CN116730736B - Preparation method of SiC composite material based on laser printing and vacuum-pressure assisted in-situ infiltration resin pre-densification - Google Patents

Preparation method of SiC composite material based on laser printing and vacuum-pressure assisted in-situ infiltration resin pre-densification Download PDF

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CN116730736B
CN116730736B CN202310681980.5A CN202310681980A CN116730736B CN 116730736 B CN116730736 B CN 116730736B CN 202310681980 A CN202310681980 A CN 202310681980A CN 116730736 B CN116730736 B CN 116730736B
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sic
printing
vacuum
impregnation
temperature
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CN116730736A (en
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殷杰
王力
陈晓
黄政仁
刘学建
陈忠明
姚秀敏
孙安乐
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a preparation method base of an SiC composite material based on laser printing and vacuum-pressure assisted in-situ infiltration resin pre-densification. The preparation method comprises the following steps: (1) Placing the porous Cf/SiC biscuit obtained by laser 3D printing in an organic resin solution, sequentially carrying out vacuum impregnation and pressure auxiliary impregnation, and then carrying out heating and curing to obtain a heat-curing sample; (2) And (3) performing debonding and siliconizing treatment on the obtained heat-cured sample to obtain the SiC composite material.

Description

Preparation method of SiC composite material based on laser printing and vacuum-pressure assisted in-situ infiltration resin pre-densification
Technical Field
The invention relates to a high-efficiency preparation method of an SiC composite material based on laser 3D printing (also called selective laser sintering Selective Laser Sintering, SLS) and organic resin infiltration in-situ pre-densification, which can be applied to porous SiC biscuit prepared by reinforced SLS rapid prototyping and belongs to the field of material post-treatment in additive manufacturing.
Background
Additive manufacturing technology, also known as 3D printing technology, has evolved significantly and rapidly over the last decades and has received great attention. The principle is based on a discrete stacking mechanism, a three-dimensional model is built through computer CAD, the model is cut, and then raw materials are deposited layer by layer under the control of a computer, so that a part is built. Compared with the traditional equal material manufacturing and material reduction manufacturing technologies, the material addition manufacturing is not limited by a die or a processing technology, the problem that the structure of a product with a complex shape is difficult to form is solved, the processing procedures are reduced, the processing period is shortened, and the processing cost is greatly saved. And the more complex the product structure, the more obvious the advantage of additive manufacturing. Therefore, it is widely used in the manufacture of polymers, metals and some ceramic components. In particular, additive manufacturing has incomparable advantages for manufacturing materials with high hardness and high brittleness, such as SiC. The laser 3D printing (also called selective laser sintering Selective Laser Sintering, SLS) technology is one of the more mature technologies developed in the additive manufacturing technology, and the working principle thereof is as follows: raw material powder is paved on a powder bed through a roller or a scraper, and is sintered together by utilizing high-energy laser pulse, and then the powder paving and sintering are carried out, so that the process is repeated until the construction of the part is completed. The SLS forming is quick and simple, and quick near-net type manufacturing of parts with complex structures can be realized, but because laser printing is a powder-laying type printing method, no external pressure is applied in the Z direction, powder is almost in a natural accumulation state, powder is required to have better fluidity and better large particle fluidity in the powder-laying process, so that the porous biscuit prepared by the SLS printing method taking large-particle-size particles as raw materials is large in pore diameter, high in porosity, poor in strength and reliability, and further the mechanical property and the thermal property of the SiC composite material obtained after reaction infiltration are low, and the application of the SLS technology in ceramic 3D printing is greatly limited.
Currently, densification of SLS preforms is achieved mainly by PCS cracking techniques. Polycarbosilane (PCS) has a main chain composed of silicon and carbon atoms alternately, hydrogen or an organic group is connected to the silicon and carbon atoms, and a molecular chain is in a linear or branched structure. Because the solid product generated by cracking polycarbosilane in a high-temperature environment is mainly SiC, and the rest components escape in the form of gas, PCS is widely applied to densification of SiC parts. However, because volume shrinkage and gas release exist in the PCS cracking process, the part after single strengthening also has higher porosity, and the density does not reach a very high level. Thus, many times of PCS dip cracking are required to achieve a higher bulk density, but the bulk density does not increase all the time but remains stable due to the presence of closed pores that may be created during the cracking process. And the high cost of PCS determines the limited applicability of this approach in the industrialized direction.
