CN114560714A - Fiber-toughened ceramic-based composite material and preparation method and application thereof - Google Patents

Fiber-toughened ceramic-based composite material and preparation method and application thereof Download PDF

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CN114560714A
CN114560714A CN202210244772.4A CN202210244772A CN114560714A CN 114560714 A CN114560714 A CN 114560714A CN 202210244772 A CN202210244772 A CN 202210244772A CN 114560714 A CN114560714 A CN 114560714A
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fiber
layer
matrix composite
ceramic matrix
toughened
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周小兵
蒋龙飞
徐惠东
秦刚
黄庆
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Ningbo Hangzhou Bay New Materials Research Institute
Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Hangzhou Bay New Materials Research Institute
Ningbo Institute of Material Technology and Engineering of CAS
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Publication of CN114560714A publication Critical patent/CN114560714A/en
Priority to PCT/CN2023/080635 priority patent/WO2023174160A1/en
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Abstract

The invention discloses a fiber toughened ceramic matrix composite material and a preparation method and application thereof. The fiber-toughened ceramic matrix composite includes: a ceramic material matrix, an interfacial layer, and fibers; the interfacial layer comprises RExByCzThe material layer, wherein RE is one or a combination of more than two of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, x is 1-10, Y is 1-20, and z is 1-20. RE in the fiber-toughened ceramic matrix composite of the present inventionxByCzThe material layer has the characteristics of high melting point, good oxidation resistance, corrosion resistance and the like, and the obtained fiber toughened ceramic matrix composite material can be used in aerospace, nuclear energy, semiconductors, electromagnetic absorption or shielding, neutron absorption or shielding, radiochemistry and radiology medicineThe field of science and the like.

Description

Fiber-toughened ceramic-based composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of ceramic matrix composite materials, and particularly relates to a fiber toughened ceramic matrix composite material and a preparation method and application thereof.
Background
The fiber toughened ceramic matrix composite has the advantages of light weight, high strength, high temperature resistance, oxidation resistance, corrosion resistance, creep resistance and the like, and has wide application prospects in the fields of aerospace, nuclear energy and the like. The fiber toughened ceramic matrix composite mainly comprises fibers, a matrix and an interface layer between the fibers and the matrix. The fiber forms the framework of the ceramic matrix composite material and is the main bearing unit. The ceramic matrix is mainly used for filling the internal gaps of the fiber prefabricated part in the composite material, wrapping the fiber bundles, and connecting the fiber bundles into a whole, thereby playing the dual functions of transferring load and protecting fibers. The interface layer is positioned at the joint between the fiber and the matrix, on one hand, the fiber is protected, on the other hand, the bridge function is realized between the matrix and the fiber, and the load is transferred to the fiber through the matrix; meanwhile, when the crack is expanded, the crack is prevented from expanding to the interior of the fiber through energy dissipation mechanisms such as interface debonding, crack deflection and branching.
Therefore, the fiber surface coating is one of the most key structural units of the fiber toughened ceramic matrix composite, is a ligament connecting the fiber and the matrix, and is also a stress transmission bridge, the interface bonding strength of the fiber surface coating directly determines the mechanical property and the failure/failure mode of the composite, and the fiber surface coating is the key for realizing the toughening of the composite. The weak interface combination is beneficial to the debonding and the pulling-out of the silicon carbide fiber interface, and is beneficial to improving the toughness of the composite material. And the proper strong interface combination can lead the matrix cracks to deflect and branch at the interface, thereby improving the toughness of the composite material, and can transfer the load from the matrix to the fiber, thereby improving the strength of the composite material. Under extreme environmental conditions such as high temperature and oxygen, the performances of the interface layer such as high temperature resistance, corrosion resistance and oxidation resistance face a serious challenge, and the interface layer is often the weakest link and fails first. Therefore, the structural stability of the interface layer is crucial, and the service cycle of the composite material is determined to a certain extent.
