CN113929480B - C/SiC ceramic matrix composite material and preparation method thereof - Google Patents
C/SiC ceramic matrix composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a C/SiC ceramic matrix composite material, which comprises the following steps: (1) Placing the chopped carbon fiber prepreg strip into a die cavity, and sequentially carrying out die pressing treatment and cracking reaction to obtain a carbon fiber framework; (2) Mixing the carbon fiber skeleton with solid powder, and sequentially carrying out mould pressing treatment and cracking reaction to obtain a composite material green body; (3) Performing densification treatment on the composite material green body by adopting a chemical vapor deposition method to obtain a densified composite material green body; (4) And mixing the densified composite material green body with silicon powder, and then carrying out a silicon infiltration reaction to obtain the C/SiC ceramic matrix composite material. The preparation method provided by the invention is simple and low in cost, and the prepared ceramic matrix composite material is uniform in mechanical property, has excellent high temperature resistance and friction performance, and has a wide application prospect in brake disc materials of automobiles.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a C/SiC ceramic matrix composite material and a preparation method thereof, which can be applied to the preparation of automobile brake discs.
Background
The conventional preparation method of the carbon fiber reinforced ceramic matrix composite material comprises CVI (chemical vapor infiltration) +PIP (precursor impregnation pyrolysis), CVI (chemical vapor infiltration) +RMI (silicon infiltration) and other processes; the process mainly relies on a prefabricated body woven by long carbon fibers as a matrix skeleton and a toughening component, and then ceramic-based materials are gradually filled around the prefabricated body, so that a strong heat-resistant composite material with compact and hard structure and certain toughness is finally formed. In the preparation process, the fiber preform can be formulated into the required fiber orientation through different braiding processes, so that the requirements of the composite material on shape and performance are met. However, in the cost accounting for material preparation, long carbon fiber braids occupy a high proportion, and the preform requires a certain preparation and turnaround period.
The mould pressing is a common material forming process, and the material is formed and shaped in a fixed space by providing a certain temperature and pressure for substances in a cavity. In the prior art, however, chopped fibers and resin powder are generally directly molded, and in the compression molding process, the chopped fibers inevitably flow in a molten resin powder matrix; under the action of gravity, the chopped carbon fibers are finally in an orientation state of high X-Y plane distribution and low Z direction distribution, so that the toughening effect is uneven, and the anisotropy of the mechanical properties of the prepared composite material is obvious, so that the chopped carbon fiber toughened ceramic matrix composite material is severely braked. Therefore, there is a need to develop a ceramic matrix composite material with uniform mechanical properties, simple method and low cost.
The Chinese patent 201810348023.X discloses a method for preparing an automobile brake disc by molding chopped carbon fibers, wherein a green body is prepared by molding chopped carbon fibers and resin powder, and then the green body is assisted with a CVI+RMI process to prepare a ceramic matrix composite material. However, in compression molding, the chopped carbon fibers flow in the resin matrix, eventually making the mechanical anisotropy of the composite material obvious.
Disclosure of Invention
The invention provides a C/SiC ceramic matrix composite material and a preparation method thereof, wherein the preparation method is simple and low in cost, and the prepared ceramic matrix composite material is uniform in mechanical property and has excellent high temperature resistance and friction performance.
In a first aspect, the invention provides a preparation method of a C/SiC ceramic matrix composite, which comprises the following steps:
(1) Placing the chopped carbon fiber prepreg strip into a die cavity, and sequentially carrying out die pressing treatment and cracking reaction to obtain a carbon fiber framework;
(2) Mixing the carbon fiber skeleton with solid powder, and sequentially carrying out mould pressing treatment and cracking reaction to obtain a composite material green body;
(3) Performing densification treatment on the composite material green body by adopting a chemical vapor deposition method to obtain a densified composite material green body;
(4) And mixing the densified composite material green body with silicon powder, and then carrying out a silicon infiltration reaction to obtain the C/SiC ceramic matrix composite material.
Preferably, in the step (1), the fiber volume fraction of the chopped carbon fiber prepreg strip is 50% to 85%.
Preferably, in the step (1), the length of the chopped carbon fiber prepreg strip is 10-80 mm, the width is 2-10 mm, and the height is 1-3 mm.
Preferably, in step (2), the solid powder comprises phenolic resin powder, carbon powder and silicon powder;
the ratio of the sum of the mass of the carbon powder and the mass of the silicon powder to the mass of the phenolic resin powder is (1-5): 10.
preferably, the powder particle size of the silicon powder is 35-1000 mu m.
