WO2015016071A1 - SiC FIBER-REINFORCED SiC COMPOSITE MATERIAL AND PRODUCTION METHOD FOR SiC FIBER-REINFORCED SiC COMPOSITE MATERIAL - Google Patents

SiC FIBER-REINFORCED SiC COMPOSITE MATERIAL AND PRODUCTION METHOD FOR SiC FIBER-REINFORCED SiC COMPOSITE MATERIAL Download PDF

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WO2015016071A1
WO2015016071A1 PCT/JP2014/068945 JP2014068945W WO2015016071A1 WO 2015016071 A1 WO2015016071 A1 WO 2015016071A1 JP 2014068945 W JP2014068945 W JP 2014068945W WO 2015016071 A1 WO2015016071 A1 WO 2015016071A1
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sic
composite material
fiber
reinforced
matrix
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PCT/JP2014/068945
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French (fr)
Japanese (ja)
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真緒 棚橋
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イビデン株式会社
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Definitions

  • the present invention relates to a SiC fiber reinforced SiC composite material and a method for producing a SiC fiber reinforced SiC composite material.
  • Ceramic materials such as silicon carbide (SiC) and silicon nitride (Si 3 N 4 ) are excellent in heat resistance, chemical stability, and mechanical properties. Therefore, these ceramic materials are being developed as materials used in harsh environments such as the nuclear field, aerospace field, and power generation field, and in general fields such as pump mechanical seals. Of these ceramic materials, SiC is a structural material that is promising in a wide range of fields because of its excellent properties.
  • SiC itself is a brittle material
  • SiC fiber / SiC composite material composed of a SiC fiber and a SiC matrix
  • the crack propagates in the matrix and the crack may propagate to the SiC fiber.
  • Patent Document 1 includes SiC fine powder and a sintering aid for a coated SiC fiber in which a coating layer containing at least one of carbon, boron nitride, and silicon carbide is formed on the surface of the SiC fiber. And a SiC fiber reinforced mold comprising a first step of obtaining a preform by impregnating a slurry containing no organosilicon polymer and a second step of pressure-sintering the preform.
  • a method of manufacturing a SiC composite material is disclosed.
  • the present invention has been made to solve the above-described problems, and does not include a coating layer of a different material, and the SiC fiber-reinforced SiC composite material having high strength only by SiC and the production of the SiC fiber-reinforced SiC composite material. It aims to provide a method.
  • the SiC fiber reinforced SiC composite material of the present invention is a SiC fiber reinforced SiC composite material composed of SiC fibers and a SiC matrix, and has substantially spherical bubbles in the SiC matrix, and is a structural member for nuclear power.
  • the constituent material is SiC
  • high strength can be realized.
  • the SiC matrix becomes low elastic. Therefore, in the composite material of the present invention, even if a crack occurs in the SiC matrix, the progress of the crack can be prevented by the bubbles present in the SiC matrix, and the crack can be prevented from propagating to the SiC fiber. Further, when the bubbles are substantially spherical, energy due to cracks generated by external impact is dispersed to the surroundings, and the progress of cracks can be prevented.
  • the “substantially spherical shape” may be a spherical shape to the extent that each effect of the present invention is exhibited, and may be a complete spherical shape or a substantially spherical shape.
  • the composite material of the present invention can be a high-strength composite material without including a coating layer or the like for preventing the propagation of cracks.
  • the bubbles are surrounded by a shell made of SiC.
  • the propagation of cracks can be further prevented by the shell forming the bubbles.
  • the diameter of the bubbles is preferably smaller than the diameter of the SiC fiber.
  • the diameter of the bubbles is small, the portion having a high elastic modulus of the SiC matrix can be reduced, so that the propagation of cracks can be further prevented.
  • SiC fibers are combined to form a SiC fiber bundle.
  • the SiC fibers are present in a bundle, it is difficult to form a space between the SiC fibers. Therefore, the existence ratio of the SiC fibers in the composite material can be increased, and a high-strength composite material can be obtained.
  • the content rate of the bubbles in the SiC matrix in the range of the diameter of the SiC fiber from the surface of the SiC fiber is preferably 10 to 50 vol%.
  • a bubble content of 10 to 50 vol% in the above range means that bubbles are present in the vicinity of the SiC fiber. In this case, since the surface of the SiC fiber is covered with the low-elasticity matrix, the scratch that becomes the starting point of the crack is hardly attached to the surface of the SiC fiber.
  • the SiC fiber reinforced SiC composite material of the present invention is preferably a structural member for a light water reactor.
  • the composite material of the present invention is used as a material for a nuclear structural member such as a light water reactor structural member, the surface of the SiC fiber is thermally decomposed even if the composite material is deformed by a stress and a crack reaching the SiC fiber occurs. Since the coating layer made of carbon or the like is not formed, the problem that the coating layer reacts with water and the strength of the composite material is reduced can be prevented.
  • a method for producing a SiC fiber reinforced SiC composite material according to the present invention is a method for producing a SiC fiber reinforced SiC composite material that is a nuclear structural member, wherein a matrix precursor and a hollow body are added to a fiber assembly made of SiC fibers.
  • An impregnation step of impregnating a slurry containing the impregnation product and a firing step of firing the impregnation product are characterized.
  • bubbles can be formed in the matrix by mixing a hollow body into the slurry.
  • the above-described SiC fiber reinforced SiC composite material of the present invention can be manufactured.
  • the matrix precursor may be an organosilicon compound.
  • a matrix made of SiC can be formed.
  • the matrix precursor may be composed of SiC particles and a sintering aid.
  • a SiC matrix can be formed by sintering SiC particles using a sintering aid.
  • the average particle diameter of the SiC particles is preferably smaller than the average bubble diameter of the hollow body.
  • SiC fiber bundle It is desirable that a plurality of the SiC fibers are combined to form a SiC fiber bundle.
  • the fiber assembly is preferably at least one fiber assembly selected from the group consisting of a woven fabric, a mat, a braided (braided) molded body, and a filament winding molded body.
  • the present invention it is possible to provide a high-strength SiC fiber reinforced SiC composite material containing only a SiC material and a method for producing the SiC fiber reinforced SiC composite material without including a coating layer of a different material.
  • FIG.1 (a) is sectional drawing which shows typically an example of the SiC fiber reinforced SiC composite material of this invention
  • FIG.1 (b) is A of SiC fiber reinforced SiC composite material shown to Fig.1 (a).
  • FIG. FIG. 2 is an enlarged cross-sectional view of the SiC fiber-reinforced SiC composite material shown in FIG.
  • FIG. 3 is a cross-sectional view schematically showing another example of the SiC fiber-reinforced SiC composite material of the present invention.
  • the SiC fiber reinforced SiC composite material of the present invention is a SiC fiber reinforced SiC composite material composed of SiC fibers and a SiC matrix, and has substantially spherical bubbles in the SiC matrix, and is a structural member for nuclear power.
  • FIG.1 (a) is sectional drawing which shows typically an example of the SiC fiber reinforced SiC composite material of this invention
  • FIG.1 (b) is A of SiC fiber reinforced SiC composite material shown to Fig.1 (a).
  • FIG. Fig.1 (a) is sectional drawing of the direction perpendicular
  • FIG.1 (b) is sectional drawing of the direction parallel to the length direction of a SiC fiber.
  • the SiC fiber reinforced SiC composite material 10 shown in FIGS. 1A and 1B is a composite material composed of SiC fibers 11 and a SiC matrix 12.
  • the SiC fiber-reinforced SiC composite material 10 has bubbles 13 in the SiC matrix 12.
  • SiC fiber-reinforced SiC composite material of the present invention As the SiC fiber, Hi-Nicalon made by NGS Advanced Fiber, Tyranno-SA made by Ube Industries, etc. can be used.
  • the diameter of the SiC fiber can be appropriately set according to the use of the SiC fiber-reinforced SiC composite material, but is preferably 5 to 25 ⁇ m.
  • the diameter of the SiC fiber is 5 ⁇ m or more, a sufficiently large diameter can be secured for the SiC particles and the hollow body to be used, so that a high-strength composite material can be obtained.
  • the diameter of the SiC fiber is 25 ⁇ m or less, the elongation rate of the surface can be reduced even if the SiC fiber is bent, so that it is difficult to break.
  • the number of SiC fibers constituting the SiC fiber bundle is, for example, 50 to 2000.
  • the diameter of the SiC fiber can be measured by observing a cross section of the SiC fiber-reinforced SiC composite material with a scanning electron microscope (SEM).
  • the matrix is a matrix made of SiC.
  • the SiC fiber-reinforced SiC composite material of the present invention has bubbles in the SiC matrix, but the bubbles may be dispersed throughout the SiC matrix or may be unevenly distributed in a part of the SiC matrix.