Later, the scholars proposed to further strengthen the PCS cracked parts by impregnating the parts with molten Si by a reaction infiltration method. Although LSI can greatly improve the bulk density and mechanical properties of the preform, closed pores inside the preform cannot be eliminated, and residual silicon is introduced into the preform, which has a negative effect on the performance of the preform.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides a simple and efficient preparation method of an SiC composite material based on laser printing and organic resin infiltration in-situ pre-densification. On the one hand, the long period of repeated cyclic impregnation is avoided, and on the other hand, the carbon content and the performance are improved, and meanwhile, the complete densification is realized. In addition, compared with PCS, the resin raw material used for impregnation is low in price, and the cost of a final product can be effectively reduced. The introduction of Cf can improve the strength of the SiC biscuit printed by SLS to a certain extent.
In one aspect, the invention provides a method for preparing a SiC composite material based on laser printing and vacuum-pressure assisted in-situ infiltration resin pre-densification, comprising the following steps:
(1) Placing the porous Cf/SiC biscuit obtained by laser 3D printing in an organic resin solution, sequentially carrying out vacuum impregnation and pressure auxiliary impregnation, and then carrying out heating and curing to obtain a heat-curing sample;
(2) And (3) performing debonding and siliconizing treatment on the obtained heat-cured sample to obtain the SiC composite material.
In the invention, an organic resin solution (such as a phenolic resin solution) is adopted to carry out impregnation strengthening on the porous SiC biscuit after 3D printing. The phenolic resin is used as a reinforcing agent for impregnation reinforcement, and has the advantages of high mechanical strength, high carbon residue rate and the like. During the curing debonding stage, the phenolic resin is carbonized to highly reactive pyrolytic carbon; in the siliconizing stage, the silicon reacts with the molten silicon to generate main phase SiC, and the volume expansion is generated in the reaction process to fill the pores. The phenolic resin densified and strengthened 3D printing SiC component prepared by the method has good compactness, mechanical property and thermal property, so that the use of the 3D printing SiC component is greatly improved.
Preferably, in the step (1), the main components of the porous Cf/SiC green compact include: 5 to 70vol% of carbon fiber with a length of 30 to 200 mu m and a diameter of 6 to 12 mu m; 10 to 60vol% of SiC powder having a particle diameter of 5 to 80 [ mu ] m; and 15 to 30vol% of a thermoplastic resin.
Preferably, in step (1), the laser 3D printing is selective laser 3D printing, and the printing parameters are as follows: the thickness of the powder is 0.06-0.3 mm, the laser power is 10-55W, the scanning speed is 50-12700 mm/s, and the line spacing is 0.0762-2.54 mm.
Preferably, in the step (1), the organic resin in the organic resin solution is at least one of thermosetting phenolic resin, thermosetting epoxy resin and thermosetting asphalt resin;
the solvent in the organic resin solution is at least one selected from absolute ethyl alcohol, isopropanol, n-butanol and n-hexane;
the mass ratio of the organic resin to the solvent is (0.1-0.9): (0.9-0.1).
Preferably, in the step (1), the vacuum degree of vacuum impregnation is less than or equal to 100Pa, and the impregnation time is 20-60 min;
the pressure of the pressure auxiliary impregnation is 2-8 MPa, and the impregnation time is 10-360 min;
the temperature of the heating and curing is 100-200 ℃ and the time is 1-6 h.
Preferably, in the step (2), the temperature of the debonding treatment is 600-1200 ℃, and the atmosphere is vacuum, argon or nitrogen;
the siliconizing treatment is carried out at 1450-1700 ℃ in vacuum, argon or nitrogen atmosphere.
Preferably, the phenolic resin is thermoplastic phenolic resin, the particle size of the powder is 30-50 mu m, the particle morphology is nearly spherical, and the carbon residue rate after pyrolysis is 30-50 wt.%.
Preferably, the system for the debonding treatment includes: the temperature rising rate is 1-3 ℃/min at 0-200 ℃; the heating rate at 200-600 ℃ is 1 ℃/min; the heating rate is 1-2 ℃/min when the temperature is higher than 600 ℃, argon or nitrogen is filled into the mixture after the temperature is kept at the highest temperature for 30min, and the mixture is cooled to the room temperature.
