阅读说明：本技术 一种含难熔金属的碳碳复合材料 (Carbon-carbon composite material containing refractory metal ) 是由 吴宝林 侯振华 吴迪 于 2021-08-30 设计创作，主要内容包括：本发明提供一种含难熔金属的碳碳复合材料,包括碳基体、分布于碳基体内的碳纤维增强体、分布于碳基体内部孔隙中的金属锆-富勒烯复合纳米粉体、分布于碳基体内部空隙中的富硅的碳化硅。本发明还提供了一种含难熔金属的碳碳复合材料的制备方法。本发明提供的抗氧化碳碳复合材料通过浸渍将金属锆-富勒烯复合纳米粉体引入碳碳复合材料内部,可大大提高复合材料的耐烧蚀性能,而富硅的碳化硅的引入可在内部材料出现缺陷时通过材料内部渗透补充缺陷,进一步提高了复合材料的使用寿命；利用富勒烯将金属锆包覆因为引入金属锆导致材料内部出现的缺陷,有利于抗氧化性能的提高。(The invention provides a carbon-carbon composite material containing refractory metal, which comprises a carbon matrix, a carbon fiber reinforcement distributed in the carbon matrix, metal zirconium-fullerene composite nano powder distributed in pores inside the carbon matrix, and silicon-rich silicon carbide distributed in the pores inside the carbon matrix. The invention also provides a preparation method of the carbon-carbon composite material containing the refractory metal. The oxidation-resistant carbon-carbon composite material provided by the invention has the advantages that the metal zirconium-fullerene composite nano powder is introduced into the carbon-carbon composite material through impregnation, the ablation resistance of the composite material can be greatly improved, and the defect can be supplemented through the internal permeation of the material when the internal material has defects due to the introduction of silicon-rich silicon carbide, so that the service life of the composite material is further prolonged; the fullerene is utilized to coat the metal zirconium, so that the defect of the metal zirconium caused by the introduction of the metal zirconium is generated in the material, and the improvement of the oxidation resistance is facilitated.)

1. A refractory metal-containing carbon-carbon composite characterized by: the carbon-based composite nano-powder comprises a carbon matrix, a carbon fiber reinforcement distributed in the carbon matrix, metal zirconium-fullerene composite nano-powder distributed in pores inside the carbon matrix, and silicon-rich silicon carbide distributed in the pores inside the carbon matrix.

2. A refractory metal-containing carbon-carbon composite material according to claim 1 wherein: wherein the molar ratio of the metal zirconium-fullerene composite nano powder to the silicon carbide is 1: (5-10).

3. A preparation method of a carbon-carbon composite material containing refractory metals is characterized by comprising the following steps: the method comprises the following steps:

(1) preparing a carbon fiber preform: alternately laminating and needling carbon fiber cloth and a carbon fiber net tire to obtain a prefabricated body; placing the prefabricated body in a carbon source gas for chemical vapor infiltration treatment to obtain a carbon-carbon blank body;

(2) heating the fullerene and the metal zirconium in a vacuum environment, depositing the formed steam on the organic matrix together, and controlling the resistance value of a deposition layer to be not less than 10K omega to obtain a metal zirconium-fullerene composite film; dissolving the organic matrix deposited with the metal zirconium-fullerene composite membrane by using a solvent, and filtering and drying after the organic matrix is completely dissolved to obtain uniform metal zirconium-fullerene composite nano powder;

(3) preparing a precursor: under the protection of dry nitrogen, adding the metal zirconium-fullerene composite nano powder, silicon powder and carbon powder into water, and stirring and reacting for 2-4h at 90-100 ℃ to obtain a precursor;

(4) taking the precursor prepared in the step (2) as an impregnant to impregnate the carbon-carbon blank;

(5) placing the impregnated carbon-carbon blank in a carbonization furnace for carbonization treatment;

(6) repeating the steps (4) to (5) for three to five times to obtain a densified preform;

(7) and (4) heating the densified preform prepared in the step (5) to 1000 ℃ at the speed of 350 ℃/h in 300-350 ℃/h in the argon atmosphere, then heating to 2500 ℃ at the speed of 350 ℃/h in 300-350 ℃/h respectively, and keeping the temperature for 0.5-1h to obtain the carbon-carbon composite material containing the refractory metal.

