CN114133259A - Preparation method of resin modified C/(C-) SiC-ZrC composite material - Google Patents
Preparation method of resin modified C/(C-) SiC-ZrC composite material Download PDFInfo
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- CN114133259A CN114133259A CN202111128803.1A CN202111128803A CN114133259A CN 114133259 A CN114133259 A CN 114133259A CN 202111128803 A CN202111128803 A CN 202111128803A CN 114133259 A CN114133259 A CN 114133259A
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- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 229920005989 resin Polymers 0.000 title claims abstract description 39
- 239000011347 resin Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000002243 precursor Substances 0.000 claims abstract description 50
- 238000005470 impregnation Methods 0.000 claims abstract description 22
- 238000005336 cracking Methods 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 6
- 239000004917 carbon fiber Substances 0.000 claims abstract description 6
- 230000008595 infiltration Effects 0.000 claims abstract description 6
- 238000001764 infiltration Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002296 pyrolytic carbon Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 35
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 15
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 12
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 10
- 239000008096 xylene Substances 0.000 claims description 9
- 238000001723 curing Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 229920003257 polycarbosilane Polymers 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000001294 propane Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 239000011216 ultra-high temperature ceramic matrix composite Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002679 ablation Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000011215 ultra-high-temperature ceramic Substances 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910003862 HfB2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000012700 ceramic precursor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a resin modified C/(C-) SiC-ZrC composite material, belonging to the technical field of preparation of ultrahigh temperature ceramic matrix composite materials. The method adopts a Chemical Vapor Infiltration (CVI) process combined with a precursor impregnation cracking (PIP) process to prepare the C/(C-) SiC-ZrC composite material, can prepare a ZrC-SiC matrix with a stoichiometric ratio by directly introducing resin into the ZrC and SiC precursors as a carbon source, effectively avoids the damage of the precursors to carbon fibers, pyrolytic carbon (PyC) interfaces and the matrix in the cracking process, and can obviously improve the mechanical property of the composite material.
Description
The technical field is as follows:
the invention relates to the technical field of preparation of ultrahigh-temperature ceramic-based composite materials, in particular to a preparation method of a resin modified C/(C-) SiC-ZrC composite material.
Background art:
reentry process of hypersonic flight vehicleParts such as the nose cone and the wing leading edge generate serious pneumatic heating, so that the material is required to have good mechanical, oxidation and ablation resistance. Although the C/(C-) SiC composite material has excellent mechanical and oxidation resistance, the SiC is subjected to active oxidation at a temperature of more than 1650 ℃, so that the further application of the material is limited. The ultrahigh-temperature ceramic material has high melting point (generally 2500-3000 ℃), and excellent oxidation resistance and ablation resistance. A great deal of research has shown that ultra-high temperature ceramics (such as ZrC, ZrB)2、HfC、HfB2Etc.) into the C/C, C/(C-) SiC composite material, can obviously improve the oxidation resistance and ablation resistance of the material.
In the preparation process of the C/(C-) SiC-ZrC composite material, a PIP process is usually adopted to introduce ZrC and SiC precursor solution into the composite material and crack the ZrC and SiC precursor solution at high temperature to convert the ZrC-SiC matrix. Wherein, the ZrC precursor is transformed from organic to inorganic in the cracking process to generate ZrO firstly2And amorphous C, ZrO with increasing temperature2And C is subjected to carbothermic reduction reaction to generate ZrC. Because the ZrC precursor contains high-content oxygen, CO and CH can be formed in the high-temperature cracking process4、CO2Gas is mixed, the precursor is lack of C, and ZrO can not be caused2Conversion to ZrC completely, excess ZrO2The ZrC can be generated by reaction with the contacted carbon fiber, PyC interface and matrix, thus causing damage to the ZrC and reducing the mechanical property of the material.
How to solve the problems and accurately controlling the carbothermic reduction reaction process become important and difficult points for research of researchers.