Preferably, in the step (1) and the step (2), the temperature of the die pressing treatment is 140-280 ℃, the pressure is 0.5-20 MPa, and the time is 0.5-5 h;
the reaction temperature of the cracking reaction is 800-1100 ℃ and the reaction time is 2-18 h.
Preferably, in the step (3), the deposition temperature of the chemical vapor deposition method is 900-1100 ℃ and the deposition time is 100-500 h.
Preferably, in step (3), the densified composite green body has a density of from 0.85 to 1.25g/cm 3 。
Preferably, in step (4), the mass ratio of the densified composite green body to the silicon powder is 1: (2-5).
Preferably, in the step (4), the reaction temperature of the silicon infiltration reaction is 1460-1600 ℃ and the reaction time is 0.5-3.5 h.
Preferably, the preparation method comprises the following steps: (1) Placing chopped carbon fiber prepreg strips with the fiber volume fraction of 50% -85% into a die cavity, and sequentially carrying out die pressing treatment and cracking reaction to obtain a carbon fiber framework; wherein the length of the chopped carbon fiber prepreg strip is 10-80 mm, the width is 2-10 mm, and the height is 1-3 mm; the temperature of the mould pressing treatment is 140-280 ℃, the pressure is 0.5-20 MPa, and the time is 0.5-5 h; the temperature of the cracking reaction is 800-1100 ℃ and the reaction time is 2-8 h;
(2) Mixing the carbon fiber skeleton with solid powder, and sequentially carrying out mould pressing treatment and cracking reaction to obtain a composite material green body; wherein the solid powder comprises phenolic resin powder, carbon powder and silicon powder; the ratio of the sum of the mass of the carbon powder and the mass of the silicon powder to the mass of the phenolic resin powder is (1-5): 10; the temperature of the mould pressing treatment is 140-280 ℃, the pressure is 0.5-20 MPa, and the time is 0.5-5 h; the temperature of the cracking reaction is 800-1100 ℃ and the reaction time is 2-8 h;
(3) Densification treatment is carried out on the composite material green body by adopting a chemical vapor deposition method to obtain the density of 0.85-1.25 g/cm 3 Is a densified composite green body; wherein the deposition temperature of the chemical vapor deposition method is 900-1100 ℃ and the deposition time is 100-500 h;
(4) Mixing the densified composite material green body and silicon powder according to the following ratio of 1: mixing the materials (2-5) in mass ratio, and then carrying out a silicon infiltration reaction to obtain the C/SiC ceramic matrix composite; wherein the reaction temperature of the silicon infiltration reaction is 1460-1600 ℃ and the reaction time is 0.5-3.5 h.
In a second aspect, the invention provides a C/SiC ceramic matrix composite material, which is prepared by the preparation method in any one of the first aspects.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The preparation method comprises the steps of carrying out compression molding on the chopped carbon fiber prepreg strip, and then mixing the chopped carbon fiber prepreg strip with solid powder, wherein each component of a matrix in the prepared ceramic matrix composite material is uniformly distributed, and the ceramic matrix composite material has excellent mechanical strength, high temperature resistance and friction performance and has wide application prospect in brake disc materials;
(2) The preparation method of the invention is simple, the process is stable, and the invention has the advantages of short period and low cost.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by persons of ordinary skill in the art without making creative efforts based on the embodiments of the present invention are all within the scope of protection of the present invention.
The invention provides a preparation method of a C/SiC ceramic matrix composite, which comprises the following steps:
(1) Placing the chopped carbon fiber prepreg strip into a die cavity, and sequentially carrying out die pressing treatment and cracking reaction to obtain a carbon fiber framework;
(2) Mixing the carbon fiber skeleton with solid powder, and sequentially carrying out mould pressing treatment and cracking reaction to obtain a composite material green body;
(3) Performing densification treatment on the composite material green body by adopting a chemical vapor deposition method to obtain a densified composite material green body;
(4) And mixing the densified composite material green body with silicon powder, and then carrying out a silicon infiltration reaction to obtain the C/SiC ceramic matrix composite material.
In the prior art, chopped carbon fibers and resin powder are mixed and then molded in a compression molding mode, however, in the process of mold molding and temperature rising, the chopped carbon fibers inevitably flow in a molten resin powder matrix, and under the action of gravity, the orientation of the chopped carbon fibers is unevenly distributed, so that the anisotropy of the mechanical properties of the composite material is obvious. In order to uniformly toughen the composite material by the carbon fibers, the chopped carbon fiber prepreg strips are molded to form a carbon fiber framework, then the carbon fiber framework is mixed with solid powder, and molded again, so that the condition that the chopped carbon fibers flow in the resin due to gravity is effectively avoided, and the prepared ceramic matrix composite material is uniform in high temperature resistance and mechanical property and excellent in isotropy.
