WO2015016071A1 - Matériau composite sic renforcé de fibre sic et procédé de production de matériau composite renforcé de fibre sic - Google Patents

Matériau composite sic renforcé de fibre sic et procédé de production de matériau composite renforcé de fibre sic 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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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.

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  • Organic Chemistry (AREA)
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Abstract

L'invention concerne un matériau composite SiC renforcé de fibre SiC ayant une résistance élevée en utilisant uniquement du SiC et ne comprenant pas de couche de revêtement, etc., d'un autre type de matériau. Le matériau composite SiC renforcé de fibre SiC comprend une fibre SiC et une matrice SiC et est caractérisé en ce qu'il présente des bulles substantiellement sphériques dans la matrice SiC et en ce qu'il est un élément structurel pour l'énergie atomique.
PCT/JP2014/068945 2013-07-31 2014-07-16 Matériau composite sic renforcé de fibre sic et procédé de production de matériau composite renforcé de fibre sic WO2015016071A1 (fr)

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JP2013159940A JP6122728B2 (ja) 2013-07-31 2013-07-31 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
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JP6467290B2 (ja) * 2015-05-26 2019-02-13 イビデン株式会社 セラミック複合材

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000185979A (ja) * 1998-12-21 2000-07-04 Tokai Carbon Co Ltd 多孔質炭化珪素成形体の製造方法
WO2012063923A1 (fr) * 2010-11-11 2012-05-18 国立大学法人京都大学 Matériau céramique en sic et structure céramique en sic, et leur procédé de fabrication

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JP2010070421A (ja) * 2008-09-18 2010-04-02 Enetech Soken:Kk ＳｉＣ繊維強化型ＳｉＣ複合材料の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000185979A (ja) * 1998-12-21 2000-07-04 Tokai Carbon Co Ltd 多孔質炭化珪素成形体の製造方法
WO2012063923A1 (fr) * 2010-11-11 2012-05-18 国立大学法人京都大学 Matériau céramique en sic et structure céramique en sic, et leur procédé de fabrication

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