JP2019085292A - BN COATED SiC FIBER AND MANUFACTURING METHOD THEREFOR, SiC FIBER REINFORCED SiC COMPOSITE MATERIAL USING BN COATED SiC FIBER - Google Patents
BN COATED SiC FIBER AND MANUFACTURING METHOD THEREFOR, SiC FIBER REINFORCED SiC COMPOSITE MATERIAL USING BN COATED SiC FIBER Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 137
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 133
- 238000000034 method Methods 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000010030 laminating Methods 0.000 abstract description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 125
- 229910052582 BN Inorganic materials 0.000 description 121
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 103
- 229910010271 silicon carbide Inorganic materials 0.000 description 102
- 239000004744 fabric Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 14
- 229920006318 anionic polymer Polymers 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 229920006317 cationic polymer Polymers 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 6
- 239000011226 reinforced ceramic Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 4
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 4
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
Description
本発明は、繊維強化セラミックスに関する。 The present invention relates to fiber reinforced ceramics.
繊維強化セラミックスは、金属材料よりも軽量であり、優れた耐熱性及び剛性に加え、通常のセラミックスに比べて靱性が高いことから、従来は金属材料が使用されていた摺動材や回転材に用いられ始めている。特に、ジェットエンジンの高温部に耐熱性の高い炭化ケイ素繊維等のセラミックス材料を用いる研究が盛んになされている。 Fiber-reinforced ceramics are lighter than metal materials, have excellent heat resistance and rigidity, and have high toughness compared to ordinary ceramics, so sliding materials and rotating materials in which metal materials have been used conventionally It is beginning to be used. In particular, research has been actively conducted to use a ceramic material such as silicon carbide fiber having high heat resistance for the high temperature part of a jet engine.
例えば、特許第２９６８４７７号公報（特許文献１）には、ＳｉＣ、Ｓｉ3Ｎ4又はＢＮ等からなる緩衝層の表面に高融点金属層を付与した非酸化物系繊維強化セラミックス及びその製造方法が記載されている。この技術では、非酸化物系セラミック繊維と高融点金属層との間に化学蒸着（Chemical Vapor Deposition；ＣＶＤ）法等を用いてカーボン層やＢＮ緩衝層などの中間層を形成させている。しかしながら、緻密な中間層では製造又は使用の際に、金属層及び繊維の間で熱膨張差による応力により中間層及び金属層に亀裂などが生じ、繊維強化セラミックス材料の靱性低下を招くという問題があった。つまり、このような繊維強化セラミックス材料は、剛性に優れるが、耐衝撃性に劣るという問題があった。また、このような多層構造体を構成する場合、耐衝撃性を向上させるためには、繊維強化セラミックス材料の厚みを増さざるを得ず、重量が増加してしまうという問題があった。 For example, Japanese Patent No. 2968477 (Patent Document 1) is a non-oxide fiber reinforced ceramic in which a high melting point metal layer is provided on the surface of a buffer layer made of SiC, Si 3 N 4 or BN, etc. Have been described. In this technology, an intermediate layer such as a carbon layer or a BN buffer layer is formed between a non-oxide ceramic fiber and a high melting point metal layer by using a chemical vapor deposition (CVD) method or the like. However, in the case of a dense intermediate layer, there is a problem in that cracks and the like occur in the intermediate layer and the metal layer due to the stress due to the thermal expansion difference between the metal layer and the fiber during production or use, leading to a decrease in toughness of the fiber reinforced ceramic material. there were. That is, such a fiber-reinforced ceramic material is excellent in rigidity but has a problem of being inferior in impact resistance. Further, in the case of constructing such a multilayer structure, in order to improve the impact resistance, the thickness of the fiber-reinforced ceramic material has to be increased, and there is a problem that the weight is increased.
本発明の課題は、上記した従来技術の問題に鑑み、破壊エネルギーの高いＳｉＣ繊維強化ＳｉＣ複合材及びその製造方法を提供することにある。 An object of the present invention is to provide an SiC fiber-reinforced SiC composite having high fracture energy and a method of manufacturing the same in view of the problems of the above-described conventional technology.