At present, interface layers of fiber-toughened ceramic matrix composites mainly include several material systems such as Pyrolytic Carbon (PyC), Hexagonal boron nitride (Hexagonal-BN), and silicon carbide. The PyC is a kind of interface layer which is widely used, but under the oxidizing atmosphere of more than 400 ℃, the PyC interface layer is easy to be oxidized and decomposed, so that oxygen in the environment is diffused to the surface of the fiber, the fiber is oxidized and damaged, and the mechanical property of the composite material is reduced. In the BN interface layer, since van der waals force is a weak bond between two atomic planes, when a crack of the matrix propagates to the BN interface layer, deflection occurs between the BN weak bonding planes, and the toughness of the composite material can be improved. However, when the temperature is increased to 850 ℃, the BN interface layer also starts to be oxidized, and it is difficult to operate at a high temperature of 1000 ℃ or higher. The oxidation resistance of the SiC coating is superior to that of PyC and BN, and the oxidation damage of the fiber can be effectively prevented. But the SiC coating has stronger interface bonding, which is not beneficial to toughening of the composite material.
Disclosure of Invention
The invention mainly aims to provide a fiber toughened ceramic matrix composite material, a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a fiber toughened ceramic matrix composite material, which comprises: a ceramic material matrix, an interfacial layer, and fibers; the interfacial layer comprises RExByCzThe material layer, wherein RE is one or a combination of more than two of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, x is 1-10, Y is 1-20, and z is 1-20.
In some more specific embodiments, more than one doped phase layer and RE are disposed between the ceramic material matrix and the fiberxByCzA layer of material.
The embodiment of the invention also provides a preparation method of the fiber toughened ceramic matrix composite material, which comprises the following steps:
preparing an interface layer on the surface of the fiber by at least any one of a molten salt method, a physical vapor deposition method, a solid-phase reaction method, a chemical vapor deposition method, a precursor conversion method, an in-situ reaction sintering method and a chemical coprecipitation method;
and preparing a ceramic material matrix on the surface of the interface layer by at least adopting any one of a precursor conversion method, a chemical vapor infiltration method, a solid phase method, a melt infiltration method, a nano slurry dipping eutectic conversion method, a sol-gel method, an electrophoretic deposition method and a chemical coprecipitation method, thereby forming the fiber toughened ceramic matrix composite.
The embodiment of the invention also provides application of the fiber toughened ceramic matrix composite material in the fields of aerospace, nuclear energy, semiconductors, electromagnetic absorption or shielding, neutron absorption or shielding, radiochemistry or radiology.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention makes lanthanide boron carbide RExByCzAs an interface layer of the fiber reinforced ceramic matrix composite, by utilizing the unique layered structure, crack energy absorption mechanisms such as crack deflection, interlayer tearing, interlayer slippage, flaky crystal wrinkles and the like are generated on the interface, so that the expansion of cracks in the composite can be effectively inhibited, and the fracture toughness of the composite can be effectively improved;
(2) the interface layer material adopted by the invention is lanthanide boron carbide RExByCzThe ceramic matrix composite material can stably work at high temperature, has excellent high temperature resistance, oxidation resistance, corrosion resistance, ablation resistance and wear resistance, and can be applied to the fields of aerospace, nuclear energy, semiconductors, electromagnetic absorption or shielding, neutron absorption or shielding, radiochemistry, radiology and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows a carbon fiber surface YB of the fiber-toughened ceramic matrix composite according to example 1 of the present invention2C2A schematic diagram of an interface layer;
FIG. 2 shows the surface YB of the silicon carbide fiber of the fiber-toughened ceramic matrix composite in example 2 of the present invention2C2A schematic diagram of an interface layer;
