CN113788708A - Ablation-resistant ceramic matrix composite and preparation method thereof - Google Patents

Ablation-resistant ceramic matrix composite and preparation method thereof Download PDF

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CN113788708A
CN113788708A CN202111176668.8A CN202111176668A CN113788708A CN 113788708 A CN113788708 A CN 113788708A CN 202111176668 A CN202111176668 A CN 202111176668A CN 113788708 A CN113788708 A CN 113788708A
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matrix composite
ceramic matrix
ablation
evaporation
composite material
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CN113788708B (en
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陈昊然
于艺
杨良伟
李晓东
刘伟
孙同臣
张宝鹏
刘俊鹏
于新民
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Aerospace Research Institute of Materials and Processing Technology
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Abstract

The invention provides an ablation-resistant ceramic matrix composite and a preparation method thereof, which are applied to the technical field of aerospace materials; the preparation method comprises the following steps: putting metal zirconium in a vacuum environment, introducing carbon source gas, heating to an evaporation temperature, and then performing evaporation on the ceramic matrix composite material to obtain the ablation-resistant ceramic matrix composite material containing a ZrC layer; wherein the thickness of the ZrC layer is 20-30 μm. The invention can provide an ablation-resistant ceramic matrix composite material which can still maintain excellent ablation resistance at the temperature of 1000-2000 ℃.

Description

Ablation-resistant ceramic matrix composite and preparation method thereof
Technical Field
The invention relates to the technical field of aerospace materials, in particular to a preparation method of an ablation-resistant ceramic matrix composite material.
Background
The ceramic matrix composite is a key strategic material, which not only utilizes the advantages of high temperature resistance, low density, high specific strength, high specific modulus, ablation resistance and the like of the ceramic material, but also solves the problems of poor toughness and poor thermal shock resistance of the ceramic material by a fiber toughening method, so that the ceramic matrix composite is widely applied to spacecraft structural members, such as aircraft engine combustion chambers, tail nozzles and the like. With the increasing research and development investment on high-mach-number aircrafts, researchers have made higher requirements on the high-temperature resistance, oxidation resistance and ablation resistance of the ceramic matrix composite, and the existing ceramic matrix composite system can not meet the requirements of the high-mach-number aircrafts on materials gradually. The design of the existing high-temperature resistant and ablation resistant material mainly depends on the structure of the material, and the requirement of the current aerospace technology on the high-temperature resistance and ablation resistance of the ceramic matrix composite material cannot be met only by depending on the structure of the material. Therefore, how to improve the ablation resistance of the ceramic matrix composite is a problem that needs to be solved at present.
Disclosure of Invention
The embodiment of the invention provides an ablation-resistant ceramic matrix composite and a preparation method thereof, which can provide an ablation-resistant ceramic matrix composite which can still maintain excellent ablation resistance at the temperature of 1000-2000 ℃.
In a first aspect, the present invention provides a method for preparing an ablation-resistant ceramic matrix composite, the method comprising the steps of:
putting metal zirconium in a vacuum environment, introducing carbon source gas, heating to an evaporation temperature, and then performing evaporation on the ceramic matrix composite material to obtain the ablation-resistant ceramic matrix composite material containing a ZrC layer; wherein the thickness of the ZrC layer is 20-30 μm.
Preferably, the method further comprises the following steps: and placing the ablation-resistant ceramic matrix composite material in the atmosphere of the carbon source gas for annealing treatment.
Preferably, the temperature of the annealing treatment is 600-800 ℃.
Preferably, the time of the annealing treatment is 5-10 min.
Preferably, the pressure of the annealing treatment is 1 × 10-8-1×10-4Torr。
Preferably, before the evaporation of the ceramic matrix composite material, the method further comprises the step of pretreating the ceramic matrix composite material: at a vacuum pressure of 1X 10-8-1×10-5Annealing treatment is carried out for 10-30min under the condition that the temperature is 400-700 ℃.
Preferably, the purity of the metal zirconium is more than or equal to 95 percent.
