CN112457035B - Preparation method of Hf-Ta-C reinforced C/SiC ceramic matrix composite - Google Patents

Preparation method of Hf-Ta-C reinforced C/SiC ceramic matrix composite Download PDF

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CN112457035B
CN112457035B CN202011322696.1A CN202011322696A CN112457035B CN 112457035 B CN112457035 B CN 112457035B CN 202011322696 A CN202011322696 A CN 202011322696A CN 112457035 B CN112457035 B CN 112457035B
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CN112457035A (en
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杨良伟
刘伟
刘俊鹏
于新民
李晓东
宋环君
王鹏
霍鹏飞
金鑫
于艺
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Aerospace Research Institute of Materials and Processing Technology
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Abstract

The invention relates to a preparation method of an Hf-Ta-C reinforced C/SiC ceramic matrix composite, which comprises the following steps: (1) providing a carbon/carbon substrate; (2) preparing the carbon/carbon matrix into the C/SiC ceramic matrix composite by using a silicon alloy as a reactant and adopting a reaction infiltration method; (3) and reacting the hafnium-tantalum precursor solution serving as a reactant with the C/SiC ceramic matrix composite material by adopting a dipping pyrolysis method to prepare the Hf-Ta-C enhanced C/SiC ceramic matrix composite material. The preparation method gives full play to the high efficiency advantage of the reaction infiltration method, and further reduces the porosity and the ablation resistance of the composite material by means of the impregnation pyrolysis method, thereby effectively solving the problem of poor ablation resistance caused by more pores in the C/SiC ceramic matrix composite material.

Description

Preparation method of Hf-Ta-C reinforced C/SiC ceramic matrix composite
Technical Field
The invention relates to the technical field of preparation of ultrahigh-temperature ceramic-based composite materials, in particular to a preparation method of an Hf-Ta-C enhanced C/SiC ceramic-based composite material.
Background
When the aircraft flies at hypersonic speed or subsonic speed in the atmosphere, higher dynamic pressure is formed, which is beneficial to improving the performance of an engine on one hand, and can also generate strong pneumatic heating phenomenon on the other hand, so that the surface of the aircraft is subjected to oxidizing atmosphere ablation and high-speed airflow scouring. In recent years, in order to meet the severe requirements of aircrafts such as hypersonic velocity and subsonic velocity on thermal protection materials in severe thermal environments and improve the oxidation resistance and ablation resistance of the thermal protection materials, ultrahigh temperature ceramic materials (UHTCs) are receiving more and more attention due to the excellent performance. Ultra-high temperature ceramic materials (UHTCs) mainly comprise refractory metal borides, carbides and nitrides, have a melting point of over 3000 ℃ generally, and have a series of advantages of high melting point, high strength, high modulus and the like. Among these, tantalum carbide (TaC) has a melting point of 3890 deg.C, hafnium carbide (HfC) has a melting point of 3928 deg.C, while the Hf-Ta-C solid solution has a melting point of up to 4000 deg.C, which is the highest melting material known at present. The ultrahigh-temperature ceramic material has excellent oxidation resistance and ablation resistance even in a harsh ultrahigh-temperature environment.
The C/SiC ceramic matrix composite is a common high-temperature-resistant ceramic matrix composite and has wide application in the field of aerospace. The catalyst can be prepared by a reaction infiltration method at present, and has the advantages of high efficiency, low cost and the like. However, certain pores exist in the matrix, and in an oxidizing environment, the pores can become a channel for air to permeate into, so that the ablation speed is further accelerated, and the performance is greatly influenced. In order to further improve the oxidation resistance and ablation resistance of the C/SiC ceramic matrix composite material in an extremely harsh environment, the problem of more pores under the existing process conditions needs to be solved.
Disclosure of Invention
Technical problem to be solved
The invention aims to solve the technical problem that a certain pore exists in a matrix of the C/SiC ceramic matrix composite prepared by the traditional reaction infiltration method, and the matrix can become a channel for air to permeate into under an oxidizing environment, so that the ablation speed is further accelerated, and the performance is greatly influenced.