According to some preferred embodiments, in step (1), the chopped carbon fiber prepreg strips have a fiber volume fraction of 50% to 85% (e.g., may be 50%, 55%, 60%, 65%, 70%, 75%, 80%, or 85%).
In the invention, the fiber volume fraction of the chopped carbon fiber prepreg strips is lower than the range, so that the carbon fibers cannot achieve the toughening effect in the composite material; if the fiber volume fraction is higher than the above range, a gel-lean phenomenon occurs in the preparation process, and a carbon fiber skeleton cannot be formed.
According to some preferred embodiments, in step (1), the chopped carbon fiber prepreg strips have a length of 10 to 80mm (e.g., may be 10mm, 20mm, 30mm, 40mm, 50mm, 60mm, 70mm or 80 mm), a width of 2 to 10mm (e.g., may be 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm or 10 mm), and a height of 1 to 3mm (e.g., may be 1mm, 2mm or 3 mm).
In the invention, the carbon fiber non-woven fabric is cut into the chopped carbon fiber prepreg strips within the range, and when the chopped carbon fiber prepreg strips are placed in a die cavity, the chopped carbon fiber prepreg strips can be ensured to extend to multiple directions, and the built carbon fiber frameworks are uniform in orientation, so that the mechanical property of the composite material is excellent; if the length and width of the chopped carbon fiber prepreg strips are lower or higher than the ranges, fiber frameworks with uniform orientations cannot be built among the fibers, so that the performance of the composite material is affected.
According to some preferred embodiments, in step (2), the solid powder comprises phenolic resin powder, carbon powder and silicon powder;
the ratio of the sum of the mass of the carbon powder and the mass of the silicon powder to the mass of the phenolic resin powder is (1-5): 10 (e.g., may be 1:10, 2:10, 3:10, 4:10, or 5:10).
In the invention, phenolic resin in the solid powder can provide a shape parent blank for the carbon fiber framework, and the shape parent blank and the phenolic resin can be crosslinked and formed in the mould pressing process; the carbon powder can provide a certain protection effect for the carbon fiber skeleton; and the addition of the silicon powder can prevent the carbon fiber framework from deforming in the subsequent mould pressing process.
It should be noted that, in the present invention, the ratio of the sum of the mass of the carbon powder and the silicon powder in the solid powder to the mass of the phenolic resin powder being higher than the above range affects the overall performance of the final composite material; meanwhile, under the condition that the above range is satisfied, the carbon powder and the silicon powder in the solid powder may be mixed in any ratio, but cannot be a single carbon powder or a single silicon powder.
According to some preferred embodiments, the powder particle size of the silicon powder is 35 to 1000 μm (for example, may be 35 μm, 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm or 1000 μm).
In the invention, if the particle size of the silicon powder is higher than the above range, on one hand, the particle size of the silicon powder is reduced, and deformation can not be effectively prevented when preparing the composite material green embryo at high temperature; on the other hand, the excessive silicon powder particles can increase the difficulty of melting, can deteriorate the fluidity of the silicon powder, cannot be uniformly distributed in the fiber framework and the composite material, and finally has obvious high-temperature resistance anisotropy.
According to some preferred embodiments, in step (1) and step (2), the temperature of the molding process is 140-280 ℃ (e.g., may be 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, or 280 ℃), the pressure is 0.5-20 MPa (e.g., may be 0.5MPa, 1MPa, 2MPa, 5MPa, 8MPa, 10MPa, 13MPa, 15MPa, 18MPa, or 20 MPa), and the time is 0.5-5 h (e.g., may be 0.5h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, or 5 h);
the reaction temperature of the cleavage reaction is 800 to 1100 ℃ (for example, it may be 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃ or 1100 ℃), and the reaction time is 2 to 18 hours (for example, it may be 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours or 18 hours).
According to some preferred embodiments, in step (3), the deposition temperature of the chemical vapor deposition method is 900 to 1100 ℃ (e.g., may be 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, or 1100 ℃), and the deposition time is 100 to 500 hours (e.g., may be 100 hours, 150 hours, 200 hours, 250 hours, 300 hours, 350 hours, 400 hours, 450 hours, or 500 hours).
