CN109608235B - Gel infiltration ceramic modification method for C/C composite material special-shaped part - Google Patents
Gel infiltration ceramic modification method for C/C composite material special-shaped part Download PDFInfo
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Abstract
The invention discloses a gel infiltration ceramic modification method of a C/C composite material special-shaped piece, which comprises the following steps: (1) mixing and kneading a ceramic precursor polymer adhesive and penetrating agent powder to obtain sol with uniformly dispersed penetrating agent powder; (2) coating the sol prepared in the step (1) on the surface of a C/C composite material special-shaped piece; (3) and (3) heating the C/C composite material special-shaped piece containing the sol coating prepared in the step (2) in vacuum or inert atmosphere to raise the temperature, so that the sol is solidified and pyrolyzed to form ceramic aerogel, and preserving the heat after the temperature reaches 40-100 ℃ above the melting point of the penetrant powder, so that the penetrant powder in the gel is melted and fully infiltrates the C/C composite material special-shaped piece, thereby obtaining the carbon/carbon-ceramic composite material special-shaped piece. The method has the advantages of good infiltration effect, difficult shedding of the coating, simple process and high utilization rate of the infiltration material, and the mechanical property of the C/C composite material special-shaped piece modified by the method is greatly improved.
Description
Technical Field
The invention relates to the technical field of ceramic matrix composite material preparation, in particular to a gel infiltration ceramic modification method for a C/C composite material special-shaped piece.
Background
The C/C composite material has a series of excellent performances such as high specific strength, high specific modulus, high fracture toughness, excellent ablation resistance, excellent frictional wear resistance, good thermal shock resistance, good chemical stability and the like, and is widely applied to manufacturing throat linings of aeroengines and rockets, turbine blade parts, solid boosters of space shuttles, missile end caps, heat exchangers, heat dissipation devices of high-power electronic devices and the like. As a thermostructural material, a C/C composite material is generally used in a high-temperature aerobic environment, but a carbon material is easily oxidized by air at a higher temperature. Research shows that the C/C composite material begins to be rapidly oxidized in an aerobic environment at the temperature higher than 370 ℃ (Buckley J D. American Ceramic Bulletin,1988,67(2): 364-. C/C composites are often modified by ceramming of the carbon matrix to accommodate high temperature oxidation environments.
The processes for ceramic modification of the C/C composite material mainly comprise a Chemical Vapor Infiltration (CVI) method, a Polymer Impregnation Pyrolysis (PIP) method and a reaction infiltration (RMI) method. Among them, RMI is widely used for ceramic modified C/C composite materials because of its short cycle, near net shape, simple process, low production cost, etc. The traditional RMI ceramic modified C/C composite material process method comprises the following steps: firstly, placing a proper amount of penetrating agent fragments or powder around a C/C composite material; then, vacuumizing the high-temperature sintering furnace and heating to a specific temperature; and finally, keeping the temperature for a period of time, and cooling the sample along with the furnace to obtain the carbon/carbon-ceramic composite material. However, it should be noted that many of the C/C composites that need to be modified are not regular structures, but rather are structurally complex shaped pieces, such as rocket motor nozzles. The traditional RMI method has certain defects in modifying the C/C composite material by ceramic: firstly, the block or powder of the impregnation agent cannot be uniformly placed on a C/C composite material special-shaped piece, and the carbon/carbon-ceramic composite material obtained after RMI has uneven texture, which may cause ablation resistance and reduced mechanical property, and affect the reliability of the material; secondly, in order to obtain a carbon/carbon-ceramic composite material with a uniform structure, if too much impregnation agent is stacked on the C/C composite material special-shaped piece, carbon fibers in the composite material may be ceramized, which may cause the C/C composite material special-shaped piece to become brittle and deteriorate the mechanical property; thirdly, the traditional RMI method is difficult to carry out ceramic modification on the local part of the C/C composite material; finally, excessive infiltrants result in wasted raw materials and may also cause irreversible contamination of the high temperature sintering furnace, affecting the service life of the high temperature sintering furnace.
