JP5769519B2 - Fiber material for reinforcement, fiber-reinforced ceramic composite material using fiber material for reinforcement, and method for producing the same - Google Patents
Fiber material for reinforcement, fiber-reinforced ceramic composite material using fiber material for reinforcement, and method for producing the same Download PDFInfo
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Description
本発明は、軽量かつ高強度であり、特にブレーキ部材用などの構造部材として好適である強化用繊維材料と強化用繊維材料を用いた繊維強化セラミックス複合材料及びこれらの製造方法に関する。 The present invention relates to a reinforcing fiber material that is lightweight and has high strength, and is particularly suitable as a structural member for a brake member, a fiber-reinforced ceramic composite material using the reinforcing fiber material, and a method for manufacturing the same.
炭化ケイ素等のセラミックス材料は、金属材料に比べて軽量かつ高温耐食性、耐摩耗性に優れているが、破壊靭性が十分でない。そこで、これらの特性を向上させたものとして、例えば、短繊維と呼ばれる形態の繊維を用いた繊維強化セラミックス材料がある。 Ceramic materials such as silicon carbide are lighter in weight and superior in high-temperature corrosion resistance and wear resistance than metal materials, but their fracture toughness is not sufficient. Therefore, as an example of improving these characteristics, there is a fiber reinforced ceramic material using fibers in a form called short fibers.
炭素繊維強化ＳｉＣセラミックスでは、その繊維−マトリックス界面にすべり層を形成させることで、繊維の引き抜きを導いていることが多く、おもにＳｉＣ繊維強化ＳｉＣコンポジットにおいて、カーボン層やＢＮ層をＣＶＤ法で形成する研究が進んでいる。 Carbon fiber reinforced SiC ceramics often lead to fiber extraction by forming a slip layer at the fiber-matrix interface. Mainly, carbon fiber and BN layers are formed by CVD in SiC fiber reinforced SiC composites. Research is underway.
一例として、特許文献１には、繊維プリフォームにＳｉＣ又はＣコーティング層を直接形成することにより、ＳｉＣ又はＣ繊維／ＳｉＣマトリックスの界面に層間剥離のないＳｉＣ又はＣ繊維／ＳｉＣ複合材料を得ることを目的として、反応器に収容されたＳｉＣ又はＣ繊維プリフォームの反応ガス供給側と排気側とを同じ一定圧力に維持し、最大流量３００ｃｃ／分でメタン、エタン、プロパン等の炭化水素ガスを供給しながら、圧力１５ｋＰａ以下、最高反応温度１１００℃の条件下で炭化水素ガスを熱分解し、熱分解生成物であるＣをＳｉＣ又はＣ繊維の周りに析出させる、という技術が開示されている。 As an example, Patent Document 1 discloses that a SiC or C fiber / SiC composite material having no delamination at the interface of a SiC or C fiber / SiC matrix is obtained by directly forming a SiC or C coating layer on a fiber preform. For the purpose of the above, the reaction gas supply side and the exhaust side of the SiC or C fiber preform contained in the reactor are maintained at the same constant pressure, and hydrocarbon gas such as methane, ethane, propane, etc. is supplied at a maximum flow rate of 300 cc / min. A technique is disclosed in which a hydrocarbon gas is thermally decomposed under conditions of a pressure of 15 kPa or less and a maximum reaction temperature of 1100 ° C. while supplying, and C, which is a pyrolysis product, is precipitated around SiC or C fibers. .
また、一例として、特許文献２には、炭素繊維で構造材を強化する技術思想の例として、マトリックスが炭素繊維の繊維束の内部がピッチの炭化された炭素から主としてなり、繊維束と繊維束との間はガラス状炭素を含む炭素からなる炭素繊維／炭素複合材、という技術が開示されている。 As an example, Patent Document 2 discloses, as an example of a technical idea for reinforcing a structural material with carbon fibers, a matrix mainly composed of carbon in which carbon fiber fiber bundles are pitch carbonized, and the fiber bundles and fiber bundles. Discloses a technique of carbon fiber / carbon composite made of carbon including glassy carbon.
また、一例として、特許文献３には、高温、または腐食摩耗性環境で強度と靭性を必要とされる機械構造部品を対象とした繊維強化セラミックスの例として、成形体の空隙中にセラミックス前駆体を含浸させ、その含浸させたセラミックス前駆体をセラミックスとしたのち、全体を焼結することで、空隙率がほぼ０となり、緻密化の際のセラミック短繊維の損傷がほとんどなくなる、という技術が開示されている。 As an example, Patent Document 3 discloses, as an example of fiber reinforced ceramics for mechanical structural parts that require strength and toughness in a high temperature or corrosive wear environment, a ceramic precursor in a void of a molded body. Disclosed is a technology in which the ceramic precursor is impregnated and the entire ceramic is sintered, and then the whole is sintered, so that the porosity becomes almost zero and the ceramic short fiber is hardly damaged during densification. Has been.
また、一例として、特許文献４には、引張強度の高い炭素繊維強化ＳｉＣ系複合材の例として、炭素繊維強化複合材の炭素繊維がピッチ系炭素繊維の短繊維であり、該ピッチ系炭素短繊維が該炭素繊維強化ＳｉＣ系複合中において二次元ランダムに配向している、という技術について開示にされている。 As an example, in Patent Document 4, as an example of a carbon fiber reinforced SiC composite material having high tensile strength, the carbon fiber of the carbon fiber reinforced composite material is a short fiber of pitch carbon fiber, and the pitch carbon short A technique is disclosed in which fibers are oriented two-dimensionally randomly in the carbon fiber-reinforced SiC composite.
例えば特許文献１では、炭素繊維でプリフォームを形成した後にＣＶＤ法によってすべり層を形成している。この方法は、あらかじめＣＶＤ法により繊維へすべり層を形成し、プリフォームを形成するよりも生産性の向上やコストの低減を見込めるが、コストが十分に低減されているとはいえない。また、プリフォームの表層近くと内部との成膜厚さに違いが出やすいなど、製造上の問題がある。さらに、炭素などのコーティングが不十分である場合、破壊エネルギーが向上しない。 For example, in patent document 1, after forming a preform with carbon fiber, the slip layer is formed by CVD method. This method can be expected to improve productivity and reduce costs more than forming a slip layer on the fiber by CVD in advance and forming a preform, but it cannot be said that the cost is sufficiently reduced. In addition, there is a manufacturing problem such as a difference in film thickness between the surface layer of the preform and the inside. Furthermore, if the coating of carbon or the like is insufficient, the fracture energy is not improved.
また、例えば、特許文献２では、炭素繊維成形体にマトリックス原料を複数回炭化処理する際、マトリックス原料を初回はピッチを用いて、２回目以降の少なくとも１回は熱硬化性樹脂を用いて炭素繊維／炭素複合材を形成している。この方法は、Ｃ／Ｃ複合材の強度の向上は見込めるが、Ｃ／ＳｉＣ複合材のマトリックスはＳｉＣ、繊維はＣという構成を作製する方法としてはマトリックス、繊維の周囲共に炭素分で充填されるため、不適格である。 In addition, for example, in Patent Document 2, when carbonizing a matrix raw material a plurality of times on a carbon fiber molded body, the matrix raw material is carbon using a pitch at the first time and a thermosetting resin at least once after the second time. A fiber / carbon composite is formed. Although this method is expected to improve the strength of the C / C composite, the matrix of the C / SiC composite is made of SiC and the fiber is made of C. The matrix and the fiber are both filled with carbon. Therefore, it is ineligible.
また、例えば、特許文献３では、繊維強化セラミックスを緻密化させるために、液状のセラミックス前駆体をセラミック単繊維とセラミック粉とを混合し、成形した成形体に含浸させている。この方法は、セラミック繊維へのダメージは少ないが、繊維束の周りにはすべり層となるコーティングが別途必要であり、繊維強化セラミックスの破壊エネルギー向上のためには必ずしも十分とはいえない。また、複数回の処理が不可欠であり、高価な設備及び原料コストがかかる。 Further, for example, in Patent Document 3, in order to densify the fiber-reinforced ceramic, a liquid ceramic precursor is mixed with ceramic single fibers and ceramic powder and impregnated into a molded body. This method causes little damage to the ceramic fibers, but requires a separate coating as a slip layer around the fiber bundle, and is not necessarily sufficient for improving the fracture energy of the fiber reinforced ceramics. In addition, multiple treatments are indispensable, and expensive equipment and raw material costs are required.
また、例えば、特許文献４では、引張強度を向上させるため、ピッチ系炭素繊維が二次元ランダムに配向したシートを積層して用いている。この方法では、ピッチの炭素繊維に対する含浸及び炭化プロセスを複数回行う必要があり、簡便に炭素繊維強化ＳｉＣ系複合材を形成することができなかった。また、炭素繊維以外のマトリックス部分にも炭素が残存してしまうため、ＳｉＣマトリックスのもつ、耐酸化性、高い強度を十分に生かせる方法とはいえなかった。 For example, in patent document 4, in order to improve tensile strength, the sheet | seat in which the pitch-type carbon fiber orientated at random two-dimensionally is laminated | stacked and used. In this method, it is necessary to perform the impregnation and carbonization process of the pitch carbon fiber a plurality of times, and it has not been possible to easily form a carbon fiber-reinforced SiC composite material. Further, since carbon remains in the matrix portion other than the carbon fiber, it cannot be said that the method can sufficiently utilize the oxidation resistance and high strength of the SiC matrix.
