaction infiltration space can be provided for the preparation of a subsequent coating, but the finally obtained composite material has poor mechanical property, mainly because the fibers are easily damaged when the carbon/carbon material body is subjected to infiltration due to too low density. From the detection result of comparative example 3, the larger the density of the carbon/carbon composite material body is, the better the density is, the better the mechanical property of the material can be obtained, but the oxidation resistance of the material is sacrificed. Comprehensively, the density of the carbon/carbon composite material body used by the invention is preferably selected to be 1.7-1.85 g/cm3。
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Figure BDA0001809985210000141

Claims (13)

1. A carbon/carbon composite material comprising a carbon/carbon composite material body, wherein a composite transition coating is formed on a surface of the carbon/carbon composite material body; the composite transition coating comprises a buffer coating formed on the surface of the carbon/carbon composite material body and a silicon carbide coating formed on the surface of the buffer coating; wherein the buffer coating is a graphene film;
the composite transition coating is also provided with a multilayer structure formed by sequentially repeating the buffer coating and the silicon carbide coating on the silicon carbide coating; wherein, in the multilayer structure, the number of layers of the buffer coating and the silicon carbide coating is the same;
the graphene film has a thickness of 1-5 μm; the value range of the thickness m of the composite transition layer is more than 1 mu m and less than or equal to 100 mu m;
the carbon/carbon composite material body has a thickness of 1.70 to 1.85g/cm3The density of (c).
2. The carbon/carbon composite material according to claim 1, wherein the graphene used to form the graphene film is single-layer graphene and/or multi-layer graphene.
3. The carbon/carbon composite material according to claim 1 or 2, wherein an outer coating layer is further formed on the surface of the composite transition coating layer.
4. The carbon/carbon composite of claim 3, wherein the overcoat is a Zr-Si-O coating, a Y-Si-O coating, a Yb-Si-O coating, a ZrB2 Any of the coatings.
5. A method for preparing the carbon/carbon composite material according to any one of claims 1 to 4, comprising the steps of:
(1) providing a carbon/carbon composite body;
(2) forming a graphene film with the thickness meeting the requirement on the surface of the carbon/carbon composite material body to serve as a buffer coating;
(3) forming a silicon carbide coating on the surface of the buffer coating, thereby compositely forming a composite transition coating comprising the buffer coating and the silicon carbide coating on the surface of the carbon/carbon composite material body;
the preparation method further comprises the step (4):
and (3) repeating the step (2) and the step (3) in sequence until a composite transition coating with the thickness meeting the requirement is formed on the surface of the carbon/carbon composite material body in a composite mode.
6. The production method according to claim 5, wherein the step (2) is carried out as follows:
(21) preparing graphene into a graphene solution;
(22) compounding the graphene solution with a carbon/carbon composite material body by a dipping, brushing or spraying method;
(23) carbonizing;
(24) and (5) repeating the steps (22) and (23) in sequence until the thickness of the graphene film meets the requirement.
7. The production method according to claim 6,
the concentration of the graphene solution is 1-10 wt%.
8. The production method according to claim 7,
the graphene solution is prepared by adopting any one or more of water, methanol, ethanol, isopropanol, chloroform, carbon tetrachloride, acetone, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethyl sulfoxide, chlorobenzene, dichlorobenzene or trichlorobenzene as a solvent.
9. The production method according to claim 6,
preferably, the carbonization is performed by a sintering method, and sintering is performed at 500-1500 ℃.
10. The production method according to claim 5, wherein the step (3) is carried out as follows:
(31) preparing silicon powder, graphite powder, boron powder and alumina powder into mixed powder;
(32) and (3) embedding the carbon/carbon composite material body treated in the step (2) by using the mixed powder, and then sintering in an oxygen-free atmosphere to enable the surface of the buffer coating to be provided with the silicon carbide coating.
11. The production method according to claim 10,
in the mixed powder, the mass fraction of the silicon powder is 40-60%, the mass fraction of the graphite powder is 20-30%, the mass fraction of the boron powder is 10-15%, and the mass fraction of the alumina powder is 5-10%.
12. The production method according to claim 11,
the sintering is carried out at 1600-1800 ℃, and the heat preservation time is 4-6 hours.
13. The production method according to claim 12,
the sintering is carried out by heating as follows:
raising the temperature to 1200-1300 ℃ at a temperature raising speed of 2-3 ℃/min, and then raising the temperature to 1600-1800 ℃ at a temperature raising speed of 1-2 ℃/min.
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