Method for manufacturing carbon fiber reinforced ceramic matrix composite, carbon fiber reinforced ceramic matrix composite and use

Abstract

The present application relates to the technical field of carbon fiber composite material, and discloses a method for preparing carbon fiber reinforced ceramic matrix composite material, carbon fiber reinforced ceramic matrix composite material and application.The method comprises the following steps: first impregnation of carbon fiber braided body in a silicone polymer dispersion liquid, first solidification, second impregnation in a ceramic precursor solution, second solidification, and heat treatment of the product to obtain carbon fiber reinforced ceramic matrix composite material; the difference AW between the mass W1 of the carbon fiber braided body and the mass W2 of the carbon fiber reinforced ceramic matrix composite material is not more than 1wt% of W1; the silicone polymer dispersion liquid contains silicone polymer and inorganic particles selected from silicon carbide and / or boron carbide; and the ceramic precursor solution contains a composite precursor of polysilazane and polysiloxane.The method adds inorganic particles in the silicone polymer dispersion liquid, and uses a low-viscosity ceramic precursor solution for impregnation, so that the prepared composite material has high density and high yield of ceramic material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of carbon fiber composite materials, in particular to a method for preparing carbon fiber reinforced ceramic matrix composite material, carbon fiber reinforced ceramic matrix composite material and application. BACKGROUND

[0002] With the rapid development of modern science and technology, the temperature resistance of materials is becoming more and more demanding, and the materials are required to serve effectively in super-high temperature environment for a long time.

[0003] The ceramic matrix composite material has important application value in aerospace and nuclear industry due to its high temperature resistance and oxidation resistance. However, the high temperature ceramic material is a brittle material, and its impact resistance is poor, so it needs to be toughened by continuous fibers, and the continuous fiber reinforced super-high temperature ceramic composite material obtained after compounding not only has high temperature resistance and ablation resistance, but also has high overall strength and good fracture toughness.

[0004] Carbon fiber is the only fiber material that still has high specific strength, specific modulus and low thermal expansion coefficient above 3000℃ (non-oxygen environment), and carbon fiber can also be easily formed into a preform by winding, weaving, needling and other methods, especially for manufacturing large components with complex shape. The oxidation resistance will directly affect the service performance in high temperature environment, and the carbon fiber reinforced ceramic material prepared by the prior art has low density, poor oxidation resistance. SUMMARY

[0005] The purpose of the present application is to overcome the problems of low material density, small temperature resistance width and poor oxidation resistance in the prior art, and to provide a method for preparing carbon fiber reinforced ceramic matrix composite material, carbon fiber reinforced ceramic matrix composite material and application. The method improves the surface density of the prepared carbon fiber reinforced ceramic matrix composite material by multiple impregnation and adding inorganic particles in the silicone polymer dispersion, and at the same time has strong oxidation resistance, mechanical properties and large temperature resistance width.

[0006] In order to achieve the above purpose, the first aspect of the present application provides a method for preparing carbon fiber reinforced ceramic matrix composite material, characterized in that the method comprises the following steps:

[0007] S1, impregnating a carbon fiber woven body in a silicone polymer dispersion to obtain a carbon fiber preform attached with silicone polymer dispersion, and performing first curing to obtain an initial carbon fiber blank;

[0008] S2, second impregnating the initial carbon fiber blank in a ceramic precursor solution to obtain an initial carbon fiber blank attached with the ceramic precursor solution, and performing second curing to obtain a carbon fiber blank;

[0009] S3, heat treating the carbon fiber blank to obtain a carbon fiber reinforced ceramic matrix composite material;

[0010] The difference AW between the mass W1 of the carbon fiber braided body and the mass W2 of the carbon fiber reinforced ceramic matrix composite material is not greater than 1 wt% of W1.

[0011] The organic silicon polymer dispersion liquid contains an organic silicon polymer and inorganic particles selected from silicon carbide and / or boron carbide.

[0012] The ceramic precursor solution contains a composite precursor of polysilazane A and polysiloxane A.

[0013] The second aspect of the present application provides a carbon fiber reinforced ceramic matrix composite material, which is prepared by the method provided in the first aspect of the present application.