Preferably, the siliconizing treatment system comprises: the temperature rising rate is 5-10 ℃/min at 0-1200 ℃; the temperature rising rate is 3-5 ℃/min at 1200-1400 ℃; raising the temperature to the highest temperature at a heating rate of 1-3 ℃/min, and cooling to 1200 ℃ after the temperature is kept at the highest temperature for 30min, wherein the cooling rate is 1-2.5 ℃/min; and finally, filling argon or nitrogen gas, and cooling to room temperature.
In yet another aspect, the present invention provides a SiC composite material prepared according to the above preparation method, the main component of which includes a SiC phase, residual carbon, and free silicon.
The invention has the beneficial effects that:
1. the Cf/SiC prefabricated member prepared by the 3D printing technology can be rapidly formed, and the preparation method has great advantages in preparing complex-shaped members of high-hardness composite materials such as SiC and the like.
2. The product of the resin cracking is inorganic carbon, and can provide a carbon source for the subsequent LSI process on the basis of maintaining the strength of the porous blank. The SiC prefabricated member prepared by 3D printing is reinforced by adopting the LSI technology, the mechanical strength of the reinforced member is greatly improved, and the content of SiC is also higher.
3. The invention adopts a vacuum impregnation and pressurizing impregnation combination method to realize complete impregnation. The purpose of vacuum impregnation is to sufficiently eliminate open pores in the sample, so as to provide conditions for the subsequent complete impregnation of the resin solution; pressurized impregnation aims at allowing a resin solution having a certain viscosity to sufficiently infiltrate the sample by capillary force to achieve complete impregnation.
4. The invention solves the problem of long pre-strengthening time required by the traditional PCS strengthening to obtain better mechanical property, and avoids the cycle length caused by repeated cyclic impregnation and the non-uniformity of microstructure caused by the internal formation of closed pores and local carbon enrichment while sintering at low temperature and fast densification by a PIP+LSI method.
5. In the invention, the concentration of the resin solution is reduced to realize the impregnation of the low-viscosity solution, so that the problem of incomplete impregnation caused by the impregnation of the high-viscosity solution is avoided, and the generation of closed air holes after the impregnation is reduced. The closed pores are unfavorable for the subsequent siliconizing process, and have great adverse effect on the performance of the composite material. Complete impregnation is achieved by a combination of pressure impregnation and vacuum impregnation.
6. The invention adopts a single impregnation and pyrolysis cycle to avoid the problems of long time consumption and more closed gas holes in multiple cycles, and also provides a carbon source for the subsequent LSI process to realize complete densification.
Drawings
FIG. 1 is an SEM image of (15% -75%) SiC- (60% -0%) Cf-25% PR after impregnation with 50% phenolic resin solution;
FIG. 2 is a graph of flexural strength after impregnation of (15% to 75%) SiC- (60% to 0%) Cf-25% PR in 50% phenolic resin solution with and without impregnation after siliconizing, with the abscissa being SiC volume fraction = SiC/(SiC+Cf);
FIG. 3 is 15% SiC-60% C f After impregnation and siliconizing of the porous SiC green body printed by 25% PR in phenolic resin solutions with different concentrationsMechanical properties of the alloy.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
In the disclosure, the preparation method of the SiC composite material based on laser printing and vacuum-pressure auxiliary in-situ infiltration resin pre-densification can realize the mechanical property optimization of the SiC preform after laser 3D printing, improve the mechanical strength and provide a foundation for wider application of 3D printing SiC.
In one embodiment of the invention, a method for preparing a SiC composite based on laser printing and vacuum-pressure assisted in situ infiltration resin pre-densification comprises the steps of: laser 3D printing of a porous SiC blank, resin solution vacuum-pressure impregnation strengthening of the porous Cf/SiC blank after 3D printing, thermal curing of the impregnated and strengthened component and siliconizing treatment are carried out, and then the laser 3D printing porous C with vacuum-pressure auxiliary in-situ impregnation resin pre-densification can be obtained f SiC greenware and SiC composites.
The following illustrates an exemplary SiC composite preparation method based on laser printing and vacuum-pressure assisted in situ infiltration resin pre-densification.