一方、これまで、セラミックスの破壊エネルギーを向上させ、脆性を克服するため、単体の繊維表面へのすべり層のコーティングが研究されていた。すべり層の形成にはＣＶＤ法などが用いられ、すべり層形成用の設備導入が必要であること、すべり層の形成に時間がかかることなどから、生産性、コストの面で問題があった。 On the other hand, in order to improve the fracture energy of ceramics and overcome brittleness, coating of a slip layer on a single fiber surface has been studied. A CVD method or the like is used for forming the slip layer, and it is necessary to introduce equipment for forming the slip layer, and it takes time to form the slip layer.
本発明は、かかる事情に鑑みてなされたものであり、すべり層形成用の設備を簡略化し、かつ、すべり層の形成を短時間で行う生産性の向上及びコストの低減を図った強化用繊維材料と強化用繊維材料を用いた繊維強化セラミックス複合材料及びこれらの製造方法を提供することである。 The present invention has been made in view of such circumstances, and a reinforcing fiber that simplifies equipment for forming a sliding layer and improves productivity and reduces cost by forming the sliding layer in a short time. It is to provide a fiber reinforced ceramic composite material using a material and a reinforcing fiber material and a method for producing the same.
また、本発明は、かかる事情に鑑みてなされたものであり、炭素繊維束を多層の異なる炭素組織で充填し、炭素繊維束に界面を形成することにより高いすべり効果を炭素繊維束の内部、及び外周部分に付与し、強化用繊維材料の破壊エネルギーを向上させる強化用繊維材料と強化用繊維材料を用いた繊維強化セラミックス複合材料及びこれらの製造方法を提供することである。 Further, the present invention has been made in view of such circumstances, filling the carbon fiber bundle with different carbon structures of multiple layers, forming a high slip effect by forming an interface in the carbon fiber bundle, the inside of the carbon fiber bundle, And a fiber reinforced ceramic composite material using the reinforcing fiber material and the reinforcing fiber material which are applied to the outer peripheral portion to improve the breaking energy of the reinforcing fiber material, and a method for producing the same.
本発明の一実施形態に係る強化用繊維材料は、炭素を含む複数本の繊維束と、前記繊維束の表層の繊維間に形成され、層状構造の炭素からなる層状構造炭素組織と、前記層状構造炭素組織の内部を充填するように形成され、樹脂を含有し、等方性の組織構造を有する炭素からなる樹脂由来炭素組織と、前記層状構造炭素組織と前記樹脂由来炭素組織との間に存在する少なくとも一つ
の界面と、を備えることを特徴とする。
A reinforcing fiber material according to an embodiment of the present invention includes a plurality of fiber bundles containing carbon, a layered structure carbon structure formed of carbon having a layered structure formed between fibers of a surface layer of the fiber bundle, and the layered structure. is formed so as to fill the interior of the structure carbon tissue, between the containing resin, and a resin-derived carbon structure consisting of carbon that have a tissue structure isotropic, the resin derived carbon tissue and the layered structure of carbon tissue And at least one interface.
前記繊維束は、さらにセラミックスを含んでもよい。 The fiber bundle may further include ceramics.
前記層状構造炭素組織は、前記繊維束の表層から前記界面までの距離が５μｍ以上２００μｍ以下の範囲であってもよい。
Said layered structure carbon tissue, the distance from the surface of the front Ki繊維束to said interface may be a 200μm below the range of 5 [mu] m.
前記層状構造炭素組織は、異方性の構造を有する炭素であり、前記樹脂由来炭素組織は、等方性の構造を有する炭素であってもよい。 The layered structure carbon structure may be carbon having an anisotropic structure, and the resin-derived carbon structure may be carbon having an isotropic structure.
前記層状構造炭素組織は、黒鉛質であってもよい。 The layered structure carbon structure may be graphitic.
本発明の一実施形態に係る繊維強化セラミックス複合材料は、前記強化用繊維材料を、セラミックスのマトリックス中に配したことを特徴とする。 The fiber-reinforced ceramic composite material according to an embodiment of the present invention is characterized in that the reinforcing fiber material is arranged in a ceramic matrix.
本発明の一実施形態に係る強化用繊維材料の製造方法は、炭素を含む複数本の繊維束と樹脂とピッチ及び／またはメソフェーズピッチとを溶媒を用いて混合し炭化処理して炭素繊維束を形成し、前記炭素繊維束を樹脂と溶媒との第１の混合液に含浸させて含浸処理し、さらに、前記炭素繊維束を樹脂と溶媒との第２の混合液に含浸させて含浸処理することを特徴とする。
Method for producing a reinforcing fiber material according to one embodiment of the present invention, the carbon fiber bundles are mixed with carbonized using a solvent and a plurality of fiber bundles and tree fat and pitch and / or mesophase pitch containing carbon And impregnating the carbon fiber bundle with a first mixed liquid of a resin and a solvent, and impregnating the carbon fiber bundle with a second mixed liquid of the resin and a solvent. It is characterized by doing.
前記炭素繊維束を形成するための混合時には、溶媒分の揮発を促すことや、ピッチの溶融を目的に、加熱または減圧してもよい。 At the time of mixing for forming the carbon fiber bundle, heating or decompression may be performed for the purpose of promoting volatilization of the solvent component or melting the pitch.
前記第１の混合液及び前記第２の混合液を含浸する方法としては、加圧含浸又は減圧含浸を用いてもよい。 As a method of impregnating the first mixed liquid and the second mixed liquid, pressure impregnation or reduced pressure impregnation may be used.
前記第１の混合液及び前記第２の混合液は、同じ溶質及び溶媒からなり、前記第１の混合液及び前記第２の混合液の濃度は、同一または異なってもよい。
The first mixed solution and the second mixed solution are composed of the same solute and solvent , and the concentrations of the first mixed solution and the second mixed solution may be the same or different.
前記溶媒は、水または有機溶媒であってもよい。 The solvent may be water or an organic solvent.
本発明の一実施形態に係る繊維強化セラミックス複合材料の製造方法は、前記強化用繊維材料を、前記強化用繊維材料中の炭素繊維の体積含有率が１０％以上６０％以下になるようにセラミックス材料中に混合することを特徴とする。 In the method for manufacturing a fiber-reinforced ceramic composite material according to an embodiment of the present invention, the reinforcing fiber material is ceramics so that the volume content of carbon fibers in the reinforcing fiber material is 10% or more and 60% or less. It is characterized by mixing in the material.
本発明によれば、すべり層形成用のＣＶＤ装置などの高価な設備を不要とし、かつ、すべり層の形成を短時間で大量に行う生産性の向上及びコストの低減を図った強化用繊維材料と強化用繊維材料を用いた繊維強化セラミックス複合材料及びこれらの製造方法を提供することができる。 According to the present invention, a reinforcing fiber material that eliminates the need for expensive equipment such as a CVD apparatus for forming a slip layer and improves productivity and reduces costs by forming a slip layer in a large amount in a short time. And a fiber-reinforced ceramic composite material using the reinforcing fiber material and a method for producing them.
本発明によれば、炭素繊維束を２層の異なる炭素組織で充填し、炭素繊維束内部及び外周部に界面を形成することにより高いすべり効果を炭素繊維束の内部及び外周部に付与し、強化用繊維材料の破壊エネルギーを向上させる強化用繊維材料と強化用繊維材料を用いた繊維強化セラミックス複合材料及びこれらの製造方法を提供することができる。 According to the present invention, the carbon fiber bundle is filled with two layers of different carbon structures, and a high slip effect is imparted to the inside and the outer periphery of the carbon fiber bundle by forming an interface inside and around the carbon fiber bundle, It is possible to provide a reinforcing fiber material that improves the breaking energy of the reinforcing fiber material, a fiber-reinforced ceramic composite material using the reinforcing fiber material, and a method for manufacturing the same.
以下、本発明の実施形態について詳細に説明する。図１は、本発明の実施形態に係る繊維強化セラミックス複合材料の概念を示す断面図である。 Hereinafter, embodiments of the present invention will be described in detail. FIG. 1 is a cross-sectional view showing the concept of a fiber-reinforced ceramic composite material according to an embodiment of the present invention.
［強化用繊維材料］
図１に示すように、本発明の実施形態に係る繊維強化セラミックス複合材料１は、セラミックスマトリックス２の内部に形成された強化用繊維材料４を備えている。この強化用繊維材料４は、炭素繊維束３と、炭素繊維束３の内部を層状構造炭素組織３２と樹脂由来炭素組織３３との異なる種類の炭素組織で構成することによって、少なくとも一つの界面３４を有し、かつ、炭素繊維束３の炭素単繊維３１が分散される構造を備えている。
[Reinforcing fiber materials]
As shown in FIG. 1, a fiber reinforced ceramic composite material 1 according to an embodiment of the present invention includes a reinforcing fiber material 4 formed inside a ceramic matrix 2. The reinforcing fiber material 4 includes at least one interface 34 by configuring the carbon fiber bundle 3 and the inside of the carbon fiber bundle 3 with different types of carbon structures of a layered structure carbon structure 32 and a resin-derived carbon structure 33. And a structure in which the carbon single fibers 31 of the carbon fiber bundle 3 are dispersed.