[0014] The third aspect of the present application provides an application of the carbon fiber reinforced ceramic matrix composite material provided in the second aspect of the present application in at least one of the fields of aerospace, nuclear industry and construction.

[0015] Through the above technical solution, the method for preparing the carbon fiber reinforced ceramic matrix composite material, the carbon fiber reinforced ceramic matrix composite material and the application provided in the present application have the following beneficial effects:

[0016] 1. The high-temperature ceramic matrix is obtained by using the precursor pyrolysis method, which has a low cost compared with the powder sintering and chemical vapor deposition methods;

[0017] 2. By adding inorganic particles to the organic silicon polymer dispersion liquid, the ceramic yield of the subsequent ceramic precursor solution can be improved.

[0018] 3. The ceramic precursor solution containing the composite precursor with low viscosity is used for secondary impregnation, which avoids the problem of large surface pore of the composite material and improves the density of the carbon fiber reinforced ceramic matrix composite material. DETAILED DESCRIPTION

[0019] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values should be interpreted as approximately between the stated values and within the range. For values which are less than one, ranges falling below the lower limit of the stated values should be interpreted as approximately equal to the lower limit. Similarly, for values which are greater than one, ranges falling above the upper limit of the stated values should be interpreted as approximately equal to the upper limit. Ranges can be expressed herein with endpoints interpreted broadly, and include endpoints and any value or range of values within the stated range, unless otherwise indicated. Although the above description has been made with reference to particular embodiments, it is to be appreciated that various alterations, modifications and improvements will occur to those skilled in the art upon reading and understanding the detailed description. It is intended to embrace all such alterations, modifications and improvements in a broad aspect of the present application. In addition, where a description of a technology uses terms like "comprising", "having", "including" or "carrying" or variations thereof no requirements exist for any particular technology to more than the claims. The terms "comprising", "having", "including" or "carrying" or variations thereof as used herein are to be construed as specifying the presence of what follows the term rather than reciting means plus function, but exclude any other, additional, and / or other elements. It is intended to embrace all such alterations, modifications, and improvements in a broad aspect of the present application. In addition, where a description of a technology uses terms like "comprising", "having", "including" or "carrying" or variations thereof no requirements exist for any particular technology to more than the claims. The terms "comprising", "having", "including" or "carrying" or variations thereof as used herein are to be construed as specifying the presence of what follows the term rather than reciting means plus function, but exclude any other, additional, and / or other elements.

[0020] The first aspect of the present application provides a method for preparing a carbon fiber reinforced ceramic matrix composite material, which comprises the following steps:

[0021] S1, a carbon fiber braided body is subjected to first impregnation in a silicone polymer dispersion liquid to obtain a carbon fiber preform to which the silicone polymer dispersion liquid is attached, and the carbon fiber preform is subjected to first curing to obtain an initial carbon fiber blank;

[0022] S2, the initial carbon fiber blank is subjected to second impregnation in a ceramic precursor solution to obtain an initial carbon fiber blank to which the ceramic precursor solution is attached, and the initial carbon fiber blank is subjected to second curing to obtain a carbon fiber blank;

[0023] S3, the carbon fiber blank is subjected to heat treatment to obtain a carbon fiber reinforced ceramic matrix composite material;

[0024] wherein the difference AW between the mass W1 of the carbon fiber braided body and the mass W2 of the carbon fiber reinforced ceramic matrix composite material is not greater than 1wt% of W1;

[0025] wherein the silicone polymer dispersion liquid contains a silicone polymer and inorganic particles selected from silicon carbide and / or boron carbide;

[0026] The ceramic precursor solution contains a composite precursor of polysilazane A and polysiloxane A.

[0027] In the present application, the method improves the bonding force of the ceramic material and the carbon fiber by multiple impregnation and by adding inorganic particles in the silicone polymer dispersion liquid, and the surface density of the carbon fiber reinforced ceramic matrix composite material prepared is large, and the carbon fiber reinforced ceramic matrix composite material has strong oxidation resistance and mechanical properties.

[0028] Further, the heat treatment cracks the composite precursor in the ceramic precursor solution, and compared with powder sintering and chemical vapor deposition, the sintering temperature is low (not greater than 1200℃), and the cost is low.

[0029] According to the present application, the ratio of the total mass of the silicone polymer and the inorganic particles to the mass of the composite precursor is 1-10:2-15.

