JP2019085291A - 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
- Publication number
- JP2019085291A JP2019085291A JP2017213726A JP2017213726A JP2019085291A JP 2019085291 A JP2019085291 A JP 2019085291A JP 2017213726 A JP2017213726 A JP 2017213726A JP 2017213726 A JP2017213726 A JP 2017213726A JP 2019085291 A JP2019085291 A JP 2019085291A
- Authority
- JP
- Japan
- Prior art keywords
- sic
- sic fiber
- particles
- fiber
- coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 150
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 85
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000010030 laminating Methods 0.000 abstract description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 abstract 2
- 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
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 88
- 229910052582 BN Inorganic materials 0.000 description 85
- 239000004744 fabric Substances 0.000 description 20
- 239000010410 layer Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 13
- 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 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 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
- 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
- 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
- 239000002759 woven fabric Substances 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
- 238000003618 dip coating Methods 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
- 238000009941 weaving Methods 0.000 description 1
Images
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
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１／２０以下であることを特徴とする。
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以下であることを特徴とする。
The BN-coated SiC fiber of the present invention comprises a SiC fiber and BN particles covering the surface of the SiC fiber, and the particle diameter of the BN particle is 1/20 or less of the fiber diameter of the SiC fiber. It features.
The BN-coated SiC fiber of the present invention comprises SiC fiber and BN particles coating the surface of the SiC fiber, and the particle diameter of the BN particle is 1/100 or less of the fiber diameter of the SiC fiber. It features.
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、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 diameter 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 By laminating a plurality of sheets obtained by weaving the SiC fiber bundle in which the particles are adsorbed, it is possible to obtain a SiC fiber reinforced SiC composite material having high fracture energy.
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 coating the surface of the SiC fiber. And the particle size of BN particle | grains is 1/20 or less of the fiber diameter of the said SiC fiber, or 1/100 or less.
The BN-coated SiC fiber can be manufactured by adsorbing BN particles to the surface of a SiC fiber using an adsorption phenomenon due to the difference in surface charge. Specifically, in the method for producing a BN-coated SiC fiber, the
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。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 compound of a hexagonal solid at normal temperature and pressure. The particle size of BN is preferably 1/20 or less of the fiber diameter of the SiC fiber. When the particle size of BN exceeds 1/20, BN particles can not be closely adsorbed between fibers of SiC fibers, and the fracture strength of the resulting composite material may not be sufficiently obtained. For these reasons, the particle size of BN is preferably as fine as possible, and more preferably 1/100 or less. Specifically, the particle diameter 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 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 negatively charged BN particles, and then an anionic polymer layer is formed by immersing BN particle-attached SiC fibers in an anionic polymer aqueous solution (negative charge application liquid) having a negative charge. The BN particles having the cationic polymer layer formed thereon are adsorbed by being negatively charged and immersed in an aqueous cationic polymer solution (positive charge imparting solution) having a positive charge. By repeating this cycle, it is possible to form a coating layer in which 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、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, BN particles are added to the electrolyte polymer aqueous solution, and the BN particles are added to the SiC fiber by immersing the SiC fiber having the opposite charge to the BN particles in the electrolyte polymer aqueous solution containing the charged BN particles. Is adsorbed. This utilizes the adsorption phenomenon by the difference in surface charge. 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.
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、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 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. FIG. 3 shows a schematic view of 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。
The specific example of the manufacturing method of BN coating SiC fiber of this invention is given.
Charged 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 charged SiC fiber is charged to the opposite surface charge to adsorb charged BN particles having the opposite surface charge to the charged BN particles. At this time, when the first SiC fiber is positively charged and the first adsorption is negatively charged BN particles, the next adsorption is performed by using the positively charged BN particles. . This operation is repeated a plurality of times, for example, about 20 times in total, to produce a BN-bonded SiC fiber made of a SiC fiber having a dense BN coating.