本実施形態に係るセラミックスマトリックス２は、炭化ケイ素（ＳｉＣ）、炭素（Ｃ）及びシリコン（Ｓｉ）で構成される。これらは、セラミックスマトリックス２として適用できる材料であれば、広く既存のものを用いてもよい。また、セラミックスマトリックス２を構成する炭化ケイ素、炭素及びシリコンの重量比は、設計される強化用繊維材料１の仕様に応じて、適宜設定してもよい。 The ceramic matrix 2 according to the present embodiment is composed of silicon carbide (SiC), carbon (C), and silicon (Si). As long as these materials can be applied as the ceramic matrix 2, widely existing materials may be used. Further, the weight ratio of silicon carbide, carbon and silicon constituting the ceramic matrix 2 may be appropriately set according to the specification of the reinforcing fiber material 1 to be designed.
本実施形態で用いる繊維の材質は、炭素繊維又は炭化ケイ素繊維のいずれか１種以上の材料で構成される。いずれか一方のみでもよいし、この２つの材料を混合してもよい。しかしながら、製造が容易、強度などの諸特性が優れている点では、炭素を用いることが好適である。この場合、炭素の品質、純度は、通常のセラミックス材料に用いられるものでもよく、特に限定されない。 The material of the fiber used in the present embodiment is composed of one or more materials of carbon fiber or silicon carbide fiber. Only one of them may be used, or these two materials may be mixed. However, it is preferable to use carbon in terms of easy production and excellent properties such as strength. In this case, the quality and purity of carbon may be those used for ordinary ceramic materials and are not particularly limited.
なお、その他の繊維の材質としては、セラミックス繊維を生成できる有機物繊維、例えばセルロース繊維、アクリル繊維、ピッチ繊維なども適用できる。この場合、後述する樹脂由来炭素組織３３を形成した後、加熱処理によってセラミックス繊維となれば、繊維強化複合材料として問題なく使えるからである。また、セラミックス製造時の高温に対して耐熱性のある種々の金属も使用できる。好適にはタングステン（W）などがある。 As other fiber materials, organic fibers capable of producing ceramic fibers such as cellulose fibers, acrylic fibers, pitch fibers, and the like can also be applied. In this case, if a ceramic fiber is formed by heat treatment after forming a resin-derived carbon structure 33 described later, it can be used as a fiber-reinforced composite material without any problem. Also, various metals that are heat resistant to high temperatures during ceramic production can be used. Preferred is tungsten (W).
本発明の実施形態において、炭素繊維束３とは短繊維が複数本集合し、かつ繊維同士によって空間が形成された状態であるものをいう。ただし、炭素繊維束３の形状は特に限定されるものではなく、例えばフェルト状、不織布状でも良いが、纖維が数本から数千本束ねられ、長さが２ｍｍ〜５０ｍｍ、径が３μｍ〜５００μｍであり、全体として針状、棒状小片状、板状、塊状の形態を成している、いわゆる短繊維束が好ましい。また、断面状態が炭素繊維束３と同様である長繊維においても同様の効果が得られるため、好ましい。 In the embodiment of the present invention, the carbon fiber bundle 3 refers to a state in which a plurality of short fibers are aggregated and a space is formed by the fibers. However, the shape of the carbon fiber bundle 3 is not particularly limited. For example, a felt shape or a nonwoven fabric shape may be used, but several to several thousand fibers are bundled, the length is 2 mm to 50 mm, and the diameter is 3 μm to 500 μm. A so-called short fiber bundle having a needle-like shape, a rod-like piece-like shape, a plate-like shape, or a lump-like shape as a whole is preferable. Moreover, since the same effect is acquired also in the long fiber whose cross-sectional state is the same as that of the carbon fiber bundle 3, it is preferable.
ここで、炭素繊維束３を構成する繊維の炭素の品質、純度は通常のセラミックス材料に用いられるものでよく、特に限定されない。また、設計する繊維強化用繊維材料１に応じて、繊維の長さと径は適宜選択できるが、径については０．５μｍ以上５０μｍ以下が好ましい。０．５μｍ未満では、繊維間の空間が狭くなりすぎて、層状構造の炭素材料が形成されにくくなるため好ましくなく、５０μｍを超えると、繊維の高アスペクト比に由来する可逆変形性が失われるため好ましくない。 Here, the quality and purity of carbon of the fibers constituting the carbon fiber bundle 3 may be those used for ordinary ceramic materials, and are not particularly limited. Moreover, although the length and diameter of a fiber can be selected suitably according to the fiber material 1 for fiber reinforcement to design, 0.5 micrometers or more and 50 micrometers or less are preferable about a diameter. If it is less than 0.5 μm, the space between the fibers becomes too narrow and it becomes difficult to form a layered carbon material, and if it exceeds 50 μm, the reversible deformability derived from the high aspect ratio of the fiber is lost. It is not preferable.
本実施形態で用いる炭素材料は、ピッチ又はメソフェーズピッチの少なくともいずれか一つからなり、樹脂との重量比を適正化することで、炭素の層状または等方性の構造を決定できる。すなわち、加熱処理を行った場合に易黒鉛性を示す材料であるピッチ又はメソフェーズピッチと、難黒鉛性を示すフェノールなどの樹脂を混合することによる組織制御である。なお、炭素材料として用いるピッチとメソフェーズピッチは、それぞれ単体でもよいし、両方を混合してもよい。 The carbon material used in the present embodiment is made of at least one of pitch and mesophase pitch, and the layered or isotropic structure of carbon can be determined by optimizing the weight ratio with the resin. That is, it is the structure control by mixing pitch or mesophase pitch, which is a material showing graphitability when heat-treated, and a resin such as phenol showing non-graphite properties. Note that the pitch and mesophase pitch used as the carbon material may each be a single material or a mixture of both.
本実施形態に係る強化用繊維材料４は、炭素繊維束３の表面近傍および層状構造の炭素繊維束３内でも短繊維束を構成する短繊維周囲に形成された空間が、へき開性の高い組織及び、緻密な組織でかつ、層状、年輪状、縞状に充填される層状構造炭素組織３２で充填されていることを特徴とする。 In the reinforcing fiber material 4 according to the present embodiment, the space formed around the short fibers constituting the short fiber bundle in the vicinity of the surface of the carbon fiber bundle 3 and in the carbon fiber bundle 3 having a layered structure has a highly cleaved structure. And it is filled with the layer structure structure | tissue carbon structure 32 which is a dense structure | tissue and is filled in layer shape, annual ring shape, and stripe form.
本実施形態に係る強化用繊維材料４の層状構造炭素組織３２は、異方性の結晶構造を持った、例えば黒鉛のようにある結晶軸がファンデルワールス力で弱く結合した層状のもの、および層状の結晶構造を持つ組織が重量分率で材料全体に対して５０％以上含まれており、かつ、これらの組織が小薄片、膜、層に堆積して、マクロの形態として流れ形状を成しているものとする。 The layered structure carbon structure 32 of the reinforcing fiber material 4 according to the present embodiment has a layered structure having an anisotropic crystal structure, for example, a crystal axis such as graphite and weakly bonded by van der Waals force, and A structure having a layered crystal structure is contained in a weight fraction of 50% or more with respect to the entire material, and these structures are deposited on small flakes, films and layers to form a flow shape as a macro form. Suppose you are.
層状構造炭素組織３２において、層間は堆積方向に対して相対的に弱い結合力または非結合の構造をもち、亀裂が進展してくると容易に堆積方向と垂直な平面方向に多数の亀裂の進展を促しエネルギーを消費させるという、いわゆるすべり機能を有する。本発明の実施形態においては、層状構造炭素組織３２とマトリックスの界面及び層状構造部分の内部と樹脂由来炭素組織３３との界面３４で無数のすべり機能をもたせることにより、層状構造炭素組織３２が効率よくエネルギーを消費することを可能とする。 In the layered carbon structure 32, the interlayer has a relatively weak bonding force or non-bonding structure with respect to the deposition direction, and when a crack progresses, a number of cracks progress easily in a plane direction perpendicular to the deposition direction. It has a so-called slip function that promotes energy and consumes energy. In the embodiment of the present invention, the laminar structure carbon structure 32 is made efficient by providing an infinite number of sliding functions at the interface 34 between the layered structure carbon structure 32 and the matrix, the inside of the layered structure portion, and the interface 34 between the resin-derived carbon structure 33. It makes it possible to consume energy well.