Preferably, the particle size of the metallic zirconium is 0.1 to 50 μm.
Preferably, the carbon source gas is selected from CH4、C2H4、C2H2Or C3H6At least one of (1).
Preferably, the vacuum pressure of the vacuum environment is 1 × 10-9-1×10-3Torr。
Preferably, after the carbon source gas is introduced, the pressure of the vacuum environment is 1 × 10-7-1×10-3Torr。
Preferably, said heating to evaporation temperature comprises the following sub-steps:
putting the metal zirconium in an evaporation source, introducing a carbon source gas, and applying 0.5-2A current and 500-1000V voltage to the evaporation source to heat the evaporation source to the evaporation temperature.
Preferably, the evaporation adopts a molecular beam epitaxial growth method.
Preferably, the evaporation temperature is 1200-.
Preferably, the evaporation time of the evaporation is 30-60 min.
In a second aspect, the invention provides an ablation-resistant ceramic matrix composite material prepared by the preparation method of any one of the first aspect.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the ZrC layer which is low in porosity (1% -5%), uniform in thickness and good in bonding strength with the ceramic matrix composite is prepared by taking metal zirconium as a Zr source and taking a carbon source gas as a carbon source. As ZrC has the advantages of good thermal stability, relatively low density and extremely high melting point (3420 ℃), the ceramic matrix composite material has excellent ablation resistance and high temperature resistance under the protection of the ZrC layer. The ablation-resistant ceramic matrix composite material prepared by the invention can be applied to the high-temperature environment of 1000-2000 ℃.
(2) According to the invention, through a mode of introducing carbon source gas and carrying out evaporation in a vacuum environment, the problem that the ZrC layer with uniform thickness and low porosity (1% -5%) is difficult to prepare in the prior art is solved, the ZrC layer can be obtained more efficiently, the ZrC layer forms a compact protective layer on the outer surface layer of the ceramic matrix composite, and the ceramic matrix composite in the ZrC layer can be effectively protected from ablation.
(3) In the preparation process, a high vacuum environment is selected to introduce carbon source gas for evaporation, so that ZrC can be ensured to be evaporated on the surface of the ceramic matrix composite at the temperature of 1200-1700 ℃, and meanwhile, part of ZrC enters the ceramic matrix composite in the evaporation process, thereby further improving the ablation resistance of the ceramic matrix composite.
(4) According to the invention, the surface of the ZrC layer is flat and uniform in thickness through an annealing treatment mode, and the ZrC layer has a stable thermodynamic structure, so that the ZrC layer can keep excellent ablation resistance under a high-temperature environment.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
The invention provides a preparation method of an ablation-resistant ceramic matrix composite, which comprises the following steps:
putting metal zirconium in a vacuum environment, introducing carbon source gas, heating to an evaporation temperature, and then performing evaporation on the ceramic matrix composite material to obtain the ablation-resistant ceramic matrix composite material containing a ZrC layer; wherein the ZrC layer has a thickness of 20 to 30 μm (for example, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, or 30 μm may be used).
The ceramic matrix composite material may be an optional ceramic matrix composite material, and may be, for example, a carbon fiber reinforced SiC matrix composite material (C/SiC) or a SiC fiber reinforced SiC matrix composite material (Si/SiC).
The ZrC layer which is low in porosity (1% -5%), uniform in thickness and good in bonding strength with the ceramic matrix composite is prepared by taking metal zirconium as a Zr source and taking a carbon source gas as a carbon source. As ZrC has the advantages of good thermal stability, relatively low density and extremely high melting point (3420 ℃), the ceramic matrix composite material has excellent ablation resistance and high temperature resistance under the protection of the ZrC layer. The ablation-resistant ceramic matrix composite material prepared by the invention can be applied to the high-temperature environment of 1000-2000 ℃.