In the invention, the densification protection is carried out on the composite material blank by utilizing the chemical vapor deposition process, and the chemical vapor deposition reaction is carried out on the composite material blank in a divided manner under the condition of ensuring the total deposition time within the range, so that the situation that the surface of the material is excessively densified and the internal holes are more due to single deposition can be avoided, and the uniform densification degree of the surface and the internal of the material is ensured as much as possible.
According to some preferred embodiments, in step (3), the densified composite green body has a density of 0.85 to 1.25g/cm 3 (e.g., may be 0.85 g/cm) 3 、0.86g/cm 3 、0.87g/cm 3 、 0.88g/cm 3 、0.90g/cm 3 、0.92g/cm 3 、0.94g/cm 3 、0.96g/cm 3 、1.01g/cm 3 、1.03 g/cm 3 、1.05g/cm 3 、1.11g/cm 3 、1.15g/cm 3 、1.20g/cm 3 Or 1.25g/cm 3 )。
It should be noted that, in the present invention, if the density of the densified composite green body is higher than the above range, the pores of the composite green body are too small, and the efficiency in the subsequent silicon infiltration reaction is too low; if the density is lower than the above range, the carbon interface layer is too thin, and the carbon fibers are easily damaged; therefore, only if the density of the densified composite green body is within the scope of the present invention, the overall excellent performance of the ceramic matrix composite can be ensured.
According to some preferred embodiments, in step (4), the mass ratio of the densified composite green body to the silicon powder is 1: (2-5) (e.g., may be 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, or 1:5).
In the present invention, the silicon powder subjected to the infiltration of silicon has the same particle size as the silicon powder in the solid powder; in the silicon infiltration reaction, if the content of the silicon powder is lower than the range, the high temperature resistance of the composite material is deteriorated, and the mechanical property is lower; if the content of the silicon powder is higher than the above range, the composite material is excessively ceramic, and a large amount of metallic silicon remains on the surface of the material after infiltration.
According to some preferred embodiments, in step (4), the reaction temperature of the silicon infiltration reaction is 1460-1600 ℃ (e.g., may be 1460 ℃, 1480 ℃, 1500 ℃, 1520 ℃, 1550 ℃, 1580 ℃ or 1600 ℃), and the reaction time is 0.5-3.5 h (e.g., may be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h or 3.5 h).
In the present invention, if the reaction temperature of the infiltration of silicon is too low or the time is too short, the fluidity of the silicon melt is poor, and the infiltration of the densified composite material preform is low, so that the reaction is insufficient; if the reaction temperature is too high or too long, the carbon fiber is damaged.
According to some preferred embodiments, the preparation method comprises the steps of: (1) Placing chopped carbon fiber prepreg strips with the fiber volume fraction of 50% -85% into a die cavity, and sequentially carrying out die pressing treatment and cracking reaction to obtain a carbon fiber framework; wherein the length of the chopped carbon fiber prepreg strip is 10-80 mm, the width is 2-10 mm, and the height is 1-3 mm; the temperature of the mould pressing treatment is 140-280 ℃, the pressure is 0.5-20 MPa, and the time is 0.5-5 h; the temperature of the cracking reaction is 800-1100 ℃ and the reaction time is 2-8 h;
(2) Mixing the carbon fiber skeleton with solid powder, and sequentially carrying out mould pressing treatment and cracking reaction to obtain a composite material green body; wherein the solid powder comprises phenolic resin powder, carbon powder and silicon powder; the ratio of the sum of the mass of the carbon powder and the mass of the silicon powder to the mass of the phenolic resin powder is (1-5): 10; the temperature of the mould pressing treatment is 140-280 ℃, the pressure is 0.5-20 MPa, and the time is 0.5-5 h; the temperature of the cracking reaction is 800-1100 ℃ and the reaction time is 2-8 h;
(3) Densification treatment is carried out on the composite material green body by adopting a chemical vapor deposition method to obtain the density of 0.85-1.25 g/cm 3 Is a densified composite green body; wherein the deposition temperature of the chemical vapor deposition method is 900-1100 ℃ and the deposition time is 100-500 h;
(4) Mixing the densified composite material green body and silicon powder according to the following ratio of 1: mixing the materials (2-5) in mass ratio, and then carrying out a silicon infiltration reaction to obtain the C/SiC ceramic matrix composite; wherein the reaction temperature of the silicon infiltration reaction is 1460-1600 ℃ and the reaction time is 0.5-3.5 h.