層状構造炭素組織３２は、すべり面を有しておりエネルギーの消費効果が高い反面、層間の結合力は弱いので層状構造の材料自身は剥離しやすくもろい。よって、層状構造炭素組織３２の材料の内部に相対的に機械的強度が優れた構造材料、ここでは等方性材料で耐衝撃性を保持することで、双方の長所を併せ持つ炭素単繊維束とすることが可能となる。 The layered structure carbon structure 32 has a slip surface and has a high energy consumption effect, but the bonding force between the layers is weak, so that the layered structure material itself is easily peeled off. Therefore, a structural material having relatively high mechanical strength inside the material of the layered structure carbon structure 32, here is an isotropic material, and by maintaining impact resistance, a carbon single fiber bundle having both advantages and It becomes possible to do.
層状構造炭素組織３２の膜厚ｔは５μｍ以上５００μｍ以下であることが好ましい。層状構造炭素組織３２の膜厚ｔが５μｍ未満の場合、被膜のもつすべり機能が十分に得られず、層状構造炭素組織３２の膜厚ｔが５００μｍを超える場合、被膜の熱処理により被膜に生じる亀裂に起因して繊維束自体の分裂が生じやすく、断面の構成が変化してしまう。これが繊維強化複合材料全体の強度に影響を及ぼすことが懸念され好ましくないからである。
The film thickness t of the layered carbon structure 32 is preferably 5 μm or more and 500 μm or less. When the film thickness t of the layered carbon structure 32 is less than 5 μm, the sliding function of the film cannot be sufficiently obtained, and when the film thickness t of the layered carbon structure 32 exceeds 500 μm, cracks generated in the film due to the heat treatment of the film As a result, the fiber bundle itself is easily split and the cross-sectional configuration changes. This is because it is unfavorable that this may affect the strength of the entire fiber-reinforced composite material.
本実施形態に係る強化用繊維材料４の樹脂由来炭素組織３３は、大部分を等方性の組織構造を持った炭素で構成され、樹脂由来炭素組織３３の表面の大部分が層状構造炭素組織３２で覆われている。なお、結晶レベルでは黒鉛構造であるが、結晶のサイズが微視的で、方位がランダムなため、マクロには等方的である。結晶構造は光学偏光顕微鏡などにより確認可能である。 The resin-derived carbon structure 33 of the reinforcing fiber material 4 according to the present embodiment is mostly composed of carbon having an isotropic structure, and most of the surface of the resin-derived carbon structure 33 is a layered structure carbon structure. 32. Although it is a graphite structure at the crystal level, it is isotropic to the macro because the crystal size is microscopic and the orientation is random. The crystal structure can be confirmed with an optical polarization microscope or the like.
樹脂由来炭素組織３３の樹脂は、等方性の組織構造の材料となる炭素の供給源として、また加熱分解にて炭素を生成させる目的で用いられる。樹脂の種類は、熱硬化性または熱可塑性であることが好ましく、例えば、フェノール、シリコーン、フッ素、エポキシ、フラン、ＰＶＡ、フルフリル、メラミン、尿素ポリエステル及びポリイミドのうちから１ないし複数の混合体として選択でき、より好適には、フェノールレジンが用いられる。 The resin of the resin-derived carbon structure 33 is used as a supply source of carbon that is a material of an isotropic structure and for the purpose of generating carbon by thermal decomposition. The type of resin is preferably thermosetting or thermoplastic, for example, selected as a mixture of one or more of phenol, silicone, fluorine, epoxy, furan, PVA, furfuryl, melamine, urea polyester and polyimide. More preferably, a phenol resin is used.
フェノールレジンは、固体と液体の両方の状態で存在して、水または有機溶剤中に溶解していることがより好ましい。フェノールレジンは、等方性の炭素材料を形成する供給源となるので、固体のフェノールレジンを使用する場合、完全に融解した状態ではなく、固体のフェノールレジンが残存した状態がより高い炭化収率を得ることができるので好ましい。しかしながら、固形分が多すぎると、繊維間、炭素繊維束３間の狭い空間への浸透の妨げになるので、設計する繊維強化セラミックス複合材料１に応じて適時変更してよい。好適には、固形分は５％以下の範囲で用いられるが、５％を上回る場合、固形分が溶液中に多くなり、繊維束内部への樹脂の浸透性が低下するので好ましくない。 More preferably, the phenol resin exists in both a solid state and a liquid state and is dissolved in water or an organic solvent. Phenol resin is a source for forming isotropic carbon materials, so when using a solid phenol resin, the carbonization yield is higher when the solid phenol resin remains, rather than completely melted. Is preferable. However, if the solid content is too much, penetration into narrow spaces between fibers and between the carbon fiber bundles 3 is hindered, and may be changed as appropriate according to the fiber reinforced ceramic composite material 1 to be designed. Preferably, the solid content is used in the range of 5% or less. However, if it exceeds 5%, the solid content increases in the solution, and the permeability of the resin into the fiber bundle decreases, which is not preferable.
溶媒には、水または有機溶媒が用いられるが、樹脂を溶解できればこれらに限定されるものではなく、さらにはこれら複数の液体を混合して用いても良い。好適には、有機溶媒エタノール、２−ブタノール、アセトンを用いることができ、より好適には、エタノールが用いられる。 As the solvent, water or an organic solvent is used. However, the solvent is not limited to these as long as the resin can be dissolved, and a plurality of these liquids may be mixed and used. Preferably, organic solvent ethanol, 2-butanol, and acetone can be used, and ethanol is more preferably used.
本発明の実施形態に係る炭素単繊維３１は黒鉛質の炭素であることが好ましい。充填性、繊維表面近傍の内部への選択的な浸透性、製法の容易さを考慮すると、黒鉛質の炭素がより好適に用いられる。 The carbon single fiber 31 according to the embodiment of the present invention is preferably graphitic carbon. In consideration of filling properties, selective permeability to the inside of the vicinity of the fiber surface, and ease of production, graphitic carbon is more preferably used.
上述したように、本実施形態に係る繊維強化セラミックス複合材料１は、強化用繊維材料４として、炭素単繊維３１を分散させた炭素繊維束３に、樹脂由来炭素組織３３と層状構造炭素組織３２との界面３４を有するすべり層を含有し、結果として高いすべり機能をもち、層状構造の脆弱性を補う組織構造の異なる材料、例えば等方性構造材料と異方性構造材料との組み合わせの層を有することで、これらの構成をもたない従来技術と比べて、より効果的に破壊エネルギーを向上させることが可能となる。ここで、破壊エネルギーとは、破壊するまでに物体に加えることができるエネルギーのことで、セラミックスのような脆弱材料はその値は低く、金属のような塑性を示す材料は高い。
As described above, the fiber-reinforced ceramic composite material 1 according to the present embodiment includes the resin-derived carbon structure 33 and the layered structure carbon structure 32 in the carbon fiber bundle 3 in which the carbon single fibers 31 are dispersed as the reinforcing fiber material 4. Including a sliding layer having an interface 34 with the surface, and as a result, a material having a high sliding function and having a different structure in order to compensate for the weakness of the layered structure, for example, a layer of a combination of an isotropic structural material and an anisotropic structural material By having the above, it becomes possible to improve the destruction energy more effectively as compared with the prior art without these configurations. Here, the breaking energy is energy that can be applied to an object before breaking, and a brittle material such as ceramic has a low value and a material that exhibits plasticity such as metal is high.
また、本実施形態に係る繊維強化セラミックス複合材料１は、マトリックス２の内部に層状構造炭素組織３２と樹脂由来炭素組織３３との界面３４を有する強化用繊維材料４を用いることによって、層状構造炭素組織３２の高いへき開性及び層状構造炭素組織３２と樹脂由来炭素組織３３との界面３４による、高いすべり効果により、高い破壊エネルギーを実現することができる。 Further, the fiber reinforced ceramic composite material 1 according to the present embodiment uses the reinforcing fiber material 4 having the interface 34 between the layered structure carbon structure 32 and the resin-derived carbon structure 33 inside the matrix 2, thereby forming the layered structure carbon. High fracture energy can be realized by the high cleavage effect of the structure 32 and the high slip effect due to the interface 34 between the layer-structured carbon structure 32 and the resin-derived carbon structure 33.
［強化用繊維材料の製造方法］
次に、本発明の実施形態に係る繊維強化セラミックス複合材料１における強化用繊維材料の製造方法について図２〜図１２を参照して説明する。図２〜図１２に示すように、本発明の実施形態に係る繊維強化セラミックス複合材料１における強化用繊維材料の製造方法は、炭素繊維束３の表面近傍に層状構造の炭素を浸透、配置し、さらに、層状構造の炭素の内部に樹脂由来の炭素で充填することによって、強化用繊維材料４の内部に２層の異なる炭素組織の界面３４を形成する。強化用繊維材料４の内部に界面３４を形成することによって、微細な繊維一本一本の表面へのコーティングや、強化用繊維材料４の表面への多層のコーティングを必要とせずに、破壊エネルギーを向上させることができる。
[Method for producing reinforcing fiber material]
Next, the manufacturing method of the reinforcing fiber material in the fiber-reinforced ceramic composite material 1 according to the embodiment of the present invention will be described with reference to FIGS. As shown in FIGS. 2 to 12, the method for manufacturing a reinforcing fiber material in the fiber reinforced ceramic composite material 1 according to the embodiment of the present invention is to infiltrate and arrange a layered carbon near the surface of the carbon fiber bundle 3. Further, by filling the carbon of the layered structure with carbon derived from the resin, the interface 34 of two layers of different carbon structures is formed inside the reinforcing fiber material 4. By forming the interface 34 inside the reinforcing fiber material 4, the fracture energy can be obtained without the need to coat the surface of each fine fiber or the multilayer coating on the surface of the reinforcing fiber material 4. Can be improved.
