JP2019099989A - Production method of carbon nano structure, and carbon nano structure - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 157
- 239000004917 carbon fiber Substances 0.000 claims abstract description 157
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 122
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 41
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- 239000003575 carbonaceous material Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
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- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
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Abstract
Description
本発明は炭素ナノ構造体の製造方法及び炭素ナノ構造体に関し、より具体的には、炭素繊維の表面に炭素ナノ構造体を生成させる方法及び炭素ナノ構造体で表面被覆された炭素繊維に関する。また、本発明は、炭素ナノ構造体であるカーボンナノウォールの生成方法にも関する。 The present invention relates to a method of producing carbon nanostructures and carbon nanostructures, and more particularly, to a method of forming carbon nanostructures on the surface of carbon fibers and carbon fibers surface-coated with carbon nanostructures. The present invention also relates to a method of producing carbon nanowalls which are carbon nanostructures.
近年、カーボンナノチューブ、カーボンナノファイバー、カーボンナノウォール、フラーレン及びグラフェン等の、ナノメートルオーダーのサイズを有する微小な炭素構造体（炭素ナノ構造体）が注目されている。例えば、カーボンナノファイバーは、ガラス繊維等に比べて機械的強度や電気伝導性、熱伝導性において優れているため、プラスチック強化材料やガス吸蔵材料、電極材料等の幅広い用途に使用されている。 In recent years, minute carbon structures (carbon nanostructures) having a size of nanometer order, such as carbon nanotubes, carbon nanofibers, carbon nanowalls, fullerenes, and graphene, have attracted attention. For example, carbon nanofibers are superior in mechanical strength, electrical conductivity, and thermal conductivity compared to glass fibers and the like, and thus are used in a wide range of applications such as plastic reinforcing materials, gas storage materials, and electrode materials.
ここで、炭素ナノ構造体の大量生産には、触媒としての金属微粒子に炭素化合物を接触させる気相法が一般的に用いられるが、炭素ナノ構造体内に残存した金属微粒子が導電性等の炭素ナノ構造体の特性に悪影響を及ぼすことが問題となっている。 Here, for mass production of carbon nanostructures, a gas phase method in which a carbon compound is brought into contact with metal fine particles as a catalyst is generally used, but metal fine particles remaining in the carbon nanostructure have carbon such as conductivity. An adverse effect on the properties of the nanostructure has been a problem.
これに対し、例えば、特許文献１（特開２０１３−２１２９４８号公報）においては、カーボンナノファイバーにマイクロ波を照射することで、カーボンナノファイバー中の不純物を除去すると共に、黒鉛化度を向上させる方法が提案されている。 On the other hand, for example, in Patent Document 1 (Japanese Patent Application Laid-Open No. 2013-212948), the carbon nanofibers are irradiated with microwaves to remove impurities in the carbon nanofibers and to improve the degree of graphitization. A method has been proposed.
一方で、従来から知られている炭素繊維は各種マトリックスの強化材としての需要が高まっており、マトリックスとの相互作用を高めるために種々の表面改質方法が提案されている。例えば、特許文献２（特開２０１３−２３１２４５号公報）においては、炭素繊維にメカノケミカル処理を施すことによって、炭素繊維由来ではない原子を表面に付着させる方法が提案されており、特許文献３（特開２０１７−１９３７９１号公報）においては、炭素繊維に電解酸化処理を施すことによって、表面に凹凸を形成させる方法が提案されている。 On the other hand, carbon fibers conventionally known are in increasing demand as reinforcements for various matrices, and various surface modification methods have been proposed to enhance the interaction with the matrix. For example, in Patent Document 2 (Japanese Patent Application Laid-Open No. 2013-231245), a method is proposed in which atoms not derived from carbon fibers are attached to the surface by subjecting carbon fibers to mechanochemical treatment, In Japanese Patent Application Laid-Open No. 2017-193791), there is proposed a method of forming unevenness on the surface by subjecting carbon fibers to electrolytic oxidation treatment.
しかしながら、上記特許文献１に記載のカーボンナノファイバーの製造方法は、金属触媒を含有するカーボンナノファイバーの金属含有量を低減するものであり、金属元素を完全に除去することは極めて困難である。また、得られたカーボンナノファイバーを基材表面（例えば、炭素繊維表面）に密に配列させることはできない。 However, the method for producing carbon nanofibers described in Patent Document 1 reduces the metal content of carbon nanofibers containing a metal catalyst, and it is extremely difficult to completely remove the metal element. In addition, the obtained carbon nanofibers can not be closely arrayed on the surface of a substrate (for example, the surface of a carbon fiber).
また、上記特許文献２及び３に記載の表面処理方法では金属不純物の混入及び炭素繊維の損傷が懸念されることに加え、炭素繊維の表面積の増加という観点からは十分とは言い難い。 Further, the surface treatment methods described in Patent Documents 2 and 3 are not sufficient from the viewpoint of the increase in the surface area of carbon fibers, in addition to the concern about the contamination of metal impurities and the damage of carbon fibers.
以上のような状況に鑑み、本発明の目的は、金属触媒を使用することなく簡便に炭素ナノ構造体を製造する方法、及び炭素繊維の表面を簡便に炭素ナノ構造体化する表面改質方法を提供することにある。 In view of the above situation, an object of the present invention is to provide a method of easily producing a carbon nanostructure without using a metal catalyst, and a surface modification method of simply forming the surface of carbon fiber into a carbon nanostructure. To provide.