本発明のＢＮ被覆ＳｉＣ繊維は、ＳｉＣ繊維と、前記ＳｉＣ繊維の表面を被覆する、第１のＢＮ粒子と第２のＢＮ粒子とからなり、前記第１のＢＮ粒子の粒径が、前記ＳｉＣ繊維の繊維径の１／１０以下であり、前記第２のＢＮ粒子の粒径が、前記第１のＢＮ粒子の粒径の１／１０以下であることを特徴とする。 The BN-coated SiC fiber of the present invention comprises SiC fiber, and first BN particles and second BN particles covering the surface of the SiC fiber, wherein the particle diameter of the first BN particles is the above-mentioned SiC It is 1/10 or less of the fiber diameter of the fiber, and the particle diameter of the second BN particles is 1/10 or less of the particle diameter of the first BN particles.
本発明のＢＮ被覆ＳｉＣ繊維の製造方法は、表面電荷の違いによる吸着現象を用いてＢＮ粒子をＳｉＣ繊維表面へ吸着させる工程を有することを特徴とする。
前記工程は、正又は負に帯電したＳｉＣ繊維の表面に、該ＳｉＣ繊維とは反対の電荷に帯電した第１のＢＮ粒子を吸着させる工程１と、第１のＢＮ粒子が付着したＳｉＣ繊維の表面に、前記第１のＢＮ粒子とは反対の電荷に帯電した第２のＢＮ粒子を吸着させ、その後、正及び負に帯電した第２のＢＮ粒子を正負を交互に吸着させてＢＮ付着ＳｉＣ繊維を得る工程２と、前記ＢＮ付着ＳｉＣ繊維を加熱処理してＢＮ被覆ＳｉＣ繊維を得る工程３と、を有することが好ましい。
本発明のＳｉＣ繊維強化ＳｉＣ複合材は、上記ＢＮ被覆ＳｉＣ繊維を用いたものである。
The method for producing BN-coated SiC fibers according to the present invention is characterized by including the step of causing BN particles to be adsorbed onto the surface of SiC fibers using an adsorption phenomenon due to the difference in surface charge.
The step includes the
The SiC fiber reinforced SiC composite material of the present invention uses the above-mentioned BN coated SiC fiber.
本発明によれば、ＳｉＣ繊維の繊維径よりも小さい粒径を有する第１のＢＮ粒子と、第１のＢＮ粒子の間に第１のＢＮ粒子よりも小さい第２のＢＮ粒子をＳｉＣ繊維表面に吸着させることで、ＳｉＣ繊維束内にＢＮ粒子を緻密に吸着させることができ、該ＢＮ粒子が吸着したＳｉＣ繊維束を製織したシートを複数枚積層させることで、高い破壊エネルギーを有するＳｉＣ繊維強化ＳｉＣ複合材を得ることができる。 According to the present invention, a first BN particle having a particle size smaller than the fiber diameter of the SiC fiber, and a second BN particle smaller than the first BN particle between the first BN particle and the SiC fiber surface The BN particles can be densely adsorbed in the SiC fiber bundle by adsorbing to the SiC fiber bundle, and by laminating a plurality of woven sheets of the SiC fiber bundle in which the BN particles are adsorbed, the SiC fiber having high fracture energy A reinforced SiC composite can be obtained.
以下、本発明について詳細に説明する。
本発明のＢＮ被覆ＳｉＣ繊維は、炭化ケイ素（ＳｉＣ）繊維と、前記ＳｉＣ繊維の表面を被覆する、第１の窒化ホウ素（ＢＮ）粒子と第２の窒化ホウ素（ＢＮ）粒子とからなる。そして、第１のＢＮ粒子の粒径は、ＳｉＣ繊維の繊維径の１／１０以下であり、第２のＢＮ粒子の粒径は、第１のＢＮ粒子の粒径の１／１０以下である。
上記ＢＮ被覆ＳｉＣ繊維は、表面電荷の違いによる吸着現象を用いて第１のＢＮ粒子及び第２のＢＮ粒子をＳｉＣ繊維表面に吸着させることにより製造することができる。具体的には、上記ＢＮ被覆ＳｉＣ繊維の製造方法は、正又は負に帯電したＳｉＣ繊維の表面に、該ＳｉＣ繊維とは反対の電荷に帯電した、第１のＢＮ粒子を吸着させる工程１と、第１のＢＮ粒子が付着したＳｉＣ繊維の表面に、前記第１のＢＮ粒子とは反対の電荷に帯電した第２のＢＮ粒子を吸着させ、その後、正及び負に帯電した第２のＢＮ粒子を正負を交互に吸着させてＢＮ付着ＳｉＣ繊維を得る工程２と、前記ＢＮ付着ＳｉＣ繊維を加熱処理してＢＮ被覆ＳｉＣ繊維を得る工程３とからなる。
Hereinafter, the present invention will be described in detail.