The invention content is as follows:
aiming at the defects in the prior art, the invention aims to provide the preparation method of the resin modified C/(C-) SiC-ZrC composite material, which effectively avoids excessive ZrO by accurately controlling the carbothermic reduction reaction process based on the thought of resin modified ceramic precursor2Etching the carbon fiber, the PyC interface and the matrix; a method for preparing a ZrC-SiC matrix with stoichiometric ratio and C/(C-) SiC-ZrC composite material with excellent mechanical property and ablation property.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a resin modified C/(C-) SiC-ZrC composite material comprises the following steps:
(1) depositing a pyrolytic carbon interface/matrix in the carbon fiber preform by adopting a CVI (chemical vapor infiltration) process to obtain a porous C/C composite material;
(2) depositing a SiC matrix in the porous C/C composite material by adopting a CVI (chemical vapor infiltration) process to obtain a porous C/(C-) SiC composite material;
(3) preparing a modified precursor;
(4) introducing the modified precursor solution into the porous C/(C-) SiC composite material by using a PIP process, and curing and cracking for multiple times to prepare the C/(C-) SiC-ZrC composite material.
In the step (1), the CVI process parameters are as follows: the deposition temperature is 850-1100 ℃, and the Ar flow is 0.06-0.4 m3The flow rate of propane is 0.06-0.4 m3The density of the obtained porous C/C composite material is 0.6-1.5 g/cm3In the meantime.
In the step (2), the CVI process parameters are as follows: the deposition temperature is 1000-1200 ℃, and the Ar flow is 0.03-0.3 m3/h，H2The flow rate is 0.03-0.3 m3The flow rate of MTS is 50-250 g/h, and the density of the obtained porous C/(C-) SiC composite material is 1.0-1.8 g/cm3In the meantime.
In the step (3), the preparation process of the modified precursor comprises the following steps: firstly, respectively dissolving a ZrC precursor and PCS in an organic solvent, wherein the concentration ranges from 50 wt% to 70 wt%, and magnetically stirring for 2-10 hours to obtain a ZrC precursor solution and a polycarbosilane PCS solution; secondly, dissolving resin in an organic solvent, wherein the concentration of the resin is 50-70 wt.%, and performing magnetic stirring for 2-15 hours to obtain a resin solution; and then, mixing the ZrC precursor solution, the polycarbosilane PCS solution and the resin solution according to a certain proportion, and performing magnetic stirring for 1-5 h to obtain a resin modified ZrC precursor and PCS mixed solution, namely the modified precursor.
In the step (3), in the preparation process of the modified precursor, the amount of the ZrC precursor and the polycarbosilane PCS is selected according to the proportion of ZrC to SiC in the prepared C/(C-) SiC-ZrC composite material, and the mass ratio of the PCS to the carbon source (resin) is 1: 0.6-1: 6; the volume ratio of ZrC to SiC in the prepared C/(C-) SiC-ZrC composite material is 0.5: 1-5: 1.
In the step (3), in the preparation process of the modified precursor, the carbon source is one or more of petroleum resin, coumarone resin, alkyd resin, acrylic resin and asphalt resin.
In the step (3), the organic solvent used in the preparation of the modified precursor is xylene, divinylbenzene or tetrahydrofuran.
The PIP process of the step (4) comprises the following steps (a) to (d):
(a) dipping: introducing the modified precursor solution into the porous C/(C-) SiC composite material, vacuum impregnation is firstly carried out, and then pressure impregnation is carried out; wherein: the vacuum impregnation time is 1-5 h, and the vacuum degree is less than or equal to-0.1 MPa; the pressure impregnation time is 2-3 h, and the pressure is 2-4 MPa;
(b) and (3) curing: the curing temperature is 80-180 ℃, and the heat preservation time is 10-24 h;
(c) cracking: the cracking temperature is 1450-1550 ℃, the heat preservation time is 0.5-2 h, and the atmosphere is Ar or N2And the like in inert atmosphere;
(d) repeating the process of steps (a) - (c) 3-20 times.
The invention has the following beneficial effects:
ZrC-SiC matrix with stoichiometric ratio (as shown in figure 2) is obtained by modifying ZrC and SiC precursor with resin, thereby effectively avoiding ZrO2The mechanical property and the ablation property of the material are obviously improved by etching the carbon fiber, the PyC interface and the matrix in the pyrolysis process.
Description of the drawings:
FIG. 1 is a flow chart of the preparation of the resin modified C/(C-) SiC-ZrC composite material.
Fig. 2 is an XRD of resin modified ZrC and SiC precursors.
FIG. 3 is a sectional SEM photograph of the C/(C-) SiC-ZrC composite material prepared in comparative example 1.