  • the elastic modulus of the SiC matrix in contact with the SiC fiber is lowered, so that cracks generated in the SiC matrix can be prevented from propagating to the SiC fiber.
  • the method for forming bubbles in the SiC matrix is not particularly limited, but it is desirable that the bubbles be formed by mixing a hollow body into the slurry, as will be described later.
  • the bubbles are surrounded by a shell made of SiC. Since the shell made of SiC is made of a material denser than the structure of the SiC matrix, the propagation of cracks can be further prevented by the shell forming bubbles. As described above, in the SiC fiber-reinforced SiC composite material of the present invention, it is desirable that the bubbles are surrounded by the shell, but the bubbles need not be surrounded by the shell.
  • the bubble diameter is smaller than the SiC fiber diameter.
  • the portion having a high elastic modulus of the SiC matrix can be reduced, so that the propagation of cracks can be further prevented.
  • the bubble diameter is desirably 2 to 20 ⁇ m. If the diameter of the bubbles is 2 ⁇ m or more, bubbles that are sufficiently larger than the pores formed by the SiC particles can be formed, so that the effect of preventing the progress of cracks can be increased. When the bubble diameter is 20 ⁇ m or less, a highly flexible SiC fiber that does not break even when bent can be used, and thus a high-strength composite material can be obtained.
  • the bubble diameter indicates the diameter of a sphere (equivalent sphere) having the same volume as the bubble volume, and can be measured using a scanning electron microscope (SEM). Since it is a three-dimensional shape, the measurement is repeated using a focused ion beam (FIB) while gradually scraping to measure the bubble diameter.
  • SEM scanning electron microscope
  • the shape of the bubble is almost spherical.
  • energy due to cracks generated by an external impact is dispersed to the surroundings, and the progress of the cracks can be prevented.
  • the bubble content in the SiC matrix is not particularly limited, but the bubble content in the matrix in the range of the diameter of the SiC fiber from the surface of the SiC fiber is preferably 10 to 50 vol%, and 20 to 30 vol. % Is more desirable.
  • a bubble content of 10 to 50 vol% in the above range means that bubbles are present in the vicinity of the SiC fiber.
  • the surface of the SiC fiber is covered with the low-elasticity matrix, the scratch that becomes the starting point of the crack is hardly attached to the surface of the SiC fiber.
  • the bubble content is 10 vol% or more, the matrix has sufficient mechanical strength, so that strength as a composite material can be ensured.
  • the bubble content is 50 vol% or less, the generated crack energy is easily dispersed to the surroundings and can be made difficult to break.
  • the matrix has a higher mechanical strength, so that the strength as a composite material can be further ensured.
  • the bubble content is 30 vol% or less, the energy of the generated crack is more easily dispersed to the surroundings, and can be further prevented from cracking.
  • the bubble content is defined only for the matrix surrounding one SiC fiber.
  • FIG. 2 is an enlarged cross-sectional view of the SiC fiber-reinforced SiC composite material shown in FIG.
  • the diameter of the SiC fiber 11 is indicated by an arrow d. Therefore, the “range of the distance of the diameter of the SiC fiber from the surface of the SiC fiber” means a range at a distance d from the surface of the SiC fiber 11.
  • the porosity of the SiC matrix is preferably 10 to 50%, and more preferably 20 to 30%.
  • FIG. 3 is a cross-sectional view schematically showing another example of the SiC fiber-reinforced SiC composite material of the present invention.
  • a SiC layer 20 may be formed on the surface of the SiC fiber reinforced SiC composite material 10.
  • the SiC layer 20 is preferably a CVD-SiC layer formed by subjecting the SiC fiber-reinforced SiC composite material 10 to a CVD process.
  • a method for producing a SiC fiber reinforced SiC composite material according to the present invention is a method for producing a SiC fiber reinforced SiC composite material that is a nuclear structural member, wherein a matrix precursor and a hollow body are added to a fiber assembly made of SiC fibers.
  • An impregnation step of impregnating a slurry containing the impregnation product and a firing step of firing the impregnation product are characterized.
  • a fiber assembly made of SiC fibers is prepared.
  • the fiber assembly can be obtained by a shaping process for imparting a shape to the SiC fiber.
  • the fiber assembly is desirably at least one fiber assembly selected from the group consisting of a woven fabric, a mat, a braided (braided) molded product, and a filament winding molded product.
  • SiC fiber reinforced SiC composite material Since the SiC fiber is as described in [SiC fiber reinforced SiC composite material], detailed description thereof is omitted.
  • a fiber assembly can be formed by weaving SiC fiber bundles in which 50 to 2000 SiC fibers are bundled into a sheet shape.
  • the prepared fiber aggregate is impregnated with a slurry containing a matrix precursor and a hollow body to obtain an impregnated body (impregnation step).
  • impregnation method examples include dipping, spraying, coating, coater, vacuum pressure impregnation and the like, and any method may be used.
  • inorganic balloons such as SiC balloons, silica balloons, and carbon balloons
  • organic balloons such as resin balloons; resins; and reaction products thereof
  • the SiC balloon can be made from an organosilicon compound such as polycarbosilane.
  • the silica balloon and the carbon powder react and remain as an SiC balloon by further containing carbon powder in the slurry.
  • a hollow body is a carbon balloon
  • a carbon balloon and a silica powder react and remain as a SiC balloon by further making a slurry contain silica powder.
  • the resin is preferably a thermoplastic resin. This is because these resins are thermally decomposed by firing to eliminate the shell.
  • the average cell diameter of the hollow body is preferably 2 to 20 ⁇ m, and more preferably 5 to 15 ⁇ m.
  • the average cell diameter of the hollow body can be measured by measuring the particle diameter with a laser diffraction particle size measuring machine and reducing the film thickness of the hollow body.
  • the content of the hollow body in the slurry is not particularly limited, but the solid content is preferably 20 to 65% by weight, more preferably 40 to 65% by weight.
  • the matrix precursor contained in the slurry may be an organosilicon compound, or may be composed of SiC particles and a sintering aid.
  • a matrix made of SiC can be formed by firing the organosilicon compound.
  • organosilicon compound examples include silicon-based polymers such as polycarbosilane, polyvinylsilane, and polymethylsilane.
  • the content of the organosilicon compound in the slurry is not particularly limited, but is preferably 20 to 65% by weight in terms of solid content, more preferably 40 to 65% by weight. desirable.
  • a matrix made of SiC can be formed by sintering the SiC particles using a sintering aid.
  • the average particle diameter of the SiC particles is preferably smaller than the average bubble diameter of the hollow body.
  • the average particle size of the SiC particles is desirably 10 to 1000 nm, and more desirably 250 to 800 nm.
  • the average particle diameter of a SiC particle can be measured using a scanning electron microscope (SEM).
  • the content of the SiC particles in the slurry is not particularly limited, but is preferably 25 to 65% by weight and more preferably 45 to 65% by weight in terms of solid content.
  • the ratio of SiC particles to hollow bodies is preferably 2: 1 to 7: 1, and more preferably 2: 1 to 4: 1.
  • the sintering aid examples include Al 2 O 3 , Y 2 O 3 , SiO 2 , and CaO. These may be one type or a combination of a plurality of types. Moreover, it is desirable that the sintering aid is in a powder form.
  • the content of the sintering aid in the slurry is not particularly limited, but it is preferably 1 to 3% by weight and more preferably 1 to 2% by weight in terms of solid content.
  • the slurry contains a dispersion medium (solvent).
  • a dispersion medium water or an organic solvent can be used.
  • the organic solvent include alcohol-based organic solvents such as ethanol and isopropanol; hydrocarbon-based organic solvents such as hexane, toluene and xylene.
  • a slurry having a different hollow body content is prepared, and the fiber aggregate is impregnated with a high content slurry, and then impregnated with a low content slurry. That's fine.
  • the impregnated body is fired (firing step).
  • Examples of the method of firing the impregnated body include a method of pressure-sintering the impregnated body.
  • the pressure sintering method is not particularly limited, and examples thereof include known methods such as a hot press (HP) method and a hot isostatic press (HIP) method.
  • the sintering temperature can be appropriately set, but is preferably 1000 to 2000 ° C., more preferably 1200 to 1600 ° C.
  • the pressure is preferably 1 to 30 MPa and more preferably 5 to 20 MPa.
  • the calcination of the impregnated body may be performed in a non-oxidizing atmosphere, for example, in an inert gas atmosphere, a reducing atmosphere, a vacuum atmosphere, or the like.
  • a non-oxidizing atmosphere for example, in an inert gas atmosphere, a reducing atmosphere, a vacuum atmosphere, or the like.
  • inert gas atmosphere such as hydrogen, nitrogen, helium, and argon.
  • the SiC fiber reinforced SiC composite material of the present invention can be manufactured.
  • the SiC fiber reinforced SiC composite material of the present invention is desirably used in harsh environments such as the nuclear field, aerospace field, and power generation field, and particularly desirably in the nuclear field.
