JP6900302B2 - Method for manufacturing BN-coated SiC fiber - Google Patents
Method for manufacturing BN-coated SiC fiber Download PDFInfo
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- JP6900302B2 JP6900302B2 JP2017213726A JP2017213726A JP6900302B2 JP 6900302 B2 JP6900302 B2 JP 6900302B2 JP 2017213726 A JP2017213726 A JP 2017213726A JP 2017213726 A JP2017213726 A JP 2017213726A JP 6900302 B2 JP6900302 B2 JP 6900302B2
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- 239000000835 fiber Substances 0.000 title claims description 112
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 title description 8
- 239000002245 particle Substances 0.000 claims description 70
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 97
- 229910010271 silicon carbide Inorganic materials 0.000 description 96
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 84
- 229910052582 BN Inorganic materials 0.000 description 81
- 239000002759 woven fabric Substances 0.000 description 21
- 239000010410 layer Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 11
- 229920006318 anionic polymer Polymers 0.000 description 10
- 229920006317 cationic polymer Polymers 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 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
- 239000002131 composite material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 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
- 239000002184 metal Substances 0.000 description 3
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 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
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003475 lamination Methods 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000007769 metal material Substances 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
- 239000003870 refractory metal Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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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 higher toughness than ordinary ceramics. It is beginning to be used. In particular, research on using ceramic materials such as silicon carbide fibers with high heat resistance for high temperature parts of jet engines has been actively conducted.
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), SiC, Si 3 N 4 or a non-oxide fiber-reinforced ceramic and a method of manufacturing the surface of the buffer layer to impart a high melting point metal layer made of BN or the like Are listed. In this technique, an intermediate layer such as a carbon layer or a BN buffer layer is formed between a non-oxide ceramic fiber and a refractory metal layer by a chemical vapor deposition (CVD) method or the like. However, in the dense intermediate layer, there is a problem that during manufacturing or use, stress due to the difference in thermal expansion between the metal layer and the fiber causes cracks in the intermediate layer and the metal layer, resulting in a decrease in toughness of the fiber reinforced ceramic material. there were. That is, such a fiber-reinforced ceramic material has a problem that it is excellent in rigidity but inferior in impact resistance. Further, in the case of constructing such a multilayer structure, in order to improve the impact resistance, there is a problem that the thickness of the fiber-reinforced ceramic material must be increased and the weight increases.
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 a SiC fiber-reinforced SiC composite material having high fracture energy and a method for producing the same, in view of the above-mentioned problems of the prior art.
本発明のＢＮ被覆ＳｉＣ繊維の製造方法は、ＳｉＣ繊維と、前記ＳｉＣ繊維の表面を被覆するＢＮ粒子とからなり、前記ＢＮ粒子の粒径が、前記ＳｉＣ繊維の繊維径の１／１００以下であるＢＮ被覆ＳｉＣ繊維の製造方法であって、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粒径が０．０５μｍ以上０．８μｍ以下のＢＮ粒子を吸着させる工程１と、ＢＮ粒子が吸着したＳｉＣ繊維の表面に前記ＢＮ粒子とは反対の電荷に帯電したＢＮ粒子を吸着させ、その後、正及び負に帯電したＢＮ粒子を交互に吸着させ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、を有することを特徴とする。
The method for producing a BN-coated SiC fiber of the present invention comprises SiC fibers and BN particles that coat the surface of the SiC fibers, and the particle size of the BN particles is 1/100 or less of the fiber diameter of the SiC fibers. A method for producing a BN-coated SiC fiber, in which BN particles having a particle size of 0.05 μm or more and 0.8 μm or less charged with a charge opposite to that of the SiC fiber are formed on the surface of the positively or negatively charged SiC fiber. In step 1 of adsorbing, BN particles charged with a charge opposite to that of the BN particles are adsorbed on the surface of the SiC fiber on which the BN particles are adsorbed, and then positively and negatively charged BN particles are alternately adsorbed and adhered to the BN. It is characterized by having a
本発明によれば、ＳｉＣ繊維の繊維径よりも充分に小さい粒径を有する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, by adsorbing BN particles having a particle size sufficiently smaller than the fiber diameter of the SiC fiber on the surface of the SiC fiber, the BN particles can be densely adsorbed in the SiC fiber bundle, and the BN. A SiC fiber-reinforced SiC composite material having high fracture energy can be obtained by laminating a plurality of sheets woven from a SiC fiber bundle in which particles are adsorbed.
以下、本発明について、図面を参照しながら、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窒化ホウ素（ＢＮ）粒子とからなる。そして、ＢＮ粒子の粒径は、前記ＳｉＣ繊維の繊維径の１／２０以下、又は１／１００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ＢＮ粒子をＳｉＣ繊維表面へ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ＢＮ粒子を吸着させる工程１と、ＢＮ粒子が吸着したＳｉＣ繊維の表面に、前記ＢＮ粒子とは反対の電荷に帯電したＢＮ粒子を吸着させ、その後、正及び負に帯電したＢＮ粒子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 with reference to the drawings.