The invention also provides the C/SiC ceramic matrix composite material, which is prepared by adopting the preparation method provided by the invention.
In order to more clearly illustrate the technical scheme and advantages of the invention, a C/SiC ceramic matrix composite material and a preparation method thereof are described in detail through several embodiments.
Example 1:
(1) Cutting carbon fiber non-valuable cloth into chopped carbon fiber prepreg strips (30 mm long, 5mm wide and 2mm high), wherein the fiber volume fraction of the chopped carbon fiber prepreg strips is 50%, and then uniformly and randomly placing the chopped carbon fiber prepreg strips in a tool cavity until the chopped carbon fiber prepreg strips are full; carrying out mould pressing treatment for 2 hours at 180 ℃ and 1MPa, demoulding after forming, and carrying out cracking reaction for 8 hours at 850 ℃ to obtain a carbon fiber framework;
(2) Uniformly mixing phenolic resin, carbon powder and silicon powder (with the particle size of 35 mu m) in a mass ratio of 10:2:1 to obtain solid powder, embedding a carbon fiber skeleton in the solid powder, uniformly mixing, transferring into a tool cavity, performing compression molding at 185 ℃ and 1MPa for 2.5 hours, demolding after molding, and performing cracking reaction at 800 ℃ for 10 hours to obtain a composite material green body;
(3) The composite material green body is subjected to two chemical vapor deposition reactions at 1020 ℃ for 80h and 50h (130 h total) respectively, and densified composite material green body (density of 0.93 g/cm) is obtained 3 )；
(4) Mixing the densified composite material blank and silicon powder according to the mass ratio of 1:2, and carrying out a silicon infiltration reaction at 1500 ℃ for 0.5h to obtain the C/SiC ceramic matrix composite material.
Example 2
(1) Cutting carbon fiber non-valuable cloth into chopped carbon fiber prepreg strips (length 10mm, width 2mm and height 1 mm), wherein the fiber volume fraction of the chopped carbon fiber prepreg strips is 60%, and then uniformly and randomly placing the chopped carbon fiber prepreg strips in a tool cavity until the chopped carbon fiber prepreg strips are full; carrying out mould pressing treatment for 2.5h at 140 ℃ and 3Mpa, demoulding after forming, and carrying out cracking reaction for 10h at 900 ℃ to obtain a carbon fiber framework;
(2) Uniformly mixing phenolic resin, carbon powder and silicon powder (with the particle size of 100 mu m) in a mass ratio of 10:2:2 to obtain solid powder, embedding a carbon fiber skeleton in the solid powder, uniformly mixing, transferring into a tool cavity, performing 3h compression molding treatment at 150 ℃ and 3Mpa, demolding after molding, and performing cracking reaction at 900 ℃ for 10h to obtain a composite material green body;
(3) The composite material green body is subjected to three chemical vapor deposition reactions at 900 ℃ for 40h, 50h and 90h (180 h in total) respectively, and a densified composite material green body (density of 1.09 g/cm) is obtained 3 )；
(4) Mixing the densified composite material blank and silicon powder according to the mass ratio of 1:3, and performing a silicon infiltration reaction at 1550 ℃ for 1h to obtain the C/SiC ceramic matrix composite material.
Example 3
(1) Cutting carbon fiber non-valuable cloth into chopped carbon fiber prepreg strips (20 mm long, 4mm wide and 2mm high), wherein the fiber volume fraction of the chopped carbon fiber prepreg strips is 65%, and then uniformly and randomly placing the chopped carbon fiber prepreg strips in a tool cavity until the chopped carbon fiber prepreg strips are full; carrying out mould pressing treatment for 3 hours at 200 ℃ and 10Mpa, demoulding after forming, and carrying out cracking reaction for 10 hours at 950 ℃ to obtain a carbon fiber framework;
(2) Uniformly mixing phenolic resin, carbon powder and silicon powder (with the particle size of 200 mu m) in a mass ratio of 10:1:1 to obtain solid powder, embedding a carbon fiber skeleton in the solid powder, uniformly mixing, transferring into a tool cavity, performing 2h compression molding treatment at 185 ℃ and 10Mpa, demolding after molding, and performing cracking reaction at 900 ℃ for 15h to obtain a composite material green body;
(3) Making the composite materialThe raw blank is subjected to two chemical vapor deposition reactions at 950 ℃ for 80h and 90h (total 170 h) respectively, and a densified composite raw blank (density of 1.01 g/cm) 3 )；
(4) Mixing the densified composite material blank and silicon powder according to the mass ratio of 1:4, and performing a silicon infiltration reaction at 1490 ℃ for 2 hours to obtain the C/SiC ceramic matrix composite material.