本発明者は、上記目的を達成すべく炭素繊維の表面改質方法及び炭素ナノ構造体の製造方法について鋭意研究を重ねた結果、炭素繊維表面にマイクロ波加熱とガスプラズマを同時に作用させること等が、炭素繊維の表面を炭素ナノ構造体化する上で極めて有効であり、炭素材及び基材に対してマイクロ波加熱とガスプラズマを同時に作用させること等が、当該基材の表面にカーボンナノウォールを生成させる上で極めて有効であることを見出し、本発明に到達した。 As a result of intensive researches on the surface modification method of carbon fiber and the manufacturing method of carbon nanostructure in order to achieve the above object, the present inventors simultaneously apply microwave heating and gas plasma to the surface of carbon fiber, etc. Is extremely effective in forming carbon nanostructures on the surface of the carbon fiber, and simultaneously causing microwave heating and gas plasma to act on the carbon material and the substrate, etc. The inventors have found that the present invention is extremely effective in producing a wall.
即ち、本発明は、
ガス雰囲気下で炭素繊維にマイクロ波を照射して前記炭素繊維をマイクロ波加熱し、
前記マイクロ波によって前記ガスの励起状態を誘導し、
前記ガスの発光過程で発生する紫外線で前記炭素繊維のＣ＝Ｃ結合を切断すること、
を特徴とする炭素繊維の表面改質方法、を提供する。
なお、本発明において炭素繊維とは、直径が１μｍ〜２０μｍであり、カーボンナノチューブやカーボンナノファイバーとは全く異なるものである。
That is, the present invention
The carbon fibers are irradiated with microwaves by irradiating the carbon fibers with microwaves in a gas atmosphere,
Inducing an excited state of the gas by the microwave;
Breaking the C = C bond of the carbon fiber with ultraviolet light generated in the light emission process of the gas;
The present invention provides a method of surface modification of carbon fibers characterized by
In the present invention, carbon fibers have a diameter of 1 μm to 20 μm and are completely different from carbon nanotubes and carbon nanofibers.
本発明の炭素繊維の表面改質方法においては、炭素繊維がマイクロ波加熱さると同時にガスの発光過程で発生する紫外線によって表面近傍のＣ＝Ｃ結合が切断される結果、炭素繊維の表面にグラフェン構造を有する炭素ナノ構造体（カーボンナノチューブ、カーボンナノウォール、グラフェン及び酸化グラフェン等）が密に形成される。即ち、マイクロ波の照射による炭素繊維の加熱と雰囲気中のガスの電離（プラズマ化）が必須の条件となる。
なお、本発明において、グラフェン構造とは、１原子の厚さのｓｐ結合炭素原子のシート状の六角形格子構造を含む構造を意味する。
In the surface modification method of carbon fiber according to the present invention, the carbon fiber is subjected to microwave heating and simultaneously the C = C bond in the vicinity of the surface is broken by the ultraviolet rays generated in the light emission process of the gas. Carbon nanostructures having a structure (carbon nanotubes, carbon nanowalls, graphene, graphene oxide, and the like) are densely formed. That is, the heating of the carbon fiber by the irradiation of the microwave and the ionization (plasmatization) of the gas in the atmosphere are the essential conditions.
In the present invention, the graphene structure means a structure including a sheet-like hexagonal lattice structure of sp-bonded carbon atoms having a thickness of 1 atom.
本発明の炭素繊維の改質方法においては、前記ガスが空気、アルゴン、ヘリウム、窒素及び二酸化炭素のうちの少なくとも一つを含むこと、が好ましい。空気、アルゴン、ヘリウム、窒素及び二酸化炭素のいずれかにマイクロ波を照射することで、炭素繊維表面近傍のＣ＝Ｃ結合の切断に寄与する紫外線を効率的に発生させることができる。 In the carbon fiber reforming method of the present invention, it is preferable that the gas contains at least one of air, argon, helium, nitrogen and carbon dioxide. By irradiating microwaves to any of air, argon, helium, nitrogen and carbon dioxide, it is possible to efficiently generate ultraviolet rays that contribute to the breaking of the C = C bond in the vicinity of the surface of the carbon fiber.
また、本発明の炭素繊維の改質方法においては、前記炭素繊維が短繊維であること、が好ましい。炭素繊維を短繊維とすることでマイクロ波照射装置内への配置が容易になり、一度に大量の処理を行うことができる。 Further, in the method of modifying carbon fibers of the present invention, it is preferable that the carbon fibers be short fibers. By making the carbon fibers into short fibers, placement in the microwave irradiation apparatus becomes easy, and a large amount of processing can be performed at one time.
また、本発明の炭素繊維の改質方法においては、前記炭素繊維がミルドファイバーであること、が好ましい。ミルドファイバーは機械的な粉砕によって炭素繊維を短繊維化したものであり、表面近傍に欠陥や歪が導入されていることから、Ｃ＝Ｃ結合の切断及び再結合による炭素ナノ構造体の形成をより効率的に進行させることができる。 Further, in the method of modifying carbon fibers according to the present invention, it is preferable that the carbon fibers be milled fibers. Since milled fibers are short fibers of carbon fibers by mechanical grinding and defects and strains are introduced near the surface, formation of carbon nanostructures by breaking and recombination of CCC bonds It can be made to progress more efficiently.