According to the invention, through a mode of introducing carbon source gas and carrying out evaporation in a vacuum environment, the problem that the ZrC layer with uniform thickness and low porosity (1% -5%) is difficult to prepare in the prior art is solved, the ZrC layer can be obtained more efficiently, the ZrC layer forms a compact protective layer on the outer surface layer of the ceramic matrix composite, and the ceramic matrix composite in the ZrC layer can be effectively protected from ablation.
According to some preferred embodiments, after the ablation-resistant ceramic matrix composite material comprising the ZrC layer is obtained, the ablation-resistant ceramic matrix composite material is placed in the atmosphere of the carbon source gas for annealing.
According to some preferred embodiments, the temperature of the annealing treatment is 600-; the annealing time is 5-10min (for example, 5min, 6min, 7min, 8min, 9min or 10 min).
According to some preferred embodiments, the pressure of the annealing treatment is 1 × 10-8-1×10-4Torr (for example, it may be 1X 10-8Torr、1×10-7Torr、1×10-6Torr、1×10-5Torr or 1X 10-4Torr)。
The ZrC layer is smooth and uniform in thickness through annealing treatment, and has a stable thermodynamic structure, so that excellent ablation resistance is kept in a high-temperature environment.
According to some preferred embodiments, before the evaporation of the ceramic matrix composite material, the method further comprises the step of pretreating the ceramic matrix composite material: at a vacuum pressure of 1X 10-8-1×10-5Torr (for example, it may be 1X 10-8Torr、1×10-7Torr、1×10-6Torr or 1X 10-5Torr) at 400 ℃ and 700 ℃ (for example, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ or 700 ℃) for 10-30min (for example, 10min, 15min, 20min, 25min or 30 min).
In the invention, the ceramic matrix composite material is firstly annealed at high temperature (400-700 ℃) in an ultrahigh vacuum environment, so that surface impurities can be removed to increase the exposed surface active sites.
According to some preferred embodiments, the metallic zirconium has a purity of 95% or more (e.g., can be 95%, 96%, 97%, 98%, 99%, or 99.9%); the particle size of the metallic zirconium is 0.1 to 50 μm (for example, it may be 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm).
According to some preferred embodiments, the carbon source gas is selected from CH4、C2H4、C2H2Or C3H6At least one ofAnd (4) seed preparation.
At least one of them is a mixture of any one or any several of them mixed in any ratio.
According to some more preferred embodiments, the metallic zirconium is in the form of powder or foil. Specifically, the metal zirconium is pressed into a foil shape, so that the uniform dispersibility of the metal zirconium can be ensured, generally speaking, the better the uniformity is, the better the ablation resistance of the subsequently prepared composite material is, and the high-temperature ablation resistance of the material is improved through the angle of introducing the high-temperature ablation resistance component.
According to some preferred embodiments, the vacuum pressure of the vacuum environment is 1 × 10-9-1×10-3Torr (for example, it may be 1X 10-9Torr、1×10-8Torr、1×10-7Torr、1×10-6Torr、1×10-5Torr、1×10-4Torr or 1X 10-3Torr)。
According to some preferred embodiments, the pressure of the vacuum environment after the carbon source gas is introduced is 1 × 10-7-1×10-3Torr (for example, it may be 1X 10-7Torr、1×10-6Torr、1×10-5Torr、1×10-4Torr or 1X 10- 3Torr)。
The vacuum environment can be obtained by a vacuum pump set (such as a mechanical pump, a molecular pump, an ion pump, etc.).
According to some preferred embodiments, said heating to evaporation temperature comprises the following sub-steps:
the metal zirconium is placed in an evaporation source, carbon source gas is introduced, and then 0.5-2A (for example, 0.5A, 1A, 1.5A or 2A) current and 500-1000V (for example, 500V, 600V, 700V, 800V, 900V or 1000V) voltage are applied to the evaporation source to heat the evaporation source to the evaporation temperature.
According to some preferred embodiments, the vacuum evaporation is performed by molecular beam epitaxy.
It should be noted that the molecular beam epitaxy method is an atomic-scale processing technique, which is beneficial to realize accurate control of thickness, structure and composition, formation of a steep heterostructure, and the like, and has the advantages of low temperature of epitaxy growth and capability of avoiding pollution in a vacuum environment.