Example 4
(1) Cutting carbon fiber non-valuable cloth into chopped carbon fiber prepreg strips (50 mm long, 5mm wide and 3mm high), wherein the fiber volume fraction of the chopped carbon fiber prepreg strips is 70%, and then uniformly and randomly placing the chopped carbon fiber prepreg strips in a tool cavity until the chopped carbon fiber prepreg strips are full; carrying out mould pressing treatment for 3 hours at 210 ℃ and 0.5Mpa, demoulding after forming, and carrying out cracking reaction for 6 hours at 1000 ℃ to obtain a carbon fiber framework;
(2) Uniformly mixing phenolic resin, carbon powder and silicon powder (with the particle size of 400 mu m) in a mass ratio of 10:0.5:1 to obtain solid powder, embedding a carbon fiber skeleton in the solid powder, uniformly mixing, transferring into a tool cavity, performing die pressing treatment at 210 ℃ and 10Mpa for 2.5h, demolding after molding, and performing cracking reaction at 1000 ℃ for 10h to obtain a composite material green body;
(3) The composite material green body is subjected to three chemical vapor deposition reactions at 1000 ℃ for 80h, 80h and 90h (total 260 h) respectively, and a densified composite material green body (density of 1.00 g/cm) is obtained 3 )；
(4) Mixing the densified composite material blank and silicon powder according to the mass ratio of 1:5, and performing a silicon infiltration reaction at 1550 ℃ for 1h to obtain the C/SiC ceramic matrix composite material.
Example 5
(1) Cutting the carbon fiber-free cloth into chopped carbon fiber prepreg strips (length 60mm, width 6mm, height 2 mm), wherein the fiber volume fraction of the chopped carbon fiber prepreg strips is 80%, and then homogenizing
Randomly placing the mold cavities into the tool cavity until the mold cavities are full; carrying out mould pressing treatment for 4 hours at 230 ℃ and 10Mpa, demoulding after forming, and carrying out cracking reaction for 2 hours at 1100 ℃ to obtain a carbon fiber framework;
(2) Uniformly mixing phenolic resin, carbon powder and silicon powder (with the particle size of 500 mu m) in a mass ratio of 10:3:2 to obtain solid powder, embedding a carbon fiber skeleton in the solid powder, uniformly mixing, transferring into a tool cavity, performing compression molding treatment at 230 ℃ and 10Mpa for 5 hours, demolding after molding, and performing cracking reaction at 1100 ℃ for 2 hours to obtain a composite material green body;
(3) The composite material green body is subjected to three chemical vapor deposition reactions at 1030 ℃ for 50h, 150h and 100h (300 h total) respectively, and a densified composite material green body (density of 1.15 g/cm) is obtained 3 )；
(4) Mixing the densified composite material blank and silicon powder according to the mass ratio of 1:3, and performing a silicon infiltration reaction at 1600 ℃ for 2 hours to obtain the C/SiC ceramic matrix composite material.
Example 6
(1) Cutting carbon fiber non-valuable cloth into chopped carbon fiber prepreg strips (70 mm long, 8mm wide and 3mm high), wherein the fiber volume fraction of the chopped carbon fiber prepreg strips is 85%, and then uniformly and randomly placing the chopped carbon fiber prepreg strips in a tool cavity until the chopped carbon fiber prepreg strips are full; carrying out mould pressing treatment for 0.5h at 250 ℃ and 15Mpa, demoulding after forming, and carrying out cracking reaction for 8h at 900 ℃ to obtain a carbon fiber framework;
(2) Uniformly mixing phenolic resin, carbon powder and silicon powder (with the particle size of 800 mu m) in a mass ratio of 10:2.5:2.5 to obtain solid powder, embedding a carbon fiber skeleton in the solid powder, uniformly mixing, transferring into a tool cavity, performing die pressing treatment for 0.55h at 250 ℃ and 15Mpa, demolding after molding, and performing cracking reaction for 8h at 900 ℃ to obtain a composite material green body;
(3) The composite material green body is subjected to three chemical vapor deposition reactions at 1050 ℃ for 150h, 150h and 100h (400 h in total) respectively, and a densified composite material green body (density of 1.20 g/cm) is obtained 3 )；
(4) Mixing the densified composite material blank and silicon powder according to the mass ratio of 1:3, and performing a silicon infiltration reaction at 1550 ℃ for 3.5 hours to obtain the C/SiC ceramic matrix composite material.