And preparing a porous Cf/SiC biscuit (or Cf/SiC preform) by laser 3D printing. For example, the porous Cf/SiC greenbody comprises the following main components: 5 to 70vol% of the fiber has a length of 30 to 200 mu m, a diameter of 6 to 12 mu m, and a density of 1.76g/cm 3 Carbon fibers of (2); 10 to 60vol% of the polymer has a particle size of 5 to 80 mu m and a density of 3.20g/cm 3 SiC powder of (c); 15 to 30vol% of the polymer has a density of 1.10g/cm 3 Is a thermoplastic resin of (a).
And (3) placing the laser 3D printing porous Cf/SiC biscuit in an organic resin solution, and respectively carrying out impregnation under vacuum and certain pressure. Wherein the resin solution is composed of absolute ethyl alcohol and organic resin. Preferably, the resin solution is prepared by mixing one or more of phenolic resin, epoxy resin and asphalt resin with absolute ethyl alcohol, and the ratio of the resin solution is 0.1-0.9: 0.9 to 0.1. According to the scheme, the sample in the step (1) is immersed in vacuum (less than or equal to 100 Pa) for 20-60 min and then immersed in pressure of 2-8 MPa for 10-360 min, and as one history, the SiC preform subjected to laser 3D printing is placed in a phenolic resin solution and is immersed in vacuum and 2MPa respectively.
And heating and curing the immersed sample at 100-200 ℃. The curing time is 2-4 h at 100-200 ℃. According to the scheme, the phenolic resin used for laser printing is thermoplastic phenolic resin, the particle size of powder is 30-50 mu m, the particle morphology is nearly spherical, and the carbon residue rate after pyrolysis is 30-50 wt.%.
And (3) performing debonding treatment on the heated and solidified sample under vacuum, argon or nitrogen conditions at 600-1200 ℃. Wherein the de-bonding degree is that the temperature rising rate is 1-3 ℃/min at 0-200 ℃; the heating rate at 200-600 ℃ is 1 ℃/min; the heating rate is 1-2 ℃/min when the temperature is higher than 600 ℃, argon or nitrogen is filled into the mixture after the temperature is kept at the highest temperature for 30min, and the mixture is cooled to the room temperature.
And (3) carrying out siliconizing treatment on the de-bonded sample under vacuum, argon or nitrogen conditions at 1450-1700 ℃ to obtain the resin impregnation reinforced SiC composite material. Wherein, the siliconizing system is that the heating rate is 5-10 ℃/min at 0-1200 ℃; the temperature rising rate is 3-5 ℃/min at 1200-1400 ℃; raising the temperature to the highest temperature at a heating rate of 1-3 ℃/min, and cooling to 1200 ℃ after the temperature is kept at the highest temperature for 30min, wherein the cooling rate is 1-2.5 ℃/min; finally, argon or nitrogen is filled in to cool to room temperature
According to the invention, the prepared resin impregnation cracking pre-densification laser 3D printing porous Cf/SiC biscuit has good compactness and mechanical strength, so that the problem of insufficient mechanical strength of the porous Cf/SiC biscuit formed by SLS printing is greatly solved, and in the subsequent reaction infiltration process, inorganic carbon generated by resin impregnation cracking can provide a carbon source for infiltration reaction, and the performance of the SiC composite material is greatly improved. In addition, the method can improve the proportion of the component SiC and the toughness of the porous Cf/SiC biscuit, and provides a foundation for commercialization of the porous Cf/SiC biscuit.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1: (50% strength phenolic resin solution vacuum pressure impregnation treatment)
(1) The Cf/SiC preform after laser 3D printing (75% Cf-25% PR, 25% SiC-50% Cf-25% PR, 40% SiC-35% Cf-25% PR, 50% SiC-25% Cf-25% PR, 75% SiC-25% PR) is respectively placed in a mass ratio of phenolic resin to alcohol of 1:1, firstly, impregnating for 20 minutes under the condition of vacuum (less than or equal to 100 Pa), and then, impregnating for 30 minutes under the condition of 2 MPa; then heating and curing the sample at 150 ℃ for 2 hours to obtain a phenolic resin impregnated cured 3D printing SiC sample;
(2) And (3) performing debonding treatment on the sample obtained in the step (1) under the conditions of vacuum and 1100 ℃. The de-sticking degree is 0-200℃: heating rate is 3 ℃/min; 200-600℃: heating rate is 1 ℃/min; 600-1100℃: heating rate is 2 ℃/min, and heat preservation is carried out for 30min at 1100 ℃; argon is filled into the reactor to cool to room temperature;
(3) And (3) carrying out siliconizing treatment on the sample obtained in the step (2) under vacuum condition at 1550 ℃ to obtain the phenolic resin impregnation reinforced SiC ceramic. The siliconizing system is 0-1200℃: heating rate is 10 ℃/min; 1200-1400℃: heating rate is 5 ℃/min; 1400-1550℃: heating at a rate of 3 ℃/min, and preserving heat at 1550 ℃ for 30min; 1550-1200℃: the cooling rate is 2.5 ℃/min; argon is filled into the reactor and cooled to room temperature. Initial powder 3D printing member samples of 50% phenolic resin dip cracking pre-densified 75% cf-25% pr were obtained. The flexural strength of the sample is 217MPa, and the elastic modulus is 258GPa.