The BN-coated SiC fiber of the present invention comprises silicon carbide (SiC) fiber and boron nitride (BN) particles that coat the surface of the SiC fiber. The particle size of the BN particles is 1/20 or less or 1/100 or less of the fiber diameter of the SiC fiber.
The BN-coated SiC fiber can be produced by adsorbing BN particles on the surface of the SiC fiber using an adsorption phenomenon due to a difference in surface charge. Specifically, the method for producing the BN-coated SiC fiber includes a step 1 in which BN particles charged with a charge opposite to that of the SiC fiber are adsorbed on the surface of the positively or negatively charged SiC fiber, and the BN particles are formed.
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 the SiC fiber used as the BN-coated SiC fiber, a sheet-shaped woven fabric in which a SiC single fiber, a SiC fiber bundle, and a SiC fiber bundle are woven is used. There are no particular restrictions on the weaving method of the SiC fiber woven fabric, and any of plain weave, twill weave, satin weave, etc. may be used. Weave is preferable because it becomes dense. The fiber diameter of the SiC fiber is usually 5 μm or more and 20 μm or less, preferably 7 μm or more and 15 μm or less.
ＢＮは、常温常圧下で六方晶系の固体の化合物である。ＢＮ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。ＢＮの粒径が１／２０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。このような理由から、ＢＮの粒径は細かいほど好ましく、１／１００以下であることがより好ましい。具体的には、ＢＮの粒径は、０．０５μｍ以上２μｍ以下が好ましく、０．０５μｍ以上０．８μｍ以下がより好ましい。 BN is a hexagonal solid compound under normal temperature and pressure. The particle size of BN is preferably 1/20 or less of the fiber diameter of the SiC fiber. If the particle size of the BN exceeds 1/20, the BN particles cannot be densely adsorbed between the SiC fibers, and the fracture strength of the obtained composite material may not be sufficiently obtained. For this reason, the finer the particle size of the BN, the more preferable it is, and more preferably 1/100 or less. Specifically, the particle size of BN is preferably 0.05 μm or more and 2 μm or less, and more preferably 0.05 μm or more and 0.8 μm or less.
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ＢＮ粒子を吸着させる。この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 a BN-coated SiC fiber 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 immersing in a cationic polymer aqueous solution (positively charged liquid), and positively charged SiC fibers are charged with a negatively charged anionic polymer aqueous solution (negatively charged liquid). By immersing, an anionic polymer layer is formed to adsorb negatively charged BN particles, and then the BN particle-attached SiC fibers are immersed in a negatively charged anionic polymer aqueous solution (negatively charged liquid) to form an anionic polymer layer. The BN particles forming the cationic polymer layer are adsorbed by being negatively charged and immersed in a positively charged cationic polymer aqueous solution (positively charged liquid). By repeating this cycle, a coating layer in which BN particles are densely adsorbed can be formed on 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 the cationic polymer include vinylpyrrolidone-N, N-dimethylaminoethylmethacrylic acid copolymer sulfate solution, polydiallylmethylammonium chloride (PDDA), and the like. Of these, polydialylmethylammonium chloride (PDDA) and the like are preferable because of their water solubility.
Examples of the anionic polymer include an acrylic resin alkanolamine solution and polystyrene sulfonic acid (PSS). Of these, polystyrene sulfonic acid (PSS) and the like are preferable because they are easy to handle and have excellent water solubility.
本発明では、電解質ポリマー水溶液中に帯電処理したＢＮ粒子を添加し、該帯電ＢＮ粒子を含む電解質ポリマー水溶液中に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。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。 In the present invention, the charged BN particles are added to the aqueous electrolyte polymer solution, and the SiC fibers having a charge opposite to that of the BN particles are immersed in the aqueous electrolyte polymer solution containing the charged BN particles, whereby the BN particles are immersed in the SiC fibers. Is adsorbed. This utilizes the adsorption phenomenon due to the difference in surface charge. By repeating this operation 10 times or more, preferably 20 times or more, the SiC fiber in which the BN particles are densely adsorbed can be formed on the surface of the SiC fiber.
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 that dissolves the electrolyte polymer 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.
The cationic polymer or anionic polymer is usually dissolved in the solvent at 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、被覆の厚みが通常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、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ＢＮ被覆ＳｉＣ繊維の模式図を示す。 The BN-coated SiC fiber thus obtained has a coating thickness of usually 0.05 μm or more and 5 μm or less, preferably 0.05 μm or more and 2 μm or less. If the thickness exceeds 5 μm, the BN particles are not adsorbed to the inside of the SiC fiber, and the weight of the obtained complex increases, which may affect the handleability. FIG. 3 shows a schematic view of the BN-coated SiC fiber.
