CN111747754B - Carbon fiber reinforced SiYOC composite material and preparation method thereof - Google Patents

Carbon fiber reinforced SiYOC composite material and preparation method thereof Download PDF

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CN111747754B
CN111747754B CN202010661626.2A CN202010661626A CN111747754B CN 111747754 B CN111747754 B CN 111747754B CN 202010661626 A CN202010661626 A CN 202010661626A CN 111747754 B CN111747754 B CN 111747754B
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carbon fiber
composite material
siyoc
curing
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CN111747754A (en
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郭蕾
马青松
胡智瑜
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National University of Defense Technology
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Abstract

The invention discloses a carbon fiber reinforced SiYOC composite material and a preparation method thereof, wherein a three-dimensional carbon fiber prefabricated member is taken as a reinforcement body, yttrium modified silicon resin is taken as a precursor body, and the C/SiYOC composite material is obtained by repeated dipping-curing-cracking, wherein the carbon fiber prefabricated member (three-dimensional braided fabric, felt body and the like) is taken as a framework, a Y modified silicon resin precursor body is dipped under the vacuum condition, is subjected to heat treatment and then is crosslinked and cured, then high-temperature cracking is carried out to convert the precursor body into a SiYOC ceramic matrix, and the C/SiYOC composite material is obtained when the weight of a sample in the period is increased by not more than 1% compared with that of the sample at the end of the last period after repeated dipping-curing-cracking. The invention has the advantages of low cost, good high temperature resistance, low requirement on equipment and the like, and can effectively improve the high temperature resistance of the C/SiOC composite material.

Description

Carbon fiber reinforced SiYOC composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of high-temperature-resistant ceramic matrix composite materials, and particularly relates to a carbon fiber reinforced SiYOC composite material and a preparation method thereof.
Background
The rapid development in the aerospace field puts urgent demands on low cost, long service life and ultrahigh temperature of high-temperature structural materials. The carbon fiber reinforced ceramic matrix composite has excellent characteristics of high temperature resistance, high specific strength, corrosion resistance and the like, and is widely applied to surface thermal protection systems and propulsion systems of aerospace aircrafts. The carbon fiber reinforced Polysiloxane (PSO) converted SiOC (C/SiOC) composite material has the advantages of short flow, low cost and the like, and becomes a light high-temperature-resistant structural material with great application prospect.
However, because the SiOC ceramic matrix has a metastable ternary structure, phase separation and carbothermic reduction reaction can occur at high temperature, which leads to structural instability and performance reduction, and limits the high temperature resistance of the C/SiOC composite material. The structure of the ceramic matrix of SiOC converted from PSO can be modified to improve the thermal stability, wherein, the introduction of the heterogeneous element M into PSO molecules can not only give full play to the characteristics and advantages of PSO, but also uniformly regulate and control the fine structure of the ceramic matrix of SiOC on the molecular level or even the atomic level, and the applicability to the precursor impregnation cracking method for preparing the C/SiOC composite material is strong, and the high temperature resistance of the C/SiOC composite material can be improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a carbon fiber reinforced SiYOC composite material and a preparation method thereof, namely a C/SiYOC composite material and a preparation method thereof, and the preparation method of the carbon fiber reinforced SiYOC composite material is simple in method, convenient to operate, low in cost and good in high temperature resistance. Yttrium has the characteristics of large atomic radius and long average bond path of Y-O bond, has strong oxygen affinity and is easy to form Y-O bond, Si-O-Y bond can be formed by introducing the Y-O-Y bond into SiOC ceramic to enhance the network strength of the SiOC ceramic, and Y with high melting point and without phase separation can be formed at high temperature2SiO5Or Y2Si2O7And the high temperature resistance of the SiOC matrix and the C/SiOC composite material can be improved.