Example 2: (15% SiC-60% Cf-25% PR, 50% strength phenolic resin solution vacuum pressure impregnation treatment)
(1) Placing the Cf/SiC preform subjected to laser 3D printing in a mass ratio of phenolic resin to alcohol of 1:1, firstly, impregnating for 20 minutes under the condition of vacuum (less than or equal to 100 Pa), and then, impregnating for 30 minutes under the condition of 2 MPa; then heating and curing the sample at 150 ℃ for 2 hours to obtain a 3D printing SiC sample subjected to 50% phenolic resin impregnation curing;
(2) And (3) performing debonding treatment on the sample obtained in the step (1) under the conditions of vacuum and 1100 ℃. The de-sticking degree is 0-200℃: heating rate is 3 ℃/min; 200-600℃: heating rate is 1 ℃/min; 600-1100℃: heating rate is 2 ℃/min, and heat preservation is carried out for 30min at 1100 ℃; argon is filled into the reactor to cool to room temperature;
(3) And (3) carrying out siliconizing treatment on the sample obtained in the step (2) under vacuum condition at 1550 ℃ to obtain the phenolic resin impregnation reinforced SiC ceramic. The siliconizing system is 0-1200℃: heating rate is 10 ℃/min; 1200-1400℃: heating rate is 5 ℃/min; 1400-1550℃: heating at a rate of 3 ℃/min, and preserving heat at 1550 ℃ for 30min; 1550-1200℃: the cooling rate is 2.5 ℃/min; argon is filled into the reactor and cooled to room temperature. Initial powder 3D printing member samples of 50% phenolic resin dip cracking pre-densified 15% sic-60% cf-25% pr were obtained. The flexural strength of the sample is 181MPa, and the elastic modulus is 275GPa.
Example 3: (15% SiC-60% Cf-25% PR, 40% strength phenolic resin solution vacuum pressure impregnation treatment)
(1) Placing the Cf/SiC preform subjected to laser 3D printing in a mass ratio of phenolic resin to alcohol of 2:3, firstly carrying out dipping for 20 minutes under the vacuum condition (less than or equal to 100 Pa) and then carrying out dipping for 30 minutes under the condition of 2 MPa; then heating and curing the sample at 150 ℃ for 2 hours to obtain a 3D printing SiC sample subjected to 40% phenolic resin impregnation curing;
(2) And (3) performing debonding treatment on the sample obtained in the step (1) under the conditions of vacuum and 1100 ℃. The de-sticking degree is 0-200℃: heating rate is 3 ℃/min; 200-600℃: heating rate is 1 ℃/min; 600-1100℃: heating rate is 2 ℃/min, and heat preservation is carried out for 30min at 1100 ℃; argon is filled into the reactor to cool to room temperature;
(3) And (3) carrying out siliconizing treatment on the sample obtained in the step (2) under vacuum condition at 1550 ℃ to obtain the phenolic resin impregnation reinforced SiC ceramic. The siliconizing system is 0-1200℃: heating rate is 10 ℃/min; 1200-1400℃: heating rate is 5 ℃/min; 1400-1550℃: heating at a rate of 3 ℃/min, and preserving heat at 1550 ℃ for 30min; 1550-1200℃: the cooling rate is 2.5 ℃/min; argon is filled into the reactor and cooled to room temperature. A sample of the 40% phenolic resin dip cracking pre-densified 15% sic-60% cf-25% pr initial powder 3D printing member was obtained. The flexural strength of the sample is 311MPa, and the elastic modulus is 284GPa.