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、該帯電ＳｉＣ繊維を前記反対の表面電荷に帯電させ、前記帯電ＢＮ粒子とは反対の表面電荷を持つ帯電ＢＮ粒子を吸着させる。この時最初のＳｉＣ繊維を＋に帯電し、最初の吸着を−に帯電したＢＮ粒子を用いた場合は、次の吸着時はＳｉＣ繊維を−に帯電させ、＋に帯電させたＢＮ粒子を用いる。この操作を複数回、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付着ＳｉＣ繊維を作製する。
得られたＢＮ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繊維を得る。
Specific examples of the method for producing the BN-coated SiC fiber of the present invention will be given.
Charged BN particles having a surface charge opposite to that of the charged SiC fiber are adsorbed on the surface of the charged SiC fiber by using an adsorption phenomenon due to electrostatic force. Next, the charged SiC fiber is charged to the opposite surface charge, and the charged BN particles having a surface charge opposite to the charged BN particles are adsorbed. At this time, when the first SiC fiber is positively charged and the first adsorption is negatively charged BN particles, the SiC fiber is negatively charged and the positively charged BN particles are used at the next adsorption. .. This operation is repeated a plurality of times, for example, about 20 times in total to prepare a BN-attached SiC fiber composed of a SiC fiber having a dense BN coating.
The obtained BN-attached SiC fiber is immersed in a mixed solution of liquid pitch and polyvinyl butyral (PVB) resin in a wire mesh container, pulled up, shaken off of excess resin solution, dried at 60 ° C., and PVB. Solidify the resin. Further, a BN-coated SiC fiber is obtained by performing a 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 woven from the above-mentioned BN-coated SiC fibers are laminated. From the viewpoint of strength, specifically, the SiC fiber-reinforced SiC composite material is preferably laminated so that the BN-coated SiC fibers have a volume fraction of 30 vol% or more and 50 vol% or less.
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 an example using a SiC fiber woven fabric, but the present invention is not limited to 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、交互積層法（レイヤーバイレイヤー法）により、カチオンポリマー水溶液（正電荷付与液）及びアニオンポリマー水溶液（負電荷付与液）に交互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 charge treatment of SiC fiber woven fabric and BN particles Sheet-shaped SiC fiber woven fabric (manufactured by Ube Kosan Co., Ltd., SA8 Akiko weave SA8-S20I16PX, 1600 main yarns / 300 g / m 2 with yarn grain, fiber diameter 7. 5 μm) is alternately immersed in a cationic polymer aqueous solution (positive charge imparting solution) and an anionic polymer aqueous solution (negative charge imparting solution) by an alternating lamination method (layer-by-layer method) to coat the fibers, wash with water, and then wash the SiC. The surface of the textile fabric was charged.
ＢＮ粒子（（株）ＭＡＲＵＫＡ製、六方晶窒化ホウ素粉末 ＡＰ−１７０Ｓ、粒子径０．０５μｍ）を、ＳｉＣ繊維織物と同様にして、交互積層法（レイヤーバイレイヤー法）により、カチオンポリマー水溶液（正電荷付与液）及びアニオンポリマー水溶液（負電荷付与液）で浸漬コーティングし、水洗いをすることで、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。
BN particles (manufactured by MARUKA Co., Ltd., hexagonal boron nitride powder AP-170S, particle diameter 0.05 μm) are subjected to a cationic polymer aqueous solution (positive) by an alternating lamination method (layer-by-layer method) in the same manner as the SiC fiber woven fabric. The surface of the BN particles was charged by dipping coating with a charge-imparting solution) and an anionic polymer aqueous solution (negative charge-imparting solution) and washing with water.
Since it is alternately immersed in the positive charge-imparting liquid and the negative charge-imparting liquid, the surface polarity becomes positive (+) when it is immersed in the positive charge-imparting liquid at the end, and it is finally immersed in the negative charge-imparting liquid. If so, the polarity of the surface will be 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帯電ＢＮ粒子を、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ＢＮ粒子を吸着させた。
次いで、このＢＮ付着ＳｉＣ繊維織物を前回とは反対の表面電荷に帯電させ、該ＢＮ付着ＳｉＣ繊維織物とは反対の表面電荷を持つ帯電ＢＮ粒子を吸着させた。すなわち、先（１回目）の吸着を−の帯電ＳｉＣ繊維織物を用い、＋に帯電したＢＮ粒子を用いた場合は、今回（２回目）の吸着は、＋に帯電させたＢＮ付着ＳｉＣ繊維織物を用い、−に帯電したＢＮ粒子を用いて行った。この操作を合計して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付着ＳｉＣ繊維織物を作製した。
得られたＢＮ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℃で熱処理を行うことで、ＢＮ被覆ＳｉＣ繊維織物を得た。
(2) Charged BN particles having a surface charge opposite to that of the charged SiC fiber woven fabric were adsorbed on the surface of the obtained charged SiC fiber woven fabric by using an adsorption phenomenon due to electrostatic force. That is, when the + charged SiC fiber woven fabric was used, the negatively charged BN particles were adsorbed, and when the negatively charged SiC fiber woven fabric was used, the + charged BN particles were adsorbed.