The obtained BN-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, dried at 60 ° C., PVB Solidify the resin. Furthermore, BN-coated SiC fibers are obtained 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 has a volume ratio 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 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、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 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) is alternately dipped and coated in a cationic polymer aqueous solution (positive charge application liquid) and an anionic polymer aqueous solution (negative charge application liquid) by a layer-by-layer method (layer-by-layer method) and washed with water, The surface of the fiber 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 (hexagonal boron nitride powder AP-170S, particle diameter 0.05 μm, manufactured by MARUKA) are treated in the same manner as in a SiC fiber fabric, using a cationic polymer aqueous solution (positive by a layer-by-layer method) The surface of the BN particles was charge-treated by dip coating with a charge imparting solution) and an anionic polymer aqueous solution (negative charge imparting solution) and washing with water.
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) On the surface of the obtained charged SiC fiber fabric, charged BN particles having a surface charge opposite to that of the charged SiC fiber fabric were adsorbed using an adsorption phenomenon by electrostatic force. That is, when using a positively charged SiC fiber fabric, the negatively charged BN particles are adsorbed, and when using a negatively charged SiC fiber fabric, the positively charged BN particles are adsorbed.
Next, the BN-bonded SiC fiber fabric was charged to the surface charge opposite to the previous one, and charged BN particles having the surface charge opposite to the BN-bonded SiC fiber fabric were adsorbed. That is, when the first (first) adsorption is performed using-charged SiC fiber fabric and + charged BN particles are used, the current (second) adsorption is + charged BN attached SiC fiber fabric , And was carried out using BN particles charged to-. This operation was repeated 20 times in total to produce a BN-bonded SiC fiber fabric composed of SiC fibers having a dense BN coating.
The obtained BN-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. The PVB resin was allowed to solidify. Furthermore, heat treatment was performed at 1000 ° C. in a non-oxidizing atmosphere to obtain a BN-coated SiC fiber fabric.
［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 fabric is produced in the same manner as in Example 1, except that the operation of adsorbing charged BN particles on the surface of BN-bonded SiC fiber fabric is repeated not 20 times but 41 times. did.
［比較例１］
実施例１において、粒径０．３５μｍ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
Example 1 except that BN particles with a particle diameter of 0.7 μm (hexagonal boron nitride powder UHP-S2 manufactured by Showa Denko KK) were used instead of BN particles with a particle diameter of 0.35 μm in Example 1. Similar to 1, a BN coated SiC fiber fabric was produced.
From the SEM photograph of the BN-coated SiC fiber of Comparative Example 1, it was found that even when the adsorption of BN particles was repeated multiple times, there were gaps.
１ ＳｉＣ繊維
２ ＢＮ粒子
３ 電解質ポリマー
1
Claims (5)
前記ＢＮ粒子の粒径が、前記ＳｉＣ繊維の繊維径の１／２０以下であることを特徴とするＢＮ被覆ＳｉＣ繊維。 SiC fiber and BN particles coating the surface of the SiC fiber,
A particle diameter of the BN particles is 1/20 or less of a fiber diameter of the SiC fibers, BN-coated SiC fibers.
前記ＢＮ粒子の粒径が、前記ＳｉＣ繊維の繊維径の１／１００以下であることを特徴とするＢＮ被覆ＳｉＣ繊維。 SiC fiber and BN particles coating the surface of the SiC fiber,
A particle diameter of the BN particles is 1/100 or less of a fiber diameter of the SiC fibers, BN-coated SiC fibers.