  • the SiC fiber-reinforced SiC composite material of the present invention is a structural member for nuclear power, and is desirably a structural member for light water reactors.
  • the constituent material is SiC
  • high strength can be realized.
  • the SiC matrix becomes low elastic. Therefore, in the composite material of the present invention, even if a crack occurs in the SiC matrix, the progress of the crack can be prevented by the bubbles present in the SiC matrix, and the crack can be prevented from propagating to the SiC fiber.
  • the composite material of the present invention can be a high-strength composite material without including a coating layer or the like for preventing the propagation of cracks.
  • bubbles can be formed in the matrix by mixing a hollow body into the slurry.
  • the above-described SiC fiber reinforced SiC composite material of the present invention can be manufactured.
  • the SiC fiber-reinforced SiC composite material of the present invention has an essential constituent element that has a bubble in the SiC matrix.
  • a fiber assembly made of SiC fibers is impregnated with a slurry containing a matrix precursor and a hollow body, and after obtaining the impregnated body, the impregnated body is fired. This is an essential component requirement.
  • the various constituents detailed in the detailed description of the present invention for example, SiC fiber configuration, SiC matrix configuration, bubble configuration, hollow body configuration, SiC fiber reinforced SiC composite material manufacture) The desired effect can be obtained by appropriately combining the conditions and the like.

Abstract

Provided is an SiC fiber-reinforced SiC composite material having high strength using only SiC and not including a coating layer, etc., of another type of material. The SiC fiber-reinforced SiC composite material comprises SiC fiber and an SiC matrix and is characterized by having substantially spherical bubbles in the SiC matrix and by being a structural member for atomic energy.

Description

ＳｉＣ繊維強化ＳｉＣ複合材料及びＳｉＣ繊維強化ＳｉＣ複合材料の製造方法SiC fiber reinforced SiC composite material and method for producing SiC fiber reinforced SiC composite material
　本発明は、ＳｉＣ繊維強化ＳｉＣ複合材料及びＳｉＣ繊維強化ＳｉＣ複合材料の製造方法に関する。 The present invention relates to a SiC fiber reinforced SiC composite material and a method for producing a SiC fiber reinforced SiC composite material.
　炭化珪素（ＳｉＣ）、窒化珪素（Ｓｉ３Ｎ４）等のセラミック材料は、耐熱性、化学的安定性、機械的特性に優れている。そのため、これらのセラミック材料は、原子力分野、航空・宇宙分野、発電分野等の過酷な環境下や、ポンプメカニカルシール等の一般的な分野で使用される材料として開発が進められている。これらのセラミック材料のうち、ＳｉＣは、上記の特性に優れていることから、広範囲な分野において有望視されている構造材料である。 Ceramic materials such as silicon carbide (SiC) and silicon nitride (Si 3 N 4 ) are excellent in heat resistance, chemical stability, and mechanical properties. Therefore, these ceramic materials are being developed as materials used in harsh environments such as the nuclear field, aerospace field, and power generation field, and in general fields such as pump mechanical seals. Of these ceramic materials, SiC is a structural material that is promising in a wide range of fields because of its excellent properties.
　ただし、ＳｉＣ自体は脆い材料であるため、ＳｉＣ繊維とＳｉＣマトリックスとからなるＳｉＣ繊維／ＳｉＣ複合材料が提案されている。しかしながら、ＳｉＣ繊維／ＳｉＣ複合材料であっても、ＳｉＣマトリックスに亀裂が生じると、マトリックス中に亀裂が進展し、ＳｉＣ繊維にまで亀裂が伝播することがあった。 However, since SiC itself is a brittle material, a SiC fiber / SiC composite material composed of a SiC fiber and a SiC matrix has been proposed. However, even in the SiC fiber / SiC composite material, when a crack occurs in the SiC matrix, the crack propagates in the matrix and the crack may propagate to the SiC fiber.
　そこで、例えば、特許文献１には、ＳｉＣ繊維表面に炭素、窒化ホウ素及び炭化ケイ素の少なくとも１種を含む被覆層が形成されてなる被覆ＳｉＣ繊維に対し、ＳｉＣ微粉末及び焼結助剤を含み、かつ、有機ケイ素高分子を含まないスラリーを含浸させることにより予備成形体を得る第１工程と、上記予備成形体を加圧焼結させる第２工程を含むことを特徴とするＳｉＣ繊維強化型ＳｉＣ複合材料の製造方法が開示されている。 Therefore, for example, Patent Document 1 includes SiC fine powder and a sintering aid for a coated SiC fiber in which a coating layer containing at least one of carbon, boron nitride, and silicon carbide is formed on the surface of the SiC fiber. And a SiC fiber reinforced mold comprising a first step of obtaining a preform by impregnating a slurry containing no organosilicon polymer and a second step of pressure-sintering the preform. A method of manufacturing a SiC composite material is disclosed.
特開２０１０－７０４２１号公報JP 2010-70421 A
　特許文献１に記載の方法により製造される複合材料では、ＳｉＣ繊維表面に被覆層が形成されているため、ＳｉＣマトリックスに亀裂が生じても、その亀裂がＳｉＣ繊維まで伝播することを防止することができる。そのため、特許文献１に記載の方法により製造される複合材料は高強度であるとされている。 In the composite material manufactured by the method described in Patent Document 1, since the coating layer is formed on the surface of the SiC fiber, even if a crack occurs in the SiC matrix, the crack is prevented from propagating to the SiC fiber. Can do. Therefore, it is said that the composite material manufactured by the method described in Patent Document 1 has high strength.
　しかしながら、被覆層の材料として使用されている炭素（熱分解炭素）や窒化ホウ素（熱分解窒化ホウ素：ＰＢＮ）等には耐蝕性がない。そのため、特許文献１に記載の方法により製造される複合材料を、軽水炉構造部材等の原子力構造部材の材料として使用する場合、高温下において被覆層が水と反応し、被覆層が破損する結果、複合材料の強度が低下してしまう。また、ＰＢＮの成膜温度としては１７５０℃以上が必要であるため、成膜時にＳｉＣ繊維に加わるダメージが大きく、高強度の複合材料を得ることが困難である。このように、従来の製造方法によって得られる複合材料には、さらなる改善の余地があった。 However, carbon (pyrolytic carbon), boron nitride (pyrolytic boron nitride: PBN) and the like used as the material for the coating layer do not have corrosion resistance. Therefore, when the composite material manufactured by the method described in Patent Document 1 is used as a material for a nuclear structural member such as a light water reactor structural member, the coating layer reacts with water at a high temperature, and the coating layer is damaged. The strength of the composite material is reduced. In addition, since the PBN film forming temperature is required to be 1750 ° C. or higher, the damage applied to the SiC fiber during film formation is large, and it is difficult to obtain a high-strength composite material. Thus, the composite material obtained by the conventional manufacturing method has room for further improvement.
　本発明は、上記の問題を解決するためになされたものであり、異種材料の被覆層等を含まず、ＳｉＣのみで高強度のＳｉＣ繊維強化ＳｉＣ複合材料及び該ＳｉＣ繊維強化ＳｉＣ複合材料の製造方法を提供することを目的とする。 The present invention has been made to solve the above-described problems, and does not include a coating layer of a different material, and the SiC fiber-reinforced SiC composite material having high strength only by SiC and the production of the SiC fiber-reinforced SiC composite material. It aims to provide a method.
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料は、ＳｉＣ繊維とＳｉＣマトリックスとからなるＳｉＣ繊維強化ＳｉＣ複合材料であって、上記ＳｉＣマトリックス中に略球形の気泡を有し、原子力用構造部材であることを特徴とする。 The SiC fiber reinforced SiC composite material of the present invention is a SiC fiber reinforced SiC composite material composed of SiC fibers and a SiC matrix, and has substantially spherical bubbles in the SiC matrix, and is a structural member for nuclear power. Features.
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料においては、構成材料がＳｉＣであるため、高強度を実現することができる。また、ＳｉＣマトリックス中に気泡が存在すると、ＳｉＣマトリックスが低弾性となる。そのため、本発明の複合材料では、ＳｉＣマトリックスに亀裂が生じても、ＳｉＣマトリックス中に存在する気泡によって亀裂の進展を防止し、その亀裂がＳｉＣ繊維にまで伝播することを防止することができる。
　また、気泡が略球形であると、外部からの衝撃によって発生した亀裂によるエネルギーが周囲に分散され、亀裂の進展を防ぐことができる。
　なお、「略球形」とは、本発明の各効果を奏する程度に球形であればよく、完全に球形であってもよいし、実質的に球形であってもよい。
このように、本発明の複合材料では、亀裂の伝播を防止するための被覆層等を含まずに、高強度の複合材料とすることができる。 In the SiC fiber reinforced SiC composite material of the present invention, since the constituent material is SiC, high strength can be realized. Further, when bubbles are present in the SiC matrix, the SiC matrix becomes low elastic. Therefore, in the composite material of the present invention, even if a crack occurs in the SiC matrix, the progress of the crack can be prevented by the bubbles present in the SiC matrix, and the crack can be prevented from propagating to the SiC fiber.