CN108069723A discloses a ceramic matrix composite corrugated plate obtained by mixing thermosetting resin with infiltration raw materials, then pre-curing by a special process, and then carrying out infiltration treatment. However, the method is not only complicated in process, but also only suitable for workpieces with small angles between the coating and the horizontal plane in the sintering process, otherwise, the coating is easy to fall off on the composite material in the process, and the surface appearances of special-shaped parts are various, so that the method has great limitation in use; in addition, in the infiltration process, the infiltration agent preferentially reacts with the pyrolytic carbon of the epoxy resin to form a ceramic layer, so that the loss of the infiltration raw material is caused, the ceramic layer formed on the surface of the composite material needs to be further removed in the subsequent process, and the melt flow of the infiltration agent is hindered during infiltration, so that the infiltration reaction cannot be continuously carried out.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a gel infiltration ceramic modification method of a C/C composite material special-shaped piece, which has the advantages of good infiltration effect, difficult falling of a coating, simple process and high utilization rate of an infiltration material.
In order to solve the technical problems, the invention adopts the following technical scheme:
a gel infiltration ceramic modification method for C/C composite material special-shaped pieces comprises the following steps:
(1) mixing and kneading a ceramic precursor polymer binder and penetrant powder to obtain sol with uniformly dispersed penetrant powder;
(2) coating the sol prepared in the step (1) on the surface of a C/C composite material special-shaped piece;
(3) and (3) heating the C/C composite material special-shaped piece containing the sol coating prepared in the step (2) in vacuum or inert atmosphere, curing and pyrolyzing the sol to form ceramic aerogel during heating, and preserving heat after the temperature reaches 40-100 ℃ above the melting point of the penetrant powder, so that the penetrant powder in the gel is melted and fully infiltrates the C/C composite material special-shaped piece, thereby obtaining the carbon/carbon-ceramic composite material special-shaped piece.
In the scheme, the sol can be coated on the surface of the C/C composite material special-shaped piece by a brushing or spraying method.
In the method for modifying the C/C composite material profile piece by gel infiltration ceramization, the ceramic precursor polymer preferably includes one or more of polycarbosilane, polysiloxane, polynitrosilane, polycarboborane, polynitroborane, and polycarboborosilane.
In the gel infiltration ceramization modification method of the C/C composite material special-shaped piece, preferably, the infiltrant powder includes one or more of silicon powder, titanium powder, vanadium powder, chromium powder, zirconium powder, niobium powder, molybdenum powder, hafnium powder, tantalum powder, tungsten powder and alloy powder thereof.
In the gel infiltration ceramization modification method of the C/C composite material special-shaped piece, preferably, the mass ratio of the ceramic precursor polymer to the infiltrant powder is 1: 1.5-1: 3.0.
In the method for modifying the C/C composite material special-shaped piece by gel infiltration ceramization, the grain diameter of the infiltrant powder is preferably 1 to 0.5mm, and preferably 10 to 100 μm.
In the gel infiltration ceramization modification method of the C/C composite material special-shaped piece, preferably, the shore hardness of the sol is HA 8-HA 35; the thickness of the sol coating is at least 3mm, preferably 3-5 mm.
Preferably, in the step (3), the heating rate is 1-20 ℃ per minute-1(ii) a The temperature of the heat preservation is 40-100 ℃ above the melting point of the penetrant powder; the heat preservation time is not more than 4 hours, and preferably 1-2 hours.
In the above method for modifying a special-shaped C/C composite material by gel infiltration ceramization, preferably, in step (1), if the molecular weight of the ceramic precursor polymer is high and the ceramic precursor polymer is in a solid state, the ceramic precursor polymer is dissolved into a solution by adding a solvent, and the solution is mixed with the infiltrant powder to prepare an infiltrant powder sol.
The gel infiltration ceramic modification method of the C/C composite material special-shaped piecePreferably, the C/C composite profile piece is of any configuration and size; the thickness of the C/C composite material special-shaped piece is 1-30 mm, and the density of the C/C composite material is 0.6-1.8 g-cm-3。
In the method for modifying the C/C composite profile member by gel infiltration ceramization, the preparation process of the C/C composite profile member preferably includes one of a resin impregnation pyrolysis method, a chemical vapor deposition method and a combination of the resin impregnation pyrolysis method and the chemical vapor deposition method.