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、請求項３に記載のＢＮ被覆ＳｉＣ繊維の製造方法。 Said process is
A step 1 of adsorbing BN particles charged to the opposite charge to the SiC fiber on the surface of the positively or negatively charged SiC fiber;
BN particles charged to the opposite charge to the BN particles are adsorbed on the surface of the SiC fibers to which BN particles are adsorbed, and then, positively and negatively charged BN particles are adsorbed alternately to obtain BN-bonded SiC fibers When,
4. A method of producing BN-coated SiC fiber according to claim 3, further comprising the step 3 of heat-treating the BN-deposited SiC fiber to obtain BN-coated SiC fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017213726A JP6900302B2 (en) | 2017-11-06 | 2017-11-06 | Method for manufacturing BN-coated SiC fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017213726A JP6900302B2 (en) | 2017-11-06 | 2017-11-06 | Method for manufacturing BN-coated SiC fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2019085291A true JP2019085291A (en) | 2019-06-06 |
| JP6900302B2 JP6900302B2 (en) | 2021-07-07 |
Family
ID=66762270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017213726A Active JP6900302B2 (en) | 2017-11-06 | 2017-11-06 | Method for manufacturing BN-coated SiC fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6900302B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024090513A1 (en) * | 2022-10-26 | 2024-05-02 | 大日本印刷株式会社 | Particle-including base material, and production method for particle-including base material |
-
2017
- 2017-11-06 JP JP2017213726A patent/JP6900302B2/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024090513A1 (en) * | 2022-10-26 | 2024-05-02 | 大日本印刷株式会社 | Particle-including base material, and production method for particle-including base material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6900302B2 (en) | 2021-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109206146B (en) | Carbon fiber/nanofiber synergistic tough ceramic matrix composite and preparation method thereof | |
| JP5830471B2 (en) | Method for producing carbon nanotube-introduced fiber material including carbon nanotubes arranged in parallel | |
| US7867468B1 (en) | Multiscale carbon nanotube-fiber reinforcements for composites | |
| AU2010321534B2 (en) | Ceramic composite materials containing carbon nanotube-infused fiber materials and methods for production thereof | |
| CN105152671B (en) | SiCfThe interface modification method of/SiC ceramic matrix composite material | |
| JP6774863B2 (en) | Manufacturing method of ceramic-based composite material | |
| JP6490915B2 (en) | Tubular body and manufacturing method thereof | |
| JP2019085291A (en) | BN COATED SiC FIBER AND MANUFACTURING METHOD THEREFOR, SiC FIBER REINFORCED SiC COMPOSITE MATERIAL USING BN COATED SiC FIBER | |
| Ishikawa | Ceramic fibers and their applications | |
| WO2011114810A1 (en) | Inorganic fibers for fiber bundles, process for production of the inorganic fibers, inorganic fiber bundles for composite material produced using the inorganic fibers, and ceramic-based composite material reinforced by the fiber bundles | |
| EP3061604B1 (en) | Conformal composite coatings | |
| US11220465B2 (en) | Method for producing SiC/SiC composite material | |
| JP2007015901A (en) | Manufacture of sic/sic composite material of high thermal conductivity using carbon nanotube or nanofiber | |
| JP2019085292A (en) | BN COATED SiC FIBER AND MANUFACTURING METHOD THEREFOR, SiC FIBER REINFORCED SiC COMPOSITE MATERIAL USING BN COATED SiC FIBER | |
| JPWO2010143608A1 (en) | COMPOSITE INORGANIC FIBER AND METHOD FOR PRODUCING SAME, AND COMPOSITE INORGANIC FIBER PRODUCT AND METHOD FOR PRODUCING SAME | |
| WO2015016072A1 (en) | Ceramic composite material and production method for ceramic composite material | |
| JP7085388B2 (en) | Method for manufacturing SiC fiber reinforced SiC composite material | |
| JP6122728B2 (en) | SiC fiber reinforced SiC composite material and method for producing SiC fiber reinforced SiC composite material | |
| JP2021191720A (en) | Manufacturing method of sic/sic composite material | |
| JP5668550B2 (en) | Inorganic fiber for fiber bundle, inorganic fiber bundle for composite material composed of inorganic fiber for fiber bundle, and ceramic matrix composite material reinforced with fiber bundle | |
| JP5668575B2 (en) | Inorganic fiber for fiber bundle, inorganic fiber bundle for composite material composed of inorganic fiber for fiber bundle, and ceramic matrix composite material reinforced with fiber bundle | |
| US20230192556A1 (en) | Introduction of metallic particles to enable formation of metallic carbides in a matrix | |
| US20170314587A1 (en) | Fluid flow straightening member | |
| JP7473406B2 (en) | Manufacturing method of SiC/SiC composite material | |
| JP7343360B2 (en) | Ceramic composite material and its manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20191226 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20201127 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20201222 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210120 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20210615 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210616 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6900302 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |