WO2019235624A1 - セラミック基複合材料 - Google Patents

セラミック基複合材料 Download PDF

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WO2019235624A1
WO2019235624A1 PCT/JP2019/022779 JP2019022779W WO2019235624A1 WO 2019235624 A1 WO2019235624 A1 WO 2019235624A1 JP 2019022779 W JP2019022779 W JP 2019022779W WO 2019235624 A1 WO2019235624 A1 WO 2019235624A1
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silicon carbide
gas
fiber bundle
source
ceramic matrix
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PCT/JP2019/022779
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English (en)
French (fr)
Inventor
悠太 大塚
康智 田中
飛怜 井上
久保田　渉
いづみ 松倉
Masato ISHIZAKI (石崎 雅人)
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株式会社Ihi
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Priority to EP19815583.0A priority Critical patent/EP3816140A4/en
Priority to US15/734,448 priority patent/US20210221744A1/en
Publication of WO2019235624A1 publication Critical patent/WO2019235624A1/ja

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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62272—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on non-oxide ceramics
    • C04B35/62277—Fibres based on carbides
    • C04B35/62281—Fibres based on carbides based on silicon carbide
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62844—Coating fibres
    • C04B35/62857—Coating fibres with non-oxide ceramics
    • C04B35/6286—Carbides
    • C04B35/62863—Silicon carbide
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62884—Coating the powders or the macroscopic reinforcing agents by gas phase techniques
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62897—Coatings characterised by their thickness
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • C23C16/325—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4488—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45514—Mixing in close vicinity to the substrate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5216—Inorganic
    • C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
    • C04B2235/5244—Silicon carbide

Definitions

  • the present disclosure relates to ceramic matrix composites. This application claims priority based on Japanese Patent Application No. 2018-109789 for which it applied to Japan on June 7, 2018, and uses the content here.
  • Ceramic matrix composites are known as high-strength high-temperature materials and lightweight materials, and are expected to replace nickel-base alloys. For example, by applying CMC to the high-temperature part of an aircraft jet engine, it is possible to expect a reduction in engine weight and fuel consumption. It is effective to use silicon carbide, which is excellent in heat resistance, as a matrix for application to a high-temperature part of an aircraft jet engine.
  • CMC is manufactured by a method of forming a silicon carbide film by depositing silicon carbide on the surface of each fiber of a fiber substrate by, for example, chemical vapor deposition (CVD) method or chemical vapor deposition (CVI) method.
  • CVD chemical vapor deposition
  • CVI chemical vapor deposition
  • a source gas such as CH 3 SiCl 3 (MTS) and SiCl 4
  • a carrier gas such as H 2 and He
  • an additive gas such as C 2 H 6 and C 2 H 4
  • Patent Document 1 cannot be said to have sufficient mechanical characteristics particularly when considering application to severe conditions such as a high temperature part of an aircraft jet engine. It is important to improve.
  • This disclosure is intended to provide a ceramic matrix composite material having excellent mechanical properties.
  • the ceramic matrix composite material according to the first aspect of the present disclosure has a fiber base formed of silicon carbide fiber bundles and a silicon carbide film formed on the surface of each silicon carbide fiber of the silicon carbide fiber bundle. and, wherein for the average film thickness D 1 of the said silicon carbide film formed on the surface of the silicon carbide fibers of the surface layer of the silicon carbide fiber bundle, wherein the silicon carbide of the inner layer than said surface layer inside of the silicon carbide fiber bundle the average ratio of the thickness D 2 of the silicon carbide film formed on the surface of the fiber is 1.0 to 1.3.
  • the mean thickness D 2 of the silicon carbide film may be not less than 2.6 [mu] m.
  • the ceramic matrix composite material of the present disclosure has excellent mechanical properties.
  • the ceramic matrix composite material of the present disclosure includes a fiber substrate formed of a silicon carbide fiber bundle and silicon carbide formed on the surface of each silicon carbide fiber of the silicon carbide fiber bundle.
  • a film SiC film.
  • the silicon carbide fiber bundle may contain fibers other than silicon carbide fibers in addition to the silicon carbide fibers as long as the effects of the present disclosure are not impaired.
  • fibers include alumina fibers, carbon fibers, and glass fibers.
  • the content of silicon carbide fibers in the silicon carbide fiber bundle is preferably 90% by mass or more, more preferably 95% by mass or more, and more preferably 99% by mass or more with respect to the total mass of fibers contained in the silicon carbide fiber bundle. Preferably, 100 mass% is particularly preferable.
  • the number of fibers of the silicon carbide fiber bundle, the fiber density, and the average distance between the fibers are not particularly limited, and can be set as appropriate, for example, within a range that is normally set in CMC.
  • the aspect of the fiber base material is not particularly limited, and examples thereof include woven fabrics such as plain weave, twill weave, satin weave, and triaxial weave.
  • the shape of a fiber base material is not specifically limited, It can be set as a desired shape according to a use.
  • a silicon carbide fiber bundle having powder adhered thereto may be used. It does not specifically limit as powder, A well-known powder can be used in the range which does not impair the effect of this indication. As the powder, one kind may be used alone, or two or more kinds may be used in combination.
  • CMC to the average film thickness D 1 of the silicon carbide fiber bundle surface (outermost layer) silicon carbide film formed on the surface of the silicon carbide fibers, silicon carbide fibers inside the inner than the surface layer of the silicon carbide fiber bundle
  • the ratio (D 2 / D 1 ) of the average film thickness D 2 of the silicon carbide film formed on the surface is 1.0 to 1.3.
  • the “surface layer of the silicon carbide fiber bundle” means a region from the surface (outer surface) of the silicon carbide fiber bundle to a depth of 20 ⁇ m.
  • the average film thickness D 1 of the surface layer of the silicon carbide film of the silicon carbide fiber bundle, as long as the D 2 / D 1 satisfies the above range can be appropriately set.
  • the value of D 1 is large, excellent mechanical properties.
  • the upper limit of D 1 are, for example, can be set in terms of CMC productivity.
  • the average film thickness D 2 of the inner layer of the silicon carbide film of the silicon carbide fiber bundle depending on the distance between the fibers of silicon carbide fibers in bundles, or 2.6 ⁇ m are preferred. If D 2 is more than the lower limit of the range, excellent mechanical properties.
  • the upper limit of D 2, for example, can be set in terms of CMC productivity.
  • the manufacturing method of CMC of this indication is not specifically limited.
  • a Si source gas containing SiCl 2 or SiCl is reacted with a C source gas containing C atoms, and carbonized on the surface of each fiber of the silicon carbide fiber bundle in the fiber substrate.
  • the method of forming a silicon film is mentioned. Since the method is excellent in the impregnation of silicon carbide into the silicon carbide fiber bundle, a silicon carbide film having a sufficient thickness can be formed even in the inner layer of the fiber bundle. Therefore, D 2 / D 1 can be easily controlled so as to be within the above range, and CMC having excellent mechanical characteristics can be obtained.
  • the gas of the Si source may be a gas containing SiCl 2 gas and not containing SiCl gas, or may be a gas containing both SiCl 2 gas and SiCl gas.
  • the Si source gas contains SiCl gas
  • the gas also contains SiCl 2 gas in terms of thermodynamic theory.
  • the Si source gas may include SiCl 2 such as SiCl 3 and SiCl 4 and Si source gas other than SiCl.
  • the partial pressure of SiCl 2 gas when the total pressure of the gas and 1 atm (0.1 MPa) can be appropriately set.
  • the partial pressure of the SiCl 2 gas can be set from the viewpoint of ensuring both the uniformity of the silicon carbide film on the surface of each fiber and the productivity.
  • the partial pressure of the SiCl 2 gas may be the upper limit of the thermodynamic theoretical value.
  • the partial pressure of the SiCl gas when the total gas pressure is 1 atm (0.1 MPa) can be set as appropriate.
  • the partial pressure of SiCl gas can be set from the viewpoint of ensuring both the uniformity of the silicon carbide film on the surface of each fiber and the productivity.