また、本発明は、
グラフェン構造を有する炭素ナノ構造体によって表面が被覆され、
前記炭素ナノ構造体に金属元素を含まないこと、
を特徴とする炭素繊維、も提供する。
Also, the present invention is
The surface is coated with a carbon nanostructure having a graphene structure,
That the carbon nanostructure does not contain a metal element,
Also provided is a carbon fiber characterized by
本発明の炭素繊維は直径が１μｍ〜２０μｍであり、その表面全域がグラフェン構造を有する炭素ナノ構造体によって被覆されている。また、グラフェン構造を有する炭素ナノ構造体は、グラフェン構造を有するナノメートルオーダーの大きさの炭素構造体であれば特に限定されないが、例えば、カーボンナノチューブ、カーボンナノファイバー、グラフェン及びカーボンナノウォールを挙げることができ、カーボンナノチューブ及び／又はカーボンナノウォールであることが好ましい。また、炭素ナノ構造体は酸化されていてもよく、酸化された炭素ナノ構造体としては、例えば、酸化グラフェンを挙げることができる。 The carbon fiber of the present invention has a diameter of 1 μm to 20 μm, and the entire surface is covered with a carbon nanostructure having a graphene structure. Further, the carbon nanostructure having a graphene structure is not particularly limited as long as it is a carbon structure having a nanometer order size having a graphene structure, and examples thereof include carbon nanotubes, carbon nanofibers, graphene, and carbon nanowalls. Preferably, carbon nanotubes and / or carbon nanowalls. The carbon nanostructure may be oxidized, and examples of the oxidized carbon nanostructure include graphene oxide.
また、本発明の炭素繊維においては、表面を被覆する炭素ナノ構造体に金属元素が含まれていない。一般的に、気相法では金属粒子を触媒として炭素ナノ構造体が形成されるが、本発明の炭素繊維における炭素ナノ構造体は、炭素繊維のＣの切断及び再結合によって形成したものであり、金属触媒を使用していないことから金属元素は含まれていない。 Moreover, in the carbon fiber of the present invention, the carbon nanostructure covering the surface does not contain the metal element. In general, carbon nanostructures are formed using metal particles as catalysts in the vapor phase method, but the carbon nanostructures in the carbon fiber of the present invention are formed by cutting and recombination of carbon fibers C. Since metal catalysts are not used, metal elements are not included.
また、本発明の炭素繊維は短繊維であることが好ましい。短繊維の表面に炭素ナノ構造体を形成させることで、プラスチック強化材料やガス吸蔵材料、電極材料等の用途に好適に用いることができる。 Moreover, it is preferable that the carbon fiber of this invention is a staple fiber. By forming a carbon nanostructure on the surface of a short fiber, it can be used suitably for uses, such as a plastic reinforcement material, a gas storage material, and an electrode material.
更に、本発明の炭素繊維はミルドファイバーとすることが好ましい。ミルドファイバーは機械的な粉砕によって炭素繊維を短繊維化したものであり、表面近傍に欠陥や歪が導入されていることから、Ｃ＝Ｃ結合の切断及び再結合による炭素ナノ構造体の形成をより効率的に進行させることができ、炭素ナノ構造体をより密に形成させることができる。なお、本発明の炭素繊維は、本発明の炭素繊維の表面改質方法によって好適に得ることができる。 Furthermore, it is preferable that the carbon fiber of the present invention be a milled fiber. Since milled fibers are short fibers of carbon fibers by mechanical grinding and defects and strains are introduced near the surface, formation of carbon nanostructures by breaking and recombination of CCC bonds It can be advanced more efficiently, and carbon nanostructures can be formed more densely. In addition, the carbon fiber of this invention can be suitably obtained by the surface modification method of the carbon fiber of this invention.
また、本発明は、
ガス雰囲気下で炭素材及び基材にマイクロ波を照射して、前記炭素材及び前記基材をマイクロ波加熱し、
前記マイクロ波によって前記ガスの励起状態を誘導し、
前記ガスの発光過程で発生する紫外線で前記炭素材のＣ＝Ｃ結合を切断し、
前記炭素材から分離してプラズマ化した炭素を原料として、前記基材の表面にカーボンナノウォールを生成させること、
を特徴とするカーボンナノウォールの生成方法、も提供する。
Also, the present invention is
The carbon material and the base material are irradiated with microwaves in a gas atmosphere to microwave heat the carbon material and the base material,
Inducing an excited state of the gas by the microwave;
The C す る C bond of the carbon material is broken by ultraviolet light generated in the light emission process of the gas,
Generating carbon nanowalls on the surface of the substrate, using carbon separated from the carbon material and converted into plasma as a raw material,
Also provided is a method of producing carbon nanowalls characterized by
本発明のカーボンナノウォールの生成方法においては、炭化水素系ガス及び金属触媒を用いることなく、種々の炭素材を原料として、簡便かつ短時間にカーボンナノウォールを生成することができる。また、基材表面に炭素ナノ構造体を生成させる場合、当該基材を別途昇温することが求められる場合が存在するが、本発明のカーボンナノウォールの生成方法ではマイクロ波の照射によって炭素材と基材の加熱が同時に達成されるため、基材を別途加熱する必要が無い。 In the method for producing carbon nanowalls of the present invention, carbon nanowalls can be produced simply and in a short time using various carbon materials as raw materials without using a hydrocarbon-based gas and a metal catalyst. Moreover, when producing a carbon nanostructure on the substrate surface, there are cases where it is required to separately raise the temperature of the substrate, but in the method of producing carbon nanowalls of the present invention, the carbon material is irradiated by microwaves There is no need to heat the substrate separately, since heating of the substrate and the substrate is achieved simultaneously.