(II) technical scheme
In order to solve the technical problem, the invention provides a preparation method of an Hf-Ta-C reinforced C/SiC ceramic matrix composite, which comprises the following steps:
(1) providing a carbon/carbon substrate;
(2) preparing the carbon/carbon matrix into the C/SiC ceramic matrix composite by using a silicon alloy as a reactant and adopting a reaction infiltration method;
(3) and reacting the hafnium-tantalum precursor solution serving as a reactant with the C/SiC ceramic matrix composite material by adopting a dipping pyrolysis method to prepare the Hf-Ta-C enhanced C/SiC ceramic matrix composite material.
(III) advantageous effects
The technical scheme of the invention has the following advantages:
(1) according to the invention, a carbon/carbon matrix and silicon alloy powder are adopted for reaction infiltration, and the laying area of the silicon alloy powder or the adding thickness of the silicon alloy powder is controlled by changing the placement mode of the carbon/carbon matrix, so that the carbon/carbon matrix is only partially and highly embedded in the silicon alloy powder, the porosity of the C/SiC ceramic matrix composite material can be effectively adjusted to 10-20% from 5-10%, and more hafnium-tantalum precursors can be subsequently impregnated;
(2) according to the invention, after reaction infiltration, a hafnium-tantalum precursor impregnation curing cracking technology is introduced, and the ceramic matrix composite is further filled, so that the obtained Hf-Ta-C enhanced C/SiC ceramic matrix composite has low porosity, and the ablation resistance is improved.
Drawings
The drawings of the present invention are provided for illustrative purposes only, and the scale and size in the drawings are not necessarily consistent with those of actual products.
FIG. 1 is the X-ray diffraction result (XRD) of the C/SiC ceramic matrix composite material of example 1.
FIG. 2 shows the results of porosity and pore size distribution of the C/SiC ceramic matrix composite of example 1.
FIG. 3 shows the results of porosity and pore size distribution of the C/SiC ceramic matrix composite of example 2.
FIG. 4 is the macroscopic results before, during and after oxyacetylene ablation of Hf-Ta-C reinforced C/SiC ceramic matrix composite material in example 1.
FIG. 5 is the macroscopic results before, during and after oxyacetylene ablation of Hf-Ta-C reinforced C/SiC ceramic matrix composite material in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of an Hf-Ta-C reinforced C/SiC ceramic matrix composite, which comprises the following steps:
(1) providing a carbon/carbon substrate;
(2) preparing the carbon/carbon matrix into the C/SiC ceramic matrix composite by using a silicon alloy as a reactant and adopting a reaction infiltration method;
(3) and reacting the hafnium-tantalum precursor solution serving as a reactant with the C/SiC ceramic matrix composite material by adopting a dipping pyrolysis method to prepare the Hf-Ta-C enhanced C/SiC ceramic matrix composite material.
According to some preferred embodiments, in step (1), the carbon/carbon matrix is a carbon fiber reinforced carbon matrix composite prepared by using a carbon fiber preform through a chemical vapor deposition method or other densification method;
preferably, the carbon fiber-reinforced carbon matrix has a density of 1.0 to 1.4g/cm3(ii) a The limited density is 1.0-1.4 g/cm3In order to subsequently make it easier to introduce the silicon alloy into the pores. The inventor finds that the density is too high, the silicon alloy is difficult to be introduced into the carbon/carbon composite material, the content of silicon carbide in the finally obtained composite material is low, and the performance can not meet the requirement; too low a density, silicon alloys are relatively easy to incorporate into carbon/carbon composites, but the alloys may react with the carbon fibers, causing damage to the carbon fibers and resulting composites with poor properties. The density of the carbon/carbon matrix is 1.0-1.4 g/cm3The density is higher the same when the density is changed within the rangeLow, the higher the ceramic content of the final product.
More preferably, the carbon fiber preform is woven by needle punching, stitching or fine weaving.
According to some preferred embodiments, in the step (2), the reaction infiltration method comprises the steps of:
(I) mixing silicon alloy powder with the carbon/carbon matrix in a crucible;
(II) placing the crucible loaded with the silicon alloy powder and the carbon/carbon matrix in a reaction furnace body, sealing, vacuumizing, and introducing inert gas;
(III) heating the reaction device to a first preset temperature, and keeping the temperature until the reaction is finished;
(IV) after the reaction at the first preset temperature is finished, carrying out program control to reduce the temperature to a second preset temperature, stopping introducing the inert gas, and recovering to the atmospheric pressure to obtain the C/SiC ceramic matrix composite material with the porosity of 10-20%.