According to some preferred embodiments, the evaporation temperature is 1200 ℃ 1700 ℃ (which may be, for example, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, 1600 ℃ or 1700 ℃).
According to some preferred embodiments, the ceramic matrix composite material is evaporated to the outlet of the metal evaporation source, and the evaporation time is 30-60min (for example, 30min, 35min, 40min, 45min, 50min, 55min or 60 min).
In the invention, after the metal zirconium is evaporated in the carbon source gas atmosphere, a plating layer with the thickness of 20-30 μm can be formed on the surface of the ceramic matrix composite, and partial ZrC enters the ceramic matrix composite, so that the ablation resistance of the ceramic matrix composite is further improved.
Experiments prove that when the thickness of the ZrC layer is controlled to be between 20 and 30 microns, the thickness interval can form a compact ZrC layer, ablation gas can be effectively prevented from entering the ceramic matrix composite material, the ceramic matrix composite material has ablation resistance, and the morphological structure and performance of the substrate ceramic matrix composite material cannot be influenced by the fact that the thickness of the ZrC layer is too thick.
The invention also provides an ablation-resistant ceramic matrix composite material prepared by the preparation method of the ablation-resistant ceramic matrix composite material.
The invention is further illustrated below with reference to specific examples. It is to be understood, however, that these examples are illustrative only and are not to be construed as limiting the scope of the present invention. The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
(1) Preparing an ablation-resistant ceramic matrix composite material: selecting a carbon fiber reinforced silicon carbide ceramic matrix composite (C/SiC ceramic matrix composite) as the ceramic matrix composite of the embodiment, and subjecting the ceramic matrix composite to vacuum pressure of 5 × 10-6Annealing for 15min under the environment of Torr and the temperature of 450 ℃, and pretreating the ceramic matrix composite; foil-shaped metallic zirconium (purity 95%, particle size of metallic zirconium for preparation of foil-shaped metallic zirconium 200nm) was placed in a crucible of an evaporation source and subjected to vacuum pressure of 1X 10-7Charging CH into the reactor under a vacuum atmosphere4Gas to a pressure of 5X 10-6Torr, heating an evaporation source to an evaporation temperature (1500 ℃) by applying a current of 1.7A and a voltage of 850V to the evaporation source, and then carrying out vapor deposition for 45min by aligning an outlet of the evaporation source to a ceramic matrix composite material (C/SiC ceramic matrix composite material) to obtain an ablation-resistant ceramic matrix composite material of which the outside comprises a ZrC layer with the thickness of 26 mu m; wherein both the exterior and the interior of the ablation resistant ceramic matrix composite are doped with ZrC.
(2) Annealing treatment of the ablation-resistant ceramic matrix composite: placing the ablation-resistant ceramic matrix composite material under a pressure of 5 x 10-6Torr CH4Annealing is carried out in a gas atmosphere at 650 ℃ for 7 min.
(3) Ablation resistance test: the ablation-resistant ceramic matrix composite material deposited with the ZrC protective layer in the embodiment is subjected to an oxyacetylene ablation test at 1600 ℃/4000s, and the line ablation rate and the mass ablation rate of the ablation-resistant ceramic matrix composite material are respectively 0.000065mm/s and 0.000079 g/s.
Example 2
(1) Preparing an ablation-resistant ceramic matrix composite material: selecting a carbon fiber reinforced silicon carbide ceramic matrix composite (C/C-SiC ceramic matrix composite) as the ceramic matrix composite of the embodiment, and subjecting the ceramic matrix composite to vacuum pressure of 5 x 10-6Annealing for 15min under the environment of Torr and the temperature of 450 ℃, and pretreating the ceramic matrix composite; foil-shaped metallic zirconium (purity 95%, particle size of metallic zirconium for preparation of foil-shaped metallic zirconium 200nm) was placed in a crucible of an evaporation source and subjected to vacuum pressure of 1X 10-7Charging C under a vacuum environment of Torr2H4Gas to a pressure of 5X 10-6Torr, the evaporation source was heated to an evaporation temperature (1500 ℃ C.) by applying a current of 1.7A and a voltage of 850V to the evaporation source, and then the outlet of the evaporation source was aligned with the ceramic baseCarrying out evaporation on the composite material (C/SiC ceramic matrix composite material) for 45min to obtain an ablation-resistant ceramic matrix composite material of which the outside comprises a ZrC layer with the thickness of 26 mu m; wherein both the exterior and the interior of the ablation resistant ceramic matrix composite are doped with ZrC.