  • the partial pressure of the SiCl gas may be the upper limit of the thermodynamic theoretical value.
  • Cl source examples include gases such as Cl 2 gas, SiCl 4 gas, and MTS gas.
  • the Cl source is preferably Cl 2 gas because it does not contain C atoms (the C source can be separately supplied at a free quantity ratio).
  • Cl source only one kind may be used alone, or two or more kinds may be used in combination.
  • the partial pressure of SiCl 2 or SiCl in the gas of the Si source can be adjusted by the temperature at which the Si source and the Cl source are brought into contact with each other.
  • Examples of the C source include hydrocarbons such as CH 4 , C 2 H 6 , C 3 H 8 , C 2 H 4 , C 2 H 2 , C 6 H 6 , and CCl 4 .
  • the C source is preferably at least one hydrocarbon selected from the group consisting of CH 4 , C 2 H 6 , C 3 H 8 , C 2 H 4 , C 2 H 2 , C 6 H 6 and CCl 4 .
  • a carrier gas may be used in the reaction for forming the silicon carbide film, if necessary.
  • the carrier gas include gases inert to the film formation reaction such as H 2 gas, N 2 gas, He gas, and Ar gas.
  • H 2 gas is preferable because the impregnation property of silicon carbide into the silicon carbide fiber bundle is improved.
  • the carrier gas only one kind may be used alone, or two or more kinds may be used in combination.
  • the reaction temperature for forming the silicon carbide film can be appropriately set.
  • the lower limit of the reaction temperature can be set from the viewpoint of CMC productivity.
  • the upper limit of the reaction temperature can be set from the viewpoint of improving the uniformity of the silicon carbide film formed on the surface of each fiber.
  • the reaction pressure for forming the silicon carbide film is preferably 0.1 to 20 Torr (13 to 2660 Pa), more preferably 5 to 20 Torr (670 to 2660 Pa), and further preferably 15 to 20 Torr (2000 to 2660 Pa). If the reaction pressure is less than the lower limit of the above range, the impregnation rate is low, and productivity may be impaired. When the reaction pressure exceeds the upper limit of the above range, the impregnation property to the porous substrate is impaired, and the high temperature strength may be lowered.
  • the manufacturing apparatus used for manufacturing CMC is not particularly limited.
  • the manufacturing apparatus 100 illustrated in FIG. Note that the drawings illustrated in the following description are merely examples, and the present disclosure is not necessarily limited thereto, and can be appropriately modified and implemented without changing the gist thereof.
  • the manufacturing apparatus 100 includes a tubular reaction furnace 110, a Cl source supply unit 112, a C source supply unit 114, and an exhaust unit 116.
  • a first reaction unit 118 and a second reaction unit 120 are provided in this order from the upstream side of the reaction furnace 110.
  • the 1st reaction part 118 is a part which makes Si source and Cl source contact, and is made to react.
  • the inside of the reaction furnace 110 is partitioned by providing two partition members 122 and 122 having air permeability with a gap in the gas flow direction.
  • a solid Si source 300 (Si powder) is filled between the partition members 122.
  • the partition member 122 may be a member that does not allow Si powder to pass therethrough and allows the Cl source gas and the product Si source gas to pass therethrough, and examples thereof include carbon felt.
  • the first reaction unit 118 of the reaction furnace 110 is provided with a first heater 124 that adjusts the temperature at which the Si source and the Cl source are brought into contact with each other.
  • the second reaction unit 120 is a part that reacts the Si source gas and the C source gas to form a silicon carbide film on the surface of each fiber of the fiber substrate 200.
  • the second reaction unit 120 is configured in such a manner that the fiber substrate 200 can be installed at a position where a silicon carbide film is formed on the surface of the fiber by the reaction between the Si source gas and the C source gas. Is not particularly limited.
  • the second reaction section 120 of the reaction furnace 110 is provided with a second heater 126 that adjusts the reaction temperature for film formation.
  • the Cl source supply unit 112 supplies a Cl source gas.
  • the Cl source supply unit 112 supplies a Cl source gas to the upstream side of the first reaction unit 118 of the reaction furnace 110.