The reaction infiltration method is characterized in that under the conditions of temperature higher than the melting point of silicon alloy and vacuum, the porous carbon/carbon composite material and silicon alloy powder are subjected to in-situ reaction to obtain the ceramic matrix composite material with high silicon carbide content, and the process parameters can be determined according to specific requirements.
The inventor finds that the porosity of the C/SiC ceramic matrix composite material prepared by the traditional reaction infiltration method is 5-10%, and at the moment, the impregnation efficiency of the subsequent hafnium-tantalum precursor is low, so that the Hf-Ta-C ultrahigh-temperature ceramic formed by pyrolysis is low. The silicon alloy melted at high temperature can enter the whole pores of the carbon/carbon matrix through capillary action, and the porosity is effectively controlled to be 10-20%. By properly improving the porosity of the C/SiC ceramic matrix composite material to 10-20%, the impregnation content of the hafnium-tantalum precursor can be greatly improved, and the Hf-Ta-C ultrahigh-temperature ceramic with higher content can be obtained through pyrolysis, so that the oxidation resistance and ablation resistance can be improved.
According to some preferred embodiments, the silicon alloy powder is a commercially available high purity silicon alloy, purchased from jinan yingfeng silicon products, llc; the grain diameter of the silicon alloy powder is 0.5-10 mu m, and the mass fraction of silicon is 99%;
the mass of the carbon/carbon matrix and the silicon alloy is not particularly required, and it is preferable that the mass ratio of the carbon/carbon matrix to the silicon alloy is 1:3 to 1: 7; the inventor finds that if the addition amount of the silicon alloy powder is too much, the silicon alloy powder is not beneficial to the uniform dispersion of the alloy powder; if the addition amount of the silicon alloy powder is too small, the alloy proportion in the carbon matrix is low, and the uniformity and the performance of the subsequent matrix are greatly influenced. Under the same condition, in the range, the higher the proportion of the silicon alloy powder is, the higher the SiC content in the final product is, the more uniform the matrix distribution is, and the stronger the performance is.
According to some preferred embodiments, the carbon/carbon matrix is placed vertically in a crucible;
the silicon alloy powder is spread in a crucible.
The inventor finds that the carbon/carbon matrix is only partially embedded in the silicon alloy powder in a high degree by changing the placement mode of the carbon/carbon matrix and controlling the tiled area of the silicon alloy or the added thickness of the silicon alloy, so that the porosity of the C/SiC ceramic matrix composite can be effectively adjusted to 10-20% from 5-10%. The porosity of the C/SiC ceramic matrix composite material is reduced due to the fact that the tiled area of the silicon alloy powder is too large or the added thickness is too high, and therefore the tiled area of the silicon alloy powder is preferably 80-120cm2(ii) a And/or
The thickness of the added silicon alloy powder is 1/6-1/3 of the vertical height of the carbon/carbon matrix, and preferably, the thickness of the added silicon alloy powder is 5-20 cm.
According to some preferred embodiments, the inert gas is argon or nitrogen;
the flow rate of the introduced inert gas is 1-1500 sccm.
According to some preferred embodiments, the first preset temperature is 1500 to 1700 ℃ (e.g. 1500 ℃, 1550 ℃, 1600 ℃, 1650 ℃, 1700 ℃), and the constant temperature is kept for 1 to 300 minutes (e.g. 50min, 100min, 150min, 200min, 250min, 300min) at the preset temperature;
the second predetermined temperature is 40-60 deg.C (e.g., 40 deg.C, 42 deg.C, 45 deg.C, 47 deg.C, 50 deg.C, 53 deg.C, 60 deg.C);
the temperature rise rate of the temperature rising to the first preset temperature and the temperature reduction rate of the temperature lowering to the second preset temperature controlled by the program are independently 1-50 ℃/min.
According to some preferred embodiments, in step (3), the impregnation cracking method comprises the steps of:
(I) dipping the C/SiC ceramic matrix composite in a hafnium tantalum precursor solution to ensure that the hafnium tantalum precursor is fully dipped in pores in the C/SiC ceramic matrix composite;
(II) placing the C/SiC ceramic matrix composite material impregnated with the hafnium-tantalum precursor in a reaction furnace body, sealing, vacuumizing, introducing inert gas, and then sequentially carrying out a curing reaction and a cracking reaction;
(III) after the cracking reaction is finished, carrying out program control cooling at the cooling rate of 1-50 ℃/min, cooling to room temperature, stopping introducing inert gas, and recovering to atmospheric pressure;
(IV) repeating steps (I) to (III) at least once.
According to some preferred embodiments, the impregnation is by vacuum impregnation and pressure impregnation;
the soaking time is 30-120min (such as 30min, 50min, 70min, 90min, 110min, 120 min);
the inert gas is argon or nitrogen;
the flow rate of the introduced inert gas is 1-1500 sccm (e.g., 200sccm, 500sccm, 700sccm, 900sccm, 1100sccm, 1300sccm, 1500 sccm).
The hafnium-tantalum precursor is an inorganic high molecular polymer constructed by taking hafnium and tantalum elements as main components, for example, a tantalum-carbon complex phase coordination polymer formed by cohydrolysis of hafnate and tantalate; the Hf-Ta-C ceramic material can be obtained by heat treatment at the temperature of 1500-1700 ℃ under the protection of nitrogen. The inorganic high molecular polymer can be dispersed in a certain solvent and has the characteristic of a high molecular solution. The hafnium tantalum precursor solution may have a solid content of 50-70%.
According to some preferred embodiments, the temperature of the curing reaction is 100-200 ℃, and the time of the curing reaction is 1-3 h;
the cracking reaction is carried out according to the following steps: under an inert atmosphere, raising the temperature of the cured composite material to 1200-1500 ℃ at a heating rate of 1-50 ℃/min, and then keeping the temperature for 1-300 min; raising the temperature to 1500-1700 ℃ at the heating rate of 1-50 ℃/min, and then reacting at the temperature for 1-240 min;
the inert atmosphere is argon or nitrogen.
According to some preferred embodiments, steps (I) to (III) are repeated until the density of the produced composite material changes by less than 1% from the density of the produced composite material before the present repetition.
Example 1
(1) Providing a carbon/carbon matrix: providing a density of 1.2g/cm3The carbon/carbon matrix is prepared by carrying out carbon matrix deposition on the carbon fiber preform with the needle structure by adopting a chemical vapor deposition method.
(2) And (3) reaction infiltration treatment: vertically placing the carbon/carbon matrix in a graphite crucible, mixing the carbon/carbon matrix with silicon alloy powder according to the mass ratio of 1:3, flatly paving the silicon alloy powder in the crucible, wherein the flat area is 100cm2The height of the silicon alloy powder is 1/6 of a carbon/carbon matrix, wherein the particle size of the silicon alloy powder is 3 mu m, and the mass fraction of silicon is 99 percent. Placing the crucible in a high-temperature furnace body, vacuumizing, introducing argon gas with the flow rate of 1000sccm, heating to 1600 ℃ at the heating rate of 10 ℃/min, preserving the heat for 120min, then cooling to 50 ℃ at the cooling rate of 10 ℃/min, stopping introducing the inert gas, and recovering to the atmospheric pressure to obtain the C/SiC ceramic matrix composite, wherein the XRD result is shown in figure 1, the porosity is 15.67%, the pore size distribution is shown in figure 2, and the total pore volume (54964.41 psia): 0.0933mL/g, total pore area (54964.41 psia): 3.3312m2(iv)/g, median pore diameter (calculated by volume, 3.70psia, 0.047 mL/g): 48943.51nm, median pore diameter (calculated as area, 24157.35psia, 1.666 m)2(iv)/g): 7.49nm, mean pore diameter (4V/A): 111.95nm, true density (0.55 psia): 1.6802g/mL, apparent density (54964.41 psia): 1.9924 g/mL.
(3) Dipping, curing and cracking treatment: melting the reacted meltPutting the C/SiC ceramic matrix composite material obtained by infiltration treatment into a container filled with a hafnium-tantalum precursor solution (with the solid content of 55 percent), carrying out vacuum impregnation and pressurized impregnation, wherein the impregnation time is 30min, then putting the C/SiC ceramic matrix composite material impregnated with the hafnium-tantalum precursor into a reaction furnace body, sealing, vacuumizing, introducing argon gas, having the flow of 1000sccm, carrying out curing treatment at 200 ℃ for 2h, then raising the temperature to 1200 ℃ at the heating rate of 10 ℃/min, and then keeping the temperature at the temperature for 300 min; heating to 1700 ℃ at the heating rate of 10 ℃/min, reacting at the temperature for 240 min, cooling to room temperature at the cooling rate of 10 ℃/min after the reaction is finished, stopping introducing the inert gas, and returning to the atmospheric pressure. Repeating the above dipping-curing-cracking process for 3 times to obtain the final product with a density of 2.47g/cm3The Hf-Ta-C reinforced C/SiC ceramic matrix composite.
(4) And (3) ablation resistance test: carrying out oxyacetylene ablation test on the obtained Hf-Ta-C reinforced C/SiC ceramic matrix composite material, wherein the specific conditions are shown in Table 1:
TABLE 1 Process conditions for oxyacetylene ablation testing
Figure BDA0002793430940000081
The macro-photographs before, after and after the oxyacetylene ablation are shown in fig. 4. As can be seen from the figure, the thickness direction is slightly thickened after ablation, and the residual metal in the sample is melted and seeped out of the surface at high temperature to form SiO with a certain thickness on the surface2The oxide layer, plus the Hf-Ta-C layer, showed some increase in thickness, but the final mass ablation rate was only 0.00025g/s due to the ultra high temperature oxidation resistance of the Hf-Ta-C component, as detailed in Table 2.
TABLE 2 ablation resistance of Hf-Ta-C reinforced C/SiC ceramic matrix composites
Figure BDA0002793430940000091
Example 2
(1) Providing carbon/carbon radicalsBody: providing a density of 1.3g/cm3The carbon/carbon matrix is prepared by carrying out carbon matrix deposition on the carbon fiber preform with the needle structure by adopting a chemical vapor deposition method.
(2) And (3) reaction infiltration treatment: vertically placing the carbon/carbon matrix in a graphite crucible, mixing the carbon/carbon matrix with silicon alloy powder according to the mass ratio of 1:3, flatly paving the silicon alloy powder in the crucible, wherein the flat area is 100cm2The height of the silicon alloy powder is 1/4 of a carbon/carbon matrix, wherein the particle size of the silicon alloy powder is 3 mu m, and the mass fraction of silicon is 99 percent. Placing the crucible in a high-temperature furnace body, vacuumizing, introducing argon gas with the flow rate of 1000sccm, heating to 1600 ℃ at the heating rate of 10 ℃/min, preserving the heat for 120min, then cooling to 50 ℃ at the cooling rate of 10 ℃/min, stopping introducing the inert gas, and recovering to the atmospheric pressure to obtain the C/SiC ceramic matrix composite material, wherein the porosity is 13.85%, the pore diameter distribution is shown in figure 3, and the total pore volume (54965.64 psia): 0.0792mL/g, total pore area (54965.64 psia): 5.924m2(iv)/g, median pore diameter (by volume, 12.04psia, 0.040 mL/g): 15016.18nm, median pore diameter (calculated as area, 38070.45psia, 2.962 m)2(iv)/g): 4.75nm, mean pore diameter (4V/A): 53.49nm, true density (0.55 psia): 1.7481g/mL, apparent density (54965.64 psia): 2.0291 g/mL.
(3) Dipping, curing and cracking treatment: placing the C/SiC ceramic matrix composite material obtained through the reaction infiltration treatment in a container filled with a hafnium-tantalum precursor solution (with the solid content of 50%), carrying out vacuum impregnation and pressurized impregnation, wherein the impregnation time is 30min, then placing the C/SiC ceramic matrix composite material impregnated with the hafnium-tantalum precursor in a reaction furnace, sealing, vacuumizing, introducing argon gas, wherein the flow rate is 1000sccm, curing at 200 ℃ for 2h, then increasing the temperature to 1200 ℃ at the heating rate of 10 ℃/min, and then keeping the temperature at the temperature for 300 min; heating to 1700 ℃ at a heating rate of 10 ℃/min, reacting at the temperature for 240 min, cooling to room temperature at a cooling rate of 10 ℃/min after the reaction is finished, stopping introducing inert gas, recovering to atmospheric pressure, repeating the impregnation-solidification-cracking process for 3 times, and finally preparing the product with the density of 2.45g/cm3Hf-Ta-C reinforced C/SiC ceramic matrix compositeAnd (5) feeding.
(4) And (3) ablation resistance test: carrying out oxyacetylene ablation test on the obtained Hf-Ta-C reinforced C/SiC ceramic matrix composite material, wherein the specific conditions are shown in Table 3:
TABLE 3 Process conditions for oxyacetylene ablation test
Figure BDA0002793430940000101
The macro-photograph before, during and after the oxyacetylene ablation is shown in fig. 5, and it can be seen from the figure that compared with example 1, the porosity of the obtained C/SiC ceramic matrix composite material after infiltration is 13.85%, and the lower porosity enables the subsequent impregnation content of the hafnium-tantalum precursor to be reduced, which finally results in the reduction of the Hf-Ta-C content. As can be seen from the results, the thickness direction after ablation is slightly increased, because the residual metal in the sample is melted and seeped out of the surface at high temperature to form SiO with a certain thickness on the surface2The oxide layer, together with the Hf-Ta-C composition, showed some increase in thickness, but the lower proportion of Hf-Ta-C composition than that of example 1 resulted in a decrease in ablation resistance and a final mass ablation rate of 0.00030g/s, as specified in Table 4.
TABLE 4 ablation resistance of Hf-Ta-C reinforced C/SiC ceramic matrix composites
Figure BDA0002793430940000111
Example 3
This example 3 is substantially the same as example 2 except that: the density of the carbon/carbon matrix was 1.2g/cm3The mass ratio of the carbon/carbon matrix to the silicon alloy powder is 1:4, the height of the silicon alloy powder is 1/3 of the carbon/carbon matrix, and the porosity of the obtained C/SiC ceramic matrix composite material is 13.45%.
The final density of the prepared product is 2.38g/cm3The Hf-Ta-C reinforced C/SiC ceramic matrix composite of (1) is shown in Table 5.
Example 4
This example 4 is substantially the same as example 2 except that: the height of the silicon alloy powder is 1/3 of the carbon/carbon matrix, and the porosity of the obtained C/SiC ceramic matrix composite material is 12.91 percent.
The final density of the prepared product is 2.33g/cm3The Hf-Ta-C reinforced C/SiC ceramic matrix composite of (1) is shown in Table 5.
Example 5
This example 5 is substantially the same as example 2 except that: the mass ratio of the carbon/carbon matrix to the silicon alloy powder is 1:4, the height of the silicon alloy powder is 1/3 of the carbon/carbon matrix, and the porosity of the obtained C/SiC ceramic matrix composite material is 12.26%.
The final density of the prepared product is 2.29g/cm3The Hf-Ta-C reinforced C/SiC ceramic matrix composite of (1) is shown in Table 5.
Example 6
This example 6 is substantially the same as example 2 except that: the density of the carbon/carbon matrix was 1.4g/cm3The mass ratio of the carbon/carbon matrix to the silicon alloy powder is 1:5, and the tiled area of the silicon alloy powder is 120cm2The height of the silicon alloy powder is 1/2 of a carbon/carbon matrix, and the porosity of the obtained C/SiC ceramic matrix composite material is 11.20%.
The final density of the prepared product is 2.24g/cm3The Hf-Ta-C reinforced C/SiC ceramic matrix composite of (1) is shown in Table 5.
Example 7
This embodiment 7 is substantially the same as embodiment 2 except that: the density of the carbon/carbon matrix was 1.4g/cm3The mass ratio of the carbon/carbon matrix to the silicon alloy powder is 1:7, and the tiled area of the silicon alloy powder is 140cm2The silicon alloy powder fully embeds the carbon/carbon matrix to obtain the C/SiC ceramic matrix composite material, and the porosity of the C/SiC ceramic matrix composite material is 5.82%.
The final density of the prepared product is 2.09g/cm3The Hf-Ta-C reinforced C/SiC ceramic matrix composite of (1) is shown in Table 5.
TABLE 5 Process conditions of the examples and properties of the prepared Hf-Ta-C reinforced C/SiC ceramic matrix composite
Figure BDA0002793430940000121
Figure BDA0002793430940000131
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.

Claims (9)

1. A preparation method of an Hf-Ta-C reinforced C/SiC ceramic matrix composite is characterized by comprising the following steps:
(1) providing a carbon/carbon substrate;
(2) preparing the carbon/carbon matrix into a C/SiC ceramic matrix composite material with the porosity of 10-20% by using a silicon alloy as a reactant and adopting a reaction infiltration method;
(3) taking a hafnium-tantalum precursor solution as a reactant, and reacting with the C/SiC ceramic matrix composite material by adopting a dipping pyrolysis method to prepare the Hf-Ta-C enhanced C/SiC ceramic matrix composite material;
in the step (1), the carbon/carbon matrix is a carbon fiber reinforced carbon matrix composite material prepared by a chemical vapor deposition method by utilizing a carbon fiber preform;
the carbon fiber reinforced carbon matrix composite material has a density of 1.0-1.35 g/cm3；
In step (2), mixing silicon alloy powder with the carbon/carbon matrix in a crucible;
the carbon/carbon matrix is vertically placed in a crucible;
the silicon alloy powder is flatly paved in a crucible;
the silicon alloy powder is flatThe area of the paving is 80-120cm2；
The mass ratio of the carbon/carbon matrix to the silicon alloy is 1:3-1: 7;
the thickness of the added silicon alloy powder is 1/6-1/3 of the vertical height of the carbon/carbon matrix, and the thickness of the added silicon alloy powder is 5-20 cm;
the particle size of the silicon alloy powder is 0.5-3 mu m, and the mass fraction of silicon is 99%.
2. The method of claim 1, wherein:
the weaving mode of the carbon fiber preform is needling, sewing or fine weaving and puncturing.
3. The method of claim 1, wherein:
in the step (2), after the silicon alloy powder and the carbon/carbon matrix are mixed in the crucible, the reaction infiltration method further includes the steps of:
(I) placing the crucible loaded with the silicon alloy powder and the carbon/carbon matrix in a reaction furnace body, sealing, vacuumizing, and introducing inert gas;
(II) heating the reaction device to a first preset temperature, and keeping the temperature until the reaction is finished;
(III) after the reaction at the first preset temperature is finished, carrying out program control to reduce the temperature to a second preset temperature, stopping introducing the inert gas, and recovering to the atmospheric pressure to obtain the C/SiC ceramic matrix composite material with the porosity of 10-20%.
4. The production method according to claim 3, characterized in that:
the inert gas is argon or nitrogen;
the flow rate of the introduced inert gas is 1-1500 sccm.
5. The production method according to any one of claims 3 to 4, characterized in that:
the first preset temperature is 1500-1700 ℃, and the constant temperature is kept for 1-300 minutes at the preset temperature;
the second preset temperature is 40-60 ℃;
the temperature rise rate of the temperature rising to the first preset temperature and the temperature reduction rate of the temperature lowering to the second preset temperature controlled by the program are independently 1-50 ℃/min.
6. The method of claim 1, wherein:
in the step (3), the impregnation cracking method comprises the following steps:
(I) dipping the C/SiC ceramic matrix composite in a hafnium-tantalum precursor solution;
(II) placing the C/SiC ceramic matrix composite material impregnated with the hafnium-tantalum precursor in a reaction furnace body, sealing, vacuumizing, introducing inert gas, and then sequentially carrying out a curing reaction and a cracking reaction;
(III) after the cracking reaction is finished, carrying out program control cooling at the cooling rate of 1-50 ℃/min, cooling to room temperature, stopping introducing inert gas, and recovering to atmospheric pressure;
(IV) repeating steps (I) to (III) at least once.
7. The method of claim 6, wherein:
the impregnation mode is vacuum impregnation and pressure impregnation;
the dipping time is 30-120 min;
the inert gas is argon or nitrogen;
the flow rate of the introduced inert gas is 1-1500 sccm.
8. The method of claim 6, wherein:
the temperature of the curing reaction is 100-200 ℃, and the time of the curing reaction is 1-3 h;
the cracking reaction is carried out according to the following steps: under an inert atmosphere, raising the temperature of the cured composite material to 1200-1500 ℃ at a heating rate of 1-50 ℃/min, and then keeping the temperature for 1-300 min; raising the temperature to 1500-1700 ℃ at the heating rate of 1-50 ℃/min, and then reacting at the temperature for 1-240 min;
the inert atmosphere is nitrogen or argon.
9. The production method according to any one of claims 6 to 8, characterized in that:
repeating steps (I) through (III) until the density of the composite material produced changes by less than 1% from the density of the composite material produced prior to the repetition.
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