(2) Annealing treatment of the ablation-resistant ceramic matrix composite: placing the ablation-resistant ceramic matrix composite material under a pressure of 5 x 10-6C of Torr2H4Annealing is carried out in a gas atmosphere at 650 ℃ for 7 min.
(3) Ablation resistance test: the ablation-resistant ceramic matrix composite material deposited with the ZrC protective layer in the embodiment is subjected to an oxyacetylene ablation test at 1600 ℃/4000s, and the line ablation rate and the mass ablation rate of the ablation-resistant ceramic matrix composite material are respectively 0.000068mm/s and 0.000077 g/s.
Example 3
(1) Preparing an ablation-resistant ceramic matrix composite material: selecting a carbon fiber reinforced silicon carbide ceramic matrix composite (C/SiC-TaC ceramic matrix composite) as the ceramic matrix composite of the embodiment, and subjecting the ceramic matrix composite to vacuum pressure of 5 × 10-6Annealing for 15min under the environment of Torr and the temperature of 450 ℃, and pretreating the ceramic matrix composite; foil-shaped metallic zirconium (purity 95%, particle size of metallic zirconium for preparation of foil-shaped metallic zirconium 200nm) was placed in a crucible of an evaporation source and subjected to vacuum pressure of 1X 10-7Charging C under a vacuum environment of Torr2H2Gas to a pressure of 5X 10-6Torr, heating an evaporation source to an evaporation temperature (1500 ℃) by applying a current of 1.7A and a voltage of 850V to the evaporation source, and then carrying out vapor deposition for 45min by aligning an outlet of the evaporation source to a ceramic matrix composite material (C/SiC ceramic matrix composite material) to obtain an ablation-resistant ceramic matrix composite material of which the outside comprises a ZrC layer with the thickness of 26 mu m; wherein both the exterior and the interior of the ablation resistant ceramic matrix composite are doped with ZrC.
(2) Annealing treatment of the ablation-resistant ceramic matrix composite: placing the ablation-resistant ceramic matrix composite material under a pressure of 5 x 10-6C of Torr2H2Annealing at 650 deg.C in gas atmosphereThe time period is 7 min.
(3) Ablation resistance test: the ablation-resistant ceramic matrix composite material with the ZrC protective layer deposited in the embodiment is subjected to an oxyacetylene ablation test at 2000 ℃/3000s, and the ablation rate of the ablation-resistant ceramic matrix composite material is 0.000068mm/s, and the mass ablation rate is 0.000077 g/s.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that: the carbon fiber reinforced silicon carbide ceramic matrix composite (C/SiC ceramic matrix composite) is directly selected for ablation resistance test, and the measured linear ablation rate of the ceramic matrix composite is 0.00067mm/s, and the mass ablation rate is 0.00089 g/s.
Comparative example 2
Comparative example 2 is substantially the same as example 2 except that: the carbon fiber reinforced silicon carbide ceramic matrix composite (C/C-SiC ceramic matrix composite) is directly selected for ablation resistance test, and the measured linear ablation rate of the ceramic matrix composite is 0.00059mm/s, and the mass ablation rate is 0.00083 g/s.
Comparative example 3
Comparative example 3 is substantially the same as example 3 except that: the carbon fiber reinforced silicon carbide ceramic matrix composite (C/SiC-TaC ceramic matrix composite) is directly selected for ablation resistance test, and the measured line ablation rate of the ceramic matrix composite is 0.00069mm/s, and the mass ablation rate is 0.00091 g/s.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that: the annealing treatment of step (2) was not performed.
Ablation resistance test: the ablation-resistant ceramic matrix composite material deposited with the ZrC protective layer in the embodiment is subjected to an oxyacetylene ablation test at 1600 ℃/4000s, and the linear ablation rate and the mass ablation rate of the ceramic matrix composite material are respectively 0.000096mm/s and 0.00013 g/s.
Comparative example 5
Comparative example 5 is substantially the same as example 1 except that: the evaporation time was 20min, and the ZrC layer obtained was 12 μm.
Ablation resistance test: the ablation-resistant ceramic matrix composite material deposited with the ZrC protective layer in the embodiment is subjected to an oxyacetylene ablation test at 1600 ℃/4000s, and the linear ablation rate and the mass ablation rate of the ceramic matrix composite material are respectively measured to be 0.00021mm/s and 0.00042 g/s.
Comparing the data from the comparative ablation experiments with the examples results in table 1 below.
TABLE 1
Line ablation Rate (mm/s) Mass ablation Rate (g/s)
Example 1 0.000065 0.000079
Example 2 0.000068 0.000077
Example 3 0.000058 0.000076
Comparative example 1 0.00067 0.00089
Comparative example 2 0.00059 0.00083
Comparative example 3 0.00069 0.00091
Comparative example 4 0.000096 0.00013
Comparative example 5 0.00021 0.00042
As can be seen from Table 1, compared with the comparative example, the invention can effectively improve the ablation resistance of the ceramic matrix composite material at high temperature (1600-.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention. The invention has not been described in detail and is in part known to those of skill in the art.

Claims (10)

1. A preparation method of an ablation-resistant ceramic matrix composite is characterized by comprising the following steps:
putting metal zirconium in a vacuum environment, introducing carbon source gas, heating to an evaporation temperature, and then performing evaporation on the ceramic matrix composite material to obtain the ablation-resistant ceramic matrix composite material containing a ZrC layer; wherein the thickness of the ZrC layer is 20-30 μm.
2. The method of claim 1, further comprising:
and placing the ablation-resistant ceramic matrix composite material in the atmosphere of the carbon source gas for annealing treatment.
3. The method of claim 2, wherein:
the temperature of the annealing treatment is 600-800 ℃;
the time of the annealing treatment is 5-10 min; and/or
The pressure of the annealing treatment is 1 x 10-8-1×10-4Torr。
4. The production method according to claim 1 or 2, characterized in that:
before the evaporation is carried out on the ceramic matrix composite material, the method also comprises the step of pretreating the ceramic matrix composite material: at a vacuum pressure of 1X 10-8-1×10-5Annealing treatment is carried out for 10-30min under the condition that the temperature is 400-700 ℃.
5. The method of claim 1, wherein:
the purity of the metal zirconium is more than or equal to 95 percent;
the particle size of the metal zirconium is 0.1-50 μm; and/or
The carbon source gas is selected from CH4、C2H4、C2H2Or C3H6At least one of (1).
6. The method of claim 1, wherein:
the vacuum pressure of the vacuum environment is 1 x 10-9-1×10-3Torr; and/or
After the carbon source gas is introduced, the pressure of the vacuum environment is 1 x 10-7-1×10-3Torr。
7. The method of claim 1, wherein:
the heating to the evaporation temperature comprises the following substeps:
putting the metal zirconium in an evaporation source, introducing a carbon source gas, and applying 0.5-2A current and 500-1000V voltage to the evaporation source to heat the evaporation source to the evaporation temperature.
8. The method of claim 1, wherein:
the evaporation adopts a molecular beam epitaxial growth method; and/or
The evaporation temperature is 1200-1700 ℃.
9. The method of claim 1, wherein:
the evaporation time of the evaporation is 30-60 min.
10. An ablation-resistant ceramic matrix composite characterized by being prepared by the preparation method of any one of claims 1 to 9.
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