FIG. 3 shows PrB on the surface of silicon nitride fiber of the fiber-toughened ceramic matrix composite according to example 3 of the present invention2C2A schematic diagram of an interface layer;
FIG. 4 is a schematic view of a ScBC interface layer on the surface of carbon fiber of the fiber-toughened ceramic matrix composite according to example 4 of the present invention;
FIG. 5 shows the surface NdB of the carbon fiber of the fiber-toughened ceramic matrix composite of example 5 of the present invention2A schematic diagram of a C interface layer;
FIG. 6 shows the GdB of the surface of the carbon fiber of the fiber-toughened ceramic-based composite material in example 6 of the present invention2C2A schematic illustration of an interfacial layer;
FIG. 7 is a schematic representation of the Y-B/DyB carbon fiber surface of the fiber-toughened ceramic matrix composite of example 7 of the present invention2C2A schematic representation of a coating;
FIG. 8 is a schematic illustration of a Yb-C/ErBC coating on the surface of a silicon carbide whisker in a fiber toughened ceramic matrix composite of example 8 in accordance with the present invention;
FIG. 9 is a BN/HoB fiber surface of basalt fiber of fiber toughened ceramic matrix composite according to example 9 of the present invention2C schematic diagram of coating;
FIG. 10 is a SiC/LuB on the surface of the alumina fiber of the fiber toughened ceramic matrix composite in example 10 of the present invention2C2A schematic representation of a coating;
FIG. 11 shows SiC/PyC/YB on the surface of the carbon fiber of the fiber-toughened ceramic matrix composite according to example 11 of the present invention2C2A schematic representation of a coating;
FIG. 12 is a schematic view of a BN/PyC/YbBC interface layer on the surface of the silica carbon fiber of the fiber-toughened ceramic matrix composite in example 12 of the present invention.
Detailed Description
Lanthanide boron carbide RExByCzThe composite material has a layered structure, mainly comprises a REBC phase, a REB2C phase and a REB2C2 phase, wherein RE is Sc and Y and one or the combination of two or more of lanthanide elements of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the like, has good mechanical, thermal and electrical properties, can form a boron oxide, rare earth oxide and/or rare earth borate protective film after high-temperature oxidation, and has good oxidation resistance in different temperature regions. Meanwhile, due to the unique layered structure, the material has various fracture energy absorption mechanisms when subjected to external loads, such as interlayer tearing, interlayer slippage, lamellar crystal wrinkles, crack deflection and the like. Thus, lanthanide boron carbide RExByCzThe interface layer used as the fiber reinforced ceramic matrix composite material has wide application prospect in the fields of aerospace, nuclear energy and the like.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Specifically, as an aspect of the present invention, a fiber-toughened ceramic matrix composite material comprises: a ceramic material matrix, an interfacial layer, and fibers; the interfacial layer comprises RExByCzThe material layer, wherein RE is one or a combination of more than two of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, x is 1-10, Y is 1-20, and z is 1-20.
In some preferred embodiments, the RE isxByCzRE in a material layerxByCzThe material comprises REBC phase and REB2Phase C, REB2C2Any one of or a combination of two of the phases, and is not limited thereto.
In some preferred embodiments, the interfacial layer is formed from multiple REsxByCzThe material layers are alternately laminated, and the plurality of REsxByCzThe material layer at least contains one RExByCzA material.
In some preferred embodiments, more than one doped phase layer and RE are disposed between the ceramic material matrix and the fiberxByCzA layer of material.
Further, the doped phase layer and RExByCzThe material layers are alternately stacked.
Further, the material of the doped phase layer includes any one or a combination of two or more of RE-B, RE-C, PyC, MAX phase, BN, and SiC, but is not limited thereto.
In some preferred embodiments, the interface layer has a thickness of 5nm to 100 μm.
Further, the interface layer has a thickness of 20nm to 5 μm.
In some preferred embodiments, the fiber-toughened ceramic matrix composite has a volume fraction of fibers in the range of 1 to 95%, preferably 5 to 70%, and more preferably 10 to 60%.