本発明の効果を損なわない限りにおいて、炭素材と基材との位置関係は特に限定されず、炭素材から分離してプラズマ化した炭素が基材の表面に供給される位置とすればよく、例えば、一般的に市販されているアルミナボート内に炭素材と基材とを並べて配置すればよい。 The positional relationship between the carbon material and the base material is not particularly limited as long as the effects of the present invention are not impaired, and it is sufficient that the carbon separated from the carbon material and plasmatized is supplied to the surface of the base material. For example, the carbon material and the base material may be arranged side by side in a commercially available alumina boat.
また、本発明のカーボンナノウォールの生成方法においては、前記ガスが空気、アルゴン、窒素、二酸化炭素の少なくとも１つを含むこと、が好ましい。空気、アルゴン、ヘリウム、窒素及び二酸化炭素のいずれかにマイクロ波を照射することで、炭素材のＣ＝Ｃ結合の切断に寄与する紫外線を効率的に発生させることができる。 Further, in the method of producing carbon nanowalls of the present invention, it is preferable that the gas contains at least one of air, argon, nitrogen and carbon dioxide. By irradiating microwaves to any of air, argon, helium, nitrogen, and carbon dioxide, it is possible to efficiently generate ultraviolet light that contributes to the breaking of the CCC bond of the carbon material.
また、本発明のカーボンナノウォールの生成方法においては、前記炭素材が炭素繊維であること、が好ましい。炭素材を炭素繊維とすることで、基材表面へのカーボンナノウォールの生成と炭素ナノ構造体による炭素繊維表面の被覆を同時に達成することができる。 Further, in the method of producing carbon nanowalls of the present invention, it is preferable that the carbon material is a carbon fiber. By using a carbon material as the carbon fiber, it is possible to simultaneously achieve the formation of carbon nanowalls on the substrate surface and the coating of the carbon fiber surface by the carbon nanostructure.
更に、本発明のカーボンナノウォールの生成方法においては、前記カーボンナノウォールが金属元素を含まないこと、が好ましい。カーボンナノウォールが金属元素を含まないことで、金属元素がカーボンナノウォールの導電性等に悪影響を及ぼすことを抑制することができる。なお、カーボンナノウォールとは、グラフェンシートが数枚から数百枚重なり、厚さ数ｎｍから数十ｎｍの２次元に広がる板状の炭素ナノ構造体であり、表面積が非常に大きく、強靭であるという特徴を有している。 Furthermore, in the method for producing carbon nanowalls of the present invention, it is preferable that the carbon nanowalls do not contain a metal element. Since the carbon nanowalls do not contain a metal element, it is possible to suppress that the metal element adversely affects the conductivity and the like of the carbon nanowalls. A carbon nanowall is a two-dimensional plate-like carbon nanostructure that has several to several hundreds graphene sheets stacked and has a thickness of several nm to several tens of nm, has a very large surface area, and is tough. It has the feature of being.
本発明によれば、金属触媒を使用することなく簡便に炭素ナノ構造体を製造する方法を提供することができる。更に、本発明によれば、炭素繊維の表面を簡便に炭素ナノ構造体化する表面改質方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing a carbon nanostructure easily can be provided, without using a metal catalyst. Furthermore, according to the present invention, it is possible to provide a surface modification method for simply forming a carbon fiber surface into a carbon nanostructure.
以下、本発明の炭素ナノ構造体の生成方法及び当該方法で得られる炭素ナノ構造体及び炭素ナノ構造体で被覆された炭素繊維の好適な一実施形態について詳細に説明する。なお、以下の説明では、本発明の一実施形態を示すに過ぎず、これらによって本発明が限定されるものではなく、また、重複する説明は省略することがある。 Hereinafter, a preferred embodiment of the method for producing a carbon nanostructure of the present invention and the carbon nanostructure obtained by the method and the carbon fiber coated with the carbon nanostructure are described in detail. In the following description, only one embodiment of the present invention is shown, and the present invention is not limited by these, and overlapping descriptions may be omitted.
（１）炭素繊維の表面改質方法（炭素ナノ構造体の生成方法）
本発明の炭素繊維の表面改質方法は、ガス雰囲気下で炭素繊維にマイクロ波を照射して炭素繊維をマイクロ波加熱し、マイクロ波によってガスの励起状態を誘導し、ガスの発光過程で発生する紫外線で炭素繊維のＣ＝Ｃ結合を切断すること、を特徴としている。以下、これらの各構成要件について詳しく説明する。
(1) Surface modification method of carbon fiber (generation method of carbon nanostructure)
In the surface modification method of carbon fiber according to the present invention, carbon fibers are irradiated with microwaves in a gas atmosphere to microwave-heat carbon fibers, microwaves induce excited states of the gases, and are generated in the light emission process of the gases. It is characterized in that the C = C bond of carbon fiber is broken by ultraviolet light. Each of these configuration requirements will be described in detail below.