  • the C source supply unit 114 supplies C source gas.
  • the C source supply unit 114 supplies a C source gas between the first reaction unit 118 and the second reaction unit 120 in the reaction furnace 110.
  • the C source gas may be supplied from the C source supply unit 114 together with the carrier gas.
  • the exhaust unit 116 is provided on the downstream side of the reaction furnace 110 and includes a pressure regulating valve 128 and a vacuum pump 130.
  • the exhaust unit 116 depressurizes the inside of the reaction furnace 110 by a pressure regulating valve 128 and a vacuum pump 130 to adjust to a desired pressure.
  • a Cl source gas such as Cl 2 gas is supplied from the Cl source supply unit 112 to the reaction furnace 110, and the Cl source gas and the solid Si in the first reaction unit 118 And contact.
  • a Si source gas containing SiCl 2 or SiCl as a product is generated by contact between the Cl source gas and solid Si, and is sent to the second reaction unit 120.
  • the Si source gas generated in the first reaction unit 118 reacts with the C source gas supplied from the C source supply unit 114, and is formed on the surface of each fiber of the fiber substrate 200. Silicon carbide is deposited to form a silicon carbide film.
  • a silicon carbide matrix is further formed by a liquid phase impregnation (SPI) method or a melt impregnation (PIP) method. Also good.
  • the average film thickness D 1 of the surface layer of the silicon carbide film in the silicon carbide fiber bundle, the average film thickness D 2 of the inner layer of the silicon carbide film is an average film thickness of the silicon carbide film formed by CVI method.