Further, when the bubbles are substantially spherical, energy due to cracks generated by external impact is dispersed to the surroundings, and the progress of cracks can be prevented.
The “substantially spherical shape” may be a spherical shape to the extent that each effect of the present invention is exhibited, and may be a complete spherical shape or a substantially spherical shape.
As described above, the composite material of the present invention can be a high-strength composite material without including a coating layer or the like for preventing the propagation of cracks.
　上記気泡は、ＳｉＣからなる殻で囲まれていることが望ましい。気泡を形成する殻によって、亀裂の伝播をより防止することができる。 It is desirable that the bubbles are surrounded by a shell made of SiC. The propagation of cracks can be further prevented by the shell forming the bubbles.
　上記気泡の直径は、上記ＳｉＣ繊維の直径より小さいことが望ましい。気泡の直径が小さいと、ＳｉＣマトリックスの弾性率が高い部分を少なくすることができるため、亀裂の伝播をより防止することができる。 The diameter of the bubbles is preferably smaller than the diameter of the SiC fiber. When the diameter of the bubbles is small, the portion having a high elastic modulus of the SiC matrix can be reduced, so that the propagation of cracks can be further prevented.
　上記ＳｉＣ繊維は、複数本がまとまってＳｉＣ繊維束を構成していることが望ましい。ＳｉＣ繊維がまとまって束で存在すると、ＳｉＣ繊維間に空間ができにくいので、複合材料中のＳｉＣ繊維の存在比率を高くすることができ、高強度の複合材料を得ることができる。 It is desirable that a plurality of the SiC fibers are combined to form a SiC fiber bundle. When the SiC fibers are present in a bundle, it is difficult to form a space between the SiC fibers. Therefore, the existence ratio of the SiC fibers in the composite material can be increased, and a high-strength composite material can be obtained.
　上記ＳｉＣ繊維の表面から上記ＳｉＣ繊維の直径の距離の範囲における上記ＳｉＣマトリックス中の上記気泡の含有率は、１０～５０ｖｏｌ％であることが望ましい。上記の範囲における気泡の含有率が１０～５０ｖｏｌ％であることは、ＳｉＣ繊維の近傍に気泡が存在することを意味する。この場合、ＳｉＣ繊維の表面が低弾性のマトリックスで覆われるため、亀裂の起点となる傷がＳｉＣ繊維の表面に付きにくくなる。 The content rate of the bubbles in the SiC matrix in the range of the diameter of the SiC fiber from the surface of the SiC fiber is preferably 10 to 50 vol%. A bubble content of 10 to 50 vol% in the above range means that bubbles are present in the vicinity of the SiC fiber. In this case, since the surface of the SiC fiber is covered with the low-elasticity matrix, the scratch that becomes the starting point of the crack is hardly attached to the surface of the SiC fiber.
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料は、軽水炉用構造部材であることが望ましい。軽水炉用構造部材等の原子力用構造部材の材料として本発明の複合材料を使用する場合、応力によって複合材料が変形し、ＳｉＣ繊維に達する亀裂が生じたとしても、ＳｉＣ繊維の表面には熱分解炭素等からなる被覆層が形成されていないため、被覆層が水と反応して複合材料の強度が低下するという問題を防止することができる。 The SiC fiber reinforced SiC composite material of the present invention is preferably a structural member for a light water reactor. When the composite material of the present invention is used as a material for a nuclear structural member such as a light water reactor structural member, the surface of the SiC fiber is thermally decomposed even if the composite material is deformed by a stress and a crack reaching the SiC fiber occurs. Since the coating layer made of carbon or the like is not formed, the problem that the coating layer reacts with water and the strength of the composite material is reduced can be prevented.
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料の製造方法は、原子力用構造部材であるＳｉＣ繊維強化ＳｉＣ複合材料の製造方法であって、ＳｉＣ繊維からなる繊維集合体に、マトリックス前駆体と中空体とを含むスラリーを含浸し、含浸体を得る含浸工程と、上記含浸体を焼成する焼成工程とを含むことを特徴とする。 A method for producing a SiC fiber reinforced SiC composite material according to the present invention is a method for producing a SiC fiber reinforced SiC composite material that is a nuclear structural member, wherein a matrix precursor and a hollow body are added to a fiber assembly made of SiC fibers. An impregnation step of impregnating a slurry containing the impregnation product and a firing step of firing the impregnation product are characterized.
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料の製造方法では、スラリーに中空体を混入することによって、マトリックス中に気泡を形成することができる。その結果、上述した本発明のＳｉＣ繊維強化ＳｉＣ複合材料を製造することができる。 In the method for producing a SiC fiber-reinforced SiC composite material of the present invention, bubbles can be formed in the matrix by mixing a hollow body into the slurry. As a result, the above-described SiC fiber reinforced SiC composite material of the present invention can be manufactured.
　上記マトリックス前駆体は、有機珪素化合物であってもよい。有機珪素化合物を焼成することによって、ＳｉＣからなるマトリックスを形成することができる。 The matrix precursor may be an organosilicon compound. By baking the organosilicon compound, a matrix made of SiC can be formed.
　また、上記マトリックス前駆体は、ＳｉＣ粒子と焼結助剤とからなっていてもよい。焼結助剤を用いてＳｉＣ粒子を焼結することによって、ＳｉＣからなるマトリックスを形成することができる。 The matrix precursor may be composed of SiC particles and a sintering aid. A SiC matrix can be formed by sintering SiC particles using a sintering aid.
　上記ＳｉＣ粒子の平均粒子径は、上記中空体の平均気泡径より小さいことが望ましい。中空体の平均気泡径よりもＳｉＣ粒子の平均粒子径を小さくすることで、マトリックス内部に発生する応力集中を小さくしつつ、弾性率の低いマトリックスを形成することができる。 The average particle diameter of the SiC particles is preferably smaller than the average bubble diameter of the hollow body. By making the average particle diameter of the SiC particles smaller than the average bubble diameter of the hollow body, it is possible to form a matrix having a low elastic modulus while reducing the concentration of stress generated inside the matrix.
　上記ＳｉＣ繊維は、複数本がまとまってＳｉＣ繊維束を構成していることが望ましい。 It is desirable that a plurality of the SiC fibers are combined to form a SiC fiber bundle.
　上記繊維集合体は、織布、マット、ブレーディング（組紐）成形体、及び、フィラメントワインディング成形体からなる群より選択される少なくとも一層の繊維集合体であることが望ましい。 The fiber assembly is preferably at least one fiber assembly selected from the group consisting of a woven fabric, a mat, a braided (braided) molded body, and a filament winding molded body.
　本発明によれば、異種材料の被覆層等を含まず、ＳｉＣのみで高強度のＳｉＣ繊維強化ＳｉＣ複合材料及び該ＳｉＣ繊維強化ＳｉＣ複合材料の製造方法を提供することができる。 According to the present invention, it is possible to provide a high-strength SiC fiber reinforced SiC composite material containing only a SiC material and a method for producing the SiC fiber reinforced SiC composite material without including a coating layer of a different material.
図１（ａ）は、本発明のＳｉＣ繊維強化ＳｉＣ複合材料の一例を模式的に示す断面図であり、図１（ｂ）は、図１（ａ）に示すＳｉＣ繊維強化ＳｉＣ複合材料のＡ－Ａ線断面図である。Fig.1 (a) is sectional drawing which shows typically an example of the SiC fiber reinforced SiC composite material of this invention, FIG.1 (b) is A of SiC fiber reinforced SiC composite material shown to Fig.1 (a). FIG. 図２は、図１（ｂ）に示したＳｉＣ繊維強化ＳｉＣ複合材料の拡大断面図である。FIG. 2 is an enlarged cross-sectional view of the SiC fiber-reinforced SiC composite material shown in FIG. 図３は、本発明のＳｉＣ繊維強化ＳｉＣ複合材料の別の一例を模式的に示す断面図である。FIG. 3 is a cross-sectional view schematically showing another example of the SiC fiber-reinforced SiC composite material of the present invention.
（発明の詳細な説明）
　以下、本発明について具体的に説明する。しかしながら、本発明は、以下の記載に限定されるものではなく、本発明の要旨を変更しない範囲において適宜変更して適用することができる。 (Detailed description of the invention)
Hereinafter, the present invention will be specifically described. However, the present invention is not limited to the following description, and can be appropriately modified and applied without departing from the scope of the present invention.