炭素繊維に表面改質を施す状況の一例を模式的に図１に示す。マイクロ波発生装置２にガラス管４が挿入され、アルミナボート６に入れられた炭素繊維８がガラス管４の内部に配置されている。また、ガラス管４にはガス流入口１０及びガス流出口１２が設けられ、ガラス管４の内部はガス雰囲気となっている。 An example of the condition which surface-reforms to carbon fiber is shown typically in FIG. A glass tube 4 is inserted into the microwave generator 2, and carbon fibers 8 contained in an alumina boat 6 are disposed inside the glass tube 4. Further, the glass tube 4 is provided with a gas inlet 10 and a gas outlet 12, and the inside of the glass tube 4 is in a gas atmosphere.
（１−１）炭素繊維
炭素繊維８は本発明の効果を損なわない限りにおいて特に限定されず、従来公知の種々の炭素繊維を用いることができる。なお、炭素繊維８は直径が１μｍ〜２０μｍであり、カーボンナノチューブやカーボンナノファイバーとは全く異なるものである。
(1-1) Carbon Fiber The carbon fiber 8 is not particularly limited as long as the effects of the present invention are not impaired, and various conventionally known carbon fibers can be used. The carbon fiber 8 has a diameter of 1 μm to 20 μm and is completely different from carbon nanotubes and carbon nanofibers.
炭素繊維８には、短繊維を用いることが好ましく、ミルドファイバーを用いることがより好ましい。ミルドファイバーは機械的な粉砕によって炭素繊維を短繊維化したものであり、表面近傍に欠陥や歪が導入されていることから、Ｃ＝Ｃ結合の切断及び再結合による炭素ナノ構造体の形成をより効率的に進行させることができる。 It is preferable to use a staple fiber as the carbon fiber 8, and it is more preferable to use a milled fiber. Since milled fibers are short fibers of carbon fibers by mechanical grinding and defects and strains are introduced near the surface, formation of carbon nanostructures by breaking and recombination of CCC bonds It can be made to progress more efficiently.
（１−２）ガス雰囲気
本発明の表面改質方法は、炭素繊維８のマイクロ加熱のみでは達成されず、ガスプラズマを利用することが必要である。炭素繊維８がマイクロ波加熱さると同時にガラス管４の内部に存在するガスの発光過程で発生する紫外線によって、炭素繊維８の表面近傍のＣ＝Ｃ結合が切断される結果、炭素繊維８の表面にグラフェン構造を有する炭素ナノ構造体（カーボンナノチューブ、グラフェン及び酸化グラフェン等）が密に形成される。
(1-2) Gas Atmosphere The surface reforming method of the present invention can not be achieved only by microheating of the carbon fibers 8, and it is necessary to use gas plasma. As a result of the CCC bond in the vicinity of the surface of the carbon fiber 8 being cut by the ultraviolet light generated in the process of light emission of the gas present inside the glass tube 4 simultaneously with the microwave heating of the carbon fiber 8, the surface of the carbon fiber 8 Carbon nanostructures having a graphene structure (such as carbon nanotubes, graphene and graphene oxide) are densely formed on the
ガスの発光過程で発生する紫外線によって炭素繊維８の表面のＣ＝Ｃ結合が切断される限りにおいて、ガラス管４に充填又は流通させるガスの種類は限定されないが、空気、アルゴン、ヘリウム、窒素及び二酸化炭素のうちの少なくとも一つを含むことが好ましい。これらのガスは１種で使用してもよいし、２種類以上を組み合わせて使用してもよい。空気、アルゴン、ヘリウム、窒素及び二酸化炭素のいずれかにマイクロ波を照射することで、炭素繊維８表面近傍のＣ＝Ｃ結合の切断に寄与する紫外線を効率的に発生させることができる。 As long as the C = C bond on the surface of the carbon fiber 8 is broken by the ultraviolet rays generated in the process of light emission of gas, the kind of gas to be filled or circulated in the glass tube 4 is not limited. It is preferred to include at least one of carbon dioxide. These gases may be used alone or in combination of two or more. By irradiating microwaves to any of air, argon, helium, nitrogen and carbon dioxide, it is possible to efficiently generate ultraviolet rays contributing to the breaking of the C = C bond in the vicinity of the surface of the carbon fiber 8.
ガラス管４内部のガス圧力やガス流量は、本発明の効果を損なわない限りにおいて特に限定されず、所望する炭素繊維８の表面状態に応じて適宜調整すればよいが、ガラス管４内部の総圧を１０００Ｐａ未満とすることが好ましい。ガラス管４内部を１０００Ｐａとしてマイクロ波を照射することで、炭素繊維８表面近傍のＣ＝Ｃ結合の切断に寄与する紫外線を効率的に発生させることができる。 The gas pressure and gas flow rate inside the glass tube 4 are not particularly limited as long as the effects of the present invention are not impaired, and may be appropriately adjusted according to the desired surface condition of the carbon fiber 8. Preferably, the pressure is less than 1000 Pa. By irradiating the inside of the glass tube 4 with 1000 Pa and irradiating the microwave, it is possible to efficiently generate the ultraviolet light which contributes to the cutting of the CCC bond in the vicinity of the surface of the carbon fiber 8.