Example 7
(1) Cutting carbon fiber non-valuable cloth into chopped carbon fiber prepreg strips (80 mm long, 10mm wide and 1mm high), wherein the fiber volume fraction of the chopped carbon fiber prepreg strips is 78%, and then uniformly and randomly placing the chopped carbon fiber prepreg strips in a tool cavity until the chopped carbon fiber prepreg strips are full; carrying out mould pressing treatment for 0.5h at 280 ℃ and 20Mpa, demoulding after forming, and carrying out cracking reaction for 8h at 900 ℃ to obtain a carbon fiber framework;
(2) Uniformly mixing phenolic resin, carbon powder and silicon powder (with the particle size of 1000 mu m) in a mass ratio of 10:1.5:2.5 to obtain solid powder, embedding a carbon fiber skeleton in the solid powder, uniformly mixing, transferring into a tool cavity, performing mould pressing treatment at 280 ℃ and 15Mpa for 5 hours, demoulding after forming, and performing cracking reaction at 900 ℃ for 8 hours to obtain a composite material green body;
(3) The composite material green body is subjected to three chemical vapor deposition reactions at 1100 ℃ for 150h, 150h and 200h (total 500 h) respectively, and a densified composite material green body (density of 1.25 g/cm) is obtained 3 )；
(4) Mixing the densified composite material blank and silicon powder according to the mass ratio of 1:3, and performing a silicon infiltration reaction at 1600 ℃ for 2.5 hours to obtain the C/SiC ceramic matrix composite material.
Example 8
Example 8 is substantially the same as example 2 except that: in step (3), the density of the densified composite green sheet is 0.75g/cm 3 。
Example 9
Example 9 is substantially the same as example 2 except that: in step (3), the density of the densified composite green sheet is 1.35g/cm 3 。
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that: and (3) directly mixing the chopped carbon fiber prepreg strip in the step (1) with the solid powder in the step (2), and then carrying out mould pressing treatment and cracking reaction in sequence.
Comparative example 2
Comparative example 1 is substantially the same as example 1 except that: directly mixing the chopped carbon fiber prepreg strip in the step (1) with resin, and then carrying out mould pressing treatment and cracking reaction in sequence.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that: the solid powder in step (2) comprises only phenolic resin powder.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that: the solid powder in the step (2) only comprises phenolic resin powder and carbon powder.
Comparative example 5
Comparative example 5 is substantially the same as example 1 except that: the solid powder in the step (2) only comprises phenolic resin powder and silicon powder.
Comparative example 6
Comparative example 6 is substantially the same as example 1 except that: the method does not comprise the step (1) and the step (2), and directly adopts a fiber preform woven by long carbon fibers as a framework, and sequentially carries out chemical vapor deposition reaction and silicon infiltration reaction.
The ceramic matrix composites prepared in examples 1 to 9 and comparative examples 1 to 6 were subjected to performance tests, respectively, and the test results are shown in table 1.
The performance tests of the invention are tested by the conventional test methods of the technicians in the field. The plane compressive strength is measured by compression downward from the upper surface of the material; the Z-direction compressive strength is measured by compression from the side of the material toward the opposite side.
TABLE 1
As can be seen from table 1, the ceramic matrix composite materials prepared in examples 1 to 7 of the present invention have uniform mechanical properties, excellent compression resistance and friction resistance, and less abrasion of the materials; in examples 8 to 9, when the density of the green compact of the prepared densified composite material is lower than the range of the present invention, the overall performance of the prepared ceramic matrix composite material is deteriorated; in comparative example 1, when the chopped carbon fibers and the solid powder are directly mixed, the chopped carbon fibers flow under the action of gravity, so that the toughening effect is uneven, the anisotropy of the ceramic matrix composite is obvious, and the compression resistance and the friction resistance are poor; in comparative example 2, when the chopped carbon fibers are directly mixed with the resin, not only the carbon fibers are unevenly distributed in the resin, but also the whole material is deformed in the subsequent molding and cracking process, and finally the performance of the ceramic matrix composite is deteriorated; in comparative examples 3 to 5, when the carbon fiber skeleton was mixed with only the phenolic resin, cracking and buckling deformation occurred on the material surface after cracking at high temperature; when the carbon fiber skeleton is only mixed with phenolic resin and carbon powder, the carbon fiber skeleton is deformed due to the lack of silicon powder; when the carbon fiber skeleton is only mixed with phenolic resin and silicon powder, the carbon fiber is damaged due to the lack of protection of carbon powder; thus, in comparative examples 3 to 5, the overall properties of the finally prepared ceramic matrix composite were poor; in comparative example 6, when a fiber preform woven from fibers was directly used as a skeleton, the overall performance of the composite material was not much different from that in the examples, but the preparation period of the whole composite material was prolonged, and the preparation cost of the whole experiment was remarkably increased.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the 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 scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention. The invention is not described in detail in a manner known to those skilled in the art.