  • the reason why it is difficult to obtain excellent mechanical properties in the conventional CMC is that the uniformity of the silicon carbide film in the surface layer and the inner layer of the fiber bundle is low due to low impregnation of silicon carbide into the silicon carbide fiber bundle. it is conceivable that.
  • the silicon carbide film formed on the surface of each fiber in the silicon carbide fiber bundle is controlled so that D 2 / D 1 is in a specific range, and the silicon carbide fiber bundle The uniformity of the silicon carbide film in the surface layer and the inner layer is excellent. Therefore, the CMC of the present disclosure is excellent in mechanical characteristics.
  • D 2 is set to 2.6 ⁇ m or more, and a sufficient silicon carbide film is formed on the surface of each fiber of the inner layer of the silicon carbide fiber bundle, thereby improving the mechanical characteristics. Further improvement can be achieved.
  • the present disclosure can be used for ceramic matrix composite materials.

Abstract

本開示のセラミック基複合材料は、炭化ケイ素繊維束で形成された繊維基材と、前記炭化ケイ素繊維束の各炭化ケイ素繊維の表面上に形成された炭化ケイ素膜とを有し、前記炭化ケイ素繊維束の表層の前記炭化ケイ素繊維の表面上に形成された前記炭化ケイ素膜の平均膜厚Ｄ１に対する、前記炭化ケイ素繊維束の前記表層よりも内側の内層の前記炭化ケイ素繊維の表面上に形成された前記炭化ケイ素膜の平均膜厚Ｄ２の比は１．０～１．３である。

Description

セラミック基複合材料
　本開示は、セラミック基複合材料に関する。
　本願は、２０１８年６月７日に日本に出願された特願２０１８－１０９７８９号に基づき優先権を主張し、その内容をここに援用する。
　セラミック基複合材料（ＣＭＣ：Ceramic Matrix Composites）は、高強度の高温材料、軽量材料として知られ、ニッケル基合金の代替として期待されている。例えばＣＭＣを航空用ジェットエンジンの高温部に適用することにより、エンジンの軽量化および低燃費化が期待できる。航空用ジェットエンジンの高温部への適用には、耐熱性に優れる炭化ケイ素をマトリックスとして用いることが有効である。
　ＣＭＣは、例えば、化学気相成長（ＣＶＤ）法又は化学気相含浸（ＣＶＩ）法によって、繊維基材の各繊維の表面上に炭化ケイ素を堆積させて炭化ケイ素膜を形成する方法で製造される。特許文献１には、ＣＨ３ＳｉＣｌ３（ＭＴＳ）、ＳｉＣｌ４等の原料ガスと、Ｈ２、Ｈｅ等のキャリアガスと、Ｃ２Ｈ６、Ｃ２Ｈ４等の添加ガスを反応炉に流し、ＣＶＤ法又はＣＶＩ法によりセラミック繊維の表面上に炭化ケイ素膜を形成したＣＭＣが開示されている。
日本国特許第５９０６３１８号公報
　しかし、特許文献１のような従来のＣＭＣは、特に航空用ジェットエンジンの高温部等の過酷な条件への適用を考えた場合には機械的特性が充分とは言えず、機械的特性をさらに向上させることが重要である。
　本開示は、機械的特性に優れたセラミック基複合材料を提供することを目的とする。
　本開示の第１の態様のセラミック基複合材料は、炭化ケイ素繊維束で形成された繊維基材と、前記炭化ケイ素繊維束の各炭化ケイ素繊維の表面上に形成された炭化ケイ素膜とを有し、前記炭化ケイ素繊維束の表層の前記炭化ケイ素繊維の表面上に形成された前記炭化ケイ素膜の平均膜厚Ｄ１に対する、前記炭化ケイ素繊維束の前記表層よりも内側の内層の前記炭化ケイ素繊維の表面上に形成された前記炭化ケイ素膜の平均膜厚Ｄ２の比は１．０～１．３である。
　本開示の前記第１の態様の前記セラミック基複合材料において、前記炭化ケイ素膜の平均膜厚Ｄ２は２．６μｍ以上であってもよい。
　本開示のセラミック基複合材料は、機械的特性に優れている。
本開示のセラミック基複合材料の製造に用いる製造装置の一例を示した模式図である。
　本開示のセラミック基複合材料（以下、「ＣＭＣ」と記す。）は、炭化ケイ素繊維束で形成された繊維基材と、炭化ケイ素繊維束の各炭化ケイ素繊維の表面上に形成された炭化ケイ素膜（ＳｉＣ膜）とを有する。
　炭化ケイ素繊維束は、本開示の効果を損なわない範囲であれば、炭化ケイ素繊維に加えて、炭化ケイ素繊維以外の他の繊維を含んでもよい。他の繊維としては、アルミナ繊維、炭素繊維、ガラス繊維等が挙げられる。
　炭化ケイ素繊維束中の炭化ケイ素繊維の含有量は、炭化ケイ素繊維束に含まれる繊維の総質量に対して、９０質量％以上が好ましく、９５質量％以上がより好ましく、９９質量％以上がさらに好ましく、１００質量％が特に好ましい。
　炭化ケイ素繊維束の繊維数、繊維密度、繊維間の平均距離は、特に限定されず、適宜設定でき、例えばＣＭＣで通常設定される範囲に設定することができる。
　繊維基材の態様は、特に限定されず、例えば、平織、綾織、朱子織、三軸織等の織物が挙げられる。
　繊維基材の形状は、特に限定されず、用途に応じて所望の形状とすることができる。
　繊維基材としては、炭化ケイ素繊維束に粉体が付着したものを用いてもよい。
　粉体としては、特に限定されず、本開示の効果を損なわない範囲で公知の粉体を使用することができる。粉体としては、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。
　ＣＭＣでは、炭化ケイ素繊維束の表層（最外層）の炭化ケイ素繊維の表面上に形成された炭化ケイ素膜の平均膜厚Ｄ１に対する、炭化ケイ素繊維束の表層よりも内側の内層の炭化ケイ素繊維の表面上に形成された炭化ケイ素膜の平均膜厚Ｄ２の比（Ｄ２／Ｄ１）が、１．０～１．３である。なお、「炭化ケイ素繊維束の表層」とは、炭化ケイ素繊維束の表面（外面）から深さ２０μｍまでの領域を意味する。Ｄ２／Ｄ１が前記範囲内であれば、炭化ケイ素繊維束の各繊維の表面に形成されたＣＭＣは、機械的特性に優れる。
　炭化ケイ素繊維束の表層の炭化ケイ素膜の平均膜厚Ｄ１は、Ｄ２／Ｄ１が前記範囲を満たす範囲であれば、適宜設定することができる。Ｄ１の値が大きいほど、機械的特性に優れる。Ｄ１の上限は、例えば、ＣＭＣの生産性の観点で設定することができる。
　炭化ケイ素繊維束の内層の炭化ケイ素膜の平均膜厚Ｄ２は、炭化ケイ素繊維束中の各繊維間の距離にもよるが、２．６μｍ以上が好ましい。Ｄ２が前記範囲の下限値以上であれば、機械的特性に優れる。Ｄ２の上限は、例えば、ＣＭＣの生産性の観点で設定することができる。
　本開示のＣＭＣの製造方法は、特に限定されない。例えば、ＣＶＩ法を用い、ＳｉＣｌ２またはＳｉＣｌを含有するＳｉ源のガスと、Ｃ原子を含有するＣ源のガスとを反応させ、繊維基材における炭化ケイ素繊維束の各繊維の表面上に炭化ケイ素膜を形成する方法が挙げられる。前記方法は、炭化ケイ素繊維束への炭化ケイ素の含浸性に優れるため、繊維束の内層においても十分な膜厚の炭化ケイ素膜を形成できる。そのため、Ｄ２／Ｄ１を前記範囲内となるように容易に制御でき、機械的特性に優れたＣＭＣが得られる。
　Ｓｉ源のガスは、ＳｉＣｌ２ガスを含有し、ＳｉＣｌガスを含有しないガスであってもよく、ＳｉＣｌ２ガスとＳｉＣｌガスの両方を含有するガスであってもよい。Ｓｉ源のガスがＳｉＣｌガスを含有する場合、熱力学理論上、そのガスはＳｉＣｌ２ガスも含有する。なお、Ｓｉ源のガスには、ＳｉＣｌ３、ＳｉＣｌ４等のＳｉＣｌ２およびＳｉＣｌ以外のＳｉ源のガスが含まれていてもよい。
　Ｓｉ源のガスがＳｉＣｌ２を含有する場合、ガスの全圧を１ａｔｍ（０．１ＭＰａ）としたときのＳｉＣｌ２ガスの分圧は、適宜設定できる。例えば、ＳｉＣｌ２ガスの分圧を、各繊維の表面上の炭化ケイ素膜の均一性の確保と生産性を両立する観点で設定することができる。ＳｉＣｌ２ガスの分圧は、熱力学理論値の上限としてもよい。
　Ｓｉ源のガスがＳｉＣｌを含有する場合、ガスの全圧を１ａｔｍ（０．１ＭＰａ）としたときのＳｉＣｌガスの分圧は、適宜設定できる。例えば、ＳｉＣｌガスの分圧を、各繊維の表面上の炭化ケイ素膜の均一性の確保と生産性を両立する観点で設定することができる。ＳｉＣｌガスの分圧は、熱力学理論値の上限としてもよい。
　Ｃｌ源としては、Ｃｌ２ガス、ＳｉＣｌ４ガス、ＭＴＳガス等のガスが挙げられる。Ｃｌ源としては、Ｃ原子を含まない（自由な量比でＣ源を別途供給できる）ことから、Ｃｌ２ガスが好ましい。Ｃｌ源としては、１種のみを単独で使用してもよく、２種以上を組み合わせて使用してもよい。
　Ｓｉ源のガス中のＳｉＣｌ２やＳｉＣｌの分圧は、Ｓｉ源とＣｌ源とを接触させる温度により調節できる。
　Ｃ源としては、ＣＨ４、Ｃ２Ｈ６、Ｃ３Ｈ８、Ｃ２Ｈ４、Ｃ２Ｈ２、Ｃ６Ｈ６、ＣＣｌ４等の炭化水素が挙げられる。Ｃ源としては、１種のみを単独で使用してもよく、２種以上を組み合わせて使用してもよい。
　Ｃ源としては、ＣＨ４、Ｃ２Ｈ６、Ｃ３Ｈ８、Ｃ２Ｈ４、Ｃ２Ｈ２、Ｃ６Ｈ６およびＣＣｌ４からなる群から選ばれる少なくとも１種の炭化水素が好ましい。
　炭化ケイ素膜の膜形成の反応には、必要に応じて、キャリアガスを使用してもよい。キャリアガスとしては、Ｈ２ガス、Ｎ２ガス、Ｈｅガス、Ａｒガス等の膜形成反応に対して不活性なガスが挙げられる。キャリアガスとしては、炭化ケイ素繊維束への炭化ケイ素の含浸性が向上する点から、Ｈ２ガスが好ましい。
　キャリアガスとしては、１種のみを単独で使用してもよく、２種以上を組み合わせて使用してもよい。
　炭化ケイ素膜の膜形成の反応温度は適宜設定できる。例えば、反応温度の下限は、ＣＭＣの生産性の観点で設定することができる。反応温度の上限は、各繊維の表面上に形成される炭化ケイ素膜の均一性の向上の観点で設定することができる。
　炭化ケイ素膜の膜形成の反応圧力は、０．１～２０Ｔｏｒｒ（１３～２６６０Ｐａ）が好ましく、５～２０Ｔｏｒｒ（６７０～２６６０Ｐａ）がより好ましく、１５～２０Ｔｏｒｒ（２０００～２６６０Ｐａ）がさらに好ましい。反応圧力が前記範囲の下限値未満であれば、含浸速度が小さく、生産性を損なう可能性がある。反応圧力が前記範囲の上限値を超えると、多孔質基材への含浸性が損なわれ、高温強度が低下する可能性がある。
　ＣＭＣの製造に用いる製造装置は、特に限定されない。例えば、図１に例示した製造装置１００が挙げられる。なお、以下の説明において例示される図は一例であって、本開示はそれらに必ずしも限定されるものではなく、その要旨を変更しない範囲で適宜変更して実施することが可能である。
　製造装置１００は、管状の反応炉１１０と、Ｃｌ源供給部１１２と、Ｃ源供給部１１４と、排気ユニット１１６とを備えている。反応炉１１０には、第１反応部１１８と第２反応部１２０が、反応炉１１０の上流側からこの順に設けられている。
　第１反応部１１８は、Ｓｉ源とＣｌ源とを接触させて反応させる部分である。
　この例の第１反応部１１８では、通気性を有する２つの仕切り部材１２２，１２２がガスの流れ方向に間隔をあけて設けられることで反応炉１１０内が仕切られる。それら仕切り部材１２２間に固体状のＳｉ源３００（Ｓｉ粉末）が充填される。仕切り部材１２２としては、Ｓｉ粉末が通過せず、Ｃｌ源のガスおよび生成物であるＳｉ源のガスが通過する部材であればよく、例えば、カーボンフェルトが挙げられる。
　反応炉１１０の第１反応部１１８には、Ｓｉ源とＣｌ源とを接触させる温度を調節する第１ヒータ１２４が設けられている。
　第２反応部１２０は、Ｓｉ源のガスとＣ源のガスとを反応させ、繊維基材２００の各繊維の表面上に炭化ケイ素膜を形成する部分である。第２反応部１２０は、Ｓｉ源のガスとＣ源のガスとの反応により繊維の表面上に炭化ケイ素膜が形成される位置に繊維基材２００を設置できるようになっていれば、その態様は特に限定されない。
　反応炉１１０の第２反応部１２０には、膜形成の反応温度を調節する第２ヒータ１２６が設けられている。
　Ｃｌ源供給部１１２は、Ｃｌ源のガスを供給する。Ｃｌ源供給部１１２は、反応炉１１０の第１反応部１１８の上流側にＣｌ源のガスを供給する。
　Ｃ源供給部１１４は、Ｃ源のガスを供給する。Ｃ源供給部１１４は、反応炉１１０内の第１反応部１１８と第２反応部１２０の間にＣ源のガスを供給する。Ｃ源供給部１１４からは、Ｃ源のガスをキャリアガスとともに供給してもよい。
　排気ユニット１１６は、反応炉１１０の下流側に設けられており、調圧弁１２８と、真空ポンプ１３０とを備えている。排気ユニット１１６は、調圧弁１２８と真空ポンプ１３０により、反応炉１１０内を減圧して所望の圧力に調節する。
　製造装置１００を用いたＣＭＣの製造方法では、Ｃｌ源供給部１１２から反応炉１１０にＣｌ２ガス等のＣｌ源のガスを供給し、第１反応部１１８においてＣｌ源のガスと固体状のＳｉとを接触させる。第１反応部１１８では、Ｃｌ源のガスと固体状のＳｉとの接触により、生成物としてＳｉＣｌ２またはＳｉＣｌを含有するＳｉ源のガスが発生し、第２反応部１２０に送られる。第２反応部１２０では、第１反応部１１８で生じたＳｉ源のガスと、Ｃ源供給部１１４から供給されるＣ源のガスとが反応し、繊維基材２００の各繊維の表面上に炭化ケイ素が堆積して炭化ケイ素膜が形成される。
　ＣＭＣの製造においては、ＣＶＩ法による炭化ケイ素膜の膜形成を行った後に、必要に応じて、液相含浸（ＳＰＩ）法や、溶融含浸（ＰＩＰ）法によりさらに炭化ケイ素のマトリックスを形成してもよい。この場合、炭化ケイ素繊維束における表層の炭化ケイ素膜の平均膜厚Ｄ１と、内層の炭化ケイ素膜の平均膜厚Ｄ２は、ＣＶＩ法で形成された炭化ケイ素膜の平均膜厚である。
　ＣＭＣの切断面を顕微鏡で観察した場合、ＣＶＩ法で形成された炭化ケイ素膜とＳＰＩ法やＰＩＰ法で形成されたマトリックスとの境界は判別可能である。そのため、ＳＰＩ法やＰＩＰ法でさらにマトリックスを形成した場合でも炭化ケイ素膜のＤ１、Ｄ２を測定できる。
　従来のＣＭＣにおいて優れた機械的特性が得られにくいのは、炭化ケイ素繊維束に対する炭化ケイ素の含浸性が低いために、繊維束の表層と内層での炭化ケイ素膜の均一性が低いことが要因と考えられる。
　これに対して、本開示のＣＭＣにおいては、炭化ケイ素繊維束における各繊維の表面に形成される炭化ケイ素膜が、Ｄ２／Ｄ１が特定の範囲となるように制御され、炭化ケイ素繊維束の表層と内層における炭化ケイ素膜の均一性に優れる。そのため、本開示のＣＭＣは、機械的特性に優れている。
　また、Ｄ２／Ｄ１を制御しつつ、さらにＤ２を２．６μｍ以上とし、炭化ケイ素繊維束の内層の各繊維の表面上に十分な炭化ケイ素膜を形成することで、機械的特性をさらに向上させることができる。
　本開示は、セラミック基複合材料に利用することができる。
　１００…製造装置
　１１０…反応炉
　１１２…Ｃｌ源供給部
　１１４…Ｃ源供給部
　１１６…排気ユニット
　１１８…第１反応部
　１２０…第２反応部
　１２２…仕切り部材
　１２４…第１ヒータ
　１２６…第２ヒータ
　１２８…調圧弁
　１３０…真空ポンプ

Claims (2)

  1. 　炭化ケイ素繊維束で形成された繊維基材と、前記炭化ケイ素繊維束の各炭化ケイ素繊維の表面上に形成された炭化ケイ素膜とを有するセラミック基複合材料であって、
    　前記炭化ケイ素繊維束の表層の前記炭化ケイ素繊維の表面上に形成された前記炭化ケイ素膜の平均膜厚Ｄ１に対する、前記炭化ケイ素繊維束の前記表層よりも内側の内層の前記炭化ケイ素繊維の表面上に形成された前記炭化ケイ素膜の平均膜厚Ｄ２の比が１．０～１．３である、セラミック基複合材料。
  2. 　前記炭化ケイ素膜の平均膜厚Ｄ２が２．６μｍ以上である、請求項１に記載のセラミック基複合材料。
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