（１−３）マイクロ波照射条件
マイクロ波発生装置２によってマイクロ波を発生させ、炭素繊維８及びガラス管４内部のガスに照射する。ここで、マイクロ波とは、波長が１００μｍ〜１ｍの範囲内であり、周波数が３０ＭＨｚ〜３ＴＨｚの電磁波を意味する。マイクロ波発生装置２としては、例えば、汎用の電子レンジを用いることができる。
(1-3) Microwave Irradiation Conditions The microwave generator 2 generates microwaves, and the carbon fibers 8 and the gas in the glass tube 4 are irradiated. Here, the microwave means an electromagnetic wave having a wavelength of 100 μm to 1 m and a frequency of 30 MHz to 3 THz. For example, a general-purpose microwave oven can be used as the microwave generator 2.
炭素繊維８の表面改質に用いるマイクロ波の出力については特に限定されず、炭素繊維８の挿入量（処理量）、処理速度及び所望の表面状態等に応じて適宜調整すればよいが、例えば、１０ｍｇの炭素繊維８を処理する場合は１０Ｗ〜１０００Ｗとすることが好ましく、１００Ｗ〜８００Ｗとすることがより好ましい。 The output of the microwave used for surface modification of the carbon fiber 8 is not particularly limited, and may be appropriately adjusted according to the insertion amount (throughput) of the carbon fiber 8, the processing speed, the desired surface condition, etc. When processing 10 mg of carbon fiber 8, it is preferable to set it as 10W-1000W, and it is more preferable to set it as 100W-800W.
マイクロ波の照射時間についても特に限定されず、炭素繊維８の挿入量（処理量）、処理速度及び所望の表面状態等に応じて適宜調整すればよいが、１０秒〜１０分とすることが好ましく、１分〜５分とすることがより好ましい。処理時間を１０秒〜１０分の範囲で長くすると、炭素繊維８の表面に形成される炭素ナノ構造体の生成量が増加して密度が高くなるが、処理時間を１０分以上とすると炭素繊維８の損傷が大きくなることに加えて、生成した炭素ナノ構造体も損傷してしまう場合がある。 The irradiation time of the microwaves is also not particularly limited, and may be appropriately adjusted according to the insertion amount (processing amount) of the carbon fiber 8, the processing speed, the desired surface condition, etc. Preferably, it is more preferably 1 minute to 5 minutes. When the treatment time is increased in the range of 10 seconds to 10 minutes, the amount of carbon nanostructures formed on the surface of the carbon fiber 8 increases to increase the density, but when the treatment time is 10 minutes or more, the carbon fiber In addition to the increased damage of 8, the generated carbon nanostructures may also be damaged.
（２）炭素ナノ構造体被覆炭素繊維
本発明の炭素繊維の表面改質方法によって、炭素ナノ構造体によって表面被覆された炭素繊維を得ることができる。図２に本発明の炭素繊維（炭素ナノ構造体被覆炭素繊維）の概略断面図を示す。
(2) Carbon nanostructure-coated carbon fiber According to the surface modification method of carbon fiber of the present invention, it is possible to obtain a carbon fiber surface-coated with a carbon nanostructure. FIG. 2 shows a schematic cross-sectional view of a carbon fiber (carbon nanostructure-coated carbon fiber) of the present invention.
炭素繊維８は直径が１μｍ〜２０μｍであり、表面に炭素ナノ構造体２０が形成している。また、炭素繊維８の長さは特に限定されず、一般的に知られている長繊維又は短繊維等を用いることができる。ここで、炭素ナノ構造体２０は密に形成されており、炭素繊維８の表面の全域を被覆した状態となっている。ここで、炭素ナノ構造体２０は炭素繊維８の表面近傍のＣによって形成されていることから、炭素繊維８と炭素ナノ構造体２０は比較的良好な密着性を有しており、炭素繊維８を各種マトリックスの強化材として使用する場合に、炭素繊維８と各種マトリックスとの間の相互作用を増加させることができる（炭素繊維の機械的性質をより反映させることができる）。 The carbon fibers 8 have a diameter of 1 μm to 20 μm, and carbon nanostructures 20 are formed on the surface. Further, the length of the carbon fiber 8 is not particularly limited, and generally known long fibers or short fibers can be used. Here, the carbon nanostructure 20 is densely formed, and covers the entire surface of the carbon fiber 8. Here, since the carbon nanostructure 20 is formed of C near the surface of the carbon fiber 8, the carbon fiber 8 and the carbon nanostructure 20 have relatively good adhesion, The interaction between the carbon fibers 8 and the various matrices can be increased (when the mechanical properties of the carbon fibers can be more reflected) when using as a reinforcement of various matrices.
炭素ナノ構造体２０はナノメートルオーダーの大きさを有する炭素構造体であり、基本的にグラフェン構造を有している。炭素ナノ構造体２０は特に限定されず、例えば、カーボンナノチューブ（単層又は多層）やグラフェンが数枚積層したカーボンナノウォールを挙げることができる。また、炭素ナノ構造体２０は酸化されていてもよく、例えば、酸化された炭素ナノ構造体２０としては、酸化グラフェンを挙げることができる。 The carbon nanostructure 20 is a carbon structure having a nanometer order size, and basically has a graphene structure. The carbon nanostructure 20 is not particularly limited, and examples thereof include carbon nanowalls in which several sheets of carbon nanotubes (single layer or multilayer) and graphene are stacked. In addition, the carbon nanostructure 20 may be oxidized, and examples of the oxidized carbon nanostructure 20 include graphene oxide.