FIG. 4 is a sectional SEM photograph of the C/(C-) SiC-ZrC composite material prepared in comparative example 2.
FIG. 5 is a sectional SEM photograph of the C/(C-) SiC-ZrC composite prepared in example 1.
FIG. 6 is a sectional SEM photograph of the C/(C-) SiC-ZrC composite prepared in example 2.
The specific implementation mode is as follows:
in order to make the technical solution of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to comparative examples and examples.
Comparative example 1
According to the process flow shown in FIG. 1, firstly, a PyC substrate is prepared by a CVI process at a deposition temperature of 900 ℃ and an Ar flow of 0.1m3Flow of propane 0.1 m/h3H, to give a density of 1.2g/cm3The porous C/C composite of (1); preparing SiC matrix by CVI process with deposition temperature of 1000 deg.C and Ar flow of 0.05m3/h，H2Flow rate 0.05m3The flow rate of MTS is 100g/h, and the obtained density is 1.6g/cm3The porous C/(C-) SiC composite material.
Secondly, respectively dissolving a ZrC precursor and PCS in dimethylbenzene to prepare 50 wt% solutions, and respectively magnetically stirring for 2 hours; and (3) preparing and mixing a 50 wt% ZrC precursor xylene solution and a 50 wt% PCS xylene solution according to the volume ratio of ZrC to SiC in the finally prepared composite material of 1:1, and fully and magnetically stirring for 2 h. Finally, preparing the C/(C-) SiC-ZrC composite material by a PIP process, wherein the vacuum degree during impregnation is-0.1 MPa, and the vacuum impregnation is carried out for 2 hours; pressure impregnation is carried out for 2 hours under the pressure of 2 MPa; curing at 100-160 deg.C for 10 hr, cracking at 1500 deg.C for 2 hr, repeating the above impregnation-curing-cracking process for 5 times to obtain the final product with density of 1.77g/cm3The bending strength of the C/(C-) SiC-ZrC composite material is 216 MPa. Fig. 3 is a microstructure of a material.
Comparative example 2
According to the process flow shown in FIG. 1, firstly, a PyC substrate is prepared by a CVI process at a deposition temperature of 900 ℃ and an Ar flow of 0.1m3Flow of propane 0.1 m/h3H, to give a density of 1.0g/cm3The porous C/C composite of (1); preparing SiC matrix by CVI process with deposition temperature of 1000 deg.C and Ar flow of 0.05m3/h，H2Flow rate 0.05m3The flow rate of MTS is 100g/h, and the obtained density is 1.4g/cm3The porous C/(C-) SiC composite material.
Secondly, respectively dissolving the ZrC precursor and the PCS in divinylbenzene to prepare 60 wt% solutions, and respectively magnetically stirring for 5 hours; and (3) preparing and mixing 60 wt% of ZrC precursor divinylbenzene solution and 60 wt% of PCS divinylbenzene solution according to the volume ratio of ZrC to SiC in the prepared composite material of 5:1, and fully and magnetically stirring for 4 hours. Finally, preparing the C/(C-) SiC-ZrC composite material by a PIP process, wherein the vacuum degree during impregnation is-0.1 MPa, and the vacuum impregnation is carried out for 4 hours; pressure impregnation is carried out for 2 hours, and the pressure is 3 MPa; curing at 80-140 deg.C for 20h, cracking at 1500 deg.C for 1h, repeating the above impregnation-curing-cracking process for 10 times to obtain the final product with density of 2.08g/cm3The bending strength of the C/(C-) SiC-ZrC composite material is 162 MPa. Fig. 4 is a microstructure of a material.
Example 1
According to the process flow shown in FIG. 1, firstly, a PyC substrate is prepared by a CVI process at a deposition temperature of 900 ℃ and an Ar flow of 0.1m3Flow of propane 0.1 m/h3H, to give a density of 1.2g/cm3The porous C/C composite of (1); preparing SiC matrix by CVI process with deposition temperature of 1000 deg.C and Ar flow of 0.05m3/h，H2Flow rate 0.05m3The flow rate of MTS is 100g/h, and the obtained density is 1.6g/cm3The porous C/(C-) SiC composite material.