In some preferred embodiments, the fibers include any one or a combination of two or more of carbon fibers, silicon carbide fibers, silicon nitride fibers, silica carbon fibers, silicon carbide whiskers, alumina fibers, quartz fibers, mullite fibers, basalt fibers, silicate fibers, aluminate fibers, and are not limited thereto.
In some preferred embodiments, the ceramic material matrix includes any one or a combination of two or more of silicon carbide, boron carbide, zirconium carbide, titanium carbide, tantalum carbide, hafnium carbide, tungsten carbide, silicon nitride, boron nitride, zirconium boride, hafnium boride, titanium boride, tantalum boride, aluminum oxide, zirconium oxide, hafnium oxide, mullite, and is not limited thereto.
In another aspect of the embodiments of the present invention, there is provided a method for preparing the fiber toughened ceramic matrix composite material, including:
preparing an interface layer on the surface of the fiber by at least any one of a molten salt method, a physical vapor deposition method, a solid-phase reaction method, a chemical vapor deposition method, a precursor conversion method, an in-situ reaction sintering method and a chemical coprecipitation method;
and preparing a ceramic material matrix on the surface of the interface layer by at least adopting any one of a precursor conversion method, a chemical vapor infiltration method, a solid phase method, a melt infiltration method, a nano slurry dipping eutectic conversion method, a sol-gel method, an electrophoretic deposition method and a chemical coprecipitation method, thereby forming the fiber toughened ceramic matrix composite.
In some preferred embodiments, the preparation method specifically comprises: and (3) pretreating the fiber (removing surface impurities) to obtain a fiber preform, and then depositing on the surface of the fiber preform to form the interface layer.
In some preferred embodiments, the preparation method specifically comprises: weaving and/or winding fibers to form fiber cloth, depositing on the surface of the fiber cloth to form the interface layer, and then pretreating the fiber cloth to form a fiber preform.
Further, the weaving mode includes any one of 2D weaving, 2.5D weaving, 3D weaving or 4D weaving.
In some preferred embodiments, the preparation method further comprises: before depositing the interface layer, a doped phase layer is deposited on the surface of the fiber.
In some more specific embodiments, the method of preparing the fiber toughened ceramic matrix composite material includes:
(1) pretreating the fiber to remove surface impurities and obtain a fiber preform;
(2) preparing an interface layer on the surface of the fiber preform;
(3) preparing pottery on the surface of the interface layerA ceramic material matrix obtained with RExByCzThe material layer is a fiber-toughened ceramic matrix composite.
Further, the fiber is wound or woven on a prefabricated part mould according to a certain angle by using a fiber winding or weaving machine to obtain a fiber prefabricated part.
In some more specific embodiments, the method of preparing the fiber-toughened ceramic matrix composite comprises:
(1) weaving or winding fibers into fiber cloth;
(2) preparing an interface layer on the surface of the fiber cloth, and then preparing the obtained fiber cloth into a fiber preform;
(3) preparing ceramic material matrix on the surface of the obtained fiber preform to obtain the fiber preform with RExByCzThe material layer is a fiber-toughened ceramic matrix composite.
Further, the method for weaving the fiber includes any one of 2D weaving, 2.5D weaving, 3D weaving, or 4D weaving, but is not limited thereto.
Further, the interface layer is prepared by using at least one of a molten salt method, a physical vapor deposition method, a solid-phase reaction method, a chemical vapor deposition method, a precursor conversion method, an in-situ reaction sintering method, and a chemical coprecipitation method, or a combination of two or more methods, but is not limited thereto.
Further, the ceramic material matrix is prepared by at least any one of a precursor conversion method, a chemical vapor infiltration method, a solid phase method, a melt infiltration method, a nano slurry impregnation eutectic conversion method, a sol-gel method, an electrophoretic deposition method and a chemical coprecipitation method, but is not limited thereto.