Example 4: (15% SiC-60% Cf-25% PR, 40% strength phenolic resin solution vacuum impregnation treatment)
(1) Placing the Cf/SiC preform subjected to laser 3D printing in a mass ratio of phenolic resin to alcohol of 2:3, only dipping for 20 minutes under vacuum condition (less than or equal to 100 Pa); then heating and curing the sample at 150 ℃ for 2 hours to obtain a phenolic resin impregnated cured 3D printing SiC sample;
(2) And (3) performing debonding treatment on the sample obtained in the step (1) under the conditions of vacuum and 1200 ℃. The de-sticking degree is 0-200℃: heating rate is 3 ℃/min; 200-600℃: heating rate is 1 ℃/min; 600-1100℃: heating rate is 2 ℃/min, and preserving heat for 30min at 1200 ℃; argon is filled into the reactor to cool to room temperature;
(3) And (3) carrying out siliconizing treatment on the sample obtained in the step (2) under vacuum condition at 1550 ℃ to obtain the phenolic resin impregnation reinforced SiC ceramic. The siliconizing system is 0-1200℃: heating rate is 10 ℃/min; 1200-1400℃: heating rate is 5 ℃/min; 1400-1550℃: heating at a rate of 3 ℃/min, and preserving heat at 1550 ℃ for 30min; 1550-1200℃: the cooling rate is 2.5 ℃/min; argon is filled into the reactor and cooled to room temperature. A sample of the initial powder 3D printing member pre-densified with 15% sic-60% cf-25% pr was obtained by 40% phenolic resin dip cracking under vacuum. The flexural strength of this sample was 286MPa and the elastic modulus was 287GPa.
Example 5: (pressurized impregnation treatment of a phenolic resin solution of 15% SiC-60% Cf-25% PR, 40% concentration)
(1) Placing the Cf/SiC preform subjected to laser 3D printing in a mass ratio of phenolic resin to alcohol of 2:3, only soaking for 30 minutes under 2 MPa; then heating and curing the sample at 150 ℃ for 2 hours to obtain a phenolic resin impregnated cured 3D printing SiC sample;
(2) And (3) performing debonding treatment on the sample obtained in the step (1) under the conditions of vacuum and 1100 ℃. The de-sticking degree is 0-200℃: heating rate is 3 ℃/min; 200-600℃: heating rate is 1 ℃/min; 600-1100℃: heating rate is 2 ℃/min, and heat preservation is carried out for 30min at 1100 ℃; argon is filled into the reactor to cool to room temperature;
(3) And (3) carrying out siliconizing treatment on the sample obtained in the step (2) under vacuum condition at 1550 ℃ to obtain the phenolic resin impregnation reinforced SiC ceramic. The siliconizing system is 0-1200℃: heating rate is 10 ℃/min; 1200-1400℃: heating rate is 5 ℃/min; 1400-1550℃: heating at a rate of 3 ℃/min, and preserving heat at 1550 ℃ for 30min; 1550-1200℃: the cooling rate is 2.5 ℃/min; argon is filled into the reactor and cooled to room temperature. An initial powder 3D printing member sample of 15% sic-60% cf-25% pr pre-densified by 40% phenolic resin dip cracking at 2MPa was obtained. The flexural strength of the sample is 278MPa, and the elastic modulus is 286GPa.
Example 6:
the SiC composite of this example 6 was prepared as described in example 3, with the only difference: placing the SiC preform subjected to laser 3D printing in a mass ratio of phenolic resin to alcohol of 3:7, the impregnation was carried out at 2MPa for 30 minutes only.
Example 7:
the SiC composite of this example 7 was prepared as described in example 3, with the only difference: placing the SiC preform subjected to laser 3D printing in a mass ratio of phenolic resin to alcohol of 2:8, the impregnation was carried out at 2MPa for 30 minutes only.
Comparative example 1:
the SiC composite of this comparative example 1 was prepared as described in example 3, with the only difference: no impregnation with the organic resin solution was performed.