[0030] In the present application, the ratio of the total mass of the silicone polymer and the inorganic particles to the mass of the composite precursor meets the above range, which can improve the efficiency of multiple impregnation and further improve the density of the composite material.

[0031] According to the present application, in the ceramic precursor solution, the mass ratio of the polysilazane A to the polysiloxane A is 5:(0.1-5).

[0032] In the present application, the mass ratio of polysilazane A and polysiloxane A in the ceramic precursor solution meets the above range, which is beneficial to the molding of carbon fiber reinforced ceramic matrix composite, and improves the ceramic yield of the ceramic precursor, and further improves the high-temperature resistance and oxidation resistance of the carbon fiber reinforced ceramic matrix composite.

[0033] According to the present application, the mass ratio of polysilazane A and polysiloxane A in the ceramic precursor solution is 5: (1-5).

[0034] According to the present application, the mass ratio of the organic silicon polymer and the inorganic particles is 1: (0.1-0.5).

[0035] In the present application, the mass ratio of the organic silicon polymer and the inorganic particles meets the above range, which can make the viscosity of the organic silicon polymer dispersion suitable, and improve the mechanical properties and density of the carbon fiber reinforced ceramic matrix composite.

[0036] Further, the mass ratio of the organic silicon polymer and the inorganic particles is 1: (0.2-0.5).

[0037] According to the present application, the particle size of silicon carbide is 10-100 microns.

[0038] According to the present application, the particle size of boron carbide is 10-100 microns.

[0039] In the present application, the particle size of silicon carbide and boron carbide respectively meets the above range, which can be uniformly dispersed in the organic silicon polymer dispersion, and further improve the impregnation efficiency.

[0040] According to the present application, the organic silicon polymer is selected from polysiloxane B and / or polysilazane B.

[0041] In the present application, the organic silicon polymer selected from polysiloxane B and / or polysilazane B can make the prepared composite material have higher mechanical properties, high-temperature resistance and oxidation resistance.

[0042] According to the present application, the viscosity of the organic silicon polymer dispersion is 100-600 mPa·s.

[0043] According to the present application, the viscosity of the ceramic precursor solution is 10-100 mPa·s.

[0044] In the present application, when the viscosity of the organic silicon polymer dispersion and the ceramic precursor solution meets the above range, the toughness and density of the carbon fiber reinforced ceramic matrix composite can be further improved.

[0045] Further, the viscosity of the organic silicon polymer dispersion is 200-500 mPa·s.

[0046] Further, the viscosity of the ceramic precursor solution is 10-50 mPa·s.

[0047] According to the present application, the number average molecular weight of the polysilazane A, the polysilazane B, the polysiloxane A and the polysiloxane B is independently 1000-8000 g / mol.

[0048] Further, the number average molecular weight of the polysilazane A and polysilazane B is independently 1000-6000 g / mol.

[0049] Further, the number average molecular weight of the polysilazane A is 1000-5000 g / mol, and the number average molecular weight of the polysilazane B is 4000-8000 g / mol.

[0050] According to the present application, the method further comprises degumming the carbon fiber braid before step S1.

[0051] Further, the degumming conditions include: temperature 50-100℃, time 1-2h.

[0052] According to the present application, the first impregnation conditions include: temperature 50-150℃, relative pressure 0.1-0.5 MPa, time 1-2h.

[0053] In the present application, the first impregnation conditions meet the above range, which can improve the density of the composite material.

[0054] According to the present application, the first impregnation conditions include: temperature 100-120℃, relative pressure 0.1-0.3 MPa, time 1-1.5h.

[0055] According to the present application, the second impregnation conditions include: temperature 50-150℃, relative pressure 0.1-0.5 MPa, time 1-2h.

[0056] In the present application, the second impregnation conditions meet the above range, which can further improve the density of the composite material.

[0057] According to the present application, the second impregnation conditions include: temperature 100-120℃, relative pressure 0.1-0.3 MPa, time 1-1.5h.

[0058] According to the present application, the method further comprises reducing the pressure to normal pressure after the second impregnation.

[0059] According to the present application, the first curing conditions include: temperature 150-300℃, time 2-4h.