Another aspect of an embodiment of the present invention also provides a use of the aforementioned fiber-toughened ceramic matrix composite material in aerospace, nuclear, semiconductor, electromagnetic absorption or shielding, neutron absorption or shielding, radiochemistry, or radiology fields.
In summary, the invention combines the lanthanide boron carbide RExByCzAs an interfacial layer in fiber reinforced ceramic matrix compositesBy using the unique layered structure, crack energy absorption mechanisms such as crack deflection, interlayer tearing, interlayer slippage, flaky crystal wrinkles and the like are generated at the interface, so that the expansion of cracks in the composite material can be effectively inhibited, and the fracture toughness of the composite material can be effectively improved.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
In the embodiment, the ceramic matrix composite material is a carbon fiber toughened silicon carbide composite material, and the interface layer between the fibers and the matrix is YB2C2The preparation method comprises the following specific steps:
(1) weaving carbon fibers into a 2D carbon fiber preform, wherein the volume fraction of the carbon fibers is controlled to be 50%;
(2) YB (Yttrium barium copper) is prepared on surface of carbon fiber by molten salt growth method2C2An interfacial layer, as shown in FIG. 1, having a thickness of about 50 nm;
(3) preparing silicon carbide substrate on the prefabricated body and the interface layer by adopting a precursor conversion method, and obtaining compact silicon carbide substrate with YB (yttrium barium copper) through 10 times of dipping and cracking2C2The carbon fiber-toughened silicon carbide composite of the interfacial layer (i.e., the aforementioned "fiber-toughened ceramic matrix composite").
Example 2
In this embodiment, the ceramic matrix composite is silicon carbide fiber-toughened silicon carbide composite, and the interface layer between the fiber and the matrix is YB2C2The preparation method comprises the following specific steps:
(1) weaving silicon carbide fibers into a 2D silicon carbide fiber preform, wherein the volume fraction of the silicon carbide fibers is controlled to be 60%;
(2) preparing YB on the surface of silicon carbide fiber by molten salt method2C2An interfacial layer, as shown in FIG. 2, having a thickness of about 500 nm;
(3) preparing silicon carbide substrate on the prefabricated body and the interface layer by adopting a precursor conversion method, and obtaining compact silicon carbide substrate with YB (yttrium barium copper) through 8 times of dipping and cracking2C2The silicon carbide fiber-toughened silicon carbide composite of the interfacial layer (i.e., the aforementioned "fiber-toughened ceramic matrix composite").
Example 3
In this embodiment, the ceramic matrix composite is a boron carbide composite toughened with silicon nitride fibers, and the interface layer between the fibers and the matrix is PrB2C2The preparation method comprises the following specific steps:
(1) weaving silicon nitride fibers into a 2.5D silicon nitride fiber preform, wherein the volume fraction of the silicon nitride fibers is controlled to be 20%;
(2) preparing PrB on the surface of silicon nitride fiber by physical vapor deposition2C2An interfacial layer, as shown in FIG. 3, having a thickness of about 20 nm;
(3) preparing boron carbide matrix on the prefabricated body and the interface layer by adopting an electrophoretic deposition method, and obtaining compact PrB with PrB by high-temperature sintering2C2The silicon nitride fiber-toughened boron carbide composite of the interface layer (i.e., the aforementioned "fiber-toughened ceramic matrix composite").
Example 4
In this embodiment, the ceramic matrix composite material is a carbon fiber toughened zirconium carbide composite material, and the interface layer between the fiber and the matrix is ScBC. The preparation method comprises the following specific steps:
(1) weaving carbon fibers into a 2.5D carbon fiber preform, wherein the volume fraction of the carbon fibers is controlled to be 5%;
(2) preparing a ScBC interface layer on the surface of the carbon fiber by adopting a chemical vapor deposition method, wherein the thickness of the ScBC interface layer is about 5nm as shown in figure 4;
(3) preparing a zirconium carbide matrix on the preform and the interface layer by a solid phase method, and sintering at high temperature to obtain the compact carbon fiber toughened zirconium carbide composite material (namely the fiber toughened ceramic matrix composite material) with the ScBC interface layer.