Table 1 shows the performance of the 50% PR impregnated and non-impregnated green bodies of different composition after debonding:
in the invention, a three-point bending test (Instron-1195, instron, USA) is adopted to test the bending strength of the debonded biscuit; and testing the bulk density and porosity of the debonded biscuit by adopting an Archimedes drainage method.
Table 2 shows the preparation of SiC composites prepared in examples and comparative examples
Table 3 shows the performance parameters of Cf/SiC composites prepared in examples and comparative examples:
strength/MPa Elastic modulus/GPa
Example 1 217 258
Example 2 181 275
Example 3 311 284
Example 4 286 287
Example 5 278 286
Example 6 280 300
Example 7 271 281
Comparative example 1 250 263
。
The Cf/SiC composites were tested for flexural strength and modulus of elasticity using a three-point bending test (Instron-1195, instron, USA) in the present invention.

Claims (7)

1. The preparation method of the SiC composite material based on laser printing and vacuum-pressure assisted in-situ infiltration resin pre-densification is characterized by comprising the following steps of:
(1) Placing the porous Cf/SiC biscuit obtained by laser 3D printing in an organic resin solution, sequentially carrying out vacuum impregnation and pressure auxiliary impregnation, and then carrying out heating and curing to obtain a heat-curing sample;
the laser 3D printing is selective laser 3D printing, and the printing parameters are as follows: the thickness of the powder is 0.06-0.3 mm, the laser power is 10-55W, the scanning speed is 50-12700 mm/s, and the line spacing is 0.0762-2.54 mm;
the main components of the porous Cf/SiC biscuit comprise: 5 to 70vol% of carbon fiber with a length of 30 to 200 mu m and a diameter of 6 to 12 mu m; 10 to 60vol% of SiC powder having a particle diameter of 5 to 80 [ mu ] m; and 15 to 30vol% of a thermoplastic resin; the thermoplastic resin is thermoplastic phenolic resin, the particle size of the powder is 30-50 mu m, the particle morphology is nearly spherical, and the carbon residue rate after pyrolysis is 30 wt-50 wt%;
the organic resin in the organic resin solution is at least one of thermosetting phenolic resin, thermosetting epoxy resin and thermosetting asphalt resin, and the mass ratio of the organic resin to the solvent is (0.2-0.4): (0.8-0.6);
the vacuum degree of the vacuum impregnation is less than or equal to 100Pa, and the impregnation time is 20-60 min; the pressure of the pressure auxiliary impregnation is 2-8 MPa, and the impregnation time is 10-360 min;
(2) And (3) performing debonding and siliconizing treatment on the obtained heat-cured sample to obtain the SiC composite material.
2. The method according to claim 1, wherein in the step (1), the solvent in the organic resin solution is at least one selected from the group consisting of absolute ethanol, isopropanol, n-butanol and n-hexane.
3. The method according to claim 1, wherein the temperature of the heat curing is 100 to 200 ℃ for 1 to 6 hours.
4. The method according to claim 1, wherein in the step (2), the temperature of the debinding is 600 ℃ to 1200 ℃ and the atmosphere is vacuum, argon or nitrogen;
the siliconizing treatment is carried out at 1450-1700 ℃ in vacuum, argon or nitrogen atmosphere.
5. The method according to claim 4, wherein the de-binding system comprises: the temperature rising rate is 1-3 ℃/min at 0-200 ℃; the heating rate at 200-600 ℃ is 1 ℃/min; the heating rate is 1-2 ℃/min when the temperature is higher than 600 ℃, argon or nitrogen is filled into the mixture after the temperature is kept at the highest temperature for 30min, and the mixture is cooled to the room temperature.
6. The method according to claim 4, wherein the siliconizing treatment system comprises: the temperature rising rate is 5-10 ℃/min at 0-1200 ℃; the temperature rising rate is 3-5 ℃/min at 1200-1400 ℃; raising the temperature to the highest temperature at a heating rate of 1-3 ℃/min, and cooling to 1200 ℃ after the temperature is kept at the highest temperature for 30min, wherein the cooling rate is 1-2.5 ℃/min; and finally, filling argon or nitrogen gas, and cooling to room temperature.
7. A SiC composite material prepared according to the preparation method of claim 1, characterized in that the main component comprises SiC phase, residual carbon and free silicon.
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