The preparation method of the carbon fiber reinforced SiYOC composite material comprises the following steps:
1) dipping: preparing a carbon fiber prefabricated part, placing the carbon fiber prefabricated part under the vacuum condition with the pressure of less than 500Pa, and soaking the carbon fiber prefabricated part for 2-8h by using a Y-modified silicon resin precursor solution; the Y modified silicon resin precursor solution is a mixed sol of yttrium sol and silicon resin ethanol solution, wherein the yttrium sol is prepared from Y (NO)3)2·6H2O in ethanol, Y (NO)3)2·6H2The mass of O is 10-50% of the mass of the silicon resin, and the mass ratio of the silicon resin to the ethanol in the silicon resin ethanol solution is (2-5): 10;
2) and (3) curing: carrying out heat preservation on the carbon fiber prefabricated part soaked in the step to form gel, and then crosslinking and curing the carbon fiber prefabricated part subjected to gel at the temperature of 150-250 ℃ for 4-8 h;
3) cracking: performing pyrolysis on the carbon fiber prefabricated part subjected to crosslinking and curing in the previous step in an inert atmosphere, wherein the pyrolysis temperature is 1000-1200 ℃, and the pyrolysis time is 30-120 min;
repeating the dipping-curing-cracking cycle for multiple times until the weight of the sample is increased by no more than 1% when the cycle is finished compared with the weight of the sample when the cycle is finished, and finishing the preparation to obtain the carbon fiber reinforced SiYOC composite material.
The carbon fiber prefabricated part in the step 1) is one of a 2.5-dimensional braided fabric, a plain cloth laminated sewing prefabricated part, a three-dimensional needled felt, a three-dimensional four-way braided fabric, a three-dimensional five-way braided fabric or a three-dimensional six-way braided fabric.
The silicone resin in step 1) is low molecular weight methyl silicone resin (MK), and MK is methyl silicone resin dissolved in toluene and has high SiO2Content, after complete oxidation, 80% SiO2Calculated as solid resin content.
And 2) performing heat preservation on the carbon fiber prefabricated part impregnated in the step 2) to form gel, namely performing heat preservation on the carbon fiber prefabricated part impregnated in the step for 24-72 hours at the temperature of 60-80 ℃ to form gel.
The above dipping-curing-cracking cycle is repeated for a plurality of times, preferably for 8 to 15 times.
The invention also relates to a carbon fiber reinforced SiYOC composite material prepared by the preparation method of the carbon fiber reinforced SiYOC composite material, under the condition of the same preparation process, the heat-resistant temperature of the C/SiYOC composite material in a low-pressure environment can be improved by more than 200 ℃ by the C/SiYOC composite material prepared by the invention, and the prepared C/SiYOC composite material has better high-temperature resistance.
Compared with the prior art, the invention has the following advantages:
1. the C/SiYOC composite material is prepared by modifying Y element, and yttrium has the characteristics of large ionic radius and long average bond path of Y-O bond, and has strong oxygen affinity and is easy to form Y-O bond. The SiOC ceramic is introduced into the SiOC ceramic, and Si-O-Y bonds are hopefully formed to enhance the network strength of the SiOC ceramic, so that the structural stability of the SiOC ceramic is improved. In high temperature environment, Y will consume O to form Y2O3，Y2O3Not only does not generate carbothermal reduction reaction with C, but also consumes SiO2Forming Y with higher melting point and without phase separation2SiO5Or Y2Si2O7. In addition, the micromolecular silicon resin and inorganic yttrium salt are adopted to carry out hydrolysis-polycondensation reaction to generate Y modified silicon resin precursor, the introduction amount of Y element can be increased, the gel yield is improved, the compactness of the C/SiYOC composite material is further improved, and the mechanical property is not sacrificedThe high temperature resistance of the alloy is obviously improved.
2. The preparation method is simple, the operation is convenient, the cost is low, and the obtained C/SiYOC composite material can increase the long-life service temperature of the C/SiOC composite material under low pressure to more than 1500.