Compared with the prior art, the invention has the advantages that:
(1) according to the method, a ceramic precursor polymer is used as a binder and is mixed with an infiltrant powder at normal temperature to prepare an infiltrant powder sol, the infiltrant powder sol is coated on the surface of the C/C composite material special-shaped piece, then the temperature is raised to be higher than the melting point of the infiltrant agent by 40-100 ℃, the ceramic precursor polymer is solidified and pyrolyzed into ceramic aerogel in the temperature raising process, and the molten infiltrant agent enters the C/C composite material special-shaped piece through the pores of the ceramic aerogel and reacts with a matrix of the C/C composite material special-shaped piece to obtain the carbon/carbon-ceramic composite material special-shaped piece. The density of the modified composite material is greatly improved, and the mechanical property of the modified composite material is also greatly improved. The method has simple process operation, does not need a special process for solidification, has low equipment investment and process treatment cost, is suitable for modification of various special-shaped pieces, and has industrial feasibility.
(2) The ceramic precursor polymer has higher ceramic yield and small volume shrinkage of the coating in the pyrolysis process, so the coating is not easy to fall off from a C/C composite material special-shaped piece due to small thermal mismatch. The ceramic formed by the pyrolysis of the ceramic precursor polymer does not react with the infiltration agent, and the utilization rate of the infiltration raw material is high.
(3) The method is suitable for different penetrating agents, can prepare different types of penetrating agent powder sols, and has good universality; the penetrant powder sol can be prepared at normal temperature and coated on a C/C composite material special-shaped piece, the sol coating does not need to be solidified, and the penetrant powder sol can be placed in a high-temperature sintering furnace for infiltration reaction after being brushed or sprayed.
(4) In the invention, ceramic formed by infiltration reaction is not remained on the surface of the C/C composite material special-shaped piece after infiltration, and only ceramic powder formed by pyrolysis of a ceramic precursor polymer is remained, so that the ceramic powder is easy to process and remove.
(5) The method can adjust the sol coating required by infiltration of different parts, is suitable for uniform ceramic modification of various complex components with different thicknesses, and overcomes the limitation that the modification method in the prior art is limited by the appearance of a special-shaped piece.
(6) The invention does not need to process an infiltration crucible and arrange a profiling tool of the infiltration raw material, can greatly reduce the cost and has less pollution to a high-temperature sintering furnace, and the C/C composite material special-shaped piece can be fully infiltrated and ceramic-modified.
Drawings
FIG. 1 is a process flow diagram of a gel infiltration ceramization modification method for a C/C composite material special-shaped piece according to an embodiment of the present invention.
FIG. 2 is a schematic view of the surface of a C/C composite material profile coated with an infiltrant powder sol according to an embodiment of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention. The materials and equipment used in the following examples are commercially available.
The invention relates to a gel infiltration ceramic modification method of a C/C composite material special-shaped piece, which comprises the following steps:
(1) mixing and kneading a ceramic precursor polymer adhesive and penetrating agent powder to obtain high-viscosity sol with uniformly dispersed penetrating agent powder;
(2) coating the sol prepared in the step (1) on the surface of a C/C composite material special-shaped piece by a brush coating or spraying method;
(3) and (3) placing the C/C composite material special-shaped piece containing the sol coating prepared in the step (2) in a high-temperature sintering furnace, vacuumizing, heating the sintering furnace by a program, solidifying and pyrolyzing the sol to form ceramic aerogel during heating, and preserving heat after the temperature of the sintering furnace reaches 40-100 ℃ above the melting point of the permeating agent, so that the permeating agent in the gel is melted and fully infiltrates the C/C composite material, thereby obtaining the carbon/carbon-ceramic composite material special-shaped piece.
Preferably, the binder comprises one or two or more of polycarbosilane, polysiloxane, polyazosilane, polycarboborane, polyazoborane, and polycarboborosilane. In the present invention, the ceramic precursor polymer is not limited to the above-mentioned examples, and may be other ceramic precursor polymers, and when the ceramic precursor polymer has a high molecular weight and is in a solid state, the ceramic precursor polymer may be dissolved into a solution by adding a solvent, and the solution may be mixed with a penetrant powder and subjected to a conventional treatment process to prepare a penetrant powder sol.