Claims (7)
1. The preparation method of the C/SiC ceramic matrix composite material is characterized by comprising the following steps of:
(1) Placing the chopped carbon fiber prepreg strip into a die cavity, and sequentially carrying out die pressing treatment and cracking reaction to obtain a carbon fiber framework; the length of the chopped carbon fiber prepreg strip is 10-80 mm, the width is 2-10 mm, and the height is 1-3 mm;
(2) Mixing the carbon fiber skeleton with solid powder, and sequentially carrying out mould pressing treatment and cracking reaction to obtain a composite material green body; the solid powder comprises phenolic resin powder, carbon powder and silicon powder;
the ratio of the sum of the mass of the carbon powder and the mass of the silicon powder to the mass of the phenolic resin powder is (1-5): 10; the grain diameter of the silicon powder is 35-1000 mu m;
(3) Performing densification treatment on the composite material green body by adopting a chemical vapor deposition method to obtain a densified composite material green body; the density of the densified composite green body is 0.85-1.25 g/cm 3 ；
(4) Mixing the densified composite material green body with silicon powder, and then carrying out a silicon infiltration reaction to obtain the C/SiC ceramic matrix composite material; the mass ratio of the densified composite material green body to the silicon powder is 1: (2-5).
2. The method of claim 1, wherein in step (1):
the fiber volume fraction of the chopped carbon fiber prepreg strip is 50% -85%.
3. The method according to claim 1, wherein in step (1) and step (2):
the temperature of the mould pressing treatment is 140-280 ℃, the pressure is 0.5-20 MPa, and the time is 0.5-5 h;
the reaction temperature of the cracking reaction is 800-1100 ℃ and the reaction time is 2-18 h.
4. The method of claim 1, wherein in step (3):
the deposition temperature of the chemical vapor deposition method is 900-1100 ℃, and the deposition time is 100-500 h.
5. The method of claim 1, wherein in step (4):
the reaction temperature of the silicon infiltration reaction is 1460-1600 ℃ and the reaction time is 0.5-3.5 h.
6. The production method according to any one of claims 1 to 5, characterized in that the production method comprises the steps of:
(1) Placing chopped carbon fiber prepreg strips with the fiber volume fraction of 50% -85% into a die cavity, and sequentially carrying out die pressing treatment and cracking reaction to obtain a carbon fiber framework; wherein the length of the chopped carbon fiber prepreg strip is 10-80 mm, the width is 2-10 mm, and the height is 1-3 mm; the temperature of the mould pressing treatment is 140-280 ℃, the pressure is 0.5-20 MPa, and the time is 0.5-5 h; the temperature of the cracking reaction is 800-1100 ℃ and the reaction time is 2-8 h;
(2) Mixing the carbon fiber skeleton with solid powder, and sequentially carrying out mould pressing treatment and cracking reaction to obtain a composite material green body; wherein the solid powder comprises phenolic resin powder, carbon powder and silicon powder; the ratio of the sum of the mass of the carbon powder and the mass of the silicon powder to the mass of the phenolic resin powder is (1-5): 10; the temperature of the mould pressing treatment is 140-280 ℃, the pressure is 0.5-20 MPa, and the time is 0.5-5 h; the temperature of the cracking reaction is 800-1100 ℃ and the reaction time is 2-8 h;
(3) Densification treatment is carried out on the composite material green body by adopting a chemical vapor deposition method to obtain the density of 0.85-1.25 g/cm 3 Is a densified composite green body; wherein the deposition temperature of the chemical vapor deposition method is 900-1100 ℃ and the deposition time is 100-500 h;
(4) Mixing the densified composite material green body and silicon powder according to the following ratio of 1: mixing the materials (2-5) in mass ratio, and then carrying out a silicon infiltration reaction to obtain the C/SiC ceramic matrix composite; wherein the reaction temperature of the silicon infiltration reaction is 1460-1600 ℃ and the reaction time is 0.5-3.5 h.
7. A C/SiC ceramic matrix composite prepared by the method of any one of claims 1 to 6.
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