Drawings
FIG. 1 is a graph of load-displacement curves of the C/SiOC composite material prepared in example 1 of the present invention, which is tested for mechanical properties after heat treatment at different temperatures under low pressure conditions.
FIG. 2 is a graph of load-displacement curves for testing mechanical properties of the carbon fiber reinforced SiYOC (C/SiYOC) composite material prepared in example 1 of the present invention after heat treatment at different temperatures under low pressure conditions.
Detailed Description
The present invention is described in further detail below by way of examples, which should not be construed as limiting the invention thereto.
Example 1:
a preparation method of a carbon fiber reinforced SiYOC composite material comprises the following steps:
(1) dipping: preparing a 2.5-dimensional woven fabric, placing the 2.5-dimensional woven fabric under a vacuum condition with the pressure of less than 500Pa, and soaking the 2.5-dimensional woven fabric for 3 hours by using a modified precursor solution with the Y content of 10% of the mass of the silicon resin; the Y modified silicon resin precursor solution is a mixed sol of yttrium sol and silicon resin ethanol solution, wherein the yttrium sol is prepared from Y (NO)3)2·6H2Dissolving O in ethanol to obtain the product, wherein the mass ratio of the silicone resin to the ethanol in the silicone resin ethanol solution is 2: 10, the silicone resin is low molecular weight methyl silicone resin (MK);
(2) and (3) curing: placing the impregnated carbon fiber prefabricated member at 60 ℃ for 72h until the carbon fiber prefabricated member is gelled, and then crosslinking and curing the gelled prefabricated member at 200 ℃ for 6 h;
(3) cracking: performing pyrolysis on the carbon fiber prefabricated part after crosslinking and curing in an inert atmosphere, wherein the pyrolysis temperature is 1000 ℃, and the pyrolysis time is 60 min;
after the dipping-curing-cracking cycle is repeated for 12 times, the weight of the obtained sample is only 0.84% compared with that of the sample at the end of the 11 th cycle, and the preparation is completed to obtain the C/SiYOC composite material.
The C/SiYOC composite material prepared by the above method and the C/SiOC composite material prepared by the same technology are subjected to heat treatment under low pressure condition and compared with each other, and the results are shown in the following table, wherein the load-displacement curves of the two materials are respectively shown in FIG. 1(C/SiOC) and FIG. 2 (C/SiYOC):
Figure BDA0002578789730000031
example 2:
a preparation method of a carbon fiber reinforced SiYOC composite material comprises the following steps:
(1) dipping: preparing a three-dimensional five-way woven fabric, placing the three-dimensional five-way woven fabric under a vacuum condition with the pressure of less than 500Pa, and soaking the three-dimensional five-way woven fabric for 2 hours by using a modified precursor solution with the Y content of 50% of the mass of the silicon resin; the Y modified silicon resin precursor solution is a mixed sol of yttrium sol and silicon resin ethanol solution, wherein the yttrium sol is prepared from Y (NO)3)2·6H2Dissolving O in ethanol to obtain the product, wherein the mass ratio of the silicone resin to the ethanol in the silicone resin ethanol solution is 5: 10, the silicone resin is low molecular weight methyl silicone resin (MK);
(2) and (3) curing: standing the impregnated carbon fiber at 70 ℃ for 36h to gel, and crosslinking and curing the gelled prefabricated member at 150 ℃ for 8 h;
(3) cracking: performing pyrolysis on the carbon fiber prefabricated part after crosslinking and curing in an inert atmosphere, wherein the pyrolysis temperature is 1200 ℃, and the pyrolysis time is 90 min;
after the dipping-curing-cracking cycle is repeated for 15 times, the weight of the obtained sample is only 0.76% compared with that of the sample at the end of the 14 th cycle, and the preparation is completed to obtain the C/SiYOC composite material.
The C/SiYOC composite material prepared by the method is subjected to heat treatment under the condition of low pressure and compared with the C/SiOC composite material prepared by the same process, and the results are shown in the following table.