In the step (1), the gel formed by each ceramic precursor polymer has certain influence on the infiltration condition of the infiltration agent, and in the ceramic precursor polymer used in the invention, the sol formed by polycarbosilane and polycarboxyborosilane has better result on the infiltration of C/C composite material special-shaped pieces by the infiltration agent in terms of the current experimental result.
Preferably, the infiltrant powder is metal powder, and the metal powder comprises one or two or more of silicon powder, titanium powder, vanadium powder, chromium powder, zirconium powder, niobium powder, molybdenum powder, hafnium powder, tantalum powder, tungsten powder and alloy powder thereof.
Preferably, the particle size of the penetrant powder is 1 to 0.5mm, preferably 10 to 100 μm.
Preferably, the Shore hardness of the sol is HA 8-HA 35, so that the coating can be stably adhered to the surface of the C/C special-shaped piece.
Preferably, the C/C composite profile is of any configuration and size.
Preferably, the wall thickness of the C/C composite material special-shaped piece is 1-30 mm, and the density of the C/C composite material is 0.6-2.2 g-cm-3Preferably 0.6 to 1.8 g/cm-3。
Preferably, in the step (3), the temperature programming speed is 1-20 ℃ min-1The heat preservation time is within 4 hours, and preferably 1-2 hours.
Preferably, in the step (3), the temperature is raised to 40-100 ℃ above the melting point of the penetrant powder for heat preservation, specifically, the melting point of the penetrant is taken as the standard.
Preferably, the preparation process of the C/C composite profile piece comprises one of a resin impregnation pyrolysis method, a chemical vapor deposition method and a combination of the resin impregnation pyrolysis method and the chemical vapor deposition method.
In the invention, the kneading time in the step (1) depends on the mixing degree of the penetrant powder and the ceramic precursor polymer, the sol mixing is not uniform due to too short time, and the process cost is increased due to too long time, wherein the preferable range of the kneading time is 5-30 min.
In the invention, the thickness of the sol coating in the step (1) depends on the thickness of the C/C composite material special-shaped piece, and in order to fully densify and ceramic-modify the C/C composite material special-shaped piece, the thickness is at least 3mm, preferably 3-5 mm.
Example 1
The invention discloses a gel infiltration ceramic modification method for a C/C composite material special-shaped piece, which has a process flow shown in figure 1 and comprises the following steps:
(1) taking 15g of silicon powder with the particle size of 10 mu m and 5g of polycarbosilane, uniformly mixing and kneading the silicon powder and the polycarbosilane for 10 min;
(2) the cutting density was 1.35g/cm310g of the C/C composite material special-shaped piece is placed in ethanol for ultrasonic cleaning for 5min to remove surface impurities and dried;
(3) coating the prepared silica sol on the surface of a C/C composite material special-shaped piece with an arc-shaped structure (the coating is vertical to the horizontal plane), wherein the thickness of the coating is 3mm, and the coating is schematically shown in FIG. 2;
(4) placing the C/C composite material special-shaped piece containing the silicon powder sol in a carbon tube sintering furnace, vacuumizing the carbon tube sintering furnace to 5Pa, heating the sintering furnace to 1500 ℃ at a speed of 10 ℃/min, preserving heat for 120min, and cooling along with the furnace to obtain the C/C-SiC composite material special-shaped piece.
The density, open porosity and three-point bending strength of the prepared C/C-SiC composite material are shown in Table 1. It can be seen from the table that the density and the bending strength are greatly improved, which indicates that the gel coat does not fall off and the C/C composite profile is fully infiltrated and ceramic-modified.
