阅读说明：本技术 一种内部抗氧化碳碳复合材料 (Internal oxidation-resistant carbon-carbon composite material ) 是由 吴宝林 侯振华 吴迪 于 2021-08-30 设计创作，主要内容包括：本发明提供一种内部抗氧化碳碳复合材料,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碳包覆的富硅的碳化硅、分布于碳基体内部空隙中的碳包覆的氧化锆、分布于碳基体内部空隙中的磷酸锆和分布于碳基体内部空隙中的氧化铝。本发明还提供了一种内部抗氧化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磷酸锆、氯化锆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。(The invention provides an internal antioxidant carbon-carbon composite material, which comprises a carbon matrix, a carbon fiber reinforcement distributed in the carbon matrix, carbon-coated silicon-rich silicon carbide distributed in pores inside the carbon matrix, carbon-coated zirconium oxide distributed in the pores inside the carbon matrix, zirconium phosphate distributed in the pores inside the carbon matrix and aluminum oxide distributed in the pores inside the carbon matrix. The invention also provides a preparation method of the internal antioxidant carbon-carbon composite material. According to the oxidation-resistant carbon-carbon composite material provided by the invention, zirconium phosphate and zirconium chloride are introduced into the carbon-carbon composite material through impregnation, so that the ablation resistance of the composite material can be greatly improved, and the defect can be compensated 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.)

1. An internal oxidation-resistant carbon-carbon composite material is characterized in that: the carbon-coated silicon-rich carbon fiber reinforced carbon fiber comprises a carbon matrix, a carbon fiber reinforcement distributed in the carbon matrix, carbon-coated silicon-rich silicon carbide distributed in pores inside the carbon matrix, carbon-coated zirconium oxide distributed in the pores inside the carbon matrix, zirconium phosphate distributed in the pores inside the carbon matrix and aluminum oxide distributed in the pores inside the carbon matrix.

2. The internal oxidation-resistant carbon-carbon composite material as claimed in claim 1, wherein: wherein the mol ratio of zirconium phosphate, zirconium oxide, silicon carbide and aluminum oxide is (1-2): 1: (1-2): (0.5-1).

3. A preparation method of an internal antioxidant carbon-carbon composite material 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) preparing a precursor: adding chitosan into water bath under the protection of dry nitrogen, adding zirconium phosphate, zirconium chloride, silicon powder, carbon powder and aluminum oxide, and stirring at 90-100 ℃ for reaction for 2-4h to obtain a precursor;

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

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

(5) repeating the steps (3) to (4) for three to five times to obtain a densified preform;

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

4. The method for preparing the internal oxidation-resistant carbon-carbon composite material according to claim 3, wherein the method comprises the following steps: 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 for preparing the internal oxidation-resistant carbon-carbon composite material according to claim 3, wherein the method comprises the following steps: in the step (2), the mass ratio of the chitosan to the total mass of the zirconium phosphate, the zirconium chloride, the carbon powder and the alumina is (4-5): 1; the molar ratio of the zirconium phosphate to the zirconium chloride to the silicon powder to the carbon powder to the aluminum oxide is (1-2): 1: (6-8): (1-2): (0.5-1).

6. The method for preparing the internal oxidation-resistant carbon-carbon composite material according to claim 3, wherein the method comprises the following steps: in the step (3), 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.

7. The method for preparing the internal oxidation-resistant carbon-carbon composite material according to claim 3, wherein the method comprises the following steps: in the step (4), 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.

8. A precursor for preparing a carbon-carbon composite material is characterized in that: comprises chitosan, zirconium phosphate, zirconium chloride, silicon powder, carbon powder and aluminum oxide; wherein the mass ratio of the chitosan to the total mass of the zirconium phosphate, the zirconium chloride, the carbon powder and the alumina is (4-5): 1; the molar ratio of the zirconium phosphate to the zirconium chloride to the silicon powder to the carbon powder to the aluminum oxide is (1-2): 1: (6-8): (1-2): (0.5-1).

Technical Field

The invention belongs to the field of new materials, and particularly relates to an internal antioxidant carbon-carbon composite material.

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 an internal oxidation-resistant carbon-carbon composite material.

The technical scheme is as follows: the invention provides an internal antioxidant carbon-carbon composite material, which comprises a carbon matrix, a carbon fiber reinforcement distributed in the carbon matrix, carbon-coated silicon-rich silicon carbide distributed in pores inside the carbon matrix, carbon-coated zirconium oxide distributed in the pores inside the carbon matrix, zirconium phosphate distributed in the pores inside the carbon matrix and aluminum oxide distributed in the pores inside the carbon matrix.

Preferably, the molar ratio of zirconium phosphate, zirconium oxide, silicon carbide and aluminum oxide is (1-2): 1: (1-2): (0.5-1).

The invention also provides a preparation method of the internal antioxidant carbon-carbon composite material, 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) preparing a precursor: adding chitosan into water bath under the protection of dry nitrogen, adding zirconium phosphate, zirconium chloride, silicon powder, carbon powder and aluminum oxide, and stirring at 90-100 ℃ for reaction for 2-4h to obtain a precursor;

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

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

(5) repeating the steps (3) to (4) for three to five times to obtain a densified preform;

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

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 mass ratio of the chitosan to the total mass of the zirconium phosphate, the zirconium chloride, the carbon powder and the alumina is (4-5): 1; the molar ratio of the zirconium phosphate to the zirconium chloride to the silicon powder to the carbon powder to the aluminum oxide is (1-2): 1: (6-8): (1-2): (0.5-1).

In the step (3), 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 (4), 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.

The invention also provides a precursor for preparing the carbon-carbon composite material, which comprises chitosan, zirconium phosphate, zirconium chloride, silicon powder, carbon powder and aluminum oxide; wherein the mass ratio of the chitosan to the total mass of the zirconium phosphate, the zirconium chloride, the carbon powder and the alumina is (4-5): 1; the molar ratio of the zirconium phosphate to the zirconium chloride to the silicon powder to the carbon powder to the aluminum oxide is (1-2): 1: (6-8): (1-2): (0.5-1).

Has the advantages that: according to the oxidation-resistant carbon-carbon composite material provided by the invention, zirconium phosphate and zirconium chloride are introduced into the carbon-carbon composite material through impregnation, so that the ablation resistance of the composite material can be greatly improved, and the defect can be compensated 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.

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 internal oxidation-resistant carbon-carbon composite material comprises a carbon matrix, a carbon fiber reinforcement distributed in the carbon matrix, carbon-coated silicon-rich silicon carbide distributed in pores inside the carbon matrix, carbon-coated zirconium oxide distributed in gaps inside the carbon matrix, zirconium phosphate distributed in the gaps inside the carbon matrix and aluminum oxide distributed in the gaps 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 80h, and the air pressure is 1400 pa; the carbon source gas is methane or propylene.

(2) Preparing a precursor: adding chitosan into water bath under the protection of dry nitrogen, adding zirconium phosphate, zirconium chloride, silicon powder, carbon powder and aluminum oxide, and stirring at 95 ℃ for reaction for 3h to obtain a precursor; the mass ratio of the chitosan to the total mass of the zirconium phosphate, the zirconium chloride, the carbon powder and the alumina is 4.5: 1; the molar ratio of the zirconium phosphate to the zirconium chloride to the silicon powder to the carbon powder to the aluminum oxide is 1.5: 1: 7: 1.5: 0.8.

(3) 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.

(4) 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.

(5) Repeating the steps (3) to (4) for three to five times to obtain a densified preform;

(6) and (4) 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 0.8h to obtain the internal antioxidant carbon-carbon composite material.

Example 2

The internal oxidation-resistant carbon-carbon composite material comprises a carbon matrix, a carbon fiber reinforcement distributed in the carbon matrix, carbon-coated silicon-rich silicon carbide distributed in pores inside the carbon matrix, carbon-coated zirconium oxide distributed in gaps inside the carbon matrix, zirconium phosphate distributed in the gaps inside the carbon matrix and aluminum oxide distributed in the gaps 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) Preparing a precursor: adding chitosan into water bath under the protection of dry nitrogen, adding zirconium phosphate, zirconium chloride, silicon powder, carbon powder and aluminum oxide, and stirring at 90 ℃ for reaction for 4h to obtain a precursor; the mass ratio of the chitosan to the total mass of the zirconium phosphate, the zirconium chloride, the carbon powder and the alumina is 4: 1; the molar ratio of the zirconium phosphate to the zirconium chloride to the silicon powder to the carbon powder to the aluminum oxide is 1: 1: 6: 1: 0.5.

(3) 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.

(4) 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.

(5) Repeating the steps (3) to (4) for three to five times to obtain a densified preform;

(6) 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 0.5h to obtain the internal antioxidant carbon-carbon composite material.

Example 3

The internal oxidation-resistant carbon-carbon composite material comprises a carbon matrix, a carbon fiber reinforcement distributed in the carbon matrix, carbon-coated silicon-rich silicon carbide distributed in pores inside the carbon matrix, carbon-coated zirconium oxide distributed in gaps inside the carbon matrix, zirconium phosphate distributed in the gaps inside the carbon matrix and aluminum oxide distributed in the gaps 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 50h, and the air pressure is 1600 pa; the carbon source gas is methane or propylene.

(2) Preparing a precursor: adding chitosan into water bath under the protection of dry nitrogen, adding zirconium phosphate, zirconium chloride, silicon powder, carbon powder and aluminum oxide, and stirring at 100 ℃ for reaction for 2h to obtain a precursor; the mass ratio of the chitosan to the total mass of the zirconium phosphate, the zirconium chloride, the carbon powder and the alumina is 5: 1; the molar ratio of the zirconium phosphate to the zirconium chloride to the silicon powder to the carbon powder to the aluminum oxide is 2: 1: 8: 2: 1.

(3) 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.

(4) 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.

(5) Repeating the steps (3) to (4) for three to five times to obtain a densified preform;

(6) 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 1h to obtain the internal antioxidant carbon-carbon composite material.

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.