Figure BDA0002578789730000041
Example 3:
a preparation method of a carbon fiber reinforced SiYOC composite material comprises the following steps:
(1) dipping: preparing a three-dimensional needled felt, placing the felt under a vacuum condition with the pressure of less than 500Pa, and soaking the felt for 4 hours by using a modified precursor solution with the Y content of 15% of the mass of the silicon resin; the Y modified silicon resin precursor solution is a mixed sol of yttrium sol and silicon resin ethanol solution, wherein the yttrium sol is prepared from Y (NO)3)2·6H2Dissolving O in ethanol to obtain the product, wherein the mass ratio of the silicone resin to the ethanol in the silicone resin ethanol solution is 3: 10, the silicone resin is low molecular weight methyl silicone resin (MK);
(2) and (3) curing: standing the impregnated carbon fiber prefabricated member at 75 ℃ for 30h until the carbon fiber prefabricated member is gelled, and then crosslinking and curing the gelled prefabricated member at 250 ℃ for 4 h;
(3) cracking: performing pyrolysis on the carbon fiber prefabricated part after crosslinking and curing in an inert atmosphere, wherein the pyrolysis temperature is 1200 ℃, and the pyrolysis time is 30 min;
after the dipping-curing-cracking cycle is repeated for 8 times, the weight of the obtained sample is only 0.91% compared with the sample at the end of the 7 th cycle, and the preparation is completed to obtain the C/SiYOC composite material.
The C/SiYOC composite material prepared by the method is subjected to heat treatment under the condition of low pressure and compared with the C/SiOC composite material prepared by the same process, and the results are shown in the following table.
Figure BDA0002578789730000042
Example 4:
a preparation method of a carbon fiber reinforced SiYOC composite material comprises the following steps:
(1) dipping: preparing a tabby cloth laminated sewing prefabricated member, placing the prefabricated member under the vacuum condition with the pressure less than 500Pa, and soaking the prefabricated member for 2 hours by using a modified precursor solution with the Y content of 35 percent of the mass of the silicon resin; the Y modified silicon resin precursor solution is a mixed sol of yttrium sol and silicon resin ethanol solution, whereinThe yttrium sol of (2) is prepared from Y (NO)3)2·6H2Dissolving O in ethanol to obtain the product, wherein the mass ratio of the silicone resin to the ethanol in the silicone resin ethanol solution is 4: 10, the silicone resin is low molecular weight methyl silicone resin (MK);
(2) and (3) curing: standing the impregnated carbon fiber prefabricated member at 80 ℃ for 24h until the carbon fiber prefabricated member is gelled, and then crosslinking and curing the gelled prefabricated member at 180 ℃ for 7 h;
(3) cracking: performing pyrolysis on the carbon fiber prefabricated part after crosslinking and curing in an inert atmosphere, wherein the pyrolysis temperature is 1100 ℃, and the pyrolysis time is 120 min;
after the dipping-curing-cracking cycle is repeated for 13 times, the weight of the obtained sample is only 0.90 percent compared with the sample at the end of the 12 th cycle, and the preparation is finished to obtain the C/SiYOC composite material.
The C/SiYOC composite material prepared by the method is subjected to heat treatment under the condition of low pressure and compared with the C/SiOC composite material prepared by the same process, and the results are shown in the following table.
Figure BDA0002578789730000051
Comparative example, compared to the example, with the difference that Y is added to the precursor solution2O3Filling:
(1) dipping: preparing a tabby cloth laminated sewing prefabricated part, placing the prefabricated part under the vacuum condition with the pressure less than 500Pa, and using a silicone resin ethanol solution and Y2O3Soaking the mixed slurry of the powder for 2 hours; the mass ratio of the silicon resin to the ethanol in the silicon resin ethanol solution is 4: 10, the silicone resin is low molecular weight methyl silicone resin (MK), and the Y is2O3The addition amount of the powder is 10 percent of the mass of the silicone resin;
(2) and (3) curing: standing the impregnated carbon fiber prefabricated part at 80 ℃ for 24 hours until the carbon fiber prefabricated part is completely dried, and then crosslinking and curing the gelled prefabricated part at 180 ℃ for 7 hours;
(3) cracking: performing pyrolysis on the carbon fiber prefabricated part after crosslinking and curing in an inert atmosphere, wherein the pyrolysis temperature is 1100 ℃, and the pyrolysis time is 120 min;
after the dipping-curing-cracking cycle is repeated for 11 times, the weight of the obtained sample is only 0.79 percent compared with that of the sample at the end of the 10 th cycle, and the preparation is completed to obtain the C/SiYOC composite material.