また、炭素ナノ構造体２０には金属元素が含まれていない。一般的に、気相法では金属粒子を触媒として炭素ナノ構造体が形成されるが、炭素ナノ構造体２０は、炭素繊維８の表面近傍のＣの切断及び再結合によって形成したものであり、金属元素は含まれていない。即ち、金属元素を内包する炭素ナノ構造体と比較して、優れた導電性等を有している。 In addition, the carbon nanostructure 20 does not contain a metal element. In general, carbon nanostructures are formed in the vapor phase method using metal particles as a catalyst, but the carbon nanostructures 20 are formed by cutting and recombining C near the surface of the carbon fiber 8, Metal elements are not included. That is, it has excellent conductivity and the like as compared with a carbon nanostructure containing a metal element.
また、炭素繊維８は、短繊維とすることが好ましく、ミルドファイバーとすることがより好ましい。ミルドファイバーは機械的な粉砕によって炭素繊維を短繊維化したものであり、表面近傍に欠陥や歪が導入されていることから、Ｃ＝Ｃ結合の切断及び再結合による炭素ナノ構造体の形成をより効率的に進行させることができ、表面により多くの炭素ナノ構造体２０を形成させることができる。 The carbon fibers 8 are preferably short fibers, more preferably milled fibers. Since milled fibers are short fibers of carbon fibers by mechanical grinding and defects and strains are introduced near the surface, formation of carbon nanostructures by breaking and recombination of CCC bonds It can be advanced more efficiently, and more carbon nanostructures 20 can be formed on the surface.
（３）カーボンナノウォールの生成方法
本発明のカーボンナノウォールの生成方法は、ガス雰囲気下で炭素材及び基材にマイクロ波を照射して炭素材及び基材をマイクロ波加熱し、マイクロ波によってガスの励起状態を誘導し、ガスの発光過程で発生する紫外線で炭素材のＣ＝Ｃ結合を切断し、炭素材から分離してプラズマ化した炭素を原料として、基材の表面にカーボンナノウォールを生成させること、を特徴としている。以下、これらの各構成要件について詳しく説明する。
(3) Method of producing carbon nanowall According to the method of producing carbon nanowall of the present invention, the carbon material and the base material are irradiated with microwaves in a gas atmosphere to microwave-heat the carbon material and the base material by microwaves A carbon nanowall is formed on the surface of a base material by inducing an excited state of gas, breaking CCC bond of carbon material by ultraviolet rays generated in light emission process of gas, separating carbon from carbon material and converting it into plasma. It is characterized by generating. Each of these configuration requirements will be described in detail below.
図１に示すアルミナボート６に炭素材と基材を並べて配置すること以外は、上述の炭素繊維の表面改質方法と同様にして、カーボンナノウォールを生成させることができる。 Carbon nanowalls can be produced in the same manner as the above-described surface modification method of carbon fibers except that the carbon material and the base material are arranged side by side in the alumina boat 6 shown in FIG.
炭素材は本発明の効果を損なわない限りにおいて特に限定されず、グラファイトや活性炭等の従来公知の種々の炭素材を用いることができる。ここで、炭素材として炭素繊維を用いることで、カーボンナノウォールの生成と炭素ナノ構造体による炭素繊維の被覆を同時に達成することができる。 The carbon material is not particularly limited as long as the effects of the present invention are not impaired, and various conventionally known carbon materials such as graphite and activated carbon can be used. Here, by using carbon fibers as the carbon material, it is possible to simultaneously achieve the formation of carbon nanowalls and the coating of carbon fibers with carbon nanostructures.
また、基材についても本発明の効果を損なわない限りにおいて特に限定されず、従来公知の種々の金属材、セラミックス材及びＳｉ材等を用いることができる。金属材としては、Ａｌ、Ｃｕ、Ｆｅを例示することができ、セラミックス材としてはガラスを例示することができる。 The base material is not particularly limited as long as the effects of the present invention are not impaired, and various conventionally known metal materials, ceramic materials, Si materials and the like can be used. As the metal material, Al, Cu and Fe can be exemplified, and as the ceramic material, glass can be exemplified.
基材表面に生成したカーボンナノウォールはその状態で使用してもよいが、基材から分離することで容易に回収することができ、カーボンナノウォール単体として使用することができる。 The carbon nanowalls formed on the surface of the substrate may be used in that state, but can be easily recovered by separating from the substrate, and can be used as a carbon nanowall alone.
以上、本発明の代表的な実施形態について説明したが、本発明はこれらのみに限定されるものではない。例えば、炭素ナノ構造体２０を炭素繊維８の表面から分離回収し、炭素ナノ構造体２０のみで用いることもできる。 Although the representative embodiments of the present invention have been described above, the present invention is not limited to these. For example, the carbon nanostructure 20 can be separated and collected from the surface of the carbon fiber 8 and used as the carbon nanostructure 20 alone.
以下、実施例において本発明の炭素ナノ構造体の生成方法及び炭素ナノ構造体について更に説明するが、本発明はこれらの実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, the method for producing a carbon nanostructure of the present invention and the carbon nanostructure are further described in Examples, but the present invention is not limited to these Examples.