Example 5
In this embodiment, the ceramic matrix composite is a tantalum carbide composite toughened by carbon fibers, and the interface layer between the fibers and the matrix is NdB2C, the specific preparation steps are as follows:
(1) weaving carbon fibers into a 3D carbon fiber preform, wherein the volume fraction of the carbon fibers is controlled to be 80%;
(2) preparing NdB on the surface of carbon fiber by adopting an in-situ reaction sintering method2C an interfacial layer, as shown in FIG. 5, having a thickness of about 10 μm;
(3) preparing a tantalum carbide matrix on the preform and the interface layer by a melt infiltration method, and obtaining the carbon fiber toughened tantalum carbide composite material (namely the fiber toughened ceramic matrix composite material) by high-temperature heat treatment.
Example 6
In this embodiment, the ceramic matrix composite is a carbon fiber toughened tungsten carbide composite, and the interface layer between the fiber and the matrix is GdB2C2The preparation method comprises the following specific steps:
(1) weaving carbon fibers into a 3D carbon fiber preform, wherein the volume fraction of the carbon fibers is controlled to be 50%;
(2) GdB is prepared on the surface of alumina fiber by adopting a chemical coprecipitation method2C2An interfacial layer, as shown in FIG. 6, having a thickness of about 5 μm;
(3) preparing tungsten carbide matrix on the preform and the interface layer by adopting a nano slurry dipping eutectic transformation method, dipping for 3 times, and then sintering at high temperature to obtain compact GdB2C2The carbon fiber-toughened tungsten carbide composite of the interfacial layer (i.e., the aforementioned "fiber-toughened ceramic matrix composite").
Example 7
In the embodiment, the ceramic matrix composite material is a carbon fiber toughened hafnium boride composite material, and the coating between the fibers and the matrix is Y-B/DyB2C2The preparation method comprises the following specific steps:
(1) weaving carbon fibers into a 2D carbon fiber preform, wherein the volume fraction of the carbon fibers is controlled to be 40%;
(2) miningPreparing Y-B layer on the surface of carbon fiber by molten salt method, as shown in FIG. 7, with thickness of about 2 μm, and preparing DyB on the Y-B layer by chemical vapor deposition2C2An interface layer having a thickness of 1 μm;
(3) preparing a hafnium boride matrix on the preform and the interface layer by a solid phase method, and sintering at a high temperature to obtain a compact hafnium boride/yttrium oxide/boron (Y-B/DyB)2C2The quartz fiber-toughened hafnium boride composite of the interfacial layer (i.e., the aforementioned "fiber-toughened ceramic matrix composite").
Example 8
In this embodiment, the ceramic matrix composite material is a silicon nitride composite material toughened by silicon carbide whiskers, the coating between the fiber and the matrix is Yb-C/ErBC, and the preparation method specifically includes the following steps:
(1) controlling the volume fraction of the silicon carbide whiskers to be 10%;
(2) preparing a Yb-C layer on the surface of the silicon carbide crystal whisker by adopting a precursor conversion method, wherein the thickness of the Yb-C layer is about 10nm as shown in figure 8, and preparing an ErBC interface layer on the Yb-C layer by adopting a physical vapor deposition method, wherein the thickness of the ErBC interface layer is 5 nm;
(3) the silicon nitride matrix is prepared on the prefabricated body and the interface layer by adopting a sol-gel method, and the compact silicon carbide whisker toughened silicon nitride composite material (namely the fiber toughened ceramic matrix composite material) with the Yb-C/ErBC interface layer is obtained by high-temperature sintering.