The BN-coated SiC fiber of the present invention comprises silicon carbide (SiC) fiber, and first boron nitride (BN) particles and second boron nitride (BN) particles which coat the surface of the SiC fiber. And, the particle diameter of the first BN particles is 1/10 or less of the fiber diameter of the SiC fiber, and the particle diameter of the second BN particles is 1/10 or less of the particle diameter of the first BN particles. .
The BN-coated SiC fiber can be produced by adsorbing the first BN particles and the second BN particles on the surface of the SiC fiber using an adsorption phenomenon due to the difference in surface charge. Specifically, the method for producing a BN-coated SiC fiber comprises the steps of: adsorbing first BN particles charged to a charge opposite to that of the SiC fiber on the surface of the positively or negatively charged SiC fiber; A second BN particle charged to the opposite charge to the first BN particle is adsorbed onto the surface of the SiC fiber to which the first BN particle is attached, and then a second BN positively and negatively charged The process comprises:
ここで、ＢＮ被覆ＳｉＣ繊維として用いるＳｉＣ繊維にはＳｉＣ単繊維、ＳｉＣ繊維束およびＳｉＣ繊維束を織ったシート状の織物が用いられる。ＳｉＣ繊維織物の織り方に特段制限はなく、平織り、綾織り、朱子織りなど、いずれでもよいが、朱子織りは平織りに比べて繊維束の間隔が広く、複合化時には原料ガスが拡散して繊維密度が緻密になるため、朱子織りが好ましい。前記ＳｉＣ繊維の繊維径は、通常５μｍ以上２０μｍ以下、好ましくは７μｍ以上１５μｍ以下である。 Here, as a SiC fiber used as the BN-coated SiC fiber, a sheet-like woven fabric in which an SiC single fiber, an SiC fiber bundle and an SiC fiber bundle are woven is used. There is no particular limitation on the weave method of the SiC fiber fabric, and any of plain weave, twill weave, satin weave, etc. may be used, but the satin weave has wider fiber bundles compared to plain weave, and the raw material gas is diffused during compounding and fiber density Yarn weave is preferred because The fiber diameter of the SiC fiber is generally 5 μm to 20 μm, preferably 7 μm to 15 μm.
ＢＮは、常温常圧下で六方晶系の固体の化合物である。第１のＢＮ粒子の粒径は、ＳｉＣ繊維の繊維径の１／１０以下であり、第２のＢＮ粒子は、第１のＢＮ粒子の粒径の１／１０以下である。第１のＢＮ粒子の粒径がＳｉＣ繊維の繊維径の１／１０を超えていると、ＳｉＣ繊維の繊維間にＢＮ粒子が緻密に吸着できず、得られる複合材の破壊強度が充分に得られないことがある。第１のＢＮ粒子の粒径は、ＳｉＣ繊維の繊維径の１／２０以下であることが好ましい。また、第２のＢＮ粒子の粒径が、第１のＢＮ粒子の粒径の１／１０を超えていると、ＳｉＣ繊維の表面を被覆した第１のＢＮ粒子間の隙間を、第２のＢＮ粒子で充分に埋めることができず、得られる複合材の破壊強度が充分に得られないことがある。具体的には、第１のＢＮ粒子の粒径は、０．５μｍ以上２μｍ以下が好ましく、０．５μｍ以上１μｍ以下がより好ましい。第２のＢＮ粒子の粒径は、０．０５μｍ以上０．３μｍ以下が好ましく、０．０５μｍ以上０．１μｍ以下がより好ましい。
なお、これらのＢＮ粒子には、必要な粒径の市販品を用いることができる。
BN is a compound of a hexagonal solid at normal temperature and pressure. The particle size of the first BN particles is 1/10 or less of the fiber diameter of the SiC fiber, and the second BN particles are 1/10 or less of the particle size of the first BN particles. If the particle size of the first BN particles exceeds 1/10 of the fiber diameter of the SiC fibers, the BN particles can not be precisely adsorbed between the fibers of the SiC fibers, and the fracture strength of the resulting composite material is sufficiently obtained. I can not do it. The particle diameter of the first BN particles is preferably 1/20 or less of the fiber diameter of the SiC fiber. In addition, when the particle diameter of the second BN particles exceeds 1/10 of the particle diameter of the first BN particles, the gaps between the first BN particles coated on the surface of the SiC fiber BN particles can not be sufficiently filled, and the fracture strength of the resulting composite may not be sufficiently obtained. Specifically, the particle diameter of the first BN particles is preferably 0.5 μm or more and 2 μm or less, and more preferably 0.5 μm or more and 1 μm or less. 0.05 micrometer or more and 0.3 micrometer or less are preferable, and, as for the particle size of 2nd BN particle | grains, 0.05 micrometer or more and 0.1 micrometer or less are more preferable.