TABLE 1 parameters of C/C and C/C-SiC composite profiles prepared in example 1
| Material | Density/g/cm3 | Open porosity/%) | Flexural strength/MPa |
| C/C composite material | 1.35 | 15.9 | 98.7 |
| C/C-SiC composite material | 1.96 | 6.1 | 314.0 |
Example 2
The invention discloses a gel infiltration ceramic modification method for a C/C composite material special-shaped piece, which has a process flow shown in figure 1 and comprises the following steps:
(1) taking 20g of silicon-zirconium alloy powder with the particle size of 10 mu m (the atomic ratio of silicon to zirconium is 90: 10) and 7g of polycarbosilane, uniformly mixing and kneading the silicon-zirconium alloy powder and the polycarbosilane for 10 min;
(2) the cutting density was 1.40g/cm3Placing 15g of the C/C composite material special-shaped piece in ethanol, performing ultrasonic cleaning for 5min to remove surface impurities, and drying;
(3) brushing the prepared silicon-zirconium alloy powder sol on the surface of a C/C composite material special-shaped piece with an arc-shaped structure (the coating is vertical to the horizontal plane), wherein the thickness of the coating is 3mm, and the schematic diagram is shown in FIG. 2;
(4) placing the C/C composite material special-shaped piece containing the silicon-zirconium alloy powder sol in a carbon tube sintering furnace, vacuumizing the carbon tube sintering furnace to 5Pa, heating the sintering furnace to 1600 ℃ at a speed of 10 ℃/min, preserving the heat for 120min, and cooling along with the furnace to obtain the C/C-SiC-ZrC composite material special-shaped piece.
The density, open porosity and three-point bending strength of the prepared C/C-SiC-ZrC composite material are shown in Table 2. It can be seen from the table that the density and the bending strength are greatly improved, which indicates that the gel coat does not fall off and the C/C composite profile is fully infiltrated and ceramic-modified.
TABLE 2C/C and C/C-SiC-ZrC composite profiles parameters prepared in example 2
| Material | Density/g/cm3 | Open porosity/%) | Flexural strength/MPa |
| C/C composite material | 1.40 | 14.2 | 114.3 |
| C/C-SiC-ZrC composite material | 1.80 | 8.3 | 160.9 |
Example 3
The invention discloses a C/C composite material special-shaped piece infiltration ceramic modification method, the process flow is shown in figure 1, and the method comprises the following steps:
(1) taking 15g of silicon powder with the particle size of 10 mu m and 5g of poly-boron carbonitride, uniformly mixing and kneading the silicon powder and the poly-boron carbonitride for 10 min;
(2) the cutting density was 1.4g/cm310g of the C/C composite material special-shaped piece is placed in ethanol for ultrasonic cleaning for 5min to remove surface impurities and dried;
(3) coating the prepared silica sol on the surface of a C/C composite material special-shaped piece (with an arc structure and a coating layer vertical to a horizontal plane) by brushing, wherein the thickness of the coating layer is 3mm, and the prepared silica sol is schematically shown in FIG. 2;
(4) placing the C/C composite material special-shaped piece containing the silicon powder sol in a carbon tube sintering furnace, vacuumizing the carbon tube sintering furnace to 5Pa, heating the sintering furnace to 1500 ℃ at a speed of 10 ℃/min, preserving heat for 120min, and cooling along with the furnace to obtain the C/C-SiC composite material special-shaped piece.
The density, open porosity and three-point bending strength of the prepared C/C-SiC composite material are shown in Table 3. It can be seen from the table that the density and the bending strength are greatly improved, which indicates that the gel coat does not fall off and the C/C composite profile is fully infiltrated and ceramic-modified.
TABLE 3C/C and C/C-SiC composite profiles parameters prepared in example 3
Comparative example 1
A C/C composite material special-shaped piece infiltration ceramic modification method is shown in a process flow of figure 1 and comprises the following steps:
(1) taking 15g of silicon powder with the particle size of 10 mu m and 5g of barium phenolic resin, uniformly mixing and kneading the silicon powder and the barium phenolic resin for 10 min;
(2) the cutting density was 1.35g/cm310g of the C/C composite material special-shaped piece is placed in ethanol for ultrasonic cleaning for 5min to remove surface impurities and dried;
(3) brushing the prepared silica sol on the surface of a C/C composite material special-shaped piece (with an arc structure and a coating vertical to a horizontal plane) and curing, wherein the curing process comprises the steps of preserving heat at 80 ℃ for 7 hours, then preserving heat at 150 ℃ for 5 hours, and enabling the thickness of the coating to be 3mm, which is schematically shown in FIG. 2;
(4) placing the C/C composite material special-shaped piece containing the silicon powder sol in a carbon tube sintering furnace, vacuumizing the carbon tube sintering furnace to 5Pa, heating the sintering furnace to 1500 ℃ at a speed of 10 ℃/min, preserving heat for 120min, opening a furnace body along with furnace cooling, finding that the coating falls off from the surface of the C/C composite material, wherein the falling layer is silicon carbide, and the silicon melt is formed by reacting with pyrolytic carbon of barium-phenolic aldehyde.