Next, the BN-attached SiC fiber woven fabric was charged with a surface charge opposite to that of the previous time, and charged BN particles having a surface charge opposite to that of the BN-attached SiC fiber woven fabric were adsorbed. That is, when the previous (first) adsorption uses a negatively charged SiC fiber woven fabric and the + charged BN particles are used, the current (second) adsorption uses a + charged BN-attached SiC fiber woven fabric. Was used, and BN particles charged with − were used. This operation was repeated 20 times in total to prepare a BN-attached SiC fiber woven fabric composed of SiC fibers having a dense BN coating.
The obtained BN-attached SiC fiber woven fabric was immersed in a mixed solution of liquid pitch and polyvinyl butyral (PVB) resin in a wire mesh container, pulled up, and then the excess resin liquid was shaken off and dried at 60 ° C. The PVB resin was solidified. Further, a BN-coated SiC fiber woven fabric was obtained by performing a heat treatment at 1000 ° C. in a non-oxidizing atmosphere.
［実施例２］
実施例１において、ＢＮ付着ＳｉＣ繊維織物の表面に、帯電ＢＮ粒子を吸着させる操作を２０回ではなく、４１回繰り返したこと以外は、実施例１と同様にして、ＢＮ被覆ＳｉＣ繊維織物を作製した。
[Example 2]
In Example 1, a BN-coated SiC fiber woven fabric was produced in the same manner as in Example 1 except that the operation of adsorbing the charged BN particles on the surface of the BN-attached SiC fiber woven fabric was repeated 41 times instead of 20 times. did.
［比較例１］
実施例１において、粒径０．０５μｍのＢＮ粒子ではなく、粒径０．７μｍのＢＮ粒子（昭和電工（株）製、六方晶窒化ホウ素粉末 ＵＨＰ−Ｓ２）を使用したこと以外は、実施例１と同様にして、ＢＮ被覆ＳｉＣ繊維織物を作製した。
比較例１のＢＮ被覆ＳｉＣ繊維のＳＥＭ写真から、ＢＮ粒子の吸着を複数回繰り返しても隙間があることがわかった。
[Comparative Example 1]
In Example 1, BN particles having a particle size of 0.7 μm (Hexagonal boron nitride powder UHP-S2 manufactured by Showa Denko KK) were used instead of BN particles having a particle size of 0.05 μm. A BN-coated SiC fiber woven fabric was produced in the same manner as in Example 1.
From the SEM photograph of the BN-coated SiC fiber of Comparative Example 1, it was found that there was a gap even if the adsorption of the BN particles was repeated a plurality of times.
１ ＳｉＣ繊維
２ ＢＮ粒子
３ 電解質ポリマー
1
Claims (1)
前記ＢＮ粒子の粒径が、前記ＳｉＣ繊維の繊維径の１／１００以下であるＢＮ被覆ＳｉＣ繊維の製造方法であって、
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粒径が０．０５μｍ以上０．８μｍ以下のＢＮ粒子を吸着させる工程１と、
ＢＮ粒子が吸着したＳｉＣ繊維の表面に前記ＢＮ粒子とは反対の電荷に帯電したＢＮ粒子を吸着させ、その後、正及び負に帯電したＢＮ粒子を交互に吸着させ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、ＢＮ被覆ＳｉＣ繊維の製造方法。 It consists of SiC fibers and BN particles that coat the surface of the SiC fibers.
A method for producing a BN-coated SiC fiber, wherein the particle size of the BN particles is 1/100 or less of the fiber diameter of the SiC fiber.
Step 1 of adsorbing BN particles having a particle size of 0.05 μm or more and 0.8 μm or less charged on the surface of a positively or negatively charged SiC fiber with a charge opposite to that of the SiC fiber.
Step 2 in which BN particles charged with a charge opposite to that of the BN particles are adsorbed on the surface of the SiC fiber on which the BN particles are adsorbed, and then positively and negatively charged BN particles are alternately adsorbed to obtain a BN-attached SiC fiber. When,
Step 3 of heat-treating the BN-adhered SiC fiber to obtain a BN-coated SiC fiber.
A method for producing a BN-coated SiC fiber.
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