Secondly, respectively dissolving a ZrC precursor and PCS in dimethylbenzene to prepare 50 wt% solutions, and respectively magnetically stirring for 2 hours; and (3) preparing and mixing a ZrC precursor xylene solution with 50 wt% and a PCS xylene solution with 50 wt% according to the volume ratio of ZrC to SiC in the prepared composite material of 1:1, and sufficiently and magnetically stirring for 2h to obtain a mixed solution of the ZrC precursor and the PCS. Dissolving petroleum resin in dimethylbenzene to prepare a 50 wt% solution, and magnetically stirring for 2 hours; and adding 50 wt% petroleum resin xylene solution into the mixed solution of the ZrC precursor and the PCS according to the mass ratio of 1:0.8 of PCS to petroleum resin, and fully and magnetically stirring for 3 hours. By resin modification of ZrC and SiC precursors, a ZrC-SiC matrix of stoichiometric ratio was obtained (as shown in fig. 2).
Finally, preparing the C/(C-) SiC-ZrC composite material by a PIP process, wherein the vacuum degree during impregnation is-0.1 MPa, and the vacuum impregnation is carried out for 2 hours; pressure impregnation is carried out for 2 hours under the pressure of 2 MPa; curing at 100-160 deg.C for 10 hr, cracking at 1500 deg.C for 2 hr, repeating the above impregnation-curing-cracking process for 5 times to obtain the final product with density of 1.79g/cm3The C/(C-) SiC-ZrC composite material. The bending strength of the material is 227MPa, and the strength is improved by 5 percent compared with that of the comparative example 1. Fig. 5 is a microstructure of a material.
Example 2
According to the process flow shown in FIG. 1, firstly, a PyC substrate is prepared by a CVI process at a deposition temperature of 900 ℃ and an Ar flow of 0.1m3Flow of propane 0.1 m/h3H, to give a density of 1.0g/cm3The porous C/C composite of (1); preparing SiC matrix by CVI process with deposition temperature of 1000 deg.C and Ar flow of 0.05m3/h，H2Flow rate 0.05m3The flow rate of MTS is 100g/h, and the obtained density is 1.4g/cm3The porous C/(C-) SiC composite material. Secondly, respectively dissolving the ZrC precursor and the PCS in divinylbenzene to prepare 60 wt% solutions, and respectively magnetically stirring for 5 hours; preparing and mixing 60 wt% of ZrC precursor divinylbenzene solution and 60 wt% of PCS divinylbenzene solution according to the volume ratio of ZrC to SiC in the prepared composite material of 5:1, and fully and magnetically stirring for 4 hours to obtain ZrC precursor and PCS mixed solution; dissolving coumarone resin in xylene to prepare a 60 wt% solution, and magnetically stirring for 4 h; and adding 60 wt% of coumarone resin xylene solution into the mixed solution of the ZrC precursor and the PCS according to the mass ratio of 1:6 of PCS to coumarone resin, and fully and magnetically stirring for 4 hours. Finally, preparing the C/(C-) SiC-ZrC composite material by a PIP process, wherein the vacuum degree during impregnation is-0.1 MPa, and the vacuum impregnation is carried out for 4 hours; pressure impregnation is carried out for 2 hours, and the pressure is 3 MPa; curing at 80-140 deg.C for 20h, cracking at 1500 deg.C for 1h, repeating the above impregnation-curing-cracking process for 10 times to obtain the final product with density of 1.96g/cm3The C/(C-) SiC-ZrC composite material. The bending strength of the material is 247MPa, and the strength is improved by 53 percent compared with that of comparative example 2. Fig. 6 is a microstructure of a material.
The data of the comparative examples and the examples are shown in Table 1.
TABLE 1
| Examples | Volume ratio of ZrC to SiC | PCS/resin mass ratio | PIP number of times | Flexural Strength/MPa |
| Comparative example 1 | 1:1 | - | 5 | 216 |
| Comparative example 2 | 5:1 | - | 10 | 162 |
| Example 1 | 1:1 | 1:0.8 | 5 | 227 |
| Example 2 | 5:1 | 1:6 | 10 | 247 |
Claims (8)
1. A preparation method of resin modified C/(C-) SiC-ZrC composite material is characterized by comprising the following steps: the composite material is prepared by adopting a Chemical Vapor Infiltration (CVI) process and a precursor impregnation cracking (PIP) process, and the method specifically comprises the following steps:
(1) depositing a pyrolytic carbon interface/matrix in the carbon fiber preform by adopting a CVI (chemical vapor infiltration) process to obtain a porous C/C composite material;
(2) depositing a SiC matrix in the porous C/C composite material by adopting a CVI (chemical vapor infiltration) process to obtain a porous C/(C-) SiC composite material;
(3) preparing a modified precursor;
(4) introducing the modified precursor solution into the porous C/(C-) SiC composite material by using a PIP process, and curing and cracking for multiple times to prepare the C/(C-) SiC-ZrC composite material.