本実施形態に係る繊維強化セラミックス複合材料１における強化用繊維材料の製造方法は、まず、図２に示すように、炭素単繊維３１を分散させた炭素繊維束３を形成する。炭素繊維束３は、樹脂とピッチ及びメソフェーズピッチの粉末と溶媒と炭素を含む複数の繊維束（長さ６ｍｍ繊維束軸方向の断面直径１ｍｍ）とを混合して形成した。ここで、炭素繊維束３を形成するための混合時に、溶媒分の揮発を促すことや、ピッチの溶融を目的に、加熱処理または減圧処理を行ってもよい。 In the method for producing a reinforcing fiber material in the fiber-reinforced ceramic composite material 1 according to the present embodiment, first, as shown in FIG. 2, a carbon fiber bundle 3 in which carbon single fibers 31 are dispersed is formed. The carbon fiber bundle 3 was formed by mixing resin, pitch and mesophase pitch powder, a solvent, and a plurality of fiber bundles containing carbon (length 6 mm, cross-sectional diameter 1 mm in the fiber bundle axis direction). Here, at the time of mixing for forming the carbon fiber bundle 3, heat treatment or reduced pressure treatment may be performed for the purpose of promoting the volatilization of the solvent or melting the pitch.
ここで、内部が表面近傍から中心にかけて異なる炭素組織で構成されている炭素繊維束３の材質、構成繊維本数、構成繊維の平均直径、長さは特に問わない。しかし、長さ２ｍｍ未満の短繊維では、浸漬、混合工程において炭素繊維束３が崩壊してしまうため、２ｍｍ以上の炭素繊維束３が好ましい。また、５０ｍｍ以上の長繊維束ではサイズが大きく、炭素繊維束３をランダムに配置することを特徴とする部材の場合、成形時の充填性が低くなるため、成形性が不良となり好ましくない。繊維を連続的に配置する部材の場合、特に上限はない。 Here, the material, the number of constituent fibers, the average diameter and the length of the constituent fibers of the carbon fiber bundle 3 whose inside is composed of different carbon structures from the vicinity of the surface to the center are not particularly limited. However, in the case of a short fiber having a length of less than 2 mm, the carbon fiber bundle 3 having a length of 2 mm or more is preferable because the carbon fiber bundle 3 is collapsed in the dipping and mixing steps. Further, in the case of a member characterized in that a long fiber bundle of 50 mm or more is large in size and the carbon fiber bundles 3 are randomly arranged, the filling property at the time of molding becomes low, and the moldability becomes poor, which is not preferable. In the case of a member in which fibers are continuously arranged, there is no particular upper limit.
次に、図３に示すように、混合した炭素繊維束３を乾燥させ、炭化処理し、層状構造炭素組織３２を含む炭素繊維束３を形成する。形成した炭素繊維束３は、炭化処理した際に発生するクラック４２を有している。 Next, as shown in FIG. 3, the mixed carbon fiber bundle 3 is dried and carbonized to form the carbon fiber bundle 3 including the layered structure carbon structure 32. The formed carbon fiber bundle 3 has a crack 42 generated when carbonized.
図３に示すように、本実施形態において、層状構造炭素組織３２は、炭素繊維束３の表層から内部にかけて浸透深さｔが５μｍ以上より好ましくは２０μｍ以上炭素繊維束３の内部に浸透するように形成され、かつ、その浸透深さｔが炭素繊維束軸方向の断面直径の２０％以下であることが望ましい。 As shown in FIG. 3, in this embodiment, the layered structure carbon structure 32 penetrates into the carbon fiber bundle 3 with a penetration depth t of 5 μm or more, more preferably 20 μm or more from the surface layer to the inside of the carbon fiber bundle 3. It is desirable that the penetration depth t be 20% or less of the cross-sectional diameter in the carbon fiber bundle axis direction.
浸透深さｔが５μｍ未満である場合、繊維により層状構造炭素組織３２が分断されやすく、炭素組織として機能しない。一方、浸透深さｔが１０μｍ以上である場合、炭素繊維束３の表面に溶融Ｓｉが接触した場合に、表面から１０μｍ以上の距離の内部の炭素繊維を保護することができる。そのため、２０μm以上の浸透深さがあることが、黒鉛質のすべり効果を得る目的においては好ましい。また、浸透深さｔが炭素繊雑束の繊維束軸方向の断面直径が２０％を超えて充填される場合、炭素繊維束３表面への層状構造炭素組織３２の被膜及び、塊状の余分な炭素付着物が生じてしまう。 When the penetration depth t is less than 5 μm, the layered structure carbon structure 32 is easily divided by the fiber and does not function as a carbon structure. On the other hand, when the penetration depth t is 10 μm or more, when molten Si is in contact with the surface of the carbon fiber bundle 3, it is possible to protect the internal carbon fibers at a distance of 10 μm or more from the surface. Therefore, a penetration depth of 20 μm or more is preferable for the purpose of obtaining a graphite slip effect. Further, when the penetration depth t is filled with the cross-sectional diameter of the carbon fiber bundle in the fiber bundle axis direction exceeding 20%, the coating of the layered structure carbon structure 32 on the surface of the carbon fiber bundle 3 and the extra lump Carbon deposits are generated.
ここで、このような工程を経て作製された炭素繊維束３を図７〜図９に示す。図７は、本発明の実施形態に係る繊維強化セラミックス複合材料における炭素繊維束の断面を示す光学顕微鏡写真であり、図８は、図７のＡ部分を拡大して示す光学顕微鏡写真であり、図９は、図８のＢ部分を拡大して示す光学顕微鏡写真である。図７〜図９に示す炭素繊維束３は、断面方向から光学顕微鏡にて観察したものである。ここでは、炭素繊維束３において、炭化処理した際に発生するクラック４２を有し、炭素繊維束３の表層近傍に層状構造炭素組織３２の炭素分が形成されていることがわかる。 Here, the carbon fiber bundle 3 produced through such a process is shown in FIGS. FIG. 7 is an optical micrograph showing a cross section of a carbon fiber bundle in the fiber-reinforced ceramic composite material according to the embodiment of the present invention, and FIG. 8 is an optical micrograph showing an enlarged portion A of FIG. FIG. 9 is an optical micrograph showing the portion B of FIG. 8 in an enlarged manner. The carbon fiber bundle 3 shown in FIGS. 7 to 9 is observed with an optical microscope from the cross-sectional direction. Here, it can be seen that the carbon fiber bundle 3 has a crack 42 generated when carbonized, and the carbon content of the layered structure carbon structure 32 is formed in the vicinity of the surface layer of the carbon fiber bundle 3.
次に、図４に示すように、第１の混合液５として樹脂を希釈した溶液を作製する。そして、この第１の濃度の混合液５（以下、第１の混合液という。）に炭素繊維束３を浸漬し、加圧含浸又は減圧含浸した。その後、第１の混合液５中から炭素繊維束３を取り出し、加熱処理し、樹脂を硬化させた後、炭化処理することで内部を充填し、層状構造炭素組織３２の内部に樹脂由来炭素組織３３を形成する。形成された樹脂由来炭素組織３３は、加熱処理した際に発生した層状構造炭素組織３２のクラック４２を通って、第１の混合液５が内部に含浸することで充填されたものである。 Next, as shown in FIG. 4, a solution in which resin is diluted is prepared as the first mixed solution 5. Then, the carbon fiber bundle 3 was immersed in the mixed solution 5 (hereinafter referred to as the first mixed solution) having the first concentration, and impregnated under pressure or under reduced pressure. Thereafter, the carbon fiber bundle 3 is taken out from the first mixed solution 5, subjected to heat treatment, and the resin is hardened, and then the inside is filled by carbonization, and the resin-derived carbon structure 32 is filled inside the layered structure carbon structure 32. 33 is formed. The formed resin-derived carbon structure 33 is filled with the first mixed liquid 5 impregnated through the cracks 42 of the layered structure carbon structure 32 generated during the heat treatment.