[0060] Further, the conditions of the first curing include: temperature of 160-200℃, time of 3-4h.

[0061] According to the present application, the conditions of the second curing include: temperature of 150-300℃, time of 2-4h.

[0062] Further, the conditions of the second curing include: temperature of 160-200℃, time of 3-4h.

[0063] According to the present application, before the second curing, the initial carbon fiber blank with the ceramic precursor solution attached is subjected to a third impregnation.

[0064] In the present application, the third impregnation before the second curing can further improve the density of the obtained carbon fiber reinforced ceramic matrix composite material.

[0065] According to the present application, the conditions of the third impregnation include: temperature of 50-150℃, relative pressure of 0.1-0.5MPa, time of 1-2h.

[0066] Further, the conditions of the third impregnation include: temperature of 100-120℃, relative pressure of 0.1-0.3MPa, time of 1-1.5h.

[0067] According to the present application, the conditions of the heat treatment include: in the presence of a protective gas, at 800-1300℃, under a relative pressure of 0.1-0.5MPa, for 1-2h.

[0068] In the present application, the conditions of the heat treatment meet the above range, so that the prepared carbon fiber reinforced ceramic matrix composite material can meet the requirements of different fields and has good oxidation resistance.

[0069] Further, the conditions of the heat treatment include: in the presence of a protective gas, at 1000-1300℃, under a relative pressure of 0.1-0.3MPa, for 1-1.5h.

[0070] In the present application, the type of the protective gas is not particularly limited, for example, it can be nitrogen or inert gas.

[0071] The second aspect of the present application provides a carbon fiber reinforced ceramic matrix composite material, characterized in that the carbon fiber reinforced ceramic matrix composite material is prepared by the method provided in the first aspect of the present application.

[0072] According to the present application, the surface density of the composite material is not less than 1.5g / cm 3 , and the weight loss rate at 1000℃ is not more than 2wt%.

[0073] In the present application, the weight loss rate of the composite material is tested by thermal gravimetric analysis in oxygen environment, and the smaller the weight loss rate of the composite material is, the greater the oxidation resistance is.

[0074] According to the present application, the composite material contains 50-80wt% of carbon fibers and 20-50wt% of ceramic material.

[0075] Further, the composite material contains 65-80wt% of carbon fibers and 20-35wt% of ceramic material.

[0076] In the present application, the ceramic material contains component A and optional component B.

[0077] In the present application, the component A contains Si3N4, SiC and SiO2, and the component B contains B4C.

[0078] The third aspect of the present application provides an application of the carbon fiber reinforced ceramic matrix composite material provided in the second aspect of the present application in at least one of aerospace, nuclear industry and construction field.

[0079] The present application will be described in detail through examples below. In the following examples,

[0080] The surface density of the composite material is measured by densitometer method;

[0081] The weight loss rate is measured by thermal gravimetric analysis method, and the test temperature is 25-1000℃, and the test atmosphere is nitrogen;

[0082] The high temperature resistance is measured by thermal gravimetric analysis method, and the test atmosphere is nitrogen, and when the weight loss rate of the composite material is greater than 10wt% during the test, it is considered that the composite material does not have high temperature resistance;

[0083] The bending strength is measured by bending mechanics method;

[0084] The fracture toughness is measured by bending mechanics method.

[0085] Example 1

[0086] S1, the carbon fiber preform is degummed at 80℃ under a relative pressure of 0.1MPa for 1h to obtain a degummed carbon fiber braided body;

[0087] The degummed carbon fiber braided body is placed into an impregnation tank, and a polysilazane dispersion liquid containing boron carbide is used to impregnate the carbon fiber preform at a relative pressure of 0.1MPa and 80℃ for 1h to obtain a carbon fiber preform attached with a silicone polymer dispersion liquid, and the carbon fiber preform is solidified at 150℃ for 4h to obtain an initial carbon fiber blank;

[0088] S2, the initial carbon fiber blank is immersed in the ceramic precursor solution for 1 h at a relative pressure of 0.1 MPa and a temperature of 80°C, then nitrogen is introduced to bring the system pressure to normal pressure, to obtain an initial carbon fiber blank with ceramic precursor solution attached, which is immersed in the ceramic precursor solution for 5 min at 80°C, and then is subjected to a second curing at 150°C for 6 h, to obtain a carbon fiber blank;

[0089] S3, the carbon fiber blank is subjected to heat treatment in the presence of nitrogen at a temperature of 1300°C and a relative pressure of 100 KPa for 2 h, to obtain a carbon fiber reinforced ceramic matrix composite material A1, the mass of the carbon fiber reinforced ceramic matrix composite material A1 is W2, the mass of the carbon fiber braid is W1, and ΔW is 0.8 wt% of W1;

[0090] In A1, 60 wt% of the carbon fiber and 40 wt% of the ceramic material are contained, and the ceramic material is Si3N4, SiC, SiO2, and B4C.

[0091] The viscosity of the boron carbide-containing polysilazane dispersion liquid is 500 mPa·s, the mass of the polysilazane B is 10 g, the mass of the boron carbide is 5 g, the mass ratio of the polysilazane B to the boron carbide is 1:0.5, and the particle size of the boron carbide is 50 microns.

[0092] The viscosity of the ceramic precursor solution is 50 mPa·s, the mass of the polysilazane A is 20 g, the mass of the polysiloxane A is 20 g, and the mass ratio of the polysilazane A to the polysiloxane A is 1:1.

[0093] The total mass of the silicone polymer and the inorganic particles is 20 g, the mass of the composite precursor is 40 g, and the mass ratio of the total mass of the silicone polymer and the inorganic particles to the mass of the composite precursor is 1:2.

[0094] Example 2

[0095] The method is consistent with that of Example 1, except that the organic polymer dispersion liquid is a polysiloxane dispersion liquid containing silicon carbide, the viscosity of the polysiloxane dispersion liquid is 300 mPa·s, the mass of the polysiloxane B is 10 g, the mass of the silicon carbide is 5 g, the mass ratio of the polysiloxane B to the silicon carbide is 1:0.3, the mass of the polysilazane A in the ceramic precursor solution is 20 g, the mass of the polysiloxane A is 10 g, the mass ratio of the polysilazane A to the polysiloxane A is 5:2, and the temperature of the heat treatment is 1100°C and the relative pressure is 0.1 MPa.

[0096] Other than the method of Example 1, the final carbon fiber reinforced ceramic matrix composite A2 containing 60wt% of carbon fiber and 40wt% of ceramic material, wherein the ceramic material is Si3N4, SiO2 and SiC, the mass of the carbon fiber reinforced ceramic matrix composite A2 is 80.48g, the mass of the carbon fiber braided body is 80g, and ΔW is 0.6wt% of W1.

[0097] The total mass of the silicone polymer and the inorganic particles is 20g, the mass of the composite precursor is 50g, and the ratio of the total mass of the silicone polymer and the inorganic particles to the mass of the composite precursor is 1:2.5.

[0098] Example 3

[0099] Other than the method of Example 1, the mass of polysiloxane B in the boron carbide-containing polysilazane dispersion is 30g, the mass of boron carbide is 20g, the mass ratio of polysilazane B to boron carbide is 1:0.2, the mass of polysilazane A in the ceramic precursor solution is 20g, the mass of polysiloxane A is 50g, the mass ratio of polysilazane A to polysiloxane A is 5:1, and the second curing condition is a temperature of 150°C for 4h.

[0100] Other than the method of Example 1, the final carbon fiber reinforced ceramic matrix composite A3 containing 65wt% of carbon fiber and 35wt% of ceramic material, wherein the ceramic material is Si3N4, SiC, SiO2 and B4C, the mass of the carbon fiber reinforced ceramic matrix composite A3 is 80.64g, the mass of the carbon fiber braided body is 80g, and ΔW is 0.8wt% of W1.

[0101] The total mass of the silicone polymer and the inorganic particles is 20g, the mass of the composite precursor is 20g, and the ratio of the total mass of the silicone polymer and the inorganic particles to the mass of the composite precursor is 1:1.

[0102] Example 4

[0103] Other than the method of Example 1, the mass of polysiloxane B in the boron carbide-containing polysilazane dispersion is 30g, the mass of boron carbide is 20g, the mass ratio of polysilazane B to boron carbide is 1:0.2, the mass of polysilazane A in the ceramic precursor solution is 20g, the mass of polysiloxane A is 50g, the mass ratio of polysilazane A to polysiloxane A is 5:1, and the second curing condition is a temperature of 150°C for 4h, a heat treatment temperature of 1100°C, and a relative pressure of 0.1MPa.

[0104] Other embodiments consistent with embodiment 1, eventually obtain carbon fiber reinforced ceramic matrix composite A4, which contains 65wt% of carbon fiber and 35wt% of ceramic material, wherein the ceramic material is Si3N4, SiC, SiO2 and B4C, the mass of the carbon fiber reinforced ceramic matrix composite A4 W2 is 80.8g, the mass of the carbon fiber braid W1 is 80g, AW is 1wt% of W1;

[0105] The total mass of the organic silicon polymer and the inorganic particles is 50g, the mass of the composite precursor is 60g, and the ratio of the total mass of the organic silicon polymer and the inorganic particles to the mass of the composite precursor is 1:1.2.

[0106] Embodiment 5

[0107] Consistent with the method of embodiment 1, except that the temperature of the first impregnation is 100℃; the temperature of the second impregnation is 110℃;

[0108] Other embodiments consistent with embodiment 1, eventually obtain carbon fiber reinforced ceramic matrix composite A5, the mass of the carbon fiber reinforced ceramic matrix composite A5 W2 is 80.96g, the mass of the carbon fiber braid W1 is 80g, AW1 is 1.2wt% of W1, repeat steps S1-S3, the mass of the carbon fiber reinforced ceramic matrix composite A5 W2 is 80.72g, AW2 is 0.9wt% of W1;

[0109] which contains 66wt% of carbon fiber and 34wt% of ceramic material, wherein the ceramic material is Si3N4, SiC, SiO2 and B4C.

[0110] Embodiment 6

[0111] Consistent with the method of embodiment 1, except that the viscosity of the ceramic precursor solution is 400mPa·s, at this time, the mass of polysilazane A in the ceramic precursor solution is 20g, the mass of polysiloxane A is 10g, the mass ratio of polysilazane A and polysiloxane A is 2:1, other embodiments consistent with embodiment 1, eventually obtain carbon fiber reinforced ceramic matrix composite A6, which contains 70wt% of carbon fiber and 30wt% of ceramic material, wherein the ceramic material is Si3N4, SiC, SiO2 and B4C, the mass of the carbon fiber reinforced ceramic matrix composite A6 W2 is 80.8g, the mass of the carbon fiber braid W1 is 80g, AW is 1wt% of W1.

[0112] Embodiment 7

[0113] Consistent with the method of embodiment 1, except that the mass ratio of polysilazane B to boron carbide in the polysilazane dispersion containing boron carbide is 1:0.1, at this time the viscosity of the polysilazane dispersion containing boron carbide is 20mPa·s;

[0114] Other than the embodiment 1, finally, the carbon fiber reinforced ceramic matrix composite A7 with a mass W2 of 80.8 g, a mass W1 of the carbon fiber braid of 80 g, and AW of 1 wt% of W1 is obtained, which contains 70 wt% of carbon fiber and 30 wt% of ceramic material, wherein the ceramic material is Si3N4, SiO2, SiC and B4C.

[0115] The total mass of the organic silicon polymer and the inorganic particles is 10 g, the mass of the composite precursor is 20 g, and the ratio of the total mass of the organic silicon polymer and the inorganic particles to the mass of the composite precursor is 1:2.

[0116] Embodiment 8

[0117] Other than the method of the embodiment 1, the mass of polysilazane A in the ceramic precursor solution is 100 g, the mass of polysiloxane A is 2 g, and the mass ratio of polysilazane A to polysiloxane A is 5:0.1; at this time, the viscosity of the ceramic precursor solution is 200 mPa·s.

[0118] Other than the embodiment 1, finally, the carbon fiber reinforced ceramic matrix composite A8 with a mass W2 of 80.8 g, a mass W1 of the carbon fiber braid of 80 g, and AW of 1 wt% of W1 is obtained, which contains 70 wt% of carbon fiber and 30 wt% of ceramic material, wherein the ceramic material is Si3N4, SiO2, SiC and B4C.

[0119] Embodiment 9

[0120] Other than the method of the embodiment 1, the first impregnation and the second impregnation are both carried out under normal pressure.

[0121] Other than the embodiment 1, finally, the carbon fiber reinforced ceramic matrix composite A9 with a mass W2 of 80.72 g, a mass W1 of the carbon fiber braid of 80 g, and AW of 0.9 wt% of W1 is obtained, which contains 50 wt% of carbon fiber and 50 wt% of ceramic material, wherein the ceramic material is Si3N4, SiO2, SiC and B4C.

[0122] Embodiment 10

[0123] Other than the method of the embodiment 1, the mass of polysilazane A in the ceramic precursor solution is 50 g, the mass of polysiloxane A is 0.05 g, and the mass ratio of polysilazane A to polysiloxane A is 5:0.05; at this time, the viscosity of the ceramic precursor solution is 30 mPa·s.

[0124] Other steps are consistent with Example 1, finally obtain carbon fiber reinforced ceramic matrix composite material A10, the mass W2 of the carbon fiber reinforced ceramic matrix composite material A10 is 80.8g, the mass W1 of the carbon fiber braided body is 80g, ΔW is 1wt% of W1, which contains 50wt% of carbon fiber and 50wt% of ceramic material, wherein the ceramic material is Si3N4, SiO2, SiC and B4C.

[0125] Comparative Example 1

[0126] Consistent with the method of Example 1, except that the organic silicon polymer dispersion liquid only contains polysilazane B, but does not contain boron carbide; At this time, the viscosity of the organic silicon polymer dispersion liquid is 20mPa·s;

[0127] Other steps are consistent with Example 1, finally obtain carbon fiber reinforced ceramic matrix composite material D1, the mass W2 of the carbon fiber reinforced ceramic matrix composite material D1 is 84g, the mass W1 of the carbon fiber braided body is 30g, ΔW is 5wt% of W1, which contains 85wt% of carbon fiber and 15wt% of ceramic material, wherein the ceramic material is Si3N4, SiO2 and SiC.

[0128] Comparative Example 2

[0129] Consistent with the method of Example 1, except that the ceramic precursor solution does not contain polysilazane A; At this time, the viscosity of the ceramic precursor solution is 30mPa·s;

[0130] Other steps are consistent with Example 1, finally obtain carbon fiber reinforced ceramic matrix composite material D2, the mass W2 of the carbon fiber reinforced ceramic matrix composite material D2 is 80.8g, the mass W1 of the carbon fiber braided body is 80g, ΔW is 1wt% of W1, which contains 50wt% of carbon fiber and 50wt% of ceramic material, wherein the ceramic material is Si3N4, SiO2, SiC and B4C.

[0131] Comparative Example 3

[0132] Consistent with Example 1, except that after the first impregnation is completed, the first solidification is not carried out, and the second impregnation is directly carried out;

[0133] Other steps are consistent with Example 1, finally obtain carbon fiber reinforced ceramic matrix composite material D3, the mass W2 of the carbon fiber reinforced ceramic matrix composite material D3 is 81.04g, the mass W1 of the carbon fiber braided body is 80g, ΔW is 1.3wt% of W1; Which contains 60wt% of carbon fiber and 40wt% of ceramic material, wherein the ceramic material is Si3N4, B4C, SiO2 and SiC.

[0134] Test Example

[0135] The carbon fiber reinforced ceramic matrix composite prepared in the examples and comparative examples was subjected to mechanical property and oxidation resistance tests, and the results are shown in Table 1.

[0136] Table 1

[0137]

[0138] As can be seen from the results in Table 1, the carbon fiber reinforced ceramic matrix composite prepared in Examples 1-10 using the method provided in the present application has good oxidation resistance, high-temperature resistance, mechanical properties and density, and the density is not less than 1.5 g / cm3 under the premise that the bending strength is not less than 60 MPa. 3 Comparative Examples 1-3 have low weight loss rate and good oxidation resistance, but their high-temperature resistance, mechanical properties and density cannot meet the application requirements.

[0139] Among them, Examples 1-5 meeting the preferred scheme of the present application have better comprehensive effects, the weight loss rate is not higher than 1.4 wt%, have good oxidation resistance, and have good high-temperature resistance, the bending strength is not less than 60 MPa, the fracture toughness is not less than 1.4 , and the density is high.

[0140] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including combining various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed in the present application and fall within the protection scope of the present application.

Claims

1. A method of manufacturing a carbon fiber reinforced ceramic matrix composite material, characterized by, The method comprises the following steps: S1, a carbon fiber braided body is first impregnated in a silicone polymer dispersion liquid to obtain a carbon fiber preform attached with the silicone polymer dispersion liquid, and the carbon fiber preform is first cured to obtain an initial carbon fiber blank; S2, the initial carbon fiber blank is second impregnated in a ceramic precursor solution to obtain an initial carbon fiber blank attached with the ceramic precursor solution, and the initial carbon fiber blank is second cured to obtain a carbon fiber blank; S3, the carbon fiber blank is heat treated to obtain a carbon fiber reinforced ceramic matrix composite material; Wherein, the difference AW between the mass W1 of the carbon fiber braided body and the mass W2 of the carbon fiber reinforced ceramic matrix composite material is not more than 1wt% of W1; The silicone polymer dispersion liquid contains a silicone polymer and inorganic particles selected from silicon carbide and / or boron carbide; The viscosity of the silicone polymer dispersion liquid is 100-600mPa·s; The ceramic precursor solution contains a composite precursor of polysilazane A and polysiloxane A; The silicone polymer is selected from polysiloxane B and / or polysilazane B; The viscosity of the ceramic precursor solution is 10-100mPa·s.

2. The method of claim 1, wherein, The ratio of the total mass of the silicone polymer and the inorganic particles to the mass of the composite precursor is 1-10:2-15; And / or, in the ceramic precursor solution, the mass ratio of the polysilazane A to the polysiloxane A is 5:(0.1-5).

3. The method of claim 2, wherein, In the ceramic precursor solution, the mass ratio of the polysilazane A to the polysiloxane A is 5:(1-5).

4. The method of claim 1, wherein, The mass ratio of the silicone polymer to the inorganic particles is 1:(0.1-0.5); And / or, the particle size of the silicon carbide is 10-100 microns; And / or, the particle size of the boron carbide is 10-100 microns.

5. The method of claim 4, wherein, The number average molecular weight of the polysilazane A, the polysilazane B, the polysiloxane A and the polysiloxane B is independently 1000-8000g / mol.

6. The method of claim 1, wherein, The method further comprises degreasing the carbon fiber braided body before step S1; Wherein, the degreasing conditions include: temperature 50-100℃, time 1-2h.

7. The method of claim 1, wherein, The first impregnation conditions include: temperature 50-150℃, relative pressure 0.1-0.5MPa, time 1-2h; And / or, the second impregnation conditions include: temperature 50-150℃, relative pressure 0.1-0.5MPa, time 1-2h; And / or, the method further comprises reducing the pressure to normal pressure after the second impregnation.

8. The method of claim 1, wherein, The first curing conditions include: temperature 150-300℃, time 2-4h; And / or, the second curing conditions include: temperature 150-300℃, time 2-4h.

9. The method of claim 1, wherein, The method further comprises: before the second curing, the initial carbon fiber blank attached with the ceramic precursor solution is third impregnated in the ceramic precursor solution; Wherein, the third impregnation conditions include: temperature 50-150℃, relative pressure 0.1-0.5MPa, time 1-2h.

10. The method of claim 1, wherein, The conditions of the heat treatment include: treating at 800-1300℃, 0.1-0.5MPa of relative pressure in the presence of a protective gas for 1-2h.

11. A carbon fiber reinforced ceramic matrix composite, characterized in that, The carbon fiber reinforced ceramic matrix composite is prepared by the method of any one of claims 1-10.

12. The composite material of claim 11, wherein, The surface density of the composite material is not less than 1.5 g / cm 3 The weight loss rate at 1000℃ is not more than 2wt%.

13. The composite material of claim 11 or 12, wherein, The composite contains 50-80wt% of carbon fibers and 20-50wt% of ceramic material. The ceramic material contains component A and optional component B. The component A contains Si3N4, SiC and SiO2, and the component B contains B4C.

14. Use of the carbon fiber reinforced ceramic matrix composite of any one of claims 11-13 in at least one of the fields of aerospace, nuclear industry and construction.

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