The density, open porosity and three-point bending strength of the prepared C/C-SiC composite material are shown in Table 4. From the table, the density and the bending strength are not improved but reduced, and the work piece analysis shows that during the modification process, the barium phenolic resin is preferentially pyrolyzed to form pyrolytic carbon, so that the volume of the coating is severely shrunk, the gel coating vertical to the horizontal plane is peeled off, the C/C composite material special-shaped piece is not subjected to infiltration ceramic modification, partial impurities in the C/C composite material special-shaped piece are removed at high temperature, and the C/C material is influenced by high temperature, so that the strength of the special-shaped piece is reduced.
TABLE 4 parameters of C/C and C/C-SiC composite profiles prepared in comparative example 1
| Material | Density/g/cm3 | Open porosity/%) | Flexural strength/MPa |
| C/C composite material | 1.35 | 14.2 | 114.3 |
| C/C-SiC composite material | 1.33 | 14.5 | 106.5 |
Comparative example 2
A C/C composite material special-shaped piece infiltration ceramic modification method is shown in a process flow of figure 1 and comprises the following steps:
(1) taking 15g of silicon powder with the particle size of 10 mu m and 5g of boron phenolic resin, uniformly mixing and kneading the silicon powder and the boron phenolic resin for 10 min;
(2) the cutting density was 1.35g/cm310g of the C/C composite material special-shaped piece is placed in ethanol for ultrasonic cleaning for 5min to remove surface impurities and dried;
(3) brushing the prepared silica sol on the surface of a C/C composite material special-shaped piece (with an arc structure and a coating vertical to a horizontal plane) and curing, wherein the curing process comprises the steps of preserving heat at 80 ℃ for 7 hours, then preserving heat at 150 ℃ for 5 hours, and enabling the thickness of the coating to be 3mm, which is schematically shown in FIG. 2;
(4) placing the C/C composite material special-shaped piece containing the silicon powder sol in a carbon tube sintering furnace, vacuumizing the carbon tube sintering furnace to 5Pa, heating the sintering furnace to 1500 ℃ at a speed of 10 ℃/min, preserving heat for 120min, opening a furnace body along with furnace cooling, finding that the coating falls off from the surface of the C/C composite material, wherein the falling layer is silicon carbide, and the silicon melt is formed by reacting with pyrolytic carbon of boron phenolic.
The density, open porosity and three-point bending strength of the prepared C/C-SiC composite material are shown in Table 5. From the table, the density and the bending strength are not improved but reduced, and the analysis of the workpiece shows that, in the modification process, boron phenolic resin is preferentially pyrolyzed to form pyrolytic carbon, so that the volume of the coating is severely shrunk, the gel coating vertical to the horizontal plane is peeled off, the C/C composite material special-shaped piece is not subjected to infiltration ceramic modification, partial impurities in the C/C composite material special-shaped piece are removed at high temperature, and the C/C material is influenced by high temperature, so that the strength of the special-shaped piece is reduced.