次に、図５に示すように、第１の混合液５よりも好ましくは濃度を低減させた樹脂の溶液または樹脂を溶媒で希釈した第２の濃度の混合液６（以下、第２の混合液という。）を作製する。そして、この第２の混合液６に炭素繊維束３を浸漬し、加圧含浸又は減圧含浸した。その後、第２の混合液６中から炭素繊維束３を取り出し、加熱処理することにより、層状構造炭素組織３２のクラック４２から第２の混合液６を含浸させて、樹脂由来の炭素組織を充填する。ここで、第２の混合液６は、第１の混合液５で用いた樹脂の溶液または樹脂を溶媒で希釈した溶液を用い、好ましくは濃度を低下させたものである。従って第１の混合液５と第２の混合液６とは同じ溶質及び溶媒からなる。本実施形態においては、溶液の濃度を低減させることによって、炭素単繊維３１同士が固着すること、すなわち、炭素単繊維３１が固まり、炭素単繊維３１の分散能力の劣化を防止している。第１の混合液５の濃度が十分薄い場合は、第２の混合液６の濃度を上昇しても炭素単繊維３１同士の固着が生じにくい。また、必要に応じて第３、第４の混合液を作製して同様の処理を通して内部を緻密化してもよい。しかし工程の増加はコストの増加につながるため、上述した本実施形態がより好ましい。なお、上述では第１の混合液５より第２の混合液６の溶液の濃度を低減させる例について説明したが、第１の混合液５の溶液濃度と第２の混合液６の溶液濃度との関係はこれに限定されるものではなく、第１の混合液５及び第２の混合液６の溶液の濃度は同じ、もしくは第１の混合液５を第２の混合液６より上昇させてもよい。
Next, as shown in FIG. 5, a resin solution having a reduced concentration or a mixed solution 6 having a second concentration obtained by diluting the resin with a solvent (hereinafter referred to as a second mixed solution) is preferable. Liquid)). And the carbon fiber bundle 3 was immersed in this 2nd liquid mixture 6, and pressure impregnation or pressure reduction impregnation was carried out. Thereafter, the carbon fiber bundle 3 is taken out from the second mixed solution 6 and is heat-treated to impregnate the second mixed solution 6 from the cracks 42 of the layered structure carbon structure 32 to fill the resin-derived carbon structure. To do. Here, the 2nd liquid mixture 6 uses the solution of the resin used by the 1st liquid mixture 5, or the solution which diluted resin with the solvent, Preferably it reduces the density | concentration. Therefore, the first mixed solution 5 and the second mixed solution 6 are composed of the same solute and solvent . In the present embodiment, by reducing the concentration of the solution, the carbon single fibers 31 are fixed to each other, that is, the carbon single fibers 31 are hardened, and deterioration of the dispersion ability of the carbon single fibers 31 is prevented. When the concentration of the first mixed solution 5 is sufficiently low, the carbon single fibers 31 are not easily fixed to each other even if the concentration of the second mixed solution 6 is increased. Further, if necessary, the third and fourth mixed liquids may be prepared and the inside may be densified through the same processing. However, since the increase in the process leads to an increase in cost, the above-described embodiment is more preferable. In addition, although the example which reduces the density | concentration of the solution of the 2nd liquid mixture 6 from the 1st liquid mixture was demonstrated above, the solution density | concentration of the 1st liquid mixture 5 and the solution density | concentration of the 2nd liquid mixture 6 were demonstrated. Is not limited to this, and the concentration of the first mixed solution 5 and the second mixed solution 6 is the same, or the first mixed solution 5 is raised from the second mixed solution 6. Also good.
以上のように、炭素繊維束３を炭化する際に発生する層状構造炭素組織３２のクラック４２に濃度を順次低減させた混合液を複数回加圧含浸又は減圧含浸することで、層状構造炭素組織３２の内部に樹脂由来炭素組織３３を形成し、層状構造炭素組織３２内に有する空隙を減少する。 As described above, the layered structure carbon structure is obtained by multiple pressure impregnation or reduced pressure impregnation of the mixed solution in which the concentration is sequentially reduced in the cracks 42 of the layered structure carbon structure 32 generated when carbonizing the carbon fiber bundle 3. The resin-derived carbon structure 33 is formed inside 32 and the voids in the layered structure carbon structure 32 are reduced.
次に、図６に示すように、炭素繊維束３の内部の樹脂は熱処理工程で炭化される。こうして炭素繊維束３の内部が表面近傍から中心にかけて異なる炭素組織で構成されることを特徴とする強化用繊維材料４が作製でき、炭素繊維束３の内部形成された異なる組織の界面３４による高いすべり効果により高い破壊エネルギーを示す。 Next, as shown in FIG. 6, the resin inside the carbon fiber bundle 3 is carbonized in a heat treatment step. In this way, a reinforcing fiber material 4 characterized in that the inside of the carbon fiber bundle 3 is composed of different carbon structures from the vicinity of the surface to the center thereof can be produced, and is high due to the interface 34 of the different structures formed inside the carbon fiber bundle 3. High destruction energy due to sliding effect.
このような工程を経て作製された強化用繊維材料４を図１０〜図１２に示す。図１０は、本発明の実施形態に係る繊維強化セラミックス複合材料における強化用繊維材料の断面を示す光学顕微鏡写真であり、図１１は、図１０のＣ部分を拡大した光学顕微鏡写真であり、図１２は、図１１のＤ部分を拡大した光学顕微鏡写真である。図１０〜図１２に示す強化用繊維材料４は、炭素繊維束３の断面方向から光学顕微鏡にて観察したものである。ここでは、炭素単繊維３１間の層状構造炭素組織３２の材料が小板状の黒鉛質の炭素で充填された状態となっていることがわかる。
The reinforcing fiber material 4 produced through such a process is shown in FIGS. FIG. 10 is an optical micrograph showing a cross-section of the reinforcing fiber material in the fiber-reinforced ceramic composite material according to the embodiment of the present invention, and FIG. 11 is an optical micrograph enlarging the portion C of FIG. 12 is an optical micrograph in which a portion D in FIG. 11 is enlarged. The reinforcing fiber material 4 shown in FIGS. 10 to 12 is observed with an optical microscope from the cross-sectional direction of the carbon fiber bundle 3. Here, it can be seen that the material of the layered structure carbon structure 32 between the carbon single fibers 31 is filled with platelet-like graphitic carbon.
次に以下において、本発明の実施形態に係る強化用繊維材料４の製造工程における留意点について記載する。 Next, points to be noted in the manufacturing process of the reinforcing fiber material 4 according to the embodiment of the present invention will be described below.
繊維と浸漬、混合させる液体（以下、含浸用材料という。）は、フェノール樹脂等の加熱分解で炭素を生成する有機材料を溶解させて調整したものに粉末状のピッチ及びメソフェーズピッチを混合したものである。 Liquid to be immersed and mixed with fibers (hereinafter referred to as impregnating material) is prepared by dissolving an organic material that generates carbon by thermal decomposition such as phenol resin, and mixing powdery pitch and mesophase pitch. It is.
溶媒としてはエタノールや水溶性のものであれば水を選択するのが作業性と環境・安全衛生の観点から的に好ましいが、これに限られるものではなく、加熱分解で炭素を生成する有機材料を溶解できれば問題なく使用できる。 As the solvent, it is preferable to select ethanol or water if it is water-soluble, from the viewpoint of workability and environment / safety and health, but it is not limited to this, and an organic material that generates carbon by thermal decomposition. If it can be dissolved, it can be used without problems.
混合物と混合した繊維は樹脂の乾燥・硬化のため４０℃〜２００℃で熱処理し、さらに樹脂と、ピッチ及びメソフェーズピッチの溶融・炭化を目的に成形以前に５００℃〜３０００℃の炭素が生成する温度域で熱処理してもかまわない。 The fibers mixed with the mixture are heat-treated at 40 ° C. to 200 ° C. to dry and cure the resin, and carbon of 500 ° C. to 3000 ° C. is formed before molding for the purpose of melting and carbonizing the resin and pitch and mesophase pitch. Heat treatment may be performed in the temperature range.
浸漬用材料を作製するにあたり、炭素材の重量分率が溶媒以外の固形分のなかで８０％以上になるように樹脂溶液を混合して浸漬用材料を作製する。ここで、浸漬用材料とは、繊維間および繊維集合体の表面に層状構造材料を形成するための役割をするもので、液体状で層状構造を形成するのに適切な炭素材料を含有しているものである。 In producing the dipping material, the dipping material is produced by mixing the resin solution so that the weight fraction of the carbon material is 80% or more in the solid content other than the solvent. Here, the dipping material serves to form a layered structure material between the fibers and on the surface of the fiber assembly, and contains a carbon material suitable for forming a layered structure in a liquid state. It is what.
炭素材料の重量分率は、重量分率が５０％を下回ると、浸漬用材料による層状構造形成がされにくい。また、炭素材が３０％以下、とくに１０％以下では炭素は等方的な構造を示す。なお、樹脂が０の場合、すなわち炭素材のみでも、層状構造を形成させることは可能であるが、粉状である炭素材を液体状の樹脂に溶かした状態のほうが、繊維束への付着性が増し、より繊維間に浸透しやすいので好ましい。 When the weight fraction of the carbon material is less than 50%, it is difficult to form a layered structure using the dipping material. Further, when the carbon material is 30% or less, particularly 10% or less, the carbon exhibits an isotropic structure. In addition, when the resin is 0, that is, it is possible to form a layered structure with only the carbon material, the state in which the powdery carbon material is dissolved in the liquid resin is more adherent to the fiber bundle. Is preferred because it increases and more easily penetrates between the fibers.
炭素繊維束３中の炭素繊維と浸漬用材料は、重量比で１：０．１〜１：０．４の範囲で混合することが好ましい。この範囲を外れると、破壊エネルギー向上の効果が顕著には得られなくなり好ましくない。 The carbon fibers in the carbon fiber bundle 3 and the dipping material are preferably mixed in a weight ratio of 1: 0.1 to 1: 0.4. If it is out of this range, the effect of improving the breaking energy cannot be obtained remarkably, which is not preferable.