　［ＳｉＣ繊維強化ＳｉＣ複合材料］
　まず、本発明のＳｉＣ繊維強化ＳｉＣ複合材料について説明する。
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料は、ＳｉＣ繊維とＳｉＣマトリックスとからなるＳｉＣ繊維強化ＳｉＣ複合材料であって、上記ＳｉＣマトリックス中に略球形の気泡を有し、原子力用構造部材であることを特徴とする。 [SiC fiber reinforced SiC composite material]
First, the SiC fiber reinforced SiC composite material of the present invention will be described.
The SiC fiber reinforced SiC composite material of the present invention is a SiC fiber reinforced SiC composite material composed of SiC fibers and a SiC matrix, and has substantially spherical bubbles in the SiC matrix, and is a structural member for nuclear power. Features.
　図１（ａ）は、本発明のＳｉＣ繊維強化ＳｉＣ複合材料の一例を模式的に示す断面図であり、図１（ｂ）は、図１（ａ）に示すＳｉＣ繊維強化ＳｉＣ複合材料のＡ－Ａ線断面図である。
　図１（ａ）は、ＳｉＣ繊維の長さ方向に垂直な方向の断面図であり、図１（ｂ）は、ＳｉＣ繊維の長さ方向に平行な方向の断面図である。 Fig.1 (a) is sectional drawing which shows typically an example of the SiC fiber reinforced SiC composite material of this invention, FIG.1 (b) is A of SiC fiber reinforced SiC composite material shown to Fig.1 (a). FIG.
Fig.1 (a) is sectional drawing of the direction perpendicular | vertical to the length direction of a SiC fiber, FIG.1 (b) is sectional drawing of the direction parallel to the length direction of a SiC fiber.
　図１（ａ）及び図１（ｂ）に示すＳｉＣ繊維強化ＳｉＣ複合材料１０は、ＳｉＣ繊維１１とＳｉＣマトリックス１２とからなる複合材料である。ＳｉＣ繊維強化ＳｉＣ複合材料１０は、ＳｉＣマトリックス１２中に気泡１３を有している。 The SiC fiber reinforced SiC composite material 10 shown in FIGS. 1A and 1B is a composite material composed of SiC fibers 11 and a SiC matrix 12. The SiC fiber-reinforced SiC composite material 10 has bubbles 13 in the SiC matrix 12.
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料において、ＳｉＣ繊維としては、ＮＧＳアドバンストファイバー製Ｈｉ－Ｎｉｃａｌｏｎ、宇部興産製Ｔｙｒａｎｎｏ－ＳＡ等を使用することができる。 In the SiC fiber-reinforced SiC composite material of the present invention, as the SiC fiber, Hi-Nicalon made by NGS Advanced Fiber, Tyranno-SA made by Ube Industries, etc. can be used.
　ＳｉＣ繊維の直径は、ＳｉＣ繊維強化ＳｉＣ複合材料の用途に応じて適宜設定できるが、５～２５μｍであることが望ましい。ＳｉＣ繊維の直径が５μｍ以上であると、使用するＳｉＣ粒子及び中空体に対して充分に大きな直径を確保できるので、高強度の複合材料を得ることができる。ＳｉＣ繊維の直径が２５μｍ以下であると、ＳｉＣ繊維が曲がっても表面の延び率を小さくすることができるので破断しにくくすることができる。ＳｉＣ繊維束を構成するＳｉＣ繊維の本数は、例えば５０～２０００本である。 The diameter of the SiC fiber can be appropriately set according to the use of the SiC fiber-reinforced SiC composite material, but is preferably 5 to 25 μm. When the diameter of the SiC fiber is 5 μm or more, a sufficiently large diameter can be secured for the SiC particles and the hollow body to be used, so that a high-strength composite material can be obtained. If the diameter of the SiC fiber is 25 μm or less, the elongation rate of the surface can be reduced even if the SiC fiber is bent, so that it is difficult to break. The number of SiC fibers constituting the SiC fiber bundle is, for example, 50 to 2000.
　ＳｉＣ繊維の直径は、ＳｉＣ繊維強化ＳｉＣ複合材料の断面を走査型電子顕微鏡（ＳＥＭ）で観察することにより測定することができる。 The diameter of the SiC fiber can be measured by observing a cross section of the SiC fiber-reinforced SiC composite material with a scanning electron microscope (SEM).
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料において、マトリックスは、ＳｉＣからなるマトリックスである。 In the SiC fiber-reinforced SiC composite material of the present invention, the matrix is a matrix made of SiC.
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料は、ＳｉＣマトリックス中に気泡を有するものであるが、気泡は、ＳｉＣマトリックス全体に分散していてもよく、ＳｉＣマトリックスの一部に偏在していてもよい。特に、ＳｉＣ繊維の近傍に気泡が存在すると、ＳｉＣ繊維に接するＳｉＣマトリックスの弾性率が低くなるため、ＳｉＣマトリックス中に生じた亀裂がＳｉＣ繊維に伝播することを防止することができる。 The SiC fiber-reinforced SiC composite material of the present invention has bubbles in the SiC matrix, but the bubbles may be dispersed throughout the SiC matrix or may be unevenly distributed in a part of the SiC matrix. In particular, if air bubbles are present in the vicinity of the SiC fiber, the elastic modulus of the SiC matrix in contact with the SiC fiber is lowered, so that cracks generated in the SiC matrix can be prevented from propagating to the SiC fiber.
　ＳｉＣマトリックス中に気泡を形成する方法は特に限定されないが、後述するように、スラリーに中空体を混入することによって気泡が形成されていることが望ましい。 The method for forming bubbles in the SiC matrix is not particularly limited, but it is desirable that the bubbles be formed by mixing a hollow body into the slurry, as will be described later.
　気泡は、ＳｉＣからなる殻で囲まれていることが望ましい。ＳｉＣからなる殻は、ＳｉＣマトリックスの組織よりも緻密な材料で構成されるため、気泡を形成する殻によって、亀裂の伝播をより防止することができる。このように、本発明のＳｉＣ繊維強化ＳｉＣ複合材料においては、気泡が殻で囲まれていることが望ましいが、殻で囲まれていなくてもよい。 It is desirable that the bubbles are surrounded by a shell made of SiC. Since the shell made of SiC is made of a material denser than the structure of the SiC matrix, the propagation of cracks can be further prevented by the shell forming bubbles. As described above, in the SiC fiber-reinforced SiC composite material of the present invention, it is desirable that the bubbles are surrounded by the shell, but the bubbles need not be surrounded by the shell.
　気泡の直径は、ＳｉＣ繊維の直径より小さいことが望ましい。気泡の直径が小さいと、ＳｉＣマトリックスの弾性率が高い部分を少なくすることができるため、亀裂の伝播をより防止することができる。 It is desirable that the bubble diameter is smaller than the SiC fiber diameter. When the diameter of the bubbles is small, the portion having a high elastic modulus of the SiC matrix can be reduced, so that the propagation of cracks can be further prevented.
　具体的には、気泡の直径は、２～２０μｍであることが望ましい。気泡の直径が２μｍ以上であると、ＳｉＣ粒子の形成する気孔より充分に大きな気泡を形成することができるので、亀裂の進展を防ぐ効果を大きくすることができる。気泡の直径が２０μｍ以下であると、曲げても折れにくい屈曲性の高いＳｉＣ繊維を使用することができるので、高強度の複合材料を得ることができる。 Specifically, the bubble diameter is desirably 2 to 20 μm. If the diameter of the bubbles is 2 μm or more, bubbles that are sufficiently larger than the pores formed by the SiC particles can be formed, so that the effect of preventing the progress of cracks can be increased. When the bubble diameter is 20 μm or less, a highly flexible SiC fiber that does not break even when bent can be used, and thus a high-strength composite material can be obtained.
　なお、気泡の直径は、気泡の体積と体積が同一の球（相当球）の直径を示し、走査型電子顕微鏡（ＳＥＭ）を用いて測定することができる。立体的な形状であるので、集束イオンビーム（ＦＩＢ）を用いて、少しずつ削りながら測定を繰り返し、気泡径を計測する。 The bubble diameter indicates the diameter of a sphere (equivalent sphere) having the same volume as the bubble volume, and can be measured using a scanning electron microscope (SEM). Since it is a three-dimensional shape, the measurement is repeated using a focused ion beam (FIB) while gradually scraping to measure the bubble diameter.
　気泡の形状は、略球形である。気泡が略球形であると、外部からの衝撃によって発生した亀裂によるエネルギーが周囲に分散され、亀裂の進展を防ぐことができる。 The shape of the bubble is almost spherical. When the bubbles are substantially spherical, energy due to cracks generated by an external impact is dispersed to the surroundings, and the progress of the cracks can be prevented.
　ＳｉＣマトリックス中の気泡の含有率は特に限定されないが、ＳｉＣ繊維の表面からＳｉＣ繊維の直径の距離の範囲におけるマトリックス中の気泡の含有率が、１０～５０ｖｏｌ％であることが望ましく、２０～３０ｖｏｌ％であることがより望ましい。上記の範囲における気泡の含有率が１０～５０ｖｏｌ％であることは、ＳｉＣ繊維の近傍に気泡が存在することを意味する。この場合、ＳｉＣ繊維の表面が低弾性のマトリックスで覆われるため、亀裂の起点となる傷がＳｉＣ繊維の表面に付きにくくなる。気泡の含有率が１０ｖｏｌ％以上であると、マトリックスに充分な機械強度があるので、複合材料としての強度を確保することができる。気泡の含有率が５０ｖｏｌ％以下であると、発生した亀裂のエネルギーが周囲に分散されやすく、割れにくくすることができる。また、気泡の含有率が２０ｖｏｌ％以上であると、マトリックスにより大きな機械強度があるので、複合材料としての強度をさらに確保することができる。気泡の含有率が３０ｖｏｌ％以下であると、発生した亀裂のエネルギーがより周囲に分散されやすく、さらに割れにくくすることができる。
　なお、ＳｉＣ繊維が、複数本まとまってＳｉＣ繊維束を構成している場合には、１本のＳｉＣ繊維を囲むマトリックスのみについて気泡の含有率を定義する。 The bubble content in the SiC matrix is not particularly limited, but the bubble content in the matrix in the range of the diameter of the SiC fiber from the surface of the SiC fiber is preferably 10 to 50 vol%, and 20 to 30 vol. % Is more desirable. A bubble content of 10 to 50 vol% in the above range means that bubbles are present in the vicinity of the SiC fiber. In this case, since the surface of the SiC fiber is covered with the low-elasticity matrix, the scratch that becomes the starting point of the crack is hardly attached to the surface of the SiC fiber. When the bubble content is 10 vol% or more, the matrix has sufficient mechanical strength, so that strength as a composite material can be ensured. When the bubble content is 50 vol% or less, the generated crack energy is easily dispersed to the surroundings and can be made difficult to break. In addition, when the bubble content is 20 vol% or more, the matrix has a higher mechanical strength, so that the strength as a composite material can be further ensured. When the bubble content is 30 vol% or less, the energy of the generated crack is more easily dispersed to the surroundings, and can be further prevented from cracking.
In addition, when a plurality of SiC fibers form a SiC fiber bundle, the bubble content is defined only for the matrix surrounding one SiC fiber.
　図２は、図１（ｂ）に示したＳｉＣ繊維強化ＳｉＣ複合材料の拡大断面図である。
　図２中、ＳｉＣ繊維１１の直径を矢印ｄで示している。したがって、「ＳｉＣ繊維の表面からＳｉＣ繊維の直径の距離の範囲」とは、ＳｉＣ繊維１１の表面から距離ｄにある範囲を意味する。 FIG. 2 is an enlarged cross-sectional view of the SiC fiber-reinforced SiC composite material shown in FIG.
In FIG. 2, the diameter of the SiC fiber 11 is indicated by an arrow d. Therefore, the “range of the distance of the diameter of the SiC fiber from the surface of the SiC fiber” means a range at a distance d from the surface of the SiC fiber 11.
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料において、ＳｉＣマトリックスの気孔率は、１０～５０％であることが望ましく、２０～３０％であることがより望ましい。 In the SiC fiber reinforced SiC composite material of the present invention, the porosity of the SiC matrix is preferably 10 to 50%, and more preferably 20 to 30%.
　図３は、本発明のＳｉＣ繊維強化ＳｉＣ複合材料の別の一例を模式的に示す断面図である。
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料においては、図３に示すように、ＳｉＣ繊維強化ＳｉＣ複合材料１０の表面にＳｉＣ層２０が形成されていてもよい。ＳｉＣ層２０は、ＳｉＣ繊維強化ＳｉＣ複合材料１０にＣＶＤ処理を施すことにより形成されたＣＶＤ－ＳｉＣ層であることが望ましい。 FIG. 3 is a cross-sectional view schematically showing another example of the SiC fiber-reinforced SiC composite material of the present invention.
In the SiC fiber reinforced SiC composite material of the present invention, as shown in FIG. 3, a SiC layer 20 may be formed on the surface of the SiC fiber reinforced SiC composite material 10. The SiC layer 20 is preferably a CVD-SiC layer formed by subjecting the SiC fiber-reinforced SiC composite material 10 to a CVD process.
［ＳｉＣ繊維強化ＳｉＣ複合材料の製造方法］
　上述した本発明のＳｉＣ繊維強化ＳｉＣ複合材料は、本発明のＳｉＣ繊維強化ＳｉＣ複合材料の製造方法により製造することができる。
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料の製造方法は、原子力用構造部材であるＳｉＣ繊維強化ＳｉＣ複合材料の製造方法であって、ＳｉＣ繊維からなる繊維集合体に、マトリックス前駆体と中空体とを含むスラリーを含浸し、含浸体を得る含浸工程と、上記含浸体を焼成する焼成工程とを含むことを特徴とする。 [Method for producing SiC fiber-reinforced SiC composite material]
The SiC fiber reinforced SiC composite material of the present invention described above can be manufactured by the method for manufacturing the SiC fiber reinforced SiC composite material of the present invention.
A method for producing a SiC fiber reinforced SiC composite material according to the present invention is a method for producing a SiC fiber reinforced SiC composite material that is a nuclear structural member, wherein a matrix precursor and a hollow body are added to a fiber assembly made of SiC fibers. An impregnation step of impregnating a slurry containing the impregnation product and a firing step of firing the impregnation product are characterized.
　まず、ＳｉＣ繊維からなる繊維集合体を準備する。
　繊維集合体は、ＳｉＣ繊維に形状を付与する賦形工程によって得ることができる。具体的には、繊維集合体は、織布、マット、ブレーディング（組紐）成形体、及び、フィラメントワインディング成形体からなる群より選択される少なくとも一層の繊維集合体であることが望ましい。 First, a fiber assembly made of SiC fibers is prepared.
The fiber assembly can be obtained by a shaping process for imparting a shape to the SiC fiber. Specifically, the fiber assembly is desirably at least one fiber assembly selected from the group consisting of a woven fabric, a mat, a braided (braided) molded product, and a filament winding molded product.
　ＳｉＣ繊維については、［ＳｉＣ繊維強化ＳｉＣ複合材料］で説明したとおりであるので、その詳細な説明を省略する。 Since the SiC fiber is as described in [SiC fiber reinforced SiC composite material], detailed description thereof is omitted.
　例えば、ＳｉＣ繊維を５０～２０００本束ねたＳｉＣ繊維束を織布してシート状にしたものを繊維集合体とすることができる。 For example, a fiber assembly can be formed by weaving SiC fiber bundles in which 50 to 2000 SiC fibers are bundled into a sheet shape.
　次に、準備した繊維集合体に、マトリックス前駆体と中空体とを含むスラリーを含浸し、含浸体を得る（含浸工程）。 Next, the prepared fiber aggregate is impregnated with a slurry containing a matrix precursor and a hollow body to obtain an impregnated body (impregnation step).
　含浸の方法としては、ディップ、吹き付け、塗布、コーター、真空加圧含浸等の方法が挙げられるが、いずれの方法であってもよい。 Examples of the impregnation method include dipping, spraying, coating, coater, vacuum pressure impregnation and the like, and any method may be used.
　スラリーに含まれる中空体としては、ＳｉＣバルーン、シリカバルーン、カーボンバルーン等の無機バルーン；樹脂バルーン等の有機バルーン；樹脂；及びこれらの反応物を用いることができる。 As the hollow body contained in the slurry, inorganic balloons such as SiC balloons, silica balloons, and carbon balloons; organic balloons such as resin balloons; resins; and reaction products thereof can be used.
　中空体がＳｉＣバルーンである場合、ＳｉＣバルーンは、ポリカルボシラン等の有機珪素化合物から作製することができる。 When the hollow body is a SiC balloon, the SiC balloon can be made from an organosilicon compound such as polycarbosilane.
　中空体がシリカバルーンである場合、スラリーに炭素粉末をさらに含有させることにより、シリカバルーンと炭素粉末が反応してＳｉＣバルーンとして残留する。また、中空体がカーボンバルーンである場合、スラリーにシリカ粉末をさらに含有させることにより、カーボンバルーンとシリカ粉末が反応してＳｉＣバルーンとして残留する。 When the hollow body is a silica balloon, the silica balloon and the carbon powder react and remain as an SiC balloon by further containing carbon powder in the slurry. Moreover, when a hollow body is a carbon balloon, a carbon balloon and a silica powder react and remain as a SiC balloon by further making a slurry contain silica powder.
　中空体が樹脂からなる場合、樹脂としては熱可塑性樹脂であることが望ましい。これらの樹脂は、焼成によって熱分解し、殻がなくなるためである。 When the hollow body is made of a resin, the resin is preferably a thermoplastic resin. This is because these resins are thermally decomposed by firing to eliminate the shell.
　中空体の平均気泡径は、２～２０μｍであることが望ましく、５～１５μｍであることがより望ましい。
　なお、中空体の平均気泡径は、レーザー回折式粒度測定機で粒子径を測定し、中空体の膜厚を減ずることで測定することができる。 The average cell diameter of the hollow body is preferably 2 to 20 μm, and more preferably 5 to 15 μm.
The average cell diameter of the hollow body can be measured by measuring the particle diameter with a laser diffraction particle size measuring machine and reducing the film thickness of the hollow body.
　スラリー中の中空体の含有量は特に限定されないが、固形分量で２０～６５重量％であることが望ましく、４０～６５重量％であることがより望ましい。 The content of the hollow body in the slurry is not particularly limited, but the solid content is preferably 20 to 65% by weight, more preferably 40 to 65% by weight.
　スラリーに含まれるマトリックス前駆体は、有機珪素化合物であってもよいし、ＳｉＣ粒子と焼結助剤とからなっていてもよい。 The matrix precursor contained in the slurry may be an organosilicon compound, or may be composed of SiC particles and a sintering aid.
　マトリックス前駆体が有機珪素化合物である場合、有機珪素化合物を焼成することによって、ＳｉＣからなるマトリックスを形成することができる。 When the matrix precursor is an organosilicon compound, a matrix made of SiC can be formed by firing the organosilicon compound.
　有機珪素化合物としては、例えば、ポリカルボシラン、ポリビニルシラン、ポリメチルシラン等のケイ素系ポリマーが挙げられる。 Examples of the organosilicon compound include silicon-based polymers such as polycarbosilane, polyvinylsilane, and polymethylsilane.
　マトリックス前駆体が有機珪素化合物である場合、スラリー中の有機珪素化合物の含有量は特に限定されないが、固形分量で２０～６５重量％であることが望ましく、４０～６５重量％であることがより望ましい。 When the matrix precursor is an organosilicon compound, the content of the organosilicon compound in the slurry is not particularly limited, but is preferably 20 to 65% by weight in terms of solid content, more preferably 40 to 65% by weight. desirable.
　マトリックス前駆体が、ＳｉＣ粒子と焼結助剤とからなる場合、焼結助剤を用いてＳｉＣ粒子を焼結することによって、ＳｉＣからなるマトリックスを形成することができる。 When the matrix precursor is composed of SiC particles and a sintering aid, a matrix made of SiC can be formed by sintering the SiC particles using a sintering aid.
　ＳｉＣ粒子の平均粒子径は、中空体の平均気泡径より小さいことが望ましい。中空体の平均気泡径よりもＳｉＣ粒子の平均粒子径を小さくすることで、マトリックス内部に発生する応力集中を小さくしつつ、弾性率の低いマトリックスを形成することができる。 The average particle diameter of the SiC particles is preferably smaller than the average bubble diameter of the hollow body. By making the average particle diameter of the SiC particles smaller than the average bubble diameter of the hollow body, it is possible to form a matrix having a low elastic modulus while reducing the concentration of stress generated inside the matrix.
　具体的には、ＳｉＣ粒子の平均粒子径は、１０～１０００ｎｍであることが望ましく、２５０～８００ｎｍであることがより望ましい。
　なお、ＳｉＣ粒子の平均粒子径は、走査型電子顕微鏡（ＳＥＭ）を用いて測定することができる。 Specifically, the average particle size of the SiC particles is desirably 10 to 1000 nm, and more desirably 250 to 800 nm.
In addition, the average particle diameter of a SiC particle can be measured using a scanning electron microscope (SEM).
　スラリー中のＳｉＣ粒子の含有量は特に限定されないが、固形分量で２５～６５重量％であることが望ましく、４５～６５重量％であることがより望ましい。
　特に、ＳｉＣ粒子及び中空体の比率（ＳｉＣ粒子：中空体）が、重量比で２：１～７：１であることが望ましく、２：１～４：１であることがより望ましい。 The content of the SiC particles in the slurry is not particularly limited, but is preferably 25 to 65% by weight and more preferably 45 to 65% by weight in terms of solid content.
In particular, the ratio of SiC particles to hollow bodies (SiC particles: hollow bodies) is preferably 2: 1 to 7: 1, and more preferably 2: 1 to 4: 1.
　焼結助剤としては、例えば、Ａｌ２Ｏ３、Ｙ２Ｏ３、ＳｉＯ２、ＣａＯ等が挙げられる。
　これらは１種類であってもよいし、複数種類を組み合わせてもよい。また、焼結助剤は、粉末状であることが望ましい。 Examples of the sintering aid include Al 2 O 3 , Y 2 O 3 , SiO 2 , and CaO.
These may be one type or a combination of a plurality of types. Moreover, it is desirable that the sintering aid is in a powder form.
　スラリー中の焼結助剤の含有量は特に限定されないが、固形分量で１～３重量％であることが望ましく、１～２重量％であることがより望ましい。 The content of the sintering aid in the slurry is not particularly limited, but it is preferably 1 to 3% by weight and more preferably 1 to 2% by weight in terms of solid content.
　スラリーには分散媒（溶媒）が含まれる。分散媒としては、水又は有機溶媒を用いることができる。有機溶媒としては、例えば、エタノール、イソプロパノール等のアルコール系有機溶媒；ヘキサン、トルエン、キシレン等の炭化水素系有機溶媒等が挙げられる。 The slurry contains a dispersion medium (solvent). As the dispersion medium, water or an organic solvent can be used. Examples of the organic solvent include alcohol-based organic solvents such as ethanol and isopropanol; hydrocarbon-based organic solvents such as hexane, toluene and xylene.
　なお、得られた含浸体を必要に応じて乾燥してもよい。 In addition, you may dry the obtained impregnated body as needed.
　また、ＳｉＣ繊維の近傍に気泡を多く形成する場合には、中空体の含有率の異なるスラリーを準備し、繊維集合体に含有率の高いスラリーを含浸した後、含有率の低いスラリーを含浸すればよい。 Also, when many bubbles are formed in the vicinity of the SiC fiber, a slurry having a different hollow body content is prepared, and the fiber aggregate is impregnated with a high content slurry, and then impregnated with a low content slurry. That's fine.
　続いて、含浸体を焼成する（焼成工程）。 Subsequently, the impregnated body is fired (firing step).
　含浸体を焼成する方法としては、例えば、含浸体を加圧焼結する方法等が挙げられる。
　加圧焼結の方法としては特に限定されず、ホットプレス（ＨＰ）法、熱間等方圧プレス（ＨＩＰ）法等の公知の方法が挙げられる。 Examples of the method of firing the impregnated body include a method of pressure-sintering the impregnated body.
The pressure sintering method is not particularly limited, and examples thereof include known methods such as a hot press (HP) method and a hot isostatic press (HIP) method.
　焼結温度は、適宜設定することができるが、１０００～２０００℃であることが望ましく、１２００～１６００℃であることがより望ましい。また、圧力は、１～３０ＭＰａであることが望ましく、５～２０ＭＰａであることがより望ましい。 The sintering temperature can be appropriately set, but is preferably 1000 to 2000 ° C., more preferably 1200 to 1600 ° C. The pressure is preferably 1 to 30 MPa and more preferably 5 to 20 MPa.
　含浸体の焼成は、非酸化性雰囲気下で行えばよく、例えば、不活性ガス雰囲気下、還元性雰囲気下、真空雰囲気下等で行うことができる。これらのなかでは、水素、窒素、ヘリウム、アルゴン等の不活性ガス雰囲気下で行うことが望ましい。 The calcination of the impregnated body may be performed in a non-oxidizing atmosphere, for example, in an inert gas atmosphere, a reducing atmosphere, a vacuum atmosphere, or the like. In these, it is desirable to carry out in inert gas atmosphere, such as hydrogen, nitrogen, helium, and argon.
　以上の工程を経ることにより、本発明のＳｉＣ繊維強化ＳｉＣ複合材料を製造することができる。 Through the above steps, the SiC fiber reinforced SiC composite material of the present invention can be manufactured.
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料は、原子力分野、航空・宇宙分野、発電分野等の過酷な環境下で使用することが望ましく、特に、原子力分野で使用することが望ましい。
　具体的には、本発明のＳｉＣ繊維強化ＳｉＣ複合材料は、原子力用構造部材であり、軽水炉用構造部材であることが望ましい。 The SiC fiber reinforced SiC composite material of the present invention is desirably used in harsh environments such as the nuclear field, aerospace field, and power generation field, and particularly desirably in the nuclear field.
Specifically, the SiC fiber-reinforced SiC composite material of the present invention is a structural member for nuclear power, and is desirably a structural member for light water reactors.