The C/SiYOC composite material prepared by the method is subjected to heat treatment under the condition of low pressure and compared with the C/SiOC composite material prepared by the same process, and the results are shown in the following table.
Figure BDA0002578789730000052
The results show that:
1. the C/SiYOC composite materials obtained in examples 1-4 can raise the long-life service temperature of the C/SiOC composite material to more than 1500 under low pressure.
2. The comparative example shows that compared with the method of adding the filler into the precursor solution, the method of example 1 adopts micromolecular silicon resin and inorganic yttrium salt to carry out hydrolysis-polycondensation reaction to generate the Y modified silicon resin precursor, can improve the introduction amount of Y element, improve the gel yield, further improve the compactness of the C/SiYOC composite material, and obviously improve the high temperature resistance of the C/SiYOC composite material without sacrificing the mechanical property.
The above is only a preferred embodiment of the present invention, the protection scope of the present invention is not limited to the above examples, and various process schemes having no substantial difference from the concept of the present invention are within the protection scope of the present invention.

Claims (3)

1. A preparation method of a carbon fiber reinforced SiYOC composite material is characterized by comprising the following steps: the method comprises the following steps:
1) dipping: preparing a carbon fiber prefabricated part, placing the carbon fiber prefabricated part under the vacuum condition with the pressure of less than 500Pa, and soaking the carbon fiber prefabricated part for 2-8h by using a Y-modified silicon resin precursor solution; the Y modified silicon resin precursor solution is a mixed sol of yttrium sol and silicon resin ethanol solution, wherein the yttrium sol is prepared from Y (NO)3)2•6H2O in ethanol, Y (NO)3)2•6H2The mass of O is 10-50% of the mass of the silicone resin, and the O is in the ethanol solution of the silicone resinThe mass ratio of the silicon resin to the ethanol is 2-5: 10; the carbon fiber prefabricated part is one of a 2.5-dimensional braided fabric, a plain cloth laminated sewing prefabricated part, a three-dimensional needled felt, a three-dimensional four-way braided fabric, a three-dimensional five-way braided fabric or a three-dimensional six-way braided fabric; the silicone resin is methyl silicone resin;
2) and (3) curing: preserving the heat of the carbon fiber prefabricated member soaked in the step at the temperature of 60-80 ℃ for 24-72h to form gel, and then crosslinking and curing the gelled prefabricated member at the temperature of 150-250 ℃ for 4-8 h;
3) cracking: performing pyrolysis on the carbon fiber prefabricated part subjected to crosslinking and curing in the previous step in an inert atmosphere, wherein the pyrolysis temperature is 1000-1200 ℃, and the pyrolysis time is 30-120 min;
repeating the dipping-curing-cracking cycle for multiple times until the weight of the sample is increased by no more than 1% when the cycle is finished compared with the weight of the sample when the cycle is finished, and finishing the preparation to obtain the carbon fiber reinforced SiYOC composite material.
2. The method of claim 1, wherein the carbon fiber reinforced SiYOC composite material is prepared by: the above dipping-curing-cracking cycle is repeated for a plurality of times, which means that the above dipping-curing-cracking cycle is repeated for 8-15 times.
3. A carbon fiber reinforced SiYOC composite material is characterized in that: the carbon fiber reinforced SiYOC composite material is prepared by the method of claim 1 or 2.
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