Example 9
In the ceramic matrix composite material of the embodiment, the basalt fiber toughened alumina composite material is taken as an example, and the coating between the fiber and the matrix is BN/HoB2C, the preparation method comprises the following specific steps:
(1) weaving basalt fibers into a 3D basalt fiber prefabricated body, wherein the volume fraction of the basalt fibers is controlled to be 80%;
(2) preparing BN layer on the surface of basalt fiber by chemical vapor deposition, as shown in figure 9, with thickness of about 20nm, and preparing HoB on the BN layer by molten salt deposition2The thickness of the C interface layer is 2 mu m;
(3) preparing alumina matrix on the prefabricated body and the interface layer by electrophoretic depositionThe dense BN/HoB is obtained by warm sintering2The basalt fiber-toughened alumina composite of the interface layer C (i.e., the aforementioned "fiber-toughened ceramic matrix composite").
Example 10
In the ceramic matrix composite material of the embodiment, the alumina fiber toughened zirconia composite material is taken as an example, and the coating between the fiber and the matrix is SiC/LuB2C2The preparation method comprises the following specific steps:
(1) weaving alumina fibers into a 4D alumina fiber preform, wherein the volume fraction of the alumina fibers is controlled to be 20%;
(2) preparing a SiC layer on the surface of the alumina fiber by adopting a physical vapor deposition method, as shown in figure 10, wherein the thickness of the SiC layer is about 10 mu m, and preparing LuB on the SiC layer by adopting a solid phase reaction method2C2An interface layer with a thickness of 30 nm;
(3) preparing zirconia matrix on the prefabricated body and the interface layer by adopting a chemical coprecipitation method, and obtaining compact SiC/LuB through high-temperature heat treatment2C2The alumina fiber toughened zirconia composite of the interfacial layer (i.e., the aforementioned "fiber toughened ceramic matrix composite").
Example 11
In the embodiment, the ceramic matrix composite material is a carbon fiber toughened hafnium boride composite material, and the coating between the fiber and the matrix is SiC/PyC/YB2C2The preparation method comprises the following specific steps:
(1) weaving carbon fibers into a 2.5D carbon fiber preform, wherein the volume fraction of the carbon fibers is controlled to be 50%;
(2) preparing SiC layer and PyC layer on the surface of the carbon fiber by chemical vapor deposition, as shown in FIG. 11, with thickness of about 50nm and 20nm, respectively, and preparing YB on the SiC/PyC layer by molten salt method2C2An interfacial layer having a thickness of 50 nm;
(3) preparing a hafnium boride substrate on the preform and the interface layer by adopting an electrophoretic deposition method, and obtaining the compact SiC/PyC/YB by high-temperature sintering2C2Carbon fiber toughened hafnium boride composites of interfacial layers (i.e., "fiber toughened ceramic matrices" as described previouslyComposite material ").
Example 12
In the ceramic matrix composite material in the embodiment, a silicon-oxygen-carbon-fiber-toughened boron nitride composite material is taken as an example, a coating between the fiber and the matrix is BN/PyC/YbBC, and the specific preparation steps are as follows:
(1) weaving silica carbon fibers into a 4D silica carbon fiber preform, wherein the volume fraction of the silica carbon fibers is controlled to be 5%;
(2) preparing a BN layer and a PyC layer on the surface of the silica carbon fiber by adopting a chemical coprecipitation method, wherein the thicknesses of the BN layer and the PyC layer are respectively about 1 mu m and 2 mu m as shown in figure 12, and preparing a YbBC interface layer on the BN/PyC layer by adopting a precursor conversion method, wherein the thickness is 60 nm;
(3) preparing a boron nitride matrix on the preform and the interface layer by adopting a chemical vapor infiltration method, and obtaining the compact silica carbon fiber toughened boron nitride composite material (namely the fiber toughened ceramic matrix composite material) with the BN/PyC/YbBC interface layer through high-temperature heat treatment.
In addition, the inventors of the present invention have also made experiments with other raw materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.