次に、炭素繊維束３と浸漬用材料を均一になるよう混合する工程を実施するが、混合方法と混合時間については、既存の製造方法を適切に適用する範囲で任意に決めてよい。なお混合時に溶媒の揮発を目的に、乾燥工程、加熱工程、またはその両方を含めてもよい。 Next, although the process which mixes the carbon fiber bundle 3 and the material for immersion so that it may become uniform is implemented, you may arbitrarily determine about the mixing method and mixing time in the range which applies the existing manufacturing method appropriately. In addition, you may include a drying process, a heating process, or both for the purpose of volatilization of a solvent at the time of mixing.
混合後は、すぐに乾燥を実施してもよく、適切な時間放置してから乾燥してもよい。放置する時間は、例えば１時間以上、あるいは溶媒が完全に気化してなくなるまで実施してよい。また、溶媒が完全に気化してなくなった以降も放置することは、工程上作業ロスとなるので、これも好ましくない。なお、溶媒が完全に気化してなくなるまでというのは、厳密な判断を必要とせず、作業者の目視による浸漬用材料の乾燥状態で判断してもよい。 After mixing, drying may be performed immediately, or it may be allowed to stand for an appropriate time and then dried. The standing time may be, for example, 1 hour or more, or until the solvent is completely evaporated. Further, it is not preferable to leave the solvent after it is completely vaporized because it causes a work loss in the process. Note that until the solvent is completely evaporated, strict judgment is not necessary, and it may be judged based on the dry state of the dipping material visually observed by the operator.
また炭素繊維束３と浸漬用材料の混合は、一回だけ浸漬用材料と混合してもよいし、一度浸漬用材料に混合した炭素繊維束３を取り出して、再度浸漬用材料と混合する作業を繰り返してもよい。その際の工程移行の間は、そのまま放置してもよく、その放置時間も特に限定されない。 The carbon fiber bundle 3 and the dipping material may be mixed only once with the dipping material, or the carbon fiber bundle 3 once mixed with the dipping material is taken out and mixed with the dipping material again. May be repeated. During the process transition at that time, it may be left as it is, and the leaving time is not particularly limited.
乾燥は、大気中に４０℃〜２００℃の範囲で数時間保持することでなされるが、不活性雰囲気で実施してもよい。また、加熱処理については、保持温度は５００℃〜３０００℃、好適には６００℃〜１０００℃の範囲にて、保持時間は５分〜３時間、好適には１時間〜２時間の範囲で、不活性雰囲気下でなされることが好ましい。この加熱処理で樹脂とピッチまたはメソフェーズピッチが炭化され、黒鉛質の層状炭素が生成して、繊維間の空間に充填される。また、炭化のための加熱処理は、マトリックスとなるセラミック材料と成形した後行ってもよい。 Drying is performed by holding in the air for several hours in the range of 40 ° C. to 200 ° C., but may be performed in an inert atmosphere. For the heat treatment, the holding temperature is 500 ° C. to 3000 ° C., preferably 600 ° C. to 1000 ° C., the holding time is 5 minutes to 3 hours, preferably 1 hour to 2 hours, It is preferably done under an inert atmosphere. With this heat treatment, the resin and pitch or mesophase pitch are carbonized to produce graphitic layered carbon, which fills the spaces between the fibers. Moreover, you may perform the heat processing for carbonization, after shape | molding with the ceramic material used as a matrix.
加熱処理の温度は、５００℃未満では炭化が不十分であり好ましくない。また、３０００℃を超える温度ではほぼ炭素の黒鉛化が収東するため、加熱処理としての作用が少なく、これも好ましくない。また、加熱処理の保持時間は、５分未満では温度の安定化が不十分のため好ましくないし、３時間を越えて保持しても、こちらもほぼ炭素の黒鉛化が収東するため好ましくない。 If the temperature of the heat treatment is less than 500 ° C., carbonization is insufficient, which is not preferable. Further, since the graphitization of carbon is almost concentrated at a temperature exceeding 3000 ° C., the action as a heat treatment is small, which is also not preferable. Also, the heat treatment holding time is preferably less than 5 minutes because the temperature is not sufficiently stabilized, and even if the heat treatment is held for more than 3 hours, this is also not preferable because carbon graphitization is almost lost.
また、Ｓｉを高温で含浸すると炭素繊維はＳｉＣへと反応し、マトリックス２と一体化して破壊エネルギーを低下させるが、炭素繊維束３の表面近傍を１０μｍ以上の層状構造の炭素組織で構成するとＳｉの融液を内部へ通しにくく、大部分の炭素繊維表面と接触しないため、炭素繊維をＳｉＣ化させないですむ。 Further, when Si is impregnated at a high temperature, the carbon fiber reacts with SiC and integrates with the matrix 2 to reduce the fracture energy. However, when the surface vicinity of the carbon fiber bundle 3 is composed of a carbon structure having a layer structure of 10 μm or more, Si It is difficult to pass the melt of the material into the interior and it does not come into contact with the surface of most of the carbon fibers, so that the carbon fibers need not be converted to SiC.
本発明の実施形態に係る繊維強化セラミックス複合材料１の一態様にかかる製造方法においては、本発明の実施形態に係る強化用繊維材料４は、マトリックス２に炭素繊維の体積含有率が１０％以上５０％以下になるように混合し、その後成型、乾燥、焼成することを特徴とする。
In the manufacturing method according to one aspect of the fiber-reinforced ceramic composite material 1 according to the embodiment of the present invention, the reinforcing fiber material 4 according to the embodiment of the present invention has a volume content of carbon fibers in the matrix 2 of 10% or more. It is characterized by mixing so as to be 50% or less, and thereafter molding, drying and firing.
このときのマトリックス２中の炭素繊維の含有率は、１０％未満では繊維集合体での亀裂進展が起こる確率が低くなってしまい、また５０％を超えるとセラミックスのマトリックスがもつ耐熱性、耐酸化性、強度などの優れた特性を損なう恐れがあり、いずれも好ましくない。より好ましくは、セラミックス複合材中の繊維の体積含有率が２０％以上４０％以下である。 At this time, if the carbon fiber content in the matrix 2 is less than 10%, the probability of crack growth in the fiber assembly decreases, and if it exceeds 50%, the ceramic matrix has heat resistance and oxidation resistance. There is a risk that excellent properties such as property and strength may be impaired, and neither is preferable. More preferably, the volume content of the fibers in the ceramic composite material is 20% or more and 40% or less.
本発明の実施形態に係る繊維強化セラミックス複合材料１における強化用繊維材料の製造方法においては、ＣＶＤ法やスパッタリング法のような、繊維１本単位の成膜を目指し、すべり面の少ない、製造コストも高くつく方法に比べて、液体材料の浸漬と混合による繊維集合体全体に層状構造の材料を含有するように材料の比率の最適化などを行うことによって、繊維表面と繊維間及び炭素繊維束表面にすべり効果を付与し、破壊エネルキーの高い繊維強化セラミックス複合材料１を、比較的簡単な装置で容易にかつ効率よく提供することが可能となる。 In the manufacturing method of the reinforcing fiber material in the fiber reinforced ceramic composite material 1 according to the embodiment of the present invention, the manufacturing cost is low with less sliding surface aiming at the film formation of one fiber unit such as CVD method or sputtering method. Compared with the more expensive method, the ratio of the fiber surface to the fiber and the carbon fiber bundle is optimized by optimizing the ratio of the material so that the entire fiber assembly contains a layered structure by dipping and mixing the liquid material. It is possible to easily and efficiently provide the fiber-reinforced ceramic composite material 1 having a slip effect on the surface and having a high breaking energy by using a relatively simple device.
また、既存の強化用繊維材料に対しても、本発明の実施形態に係る炭素繊維束３を適用することで、マトリックス材の種類にかかわらず、本発明の実施形態を適用しなかった場合に比べて、簡易に破壊エネルギーを向上させることが可能となる。 In addition, by applying the carbon fiber bundle 3 according to the embodiment of the present invention to the existing reinforcing fiber material, the embodiment of the present invention is not applied regardless of the type of the matrix material. In comparison, it is possible to easily improve the fracture energy.
以下、図２〜図６を参照して、本発明の好ましい実施形態を実施例に基づき説明するが、本発明は、この実施例に限定されるものではない。 Hereinafter, preferred embodiments of the present invention will be described based on examples with reference to FIGS. 2 to 6, but the present invention is not limited to these examples.
以下に示す条件で繊維強化セラミックス複合材料１に用いる強化用繊維材料４を作製し、破壊エネルギーを測定した。得られた強化用繊維材料４からなる３×３×４０（ｍｍ）の試験片を切り出し、これを評価サンプルとして、日本セラミックス協会規格ＪＣＲＳ−２０１「シェブロンノッチ試験片の準静的３点曲げ破壊によるセラミック系複合材料の破壊エネルギー試験方法」に準拠した破壊エネルギーの測定を行った。 The reinforcing fiber material 4 used for the fiber reinforced ceramic composite material 1 was produced under the following conditions, and the fracture energy was measured. A 3 × 3 × 40 (mm) test piece made of the reinforcing fiber material 4 was cut out, and this was used as an evaluation sample. The Japan Ceramic Society Standard JCRS-201 “Quasi-Static Three-Point Bending Fracture of Chevron Notch Test Specimen Fracture energy was measured according to the “Test method for fracture energy of ceramic composites by the method”.