In addition, the commercial item of a required particle size can be used for these BN particle | grains.
本発明のＢＮ被覆ＳｉＣ繊維の製造方法では、電解質ポリマーによる表面帯電が用いられる。図１に示すように、例えば、カチオンポリマー水溶液（正電荷付与液）に浸すことによってカチオンポリマー層を形成し正に帯電したＳｉＣ繊維に、負電荷を持つアニオンポリマー水溶液（負電荷付与液）に浸すことによってアニオンポリマー層を形成し負に帯電した第１のＢＮ粒子を吸着させ、次いで、ＢＮ粒子付着ＳｉＣ繊維を負電荷を持つアニオンポリマー水溶液（負電荷付与液）に浸すことによってアニオンポリマー層を形成し負に帯電させ、正電荷を持つカチオンポリマー水溶液（正電荷付与液）に浸すことによってカチオンポリマー層を形成した第２のＢＮ粒子を吸着させる。さらに、第２のＢＮ粒子を吸着させるサイクルを繰り返すことによって、図２に示すような、ＳｉＣ繊維にＢＮ粒子が緻密に吸着した被覆層を形成させることができる。 In the method for producing BN-coated SiC fibers of the present invention, surface charging with an electrolyte polymer is used. As shown in FIG. 1, for example, a cationic polymer layer is formed by immersion in a cationic polymer aqueous solution (positive charge imparting solution), and a positively charged SiC fiber is made into an anionic polymer aqueous solution (negative charge imparting solution) having a negative charge. An anionic polymer layer is formed by immersion to adsorb the negatively charged first BN particles, and then an anionic polymer layer is formed by immersing the BN particle-attached SiC fiber in a negatively charged anionic polymer aqueous solution (negatively charged solution) The second BN particles having the cationic polymer layer formed thereon are adsorbed by being immersed in a cationic polymer aqueous solution (positive charge imparting solution) having a positive charge. Furthermore, by repeating the cycle of adsorbing the second BN particles, it is possible to form a coating layer in which the BN particles are closely adsorbed to the SiC fiber, as shown in FIG.
ここで、電解質ポリマーは、通常、カチオンポリマー又はアニオンポリマーをいう。
カチオンポリマーには、例えば、ビニルピロリドン−Ｎ、Ｎ−ジメチルアミノエチルメタクリル酸共重合体硫酸塩液及びポリジアリルメチルアンモニウムクロライド（ＰＤＤＡ）などが挙げられる。これらのうち、水溶性の理由により、ポリジアリルメチルアンモニウムクロライド（ＰＤＤＡ）等が好ましい。
アニオンポリマーには、例えば、アクリル樹脂アルカノールアミン液及びポリスチレンスルホン酸（ＰＳＳ）などが挙げられる。これらのうち、取扱いが容易で水溶性に優れる等の理由により、ポリスチレンスルホン酸（ＰＳＳ）等が好ましい。
Here, the electrolyte polymer usually refers to a cationic polymer or an anionic polymer.