TABLE 5C/C and C/C-SiC composite profiles parameters prepared in comparative example 2
| Material | Density/g/cm3 | Open porosity/%) | Flexural strength/MPa |
| C/C composite material | 1.35 | 14.2 | 114.3 |
| C/C-silicon carbide composite material | 1.37 | 13.8 | 112.4 |
In combination with the above embodiments, the method of the present invention has the following advantages: (1) the method is suitable for ceramic modification of special-shaped pieces with various shapes, is suitable for different penetrating agents, can prepare different types of penetrating agent powder sols, and has good universality; the penetrant powder sol can be prepared at normal temperature, and the sol can be coated on a C/C composite material special-shaped piece at normal temperature, the sol coating does not need to be solidified, and the penetrant powder sol can be placed in a high-temperature sintering furnace for infiltration reaction after being brushed or sprayed; (2) the ceramic precursor polymer has higher ceramic yield, so the volume shrinkage of the coating is smaller, the coating is not easy to fall off from a C/C composite material special-shaped piece, the ceramic formed by the pyrolysis of the ceramic precursor polymer does not react with the melt of the penetrating agent, and the utilization rate of the penetrating agent is high; (3) in the invention, ceramic formed by infiltration reaction is not left on the surface of the C/C composite material special-shaped piece after infiltration, and only ceramic powder formed by pyrolysis of a ceramic precursor polymer is left, so that the ceramic powder is easy to process and remove; (4) the invention can adjust the sol coating needed by the infiltration of different parts, and is suitable for the uniform ceramic modification of complex components with different thicknesses; (5) the invention does not need to process an infiltration crucible and arrange a profiling tool of the infiltration raw material, can greatly reduce the cost and has less pollution to a high-temperature sintering furnace, and the C/C composite material special-shaped piece can be fully infiltrated and ceramic-modified; (6) the method has the advantages of simple process operation, low equipment investment and process treatment cost and industrial feasibility.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make numerous possible variations and modifications to the present invention, or modify equivalent embodiments to equivalent variations, without departing from the scope of the invention, using the teachings disclosed above. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention should fall within the protection scope of the technical scheme of the present invention, unless the technical spirit of the present invention departs from the content of the technical scheme of the present invention.
Claims (8)
1. A gel infiltration ceramic modification method for C/C composite material special-shaped parts is characterized by comprising the following steps:
(1) mixing and kneading a ceramic precursor polymer adhesive and penetrating agent powder to obtain sol with uniformly dispersed penetrating agent powder; the Shore hardness of the sol is HA 8-HA 35; the ceramic precursor polymer comprises one or more than two of polycarbosilane, polysiloxane, polynitrosilane, polycarboborane, polynitroborane and polynitroborosilane; the penetrating agent powder comprises one or more of silicon powder, titanium powder, vanadium powder, chromium powder, zirconium powder, niobium powder, molybdenum powder, hafnium powder, tantalum powder, tungsten powder and alloy powder thereof;
(2) coating the sol prepared in the step (1) on the surface of a C/C composite material special-shaped piece;
(3) heating the C/C composite material special-shaped piece containing the sol coating prepared in the step (2) in vacuum or inert atmosphere, wherein the heating rate is 1-20 ℃ per minute-1(ii) a And (3) during the temperature rise, the sol is solidified and pyrolyzed to form ceramic aerogel, and after the temperature reaches 40-100 ℃ above the melting point of the permeating agent, heat preservation is carried out, so that the permeating agent powder in the ceramic aerogel is melted and fully infiltrates the C/C composite material special-shaped piece, and the carbon/carbon-ceramic composite material special-shaped piece is obtained.
2. The method for modifying the C/C composite profile of claim 1, wherein the mass ratio of the ceramic precursor polymer to the infiltrant powder is 1: 1.5 to 1: 3.0.
3. The method for modifying the C/C composite profile of claim 1 by gel infiltration ceramization, wherein the particle size of the infiltrant powder is 1 μm to 0.5 mm.
4. The method for gel infiltration ceramming of a C/C composite profile piece according to claim 1, wherein the thickness of the sol coating is at least 3 mm.
5. The method for modifying the C/C composite profile shape by gel infiltration ceramization according to claim 1, wherein in the step (1), if the ceramic precursor polymer has a high molecular weight and is in a solid state, it is dissolved into a solution by adding a solvent, and the obtained solution is mixed with the infiltrant powder to prepare the infiltrant powder sol.
6. The method for modifying C/C composite material profile-shaped piece by gel infiltration ceramization according to claim 1, wherein in the step (3), the temperature of the heat preservation is 40-100 ℃ above the melting point of the infiltration agent; the heat preservation time is within 4 h.
7. The method of gel infiltration ceramming of C/C composite profile piece according to claim 1, characterized in that said C/C composite profile piece is of arbitrary structure and size; the thickness of the C/C composite material special-shaped piece is 1-30 mm; the density of the C/C composite material is 0.6-1.8 g-cm-3。
8. The method of gel infiltration ceramming of C/C composite profile element of claim 1, wherein said C/C composite profile element is prepared by a process comprising one of resin impregnation pyrolysis, chemical vapor deposition and a combination of resin impregnation pyrolysis and chemical vapor deposition.
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