　以下、本発明のＳｉＣ繊維強化ＳｉＣ複合材料及びＳｉＣ繊維強化ＳｉＣ複合材料の製造方法の作用効果について説明する。 Hereinafter, the function and effect of the manufacturing method of the SiC fiber-reinforced SiC composite material and the SiC fiber-reinforced SiC composite material of the present invention will be described.
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料においては、構成材料がＳｉＣであるため、高強度を実現することができる。また、ＳｉＣマトリックス中に気泡が存在すると、ＳｉＣマトリックスが低弾性となる。そのため、本発明の複合材料では、ＳｉＣマトリックスに亀裂が生じても、ＳｉＣマトリックス中に存在する気泡によって亀裂の進展を防止し、その亀裂がＳｉＣ繊維にまで伝播することを防止することができる。このように、本発明の複合材料では、亀裂の伝播を防止するための被覆層等を含まずに、高強度の複合材料とすることができる。 In the SiC fiber reinforced SiC composite material of the present invention, since the constituent material is SiC, high strength can be realized. Further, when bubbles are present in the SiC matrix, the SiC matrix becomes low elastic. Therefore, in the composite material of the present invention, even if a crack occurs in the SiC matrix, the progress of the crack can be prevented by the bubbles present in the SiC matrix, and the crack can be prevented from propagating to the SiC fiber. As described above, the composite material of the present invention can be a high-strength composite material without including a coating layer or the like for preventing the propagation of cracks.
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料の製造方法では、スラリーに中空体を混入することによって、マトリックス中に気泡を形成することができる。その結果、上述した本発明のＳｉＣ繊維強化ＳｉＣ複合材料を製造することができる。 In the method for producing a SiC fiber-reinforced SiC composite material of the present invention, bubbles can be formed in the matrix by mixing a hollow body into the slurry. As a result, the above-described SiC fiber reinforced SiC composite material of the present invention can be manufactured.
　本発明のＳｉＣ繊維強化ＳｉＣ複合材料は、ＳｉＣマトリックス中に気泡を有することを必須の構成要件としている。本発明のＳｉＣ繊維強化ＳｉＣ複合材料の製造方法は、ＳｉＣ繊維からなる繊維集合体に、マトリックス前駆体と中空体とを含むスラリーを含浸し、含浸体を得た後、上記含浸体を焼成することを必須の構成要件としている。
　係る必須の構成要件に、本発明の詳細な説明で詳述した種々の構成（例えば、ＳｉＣ繊維の構成、ＳｉＣマトリックスの構成、気泡の構成、中空体の構成、ＳｉＣ繊維強化ＳｉＣ複合材料の製造条件等）を適宜組み合わせることにより所望の効果を得ることができる。 The SiC fiber-reinforced SiC composite material of the present invention has an essential constituent element that has a bubble in the SiC matrix. In the method for producing a SiC fiber-reinforced SiC composite material according to the present invention, a fiber assembly made of SiC fibers is impregnated with a slurry containing a matrix precursor and a hollow body, and after obtaining the impregnated body, the impregnated body is fired. This is an essential component requirement.
The various constituents detailed in the detailed description of the present invention (for example, SiC fiber configuration, SiC matrix configuration, bubble configuration, hollow body configuration, SiC fiber reinforced SiC composite material manufacture) The desired effect can be obtained by appropriately combining the conditions and the like.
　１０　ＳｉＣ繊維強化ＳｉＣ複合材料
　１１　ＳｉＣ繊維
　１２　ＳｉＣマトリックス
　１３　気泡
　２０　ＳｉＣ層
　 10 SiC fiber reinforced SiC composite material 11 SiC fiber 12 SiC matrix 13 Air bubbles 20 SiC layer

Claims (12)

  1. 　ＳｉＣ繊維とＳｉＣマトリックスとからなるＳｉＣ繊維強化ＳｉＣ複合材料であって、
    　前記ＳｉＣマトリックス中に略球形の気泡を有し、原子力用構造部材であることを特徴とするＳｉＣ繊維強化ＳｉＣ複合材料。     A SiC fiber reinforced SiC composite material comprising a SiC fiber and a SiC matrix,
    A SiC fiber-reinforced SiC composite material having substantially spherical bubbles in the SiC matrix and being a structural member for nuclear power.
  2. 　前記気泡は、ＳｉＣからなる殻で囲まれている請求項１に記載のＳｉＣ繊維強化ＳｉＣ複合材料。 The SiC fiber-reinforced SiC composite material according to claim 1, wherein the bubbles are surrounded by a shell made of SiC.
  3. 　前記気泡の直径は、前記ＳｉＣ繊維の直径より小さい請求項１又は２に記載のＳｉＣ繊維強化ＳｉＣ複合材料。 The SiC fiber reinforced SiC composite material according to claim 1 or 2, wherein the diameter of the bubbles is smaller than the diameter of the SiC fibers.
  4. 　前記ＳｉＣ繊維は、複数本がまとまってＳｉＣ繊維束を構成している請求項１～３のいずれかに記載のＳｉＣ繊維強化ＳｉＣ複合材料。 The SiC fiber-reinforced SiC composite material according to any one of claims 1 to 3, wherein a plurality of the SiC fibers are combined to form a SiC fiber bundle.
  5. 　前記ＳｉＣ繊維の表面から前記ＳｉＣ繊維の直径の距離の範囲における前記ＳｉＣマトリックス中の前記気泡の含有率は、１０～５０ｖｏｌ％である請求項１～４のいずれかに記載のＳｉＣ繊維強化ＳｉＣ複合材料。 The SiC fiber reinforced SiC composite according to any one of claims 1 to 4, wherein a content ratio of the bubbles in the SiC matrix in a range of a distance of a diameter of the SiC fiber from a surface of the SiC fiber is 10 to 50 vol%. material.
  6. 　前記ＳｉＣ繊維強化ＳｉＣ複合材料は、軽水炉用構造部材である請求項１～５のいずれかに記載のＳｉＣ繊維強化ＳｉＣ複合材料。 The SiC fiber reinforced SiC composite material according to any one of claims 1 to 5, wherein the SiC fiber reinforced SiC composite material is a structural member for a light water reactor.
  7. 　原子力用構造部材であるＳｉＣ繊維強化ＳｉＣ複合材料の製造方法であって、
    　ＳｉＣ繊維からなる繊維集合体に、マトリックス前駆体と中空体とを含むスラリーを含浸し、含浸体を得る含浸工程と、
    　前記含浸体を焼成する焼成工程とを含むことを特徴とするＳｉＣ繊維強化ＳｉＣ複合材料の製造方法。     A method for producing a SiC fiber reinforced SiC composite material which is a structural member for nuclear power,
    An impregnation step of impregnating a fiber assembly composed of SiC fibers with a slurry containing a matrix precursor and a hollow body to obtain an impregnated body;
    A method for producing a SiC fiber-reinforced SiC composite material, comprising: a firing step of firing the impregnated body.
  8. 　前記マトリックス前駆体は、有機珪素化合物である請求項７に記載のＳｉＣ繊維強化ＳｉＣ複合材料の製造方法。 The method for producing a SiC fiber-reinforced SiC composite material according to claim 7, wherein the matrix precursor is an organosilicon compound.
  9. 　前記マトリックス前駆体は、ＳｉＣ粒子と焼結助剤とからなる請求項７に記載のＳｉＣ繊維強化ＳｉＣ複合材料の製造方法。 The method for producing a SiC fiber-reinforced SiC composite material according to claim 7, wherein the matrix precursor includes SiC particles and a sintering aid.
  10. 　前記ＳｉＣ粒子の平均粒子径は、前記中空体の平均気泡径より小さい請求項９に記載のＳｉＣ繊維強化ＳｉＣ複合材料の製造方法。 The method for producing a SiC fiber-reinforced SiC composite material according to claim 9, wherein an average particle diameter of the SiC particles is smaller than an average cell diameter of the hollow body.
  11. 　前記ＳｉＣ繊維は、複数本がまとまってＳｉＣ繊維束を構成している請求項７～１０のいずれかに記載のＳｉＣ繊維強化ＳｉＣ複合材料の製造方法。 The method for producing a SiC fiber-reinforced SiC composite material according to any one of claims 7 to 10, wherein a plurality of the SiC fibers are combined to form a SiC fiber bundle.
  12. 　前記繊維集合体は、織布、マット、ブレーディング（組紐）成形体、及び、フィラメントワインディング成形体からなる群より選択される少なくとも一層の繊維集合体である請求項７～１１のいずれかに記載のＳｉＣ繊維強化ＳｉＣ複合材料の製造方法。 12. The fiber assembly according to claim 7, wherein the fiber assembly is at least one fiber assembly selected from the group consisting of a woven fabric, a mat, a braiding (braid) molded body, and a filament winding molded body. Manufacturing method of SiC fiber reinforced SiC composite material.
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