Examples of cationic polymers include vinylpyrrolidone-N, N-dimethylaminoethyl methacrylic acid copolymer sulfate solution, polydiallylmethyl ammonium chloride (PDDA) and the like. Among these, polydiallylmethyl ammonium chloride (PDDA) is preferable because of its water solubility.
Anionic polymers include, for example, acrylic resin alkanolamine liquids and polystyrene sulfonic acid (PSS). Among these, polystyrene sulfonic acid (PSS) and the like are preferable because of easy handling and excellent water solubility.
本発明では、まず、電解質ポリマー水溶液中に帯電処理した第１のＢＮ粒子を分散させ、該帯電した第１のＢＮ粒子を含む電解質ポリマー水溶液中に第１のＢＮ粒子とは反対電荷を持つＳｉＣ繊維を浸漬することにより、ＳｉＣ繊維に第１のＢＮ粒子が吸着される。これは、表面電荷の違いによる吸着現象を利用したものである。次いで、第１のＢＮ粒子とは反対電荷を持つ第２のＢＮ粒子を電解質ポリマー水溶液中に分散させ、第１のＢＮ粒子が付着したＳｉＣ繊維を浸漬させる。この操作を通常１０回以上、好ましくは２０回以上繰り返すことにより、ＳｉＣ繊維の表面にＢＮ粒子が緻密に吸着されたＳｉＣ繊維を形成することができる。本発明では、粒径の大きな第１のＢＮ粒子を最初に吸着させた後、粒径の小さな第２のＢＮ粒子を吸着させることで、第１のＢＮ粒子の間を第２のＢＮ粒子で隙間なく吸着することができる。 In the present invention, first, the first BN particles charged in the electrolyte polymer aqueous solution are dispersed, and the SiC having an opposite charge to the first BN particles in the aqueous electrolyte polymer solution containing the charged first BN particles. By immersing the fibers, the first BN particles are adsorbed to the SiC fibers. This utilizes the adsorption phenomenon by the difference in surface charge. Next, the second BN particles having the opposite charge to the first BN particles are dispersed in the aqueous electrolyte polymer solution, and the SiC fibers to which the first BN particles are attached are immersed. By repeating this operation usually 10 times or more, preferably 20 times or more, it is possible to form a SiC fiber in which BN particles are closely adsorbed on the surface of the SiC fiber. In the present invention, the first BN particles having a large particle size are first adsorbed, and then the second BN particles having a small particle size are adsorbed to form second BN particles between the first BN particles. It can be adsorbed without gaps.
なお、電解質ポリマーを溶解させる水系溶媒は、極性溶媒であれば水に限られず、例えば、メタノール、エタノールなどのアルコールであってもよい。
また、カチオンポリマー又はアニオンポリマーは前記溶媒に、通常０．１ｇ／ｌ以上１０ｇ／ｌ以下、好ましくは０．５ｇ／ｌ以上２ｇ／ｌ以下となるように溶解させる。
The aqueous solvent in which the electrolyte polymer is dissolved is not limited to water as long as it is a polar solvent, and may be, for example, an alcohol such as methanol or ethanol.
In addition, the cationic polymer or the anionic polymer is dissolved in the solvent to be usually 0.1 g / l or more and 10 g / l or less, preferably 0.5 g / l or more and 2 g / l or less.
このようにして得られるＢＮ被覆ＳｉＣ繊維は、厚みが通常０．０５μｍ以上５μｍ以下、好ましくは０．０５μｍ以上２μｍ以下である。厚みが５μｍを超えると、ＳｉＣ繊維の内部までＢＮ粒子が吸着せず、また、得られる複合体の重量が増加してしまうなど、取り扱い性に影響することがある。図３に示すように、本発明のＢＮ被覆ＳｉＣ繊維では、第１のＢＮ粒子の隙間を第２のＢＮ粒子が埋めるように付着している。 The thickness of the BN-coated SiC fiber obtained in this manner is generally 0.05 μm to 5 μm, preferably 0.05 μm to 2 μm. When the thickness exceeds 5 μm, the BN particles may not be adsorbed to the inside of the SiC fiber, and the weight of the obtained composite may increase, which may affect the handling property. As shown in FIG. 3, in the BN-coated SiC fiber of the present invention, the second BN particles adhere so as to fill the gaps of the first BN particles.