Claims (10)

1. A fiber-toughened ceramic matrix composite, comprising: a ceramic material matrix, an interfacial layer, and fibers; the interfacial layer comprises RExByCzThe material layer, wherein RE is one or a combination of more than two of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, x is 1-10, Y is 1-20, and z is 1-20.
2. The fiber toughened ceramic matrix composite according to claim 1,the method is characterized in that: the RExByCzRE in a material layerxByCzThe material comprises REBC phase and REB2Phase C, REB2C2Any one or a combination of two or more of the phases.
3. The fiber toughened ceramic matrix composite according to claim 1, wherein: the interface layer is composed of a plurality of REsxByCzThe material layers are alternately laminated, and the plurality of REsxByCzThe material layer at least contains one RExByCzA material.
4. The fiber toughened ceramic matrix composite according to claim 1, wherein: more than one doped phase layer and RE are arranged between the ceramic material matrix and the fiberxByCzA layer of material;
preferably, the doped phase layer is doped with RExByCzThe material layers are alternately stacked; preferably, the material of the doped phase layer comprises any one or a combination of two or more of RE-B, RE-C, PyC, MAX phase, BN and SiC.
5. The fiber toughened ceramic matrix composite according to claim 1, wherein: the thickness of the interface layer is 5 nm-100 μm, preferably 20 nm-5 μm;
and/or the volume fraction of the fibers in the fiber toughened ceramic matrix composite material is 1-95%, preferably 5-70%, and particularly preferably 10-60%.
6. The fiber toughened ceramic matrix composite according to claim 1, wherein: the fiber comprises any one or the combination of more than two of carbon fiber, silicon carbide fiber, silicon nitride fiber, silica carbon fiber, silicon carbide whisker, alumina fiber, quartz fiber, mullite fiber, basalt fiber, silicate fiber and aluminate fiber;
and/or the ceramic material matrix comprises any one or the combination of more than two of silicon carbide, boron carbide, zirconium carbide, titanium carbide, tantalum carbide, hafnium carbide, tungsten carbide, silicon nitride, boron nitride, zirconium boride, hafnium boride, titanium boride, tantalum boride, aluminum oxide, zirconium oxide, hafnium oxide and mullite.
7. The method of making a fiber toughened ceramic matrix composite according to any one of claims 1 to 6, comprising:
preparing an interface layer on the surface of the fiber by at least any one of a molten salt method, a physical vapor deposition method, a solid-phase reaction method, a chemical vapor deposition method, a precursor conversion method, an in-situ reaction sintering method and a chemical coprecipitation method;
and preparing a ceramic material matrix on the surface of the interface layer by at least adopting any one of a precursor conversion method, a chemical vapor infiltration method, a solid phase method, a melt infiltration method, a nano slurry dipping eutectic conversion method, a sol-gel method, an electrophoretic deposition method and a chemical coprecipitation method, thereby forming the fiber toughened ceramic matrix composite.
8. The preparation method according to claim 7, characterized by specifically comprising: pretreating fibers to obtain a fiber preform, and depositing on the surface of the fiber preform to form the interface layer;
and/or the preparation method specifically comprises the following steps: weaving and/or winding fibers to form fiber cloth, depositing the fiber cloth on the surface of the fiber cloth to form the interface layer, and then pretreating the fiber cloth to form a fiber preform;
preferably, the knitting adopts any one of 2D knitting, 2.5D knitting, 3D knitting and 4D knitting.
9. The method of claim 7, further comprising: before depositing the interface layer, a doped phase layer is deposited on the surface of the fiber.
10. Use of the fiber toughened ceramic matrix composite according to any one of claims 1 to 6 in the aerospace, nuclear, semiconductor, electromagnetic absorption or shielding, neutron absorption or shielding, radiochemistry or radiology fields.
CN202210244772.4A 2022-03-14 2022-03-14 Fiber-toughened ceramic-based composite material and preparation method and application thereof Pending CN114560714A (en)

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