2. The method for preparing a resin-modified C/(C-) SiC-ZrC composite material according to claim 1, wherein: in the step (1), the CVI technological parameters are as follows: the deposition temperature is 850-1100 ℃, and the Ar flow is 0.06-0.4 m3The flow rate of propane is 0.06-0.4 m3The density of the obtained porous C/C composite material is 0.6-1.5 g/cm3In the meantime.
3. The method for preparing a resin-modified C/(C-) SiC-ZrC composite material according to claim 1, wherein: in the step (2), the CVI technological parameters are as follows: the deposition temperature is 1000-1200 ℃, and the Ar flow is 0.03-0.3 m3/h，H2The flow rate is 0.03-0.3 m3The flow rate of MTS is 50-250 g/h, and the density of the obtained porous C/(C-) SiC composite material is 1.0-1.8 g/cm3In the meantime.
4. The method for preparing a resin-modified C/(C-) SiC-ZrC composite material according to claim 1, wherein: in the step (3), the preparation process of the modified precursor comprises the following steps: dissolving a ZrC precursor in an organic solvent, wherein the concentration range is 50-70 wt%, and performing magnetic stirring for 2-10 hours to obtain a ZrC precursor solution; dissolving polycarbosilane PCS in an organic solvent, wherein the concentration range is 50-70 wt%, and performing magnetic stirring for 2-10 h to obtain a polycarbosilane PCS solution; dissolving resin in an organic solvent, wherein the concentration of the resin is 50-70 wt.%, and performing magnetic stirring for 2-15 h to obtain a resin solution; and then, mixing the ZrC precursor solution, the polycarbosilane PCS solution and the resin solution according to a certain proportion, and performing magnetic stirring for 1-5 h to obtain a resin modified ZrC precursor and PCS mixed solution, namely the modified precursor.
5. The method for preparing a resin-modified C/(C-) SiC-ZrC composite material according to claim 4, wherein: in the step (3), in the preparation process of the modified precursor, the amount of the ZrC precursor and the polycarbosilane PCS is selected according to the proportion of ZrC to SiC in the prepared C/(C-) SiC-ZrC composite material, and the mass ratio of the PCS to the carbon source (resin) is 1: 0.6-1: 6; the volume ratio of ZrC to SiC in the prepared C/(C-) SiC-ZrC composite material is 0.5: 1-5: 1.
6. The method for preparing a resin-modified C/(C-) SiC-ZrC composite material according to claim 4, wherein: in the step (3), in the process of preparing the modified precursor, the carbon source resin is one or more of petroleum resin, coumarone resin, alkyd resin, acrylic resin and asphalt resin.
7. The method for preparing a resin-modified C/(C-) SiC-ZrC composite material according to claim 4, wherein: in the step (3), in the preparation process of the modified precursor, the organic solvent selected is xylene, divinylbenzene or tetrahydrofuran, etc.
8. The method for preparing a resin-modified C/(C-) SiC-ZrC composite material according to claim 1, wherein: the process of step (4) comprises the following steps (a) to (d):
(a) dipping: introducing the modified precursor solution into the porous C/(C-) SiC composite material, vacuum impregnation is firstly carried out, and then pressure impregnation is carried out; wherein: the vacuum impregnation time is 1-5 h, and the vacuum degree is less than or equal to-0.1 MPa; the pressure impregnation time is 2-3 h, and the pressure is 2-4 MPa;
(b) and (3) curing: the curing temperature is 80-180 ℃, and the heat preservation time is 10-24 h;
(c) cracking: the cracking temperature is 1450-1550 ℃, the heat preservation time is 0.5-2 h, and the atmosphere is Ar or N2And the like in inert atmosphere;
(d) repeating the process of steps (a) - (c) 3-20 times.
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