本発明のＢＮ被覆ＳｉＣ繊維の製造方法の具体例を挙げる。
帯電ＳｉＣ繊維の表面に、該帯電ＳｉＣ繊維とは反対の表面電荷を持つ帯電第１のＢＮ粒子を、静電気力による吸着現象を用いて吸着させる。次いで、第１のＢＮ粒子付着ＳｉＣ繊維を前記反対の表面電荷に帯電させ、前記帯電第１のＢＮ粒子とは反対の表面電荷を持つ帯電第２のＢＮ粒子を吸着させる。この時最初にＳｉＣ繊維を＋に帯電し、−に帯電した第１のＢＮ粒子を用いた場合は、第２のＢＮ粒子を吸着させる際には第１のＢＮ粒子付着ＳｉＣ繊維を−に帯電させ、＋に帯電させた第２のＢＮ粒子を用いる。その後、ＢＮ付着ＳｉＣ繊維を＋に帯電させ、−に帯電させた第２のＢＮ粒子を吸着させる。第２のＢＮ粒子を吸着させる操作を複数回、例えば合計して２０回程度繰り返して、緻密なＢＮ被覆を有するＳｉＣ繊維からなるＢＮ粒子付着ＳｉＣ繊維を作製する。
得られたＢＮ粒子付着ＳｉＣ繊維を、金網容器に入れた状態で液体ピッチ及びポリビニルブチラール（ＰＶＢ）樹脂の混合溶液に浸漬し、引き上げた後、余剰樹脂液を振り落とし、６０℃で乾燥させ、ＰＶＢ樹脂を固化させる。さらに、非酸化雰囲気下に１０００℃で熱処理を行うことで、ＢＮ被覆ＳｉＣ繊維を作製する。
The specific example of the manufacturing method of BN coating SiC fiber of this invention is given.
The charged first BN particles having a surface charge opposite to that of the charged SiC fiber are adsorbed onto the surface of the charged SiC fiber using an adsorption phenomenon by electrostatic force. Then, the first BN particle-attached SiC fiber is charged to the opposite surface charge, and the charged second BN particles having the opposite surface charge to the first charged BN particles are adsorbed. At this time, in the case where the first BN particles, in which the SiC fiber is charged first to + and is charged to-, are used to adsorb the second BN particles, the first BN particle-adhered SiC fiber is charged to-. And use the second BN particles charged to +. Thereafter, the BN-adhered SiC fiber is positively charged, and the negatively charged second BN particles are adsorbed. The operation of adsorbing the second BN particles is repeated a plurality of times, for example, about 20 times in total, to produce BN particle-adhered SiC fibers composed of SiC fibers having a dense BN coating.
The obtained BN particle-adhered SiC fiber is immersed in a mixed solution of liquid pitch and polyvinyl butyral (PVB) resin in a state of being placed in a wire mesh container, pulled up, shaken off excess resin solution, and dried at 60 ° C. Solidify the PVB resin. Furthermore, BN coated SiC fibers are produced by heat treatment at 1000 ° C. in a non-oxidizing atmosphere.
本発明のＳｉＣ繊維強化ＳｉＣ複合材は、上記ＢＮ被覆ＳｉＣ繊維を織ったＢＮ被覆ＳｉＣ繊維織物を複数積層させた構造を有する。強度の観点から、具体的には、前記ＳｉＣ繊維強化ＳｉＣ複合材は、ＢＮ被覆ＳｉＣ繊維が体積率で３０ｖｏｌ％以上５０ｖｏｌ％以下になるように積層させるのが好ましい。 The SiC fiber reinforced SiC composite material of the present invention has a structure in which a plurality of BN coated SiC fiber woven fabrics in which the above-mentioned BN coated SiC fibers are woven are laminated. From the viewpoint of strength, specifically, the SiC fiber-reinforced SiC composite material is preferably laminated so that the BN-coated SiC fiber is 30 vol% or more and 50 vol% or less in volume ratio.
以下、本発明をＳｉＣ繊維織物を用いた実施例に基づいて具体的に説明するが、本発明は、下記実施例により制限されるものではない。 Hereinafter, the present invention will be specifically described based on examples using a SiC fiber fabric, but the present invention is not limited by the following examples.