4. A method of making a refractory metal-containing carbon-carbon composite as claimed in claim 3 wherein: in the step (1), the temperature of the chemical vapor infiltration treatment is 900-1150 ℃, the reaction time is 50-120 h, and the air pressure is 1200-1600 pa; the carbon source gas is methane or propylene.

5. The method of claim 3, wherein the carbon-carbon composite material comprises a refractory metalIn the following steps: in the step (2), the vacuum degree is not more than 5 multiplied by 10^-4Pa; the organic matrix is one of polypropylene film, polyethylene film and polyacrylic acid film.

6. A method of making a refractory metal-containing carbon-carbon composite as claimed in claim 3 wherein: in the step (3), the molar ratio of the metal zirconium-fullerene composite nano powder to the silicon powder to the carbon powder is 1: (20-30): (5-10).

7. A method of making a refractory metal-containing carbon-carbon composite as claimed in claim 3 wherein: in the step (4), the impregnation process is as follows: immersing the carbon-carbon blank into a container with impregnant, and placing the container in a high-pressure impregnation kettle; pumping the kettle cavity to a vacuum state, and then filling pure nitrogen with the pressure of 10-12 MPa; heating from room temperature to 200 ℃ at the speed of 2-3 ℃/min, and keeping the temperature for 1-2 h; then heating to 500 ℃ at the speed of 2-3 ℃/min, and keeping the temperature for 2 h; the pressure in the kettle is maintained at 10-12MPa all the time during the dipping process.

8. A method of making a refractory metal-containing carbon-carbon composite as claimed in claim 3 wherein: in the step (5), the carbonization process comprises the following steps: pumping the furnace chamber to a vacuum state, introducing nitrogen to normal pressure, raising the temperature to 1000 ℃ at the speed of 200 plus materials and 220 ℃/h, keeping the temperature for 2h, and keeping the nitrogen atmosphere in the whole carbonization process.

Technical Field

The invention belongs to the field of new materials, and particularly relates to a carbon-carbon composite material containing refractory metals.

Background

With the increasing demand for high-performance composite materials, carbon fiber reinforced composite materials, particularly carbon/carbon (C/C) composite materials, have excellent high-temperature mechanical properties and stability, low density and low thermal expansion coefficient, and these properties can be maintained at high temperatures above 2000 ℃, and more importantly, the strength of the carbon fiber reinforced composite materials does not decrease or increase with the increase of temperature in high-temperature environments above 1500 ℃, so that the carbon fiber reinforced composite materials become one of the most promising new high-technology materials, and are widely used as ablation materials and thermal structural materials in the technical fields of aviation and aerospace.

However, the C/C composite material has a fatal weakness that carbon starts to be oxidized in an oxygen atmosphere at 370 ℃ and is rapidly oxidized above 500 ℃. The oxidation process of carbon-carbon composites is a non-carbonizing heterogeneous reaction. Like other carbon materials, a series of lattice defects, internal stress generated in the carbonization and graphitization processes and impurities exist in the carbon-carbon composite material, so that active site sites exist in the carbon-carbon composite material. These active site sites readily adsorb oxygen in the air and initiate oxidation reactions to carbon monoxide and carbon dioxide at temperatures above 370 ℃. Even at very low oxygen partial pressure, there is a very long time of day for the Gibbs free energy difference to drive the reaction to proceed rapidly, and the oxidation rate is proportional to the oxygen partial pressure. The mechanical properties of the oxidized C/C composite material are remarkably reduced, which can cause destructive damage to the C/C composite material, and the direct application of the C/C composite material is limited by the consistent weakness.