まず、図２に示すように、炭素単繊維３１を分散させた炭素繊維束３を形成した。次に、フェノール樹脂とピッチ及びメソフェーズピッチの粉末を混合し、炭素繊維束３（長さ６ｍｍ繊維束軸方向の断面直径１ｍｍ）と混合した。 First, as shown in FIG. 2, a carbon fiber bundle 3 in which carbon single fibers 31 were dispersed was formed. Next, a phenol resin, a powder of pitch and mesophase pitch were mixed and mixed with a carbon fiber bundle 3 (length 6 mm, cross-sectional diameter 1 mm in the fiber bundle axis direction).
次に、図３に示すように、混合した炭素繊維束３を８０℃で乾燥させ、Ａｒ雰囲気中で１０００℃まで昇温し、２時間保持し炭化処理した。炭化処理した炭素繊維束３は、炭化処理した際に発生するクラック４２を有している。ここで、このような工程で作製した炭素繊維束３を図７〜図１０に示す。図７〜図１０に示すように、炭素繊維束３において、炭化処理した際に発生するクラック４２を有し、炭素繊維束３の表層近傍に層状構造炭素組織３２の炭素分が形成されている。 Next, as shown in FIG. 3, the mixed carbon fiber bundle 3 was dried at 80 ° C., heated to 1000 ° C. in an Ar atmosphere, held for 2 hours, and carbonized. The carbon fiber bundle 3 subjected to carbonization has cracks 42 that are generated when the carbonization is performed. Here, the carbon fiber bundle 3 produced by such a process is shown in FIGS. As shown in FIGS. 7 to 10, the carbon fiber bundle 3 has a crack 42 generated when carbonized, and the carbon content of the layered structure carbon structure 32 is formed in the vicinity of the surface layer of the carbon fiber bundle 3. .
次に、図４に示すように、第１の混合液５としてフェノール樹脂をエタノールで希釈した溶液に炭素繊維束３を浸漬し、圧力１０ｋＰａで減圧含浸した。その後、溶液中より炭素繊維束３を分離し、１９０℃で加熱処理し樹脂を硬化させた後、Ａｒ雰囲気中で１０００℃まで昇温し炭化することでクラック４２を介して層状構造炭素組織３２を形成した。 Next, as shown in FIG. 4, the carbon fiber bundle 3 was immersed in a solution obtained by diluting a phenol resin with ethanol as the first mixed solution 5 and impregnated under reduced pressure at a pressure of 10 kPa. Thereafter, the carbon fiber bundle 3 is separated from the solution, and the resin is cured by heat treatment at 190 ° C., and then heated to 1000 ° C. and carbonized in an Ar atmosphere to carbonize the layered structure carbon structure 32 through the crack 42. Formed.
上記処理を行った炭素繊維束３をＳｉＣと混合後、加圧成形した後、Ａｒ雰囲気２０００℃で焼成した。 The carbon fiber bundle 3 subjected to the above treatment was mixed with SiC, pressure-molded, and then fired at 2000 ° C. in an Ar atmosphere.
次に、図５に示すように、上記処理を行った炭素繊維束３に第２の混合液６として、フェノール樹脂をエタノールで希釈した溶液に炭素繊維束３を浸漬し、圧力１０ｋＰａで減圧含浸した。その後、溶液中より炭素繊維束３を分離し、１９０℃で加熱処理し樹脂を硬化させた後、真空雰囲気１５００℃でＳｉを含浸させて内部を充填して、強化用繊維材料４を作製した。ここで、このような工程で作製した繊維強化複合材料４を図１０〜図１２に示す。図１０〜図１２に示すように、強化用繊維材料４は、炭素単繊維３１間の層状構造炭素組織３２の材料が小板状の黒鉛質の炭素で充填された状態となっている。この強化用繊維材料４から３×３×４０（ｍｍ）の試験片を作製し、破壊エネルギーを計測した。 Next, as shown in FIG. 5, the carbon fiber bundle 3 is immersed in a solution obtained by diluting a phenol resin with ethanol as the second mixed solution 6 in the carbon fiber bundle 3 subjected to the above treatment, and is impregnated under reduced pressure at a pressure of 10 kPa. did. Thereafter, the carbon fiber bundle 3 was separated from the solution, and after heat treatment at 190 ° C. to cure the resin, Si was impregnated at 1500 ° C. in a vacuum atmosphere to fill the interior, thereby producing a reinforcing fiber material 4. . Here, the fiber reinforced composite material 4 produced by such a process is shown in FIGS. As shown in FIGS. 10 to 12, the reinforcing fiber material 4 is in a state in which the material of the layered structure carbon structure 32 between the carbon single fibers 31 is filled with platelet-like graphitic carbon. A test piece of 3 × 3 × 40 (mm) was produced from the reinforcing fiber material 4, and the fracture energy was measured.
強化用繊維材料４の評価は、炭素繊維束３の層状構造炭素組織３２の平面浸透深さ（μｍ）を０〜５００（μｍ）に各々変更して行なった。評価はまず、１０%以下のものを○印とし、１０％以上３０%未満のものを△、３０%以上を×として３０g程度の量をサンプリングし目視観察による選別後、重量比により測定し、破壊エネルギー（Ｊ）が、８００以上かつ、炭素繊維束の分裂が○印のものを判定○印とし、範囲外のものを判定×印とした。その結果を下記の表１に示す。 Evaluation of the reinforcing fiber material 4 was performed by changing the plane penetration depth (μm) of the layered carbon structure 32 of the carbon fiber bundle 3 to 0 to 500 (μm). The evaluation is as follows. First, samples with 10% or less are marked with ○, samples with 10% or more and less than 30% are marked with Δ, and items with 30% or more are marked with x. When the fracture energy (J) was 800 or more and the carbon fiber bundle was split, a mark with a mark “◯” was judged, and a mark outside the range was marked with a mark “X”. The results are shown in Table 1 below.
［比較例１］
コバレントマテリアル(株)製のＳｉＣセラミックスを３×３×４０（ｍｍ）の試験片に加工し、破壊エネルギーを計測したところ、２０Ｊ／ｍ２であった。
[Comparative Example 1]
When SiC ceramics manufactured by Covalent Materials Co., Ltd. were processed into 3 × 3 × 40 (mm) test pieces and the fracture energy was measured, it was 20 J / m 2 .
［比較例２］
東レ(株)製の炭素繊維６ｍｍとＳｉＣと混合後、加圧成形した後、Ａｒ雰囲気２０００℃で焼成した。得られた複合セラミックスから３×３×４０（ｍｍ）の試験片を作製し、破壊エネルギーを計測したところ、４０Ｊ／ｍ２であった。
[Comparative Example 2]
After mixing with 6 mm carbon fiber manufactured by Toray Industries, Inc. and SiC, press molding, and then firing at 2000 ° C. in an Ar atmosphere. A test piece of 3 × 3 × 40 (mm) was produced from the obtained composite ceramics, and the fracture energy was measured and found to be 40 J / m 2 .
以上、説明したとおり、本発明の実施例では、強化用繊維材料４における炭素繊維束３の内部のみを異なる組織で充填して、界面を形成することにより高いすべり効果を繊維束内部に付与し、繊維強化セラミックス複合材料の破壊エネルギーを向上させることができた。 As described above, in the embodiment of the present invention, only the inside of the carbon fiber bundle 3 in the reinforcing fiber material 4 is filled with a different structure, and a high slip effect is imparted to the inside of the fiber bundle by forming an interface. The fracture energy of the fiber reinforced ceramic composite material could be improved.
本発明は、自動車や鉄道車両などのブレーキディスク用セラミックス部材として特に好適であるが、軽量で高強度である利点を活かし、例えば、高速回転部の流体用メカニカルシール部材などにも適用が可能である。 The present invention is particularly suitable as a ceramic member for brake discs of automobiles and railway vehicles, but it can be applied to, for example, a mechanical seal member for fluids of a high-speed rotating part, taking advantage of its light weight and high strength. is there.
Claims (6)
前記繊維束の表層の繊維間に形成され、層状構造の炭素からなる層状構造炭素組織と、
前記層状構造炭素組織の内部を充填するように形成され、樹脂を含有し、等方性の組織構造を有する炭素からなる樹脂由来炭素組織と、
前記層状構造炭素組織と前記樹脂由来炭素組織との間に存在する少なくとも一つの界面と、
を備えることを特徴とする強化用繊維材料。 A plurality of fiber bundles containing carbon;
A layered structure carbon structure formed between the fibers of the surface layer of the fiber bundle and made of layered carbon; and
A resin-derived carbon structure formed of carbon that is formed so as to fill the inside of the layered structure carbon structure, contains a resin, and has an isotropic structure structure;
At least one interface existing between the layered structure carbon structure and the resin-derived carbon structure;
A reinforcing fiber material comprising:
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