［実施例１］
（１）ＳｉＣ繊維織物及びＢＮ粒子の表面帯電処理
シート状のＳｉＣ繊維織物（宇部興産（株）製、ＳＡ８朱子織 ＳＡ８−Ｓ２０Ｉ１６ＰＸ、元糸１６００本 ／ ヤーン目付３００ｇ／ｍ2、繊維径７．５μｍ）を、カチオンポリマー水溶液（正電荷付与液）またはアニオンポリマー水溶液（負電荷付与液）に浸漬させてコーティングし、水洗いをして、該ＳｉＣ繊維織物の表面を帯電処理した。
Example 1
(1) Surface charging treatment of SiC fiber fabric and BN particles Sheet-like SiC fiber fabric (manufactured by Ube Industries, Ltd., SA8 satin weave SA8-S20I16PX, base yarn 1600 / filament weight 300 g / m 2 , fiber diameter 7. 5 μm) was dipped in a cationic polymer aqueous solution (positive charging solution) or an anionic polymer aqueous solution (negative charging solution) to be coated, washed with water, and the surface of the SiC fiber fabric was charged.
第１のＢＮ粒子（昭和電工（株）製、六方晶窒化ホウ素粉末ＵＨＰ−Ｓ２、粒径０．７μｍ）と第２のＢＮ粒子（（株）ＭＡＲＵＫＡ製、六方晶窒化ホウ素粉末 ＡＰ−１７０Ｓ、粒径０．０５μｍ）を、ＳｉＣ繊維織物と同様にして、カチオンポリマー水溶液またはアニオンポリマー水溶液で浸漬コーティングし、水洗いをすることで、第１のＢＮ粒子および第２のＢＮ粒子の表面を帯電処理した。
なお、正電荷付与液及び負電荷付与液に交互に浸漬させるため、最後に正電荷付与液に浸漬させた場合は、表面の極性はプラス（＋）となり、最後に負電荷付与液に浸漬させた場合は、表面の極性はマイナス（−）となる。
The first BN particles (manufactured by Showa Denko KK, hexagonal boron nitride powder UHP-S2, particle diameter 0.7 μm) and the second BN particles (manufactured by MARUKA, hexagonal boron nitride powder AP-170S, The particle diameter of 0.05 μm is dip-coated with an aqueous solution of cationic polymer or an aqueous solution of anionic polymer in the same manner as the SiC fiber fabric, and the surfaces of the first BN particles and the second BN particles are charged by washing with water. did.
In addition, in order to immerse alternately in the positive charge imparting solution and the negative charge imparting solution, when it is finally dipped in the positive charge imparting solution, the polarity of the surface becomes plus (+), and finally it is dipped in the negative charge imparting solution. In this case, the polarity of the surface is negative (-).
（２）得られた帯電ＳｉＣ繊維織物の表面に、該帯電ＳｉＣ繊維織物とは反対の表面電荷を持つ第１のＢＮ粒子（粒径０．７μｍ）を、静電気力による吸着現象を用いて吸着させた。すなわち、＋に帯電したＳｉＣ繊維織物を用いる場合は、−に帯電した第１のＢＮ粒子を吸着させ、−に帯電したＳｉＣ繊維織物を用いる場合は、＋に帯電した第１のＢＮ粒子を吸着させた。
次いで、第１のＢＮ粒子付着ＳｉＣ繊維織物を前記反対の表面電荷に帯電させ、前記帯電第１のＢＮ粒子とは反対の表面電荷を持つ帯電第２のＢＮ粒子を吸着させた。すなわち、最初にＳｉＣ繊維織物を＋に帯電し、−に帯電した第１のＢＮ粒子を用いた場合は、第２のＢＮ粒子を吸着させる際には第１のＢＮ粒子付着ＳｉＣ繊維を−に帯電させ、＋に帯電させた第２のＢＮ粒子を用いて吸着させた。その後、ＢＮ付着ＳｉＣ繊維織物を＋に帯電させ、−に帯電させた第２のＢＮ粒子を吸着させた。第２のＢＮ粒子を吸着させる操作を合計して２０回繰り返して、緻密なＢＮ被覆を有するＳｉＣ繊維からなるＢＮ粒子付着ＳｉＣ繊維織物を作製した。
(2) On the surface of the obtained charged SiC fiber fabric, the first BN particles (particle diameter 0.7 μm) having a surface charge opposite to that of the charged SiC fiber fabric are adsorbed using an adsorption phenomenon by electrostatic force I did. That is, when using a positively charged SiC fiber fabric, the first BN particles charged with-are adsorbed, and when using a negatively charged SiC fiber fabric, the first BN particles charged with + are adsorbed. I did.