The oxidation resistance of the carbon-carbon composite material can be divided into an oxidation resistant coating and internal oxidation resistance in terms of methods. Wherein the antioxidant coating aims at modifying the surface of the material, such as preparing various coatings; the internal oxidation resistance focuses on the modification of the interior of the carbon-carbon composite material, including the oxidation resistance modification of carbon fibers and a matrix. The two methods have advantages and disadvantages respectively: the coating method has high oxidation resistance efficiency and simple and convenient process, but has high preparation cost and difficult solution of the interface problem between the coating and the material; the internal oxidation resistance method can effectively improve the oxidation resistance of the material within a certain temperature range, but the process period is long, and the reaction process is not easy to control. Nowadays, people begin to combine the two methods, and adopt a combination method to furthest improve the oxidation resistance of the carbon-carbon composite material according to local conditions.

It is generally believed that the internal oxidation resistance technology of carbon-carbon composite materials can only solve the problem of oxidation resistance below 1000 ℃, and oxidation resistance at higher temperature needs to be combined with other technologies. However, in order to improve the oxidation and ablation resistance of the carbon-carbon composite material, so that the carbon-carbon composite material can normally work under the high-temperature air flow environment, matrix modification is an effective method.

How to further improve the oxidation resistance of the carbon-carbon composite material at high temperature is a problem worthy of research.

Disclosure of Invention

The technical problem is as follows: in order to solve the defects of the prior art, the invention provides a carbon-carbon composite material containing refractory metals.

The technical scheme is as follows: the invention provides a carbon-carbon composite material containing refractory metal, which comprises a carbon matrix, a carbon fiber reinforcement distributed in the carbon matrix, metal zirconium-fullerene composite nano powder distributed in pores inside the carbon matrix, and silicon-rich silicon carbide distributed in the pores inside the carbon matrix.

Wherein the molar ratio of the metal zirconium-fullerene composite nano powder to the silicon carbide is 1: (5-10).

The invention also provides a preparation method of the carbon-carbon composite material containing the refractory metal, which comprises the following steps:

(1) preparing a carbon fiber preform: alternately laminating and needling carbon fiber cloth and a carbon fiber net tire to obtain a prefabricated body; placing the prefabricated body in a carbon source gas for chemical vapor infiltration treatment to obtain a carbon-carbon blank body;

(2) heating the fullerene and the metal zirconium in a vacuum environment, depositing the formed steam on the organic matrix together, and controlling the resistance value of a deposition layer to be not less than 10K omega to obtain a metal zirconium-fullerene composite film; dissolving the organic matrix deposited with the metal zirconium-fullerene composite membrane by using a solvent, and filtering and drying after the organic matrix is completely dissolved to obtain uniform metal zirconium-fullerene composite nano powder;

(3) preparing a precursor: under the protection of dry nitrogen, adding the metal zirconium-fullerene composite nano powder, silicon powder and carbon powder into water, and stirring and reacting for 2-4h at 90-100 ℃ to obtain a precursor;

(4) taking the precursor prepared in the step (2) as an impregnant to impregnate the carbon-carbon blank;

(5) placing the impregnated carbon-carbon blank in a carbonization furnace for carbonization treatment;

(6) repeating the steps (4) to (5) for three to five times to obtain a densified preform;

(7) and (4) heating the densified preform prepared in the step (5) to 1000 ℃ at the speed of 350 ℃/h in 300-350 ℃/h in the argon atmosphere, then heating to 2500 ℃ at the speed of 350 ℃/h in 300-350 ℃/h respectively, and keeping the temperature for 0.5-1h to obtain the carbon-carbon composite material containing the refractory metal.

In the step (1), the temperature of the chemical vapor infiltration treatment is 900-1150 ℃, the reaction time is 50-120 h, and the air pressure is 1200-1600 pa; the carbon source gas is methane or propylene.

In the step (2), the vacuum degree is not more than 5 multiplied by 10^-4Pa; the organic matrix is one of a polypropylene film, a polyethylene film and a polyacrylic acid film;

in the step (3), the molar ratio of the metal zirconium-fullerene composite nano powder to the silicon powder to the carbon powder is 1: (20-30): (5-10).

In the step (4), the impregnation process is as follows: immersing the carbon-carbon blank into a container with impregnant, and placing the container in a high-pressure impregnation kettle; pumping the kettle cavity to a vacuum state, and then filling pure nitrogen with the pressure of 10-12 MPa; heating from room temperature to 200 ℃ at the speed of 2-3 ℃/min, and keeping the temperature for 1-2 h; then heating to 500 ℃ at the speed of 2-3 ℃/min, and keeping the temperature for 2 h; the pressure in the kettle is maintained at 10-12MPa all the time during the dipping process.

In the step (5), the carbonization process comprises the following steps: pumping the furnace chamber to a vacuum state, introducing nitrogen to normal pressure, raising the temperature to 1000 ℃ at the speed of 200 plus materials and 220 ℃/h, keeping the temperature for 2h, and keeping the nitrogen atmosphere in the whole carbonization process.

Has the advantages that: the oxidation-resistant carbon-carbon composite material provided by the invention has the advantages that the metal zirconium-fullerene composite nano powder is introduced into the carbon-carbon composite material through impregnation, the ablation resistance of the composite material can be greatly improved, and the defect can be supplemented through the internal permeation of the material when the internal material has defects due to the introduction of silicon-rich silicon carbide, so that the service life of the composite material is further prolonged; the fullerene is utilized to coat the metal zirconium, so that the defect of the metal zirconium caused by the introduction of the metal zirconium is generated in the material, and the improvement of the oxidation resistance is facilitated.

Drawings

Fig. 1 is a TEM image of a carbon-carbon composite material prepared in example 1.

Detailed Description

The present invention is further explained below.

Example 1

The carbon-carbon composite material containing refractory metal comprises a carbon matrix, a carbon fiber reinforcement distributed in the carbon matrix, metal zirconium-fullerene composite nano powder distributed in pores inside the carbon matrix, and silicon-rich silicon carbide distributed in the pores inside the carbon matrix.

The preparation method comprises the following steps:

(1) preparing a carbon fiber preform: alternately laminating and needling carbon fiber cloth and a carbon fiber net tire to obtain a prefabricated body; placing the prefabricated body in a carbon source gas for chemical vapor infiltration treatment to obtain a carbon-carbon blank body; the temperature of the chemical vapor infiltration treatment is 1000 ℃, the reaction time is 800h, and the air pressure is 1400 pa; the carbon source gas is methane or propylene.

(2) Heating the fullerene and the metal zirconium in a vacuum environment, depositing the formed steam on the organic matrix together, and controlling the resistance value of a deposition layer to be not less than 10K omega to obtain a metal zirconium-fullerene composite film; dissolving the organic matrix deposited with the metal zirconium-fullerene composite membrane by using a solvent, and filtering and drying after the organic matrix is completely dissolved to obtain uniform metal zirconium-fullerene composite nano powder; vacuum degree not greater than 5 × 10^-4Pa; the organic matrix is one of a polypropylene film, a polyethylene film and a polyacrylic acid film;

(3) preparing a precursor: under the protection of dry nitrogen, adding the metal zirconium-fullerene composite nano powder, silicon powder and carbon powder into water, and stirring and reacting for 3 hours at 95 ℃ to obtain a precursor; the molar ratio of the metal zirconium-fullerene composite nano powder to the silicon powder to the carbon powder is 1: 25: 8.

(4) taking the precursor prepared in the step (2) as an impregnant to impregnate the carbon-carbon blank; the impregnation process is as follows: immersing the carbon-carbon blank into a container with impregnant, and placing the container in a high-pressure impregnation kettle; pumping the kettle cavity to a vacuum state, and then filling pure nitrogen with the pressure of 11 MPa; heating from room temperature to 200 deg.C at a speed of 2.5 deg.C/min, and holding for 1.5 h; then heating to 500 ℃ at the speed of 2.5 ℃/min, and keeping the temperature for 2 hours; the pressure in the kettle is always maintained at 11MPa in the dipping process.

(5) Placing the impregnated carbon-carbon blank in a carbonization furnace for carbonization treatment; the carbonization process comprises the following steps: and (3) pumping the furnace chamber to a vacuum state, introducing nitrogen to normal pressure, heating to 1000 ℃ at the speed of 210 ℃/h, keeping the temperature for 2h, and keeping the nitrogen atmosphere in the whole carbonization process.

(6) Repeating the steps (4) to (5) for three to five times to obtain a densified preform;

(7) and (3) heating the densified preform prepared in the step (5) to 1000 ℃ at the speed of 320 ℃/h in the argon atmosphere, then heating to 2500 ℃ at the speed of 320 ℃/h respectively, and keeping the temperature for 0.5-1h to obtain the carbon-carbon composite material containing the refractory metal.

Example 2

The carbon-carbon composite material containing refractory metal comprises a carbon matrix, a carbon fiber reinforcement distributed in the carbon matrix, metal zirconium-fullerene composite nano powder distributed in pores inside the carbon matrix, and silicon-rich silicon carbide distributed in the pores inside the carbon matrix.

The preparation method comprises the following steps:

(1) preparing a carbon fiber preform: alternately laminating and needling carbon fiber cloth and a carbon fiber net tire to obtain a prefabricated body; placing the prefabricated body in a carbon source gas for chemical vapor infiltration treatment to obtain a carbon-carbon blank body; the temperature of the chemical vapor infiltration treatment is 900 ℃, the reaction time is 120h, and the air pressure is 1200 pa; the carbon source gas is methane or propylene.

(2) Heating the fullerene and the metal zirconium in a vacuum environment, depositing the formed steam on the organic matrix together, and controlling the resistance value of a deposition layer to be not less than 10K omega to obtain a metal zirconium-fullerene composite film; dissolving the organic matrix deposited with the metal zirconium-fullerene composite membrane by using a solvent, and filtering and drying after the organic matrix is completely dissolved to obtain uniform metal zirconium-fullerene composite nano powder; vacuum degree not greater than 5 × 10^-4Pa; the organic matrix is one of a polypropylene film, a polyethylene film and a polyacrylic acid film;

(3) preparing a precursor: under the protection of dry nitrogen, adding the metal zirconium-fullerene composite nano powder, silicon powder and carbon powder into water, and stirring and reacting for 4 hours at 90 ℃ to obtain a precursor; the molar ratio of the metal zirconium-fullerene composite nano powder to the silicon powder to the carbon powder is 1: 20: 5.

(4) taking the precursor prepared in the step (2) as an impregnant to impregnate the carbon-carbon blank; the impregnation process is as follows: immersing the carbon-carbon blank into a container with impregnant, and placing the container in a high-pressure impregnation kettle; pumping the kettle cavity to a vacuum state, and then filling pure nitrogen with the pressure of 10 MPa; heating from room temperature to 200 ℃ at the speed of 2 ℃/min, and keeping the temperature for 2 h; then heating to 500 ℃ at the speed of 2 ℃/min, and keeping the temperature for 2 h; the pressure in the kettle is always maintained at 10MPa in the dipping process.

(5) Placing the impregnated carbon-carbon blank in a carbonization furnace for carbonization treatment; the carbonization process comprises the following steps: and (3) pumping the furnace chamber to a vacuum state, introducing nitrogen to normal pressure, heating to 1000 ℃ at the speed of 200 ℃/h, keeping the temperature for 2h, and keeping the nitrogen atmosphere in the whole carbonization process.

(6) Repeating the steps (4) to (5) for three to five times to obtain a densified preform;

(7) and (4) heating the densified preform prepared in the step (5) to 1000 ℃ at the speed of 300 ℃/h in the argon atmosphere, then heating to 2500 ℃ at the speed of 300 ℃/h respectively, and keeping the temperature for 1h to obtain the carbon-carbon composite material containing the refractory metal.

Example 3

The carbon-carbon composite material containing refractory metal comprises a carbon matrix, a carbon fiber reinforcement distributed in the carbon matrix, metal zirconium-fullerene composite nano powder distributed in pores inside the carbon matrix, and silicon-rich silicon carbide distributed in the pores inside the carbon matrix.

The preparation method comprises the following steps:

(1) preparing a carbon fiber preform: alternately laminating and needling carbon fiber cloth and a carbon fiber net tire to obtain a prefabricated body; placing the prefabricated body in a carbon source gas for chemical vapor infiltration treatment to obtain a carbon-carbon blank body; the temperature of the chemical vapor infiltration treatment is 1150 ℃, the reaction time is 50hh, and the air pressure is 1200 pa; the carbon source gas is methane or propylene.

(2) Heating fullerene in vacuum environmentAnd metal zirconium, the formed steam is deposited on the organic substrate together, the resistance value of the deposition layer is controlled to be not less than 10K omega, and the metal zirconium-fullerene composite film is obtained; dissolving the organic matrix deposited with the metal zirconium-fullerene composite membrane by using a solvent, and filtering and drying after the organic matrix is completely dissolved to obtain uniform metal zirconium-fullerene composite nano powder; vacuum degree not greater than 5 × 10^-4Pa; the organic matrix is one of a polypropylene film, a polyethylene film and a polyacrylic acid film;

(3) preparing a precursor: under the protection of dry nitrogen, adding the metal zirconium-fullerene composite nano powder, silicon powder and carbon powder into water, and stirring and reacting for 2 hours at 100 ℃ to obtain a precursor; the molar ratio of the metal zirconium-fullerene composite nano powder to the silicon powder to the carbon powder is 1: 30: 10.

(4) taking the precursor prepared in the step (2) as an impregnant to impregnate the carbon-carbon blank; the impregnation process is as follows: immersing the carbon-carbon blank into a container with impregnant, and placing the container in a high-pressure impregnation kettle; pumping the kettle cavity to a vacuum state, and then filling pure nitrogen with the pressure of 12 MPa; heating from room temperature to 200 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h; then heating to 500 ℃ at the speed of 3 ℃/min, and keeping the temperature for 2 h; the pressure in the kettle is maintained at 12MPa all the time during the dipping process.

(5) Placing the impregnated carbon-carbon blank in a carbonization furnace for carbonization treatment; the carbonization process comprises the following steps: and (3) pumping the furnace chamber to a vacuum state, introducing nitrogen to normal pressure, heating to 1000 ℃ at the speed of 220 ℃/h, keeping the temperature for 2h, and keeping the nitrogen atmosphere in the whole carbonization process.

(6) Repeating the steps (4) to (5) for three to five times to obtain a densified preform;

(7) and (4) heating the densified preform prepared in the step (5) to 1000 ℃ at the speed of 350 ℃/h in the argon atmosphere, then heating to 2500 ℃ at the speed of 350 ℃/h respectively, and keeping the temperature for 0.5h to obtain the carbon-carbon composite material containing the refractory metal.

Experimental example testing of the internal Oxidation resistant carbon-carbon composite Material of examples 1-3

The length, width and height of the carbon-carbon composite material are 10cm multiplied by 8 cm;

(1) placing in a high-temperature vacuum induction furnace for heat treatment at 1000 deg.C, maintaining for 2 hr, naturally cooling, and taking out the test performance;

(2) then placing the mixture in a high-temperature vacuum induction furnace for heat treatment, wherein the treatment temperature is 1500 ℃, preserving the heat for 2 hours, naturally cooling, and taking out the detection performance;

(3) then placing the mixture in a high-temperature vacuum induction furnace for heat treatment, wherein the treatment temperature is 2000 ℃, preserving heat for 2 hours, naturally cooling, and taking out the detection performance;

(4) and then placing the mixture in a high-temperature vacuum induction furnace for heat treatment, wherein the treatment temperature is 3000 ℃, preserving the heat for 2 hours, naturally cooling, and taking out the product for detection.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.