Next, the first BN particle-adhered SiC fiber fabric was charged to the opposite surface charge, and the charged second BN particles having the opposite surface charge to the first charged BN particles were adsorbed. That is, in the case where the first BN particles charged first to the SiC fiber woven fabric to + and then to − are used, when adsorbing the second BN particles, the first BN particle-adhered SiC fiber is The charged and adsorbed second BN particles were used for adsorption. Thereafter, the BN-bonded SiC fiber fabric was charged to +, and the second charged BN particles were adsorbed. The operation of adsorbing the second BN particles was repeated a total of 20 times to produce a BN particle-adhered SiC fiber fabric composed of SiC fibers having a dense BN coating.
得られたＢＮ粒子付着ＳｉＣ繊維織物を、金網容器に入れた状態で液体ピッチ及びポリビニルブチラール（ＰＶＢ）樹脂の混合溶液に浸漬し、引き上げた後、余剰樹脂液を振り落とし、６０℃で乾燥させ、ＰＶＢ樹脂を固化させた。さらに、非酸化雰囲気下に１０００℃で熱処理を行い、ＢＮ被覆ＳｉＣ繊維織物を作製した。 The obtained BN particle-adhered SiC fiber fabric is immersed in a mixed solution of liquid pitch and polyvinyl butyral (PVB) resin in a state of being placed in a wire mesh container, pulled up, shaken off excess resin solution, and dried at 60 ° C. , And solidified the PVB resin. Furthermore, heat treatment was performed at 1000 ° C. in a non-oxidizing atmosphere to produce a BN-coated SiC fiber fabric.
１ ＳｉＣ繊維
２ 第１のＢＮ粒子
２’ 第２のＢＮ粒子
３ 電解質ポリマー
1
Claims (4)
前記第１のＢＮ粒子の粒径が、前記ＳｉＣ繊維の繊維径の１／１０以下であり、
前記第２のＢＮ粒子の粒径が、前記第１のＢＮ粒子の粒径の１／１０以下である、
ことを特徴とするＢＮ被覆ＳｉＣ繊維。 SiC fiber, and a first BN particle and a second BN particle covering the surface of the SiC fiber,
The particle diameter of the first BN particles is 1/10 or less of the fiber diameter of the SiC fiber,
The particle size of the second BN particles is 1/10 or less of the particle size of the first BN particles,
BN coated SiC fiber characterized by
正又は負に帯電したＳｉＣ繊維の表面に、該ＳｉＣ繊維とは反対の電荷に帯電した第１のＢＮ粒子を吸着させる工程１と、
第１のＢＮ粒子が吸着したＳｉＣ繊維を加熱処理して、第１のＢＮ粒子付着ＳｉＣ繊維を得る工程２と、
前記第１のＢＮ付着ＳｉＣ繊維の表面に、前記第１のＢＮ粒子とは反対の電荷に帯電した第２のＢＮ粒子を吸着させ、その後、正及び負に帯電した第２のＢＮ粒子を正負を交互に吸着させてＢＮ被覆ＳｉＣ繊維を得る工程３とを有する、請求項２に記載のＢＮ被覆ＳｉＣ繊維の製造方法。 Said process is
Adsorbing first BN particles charged to the opposite charge side of the SiC fiber to the surface of the positively or negatively charged SiC fiber;
A heat treatment of the SiC fiber to which the first BN particles are adsorbed to obtain a first BN particle-adhered SiC fiber;
The second BN particles charged to the opposite charge to the first BN particles are adsorbed on the surface of the first BN-bonded SiC fiber, and then the second BN particles positively and negatively charged are positively or negatively Are alternately adsorbed to obtain BN-coated SiC fibers. 3. The method for producing BN-coated SiC fibers according to claim 2.
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