（１）炭素ナノ構造体による炭素繊維の被覆及び炭素ナノ構造体
≪実施例１≫
炭素繊維としてＰＡＮ系のミルドファイバー（東レ株式会社製，トレカＭＬＤ，直径５μｍ）を用い、図１に示す状態で表面処理を施した。具体的には、２０ｍｇの炭素繊維を入れたアルミナボートをガラス管に挿入し、市販の電子レンジを用いて出力７００Ｗでマイクロ波を照射させた。ここで、ガラス管の内部は約１００Ｐａの二酸化炭素雰囲気とし、マイクロ波の照射時間は１〜５分とした。なお、マイクロ波の照射中は発光が認められた。
(1) Coating of carbon fiber with carbon nanostructure and carbon nanostructure << Example 1 >>
Surface treatment was performed in the state shown in FIG. 1 using a PAN-based milled fiber (Toray Industries, Inc., Torayca MLD, diameter 5 μm) as the carbon fiber. Specifically, an alumina boat containing 20 mg of carbon fiber was inserted into a glass tube, and microwave irradiation was performed at a power of 700 W using a commercially available microwave oven. Here, the inside of a glass tube was made into the carbon dioxide atmosphere of about 100 Pa, and the irradiation time of the microwave was made into 1 to 5 minutes. In addition, light emission was recognized during irradiation of a microwave.
マイクロ波の照射時間を１分、３分及び５分とした場合の、照射後の炭素繊維のＳＥＭ写真を図３〜図５にそれぞれ示す。全ての炭素繊維の表面には極めて微細な構造体が形成されており、照射時間の増加に伴ってその密度及び量が増加している。 The SEM photograph of the carbon fiber after irradiation when the irradiation time of a microwave is made into 1 minute, 3 minutes, and 5 minutes is shown in FIGS. 3-5, respectively. Extremely fine structures are formed on the surface of all carbon fibers, and their density and amount increase with the increase of irradiation time.
図３に示す炭素繊維表面の高倍率のＳＥＭ写真及びＴＥＭ写真を図６及び図７にそれぞれ示す。複雑な襞状の構造物やシート状の構造物が確認でき、グラフェンシートが複数枚積層したカーボンナノウォールが密に生成しているものと考えられる。また、チューブ状になっていると考えられる領域も確認される。 High-magnification SEM and TEM photographs of the carbon fiber surface shown in FIG. 3 are shown in FIGS. 6 and 7, respectively. A complex cage-like structure or sheet-like structure can be confirmed, and it is considered that carbon nanowalls in which a plurality of graphene sheets are stacked are densely formed. Also, areas considered to be tubular are also identified.
図７のＴＥＭ観察像の〇印で示す領域の高倍率の観察像を図８に示す。グラフェンシートの面間隔（ｄ００２）は約３オングストロームとなっており、極めて純度の高いカーボンナノウォールが生成していることが分かる。 The high-magnification observation image of the area | region shown by (circle) of the TEM observation image of FIG. 7 is shown in FIG. The interplanar spacing (d 002 ) of the graphene sheet is about 3 angstrom, which indicates that extremely pure carbon nanowalls are formed.
未処理の炭素繊維表面及びマイクロ波の照射時間を１分として得られた炭素繊維表面のＸ線光電子分光分析（ＸＰＳ）の結果を図９に示す。マイクロ波の照射によってＣ−Ｏ結合に起因するピークの相対強度が増加しており、炭素繊維表面に生成した炭素ナノ構造体は酸化した領域を有することが示唆される。 The results of X-ray photoelectron spectroscopy (XPS) of the untreated carbon fiber surface and the carbon fiber surface obtained with the microwave irradiation time of 1 minute are shown in FIG. The relative intensity of the peak resulting from the C—O bond is increased by the microwave irradiation, which suggests that the carbon nanostructure formed on the surface of the carbon fiber has an oxidized region.
未処理の炭素繊維表面及びマイクロ波の照射時間を１分として得られた炭素繊維表面のラマン分光分析結果を図１０に示す。ラマン振動数分布の観測により、マイクロ波の照射によってＤ、Ｇバンド双方の信号が成長しており、炭素繊維表面に炭素構造ができたことが分かる。また、ＸＰＳ分析でマイクロ波照射後の試料で酸素が確認されていることから、炭素繊維表面には酸化グラフェンに類似した炭素構造物が生成していると考えられる。 The results of Raman spectroscopy of the untreated carbon fiber surface and the carbon fiber surface obtained with the microwave irradiation time of 1 minute are shown in FIG. From the observation of the Raman frequency distribution, it can be seen that signals of both D and G bands are grown by microwave irradiation, and a carbon structure is formed on the surface of the carbon fiber. In addition, since oxygen is confirmed in the sample after microwave irradiation by XPS analysis, it is considered that a carbon structure similar to graphene oxide is formed on the surface of the carbon fiber.
≪実施例２≫
ガラス管の内部を約１００Ｐａの空気雰囲気とし、マイクロ波の照射時間を１分又は５分としたこと以外は実施例１と同様にして、炭素繊維に表面処理を施した。なお、マイクロ波の照射中は発光が認められた。
Example 2
The carbon fibers were surface-treated in the same manner as in Example 1 except that the inside of the glass tube was in an air atmosphere of about 100 Pa and the microwave irradiation time was 1 minute or 5 minutes. In addition, light emission was recognized during irradiation of a microwave.
マイクロ波の照射時間を１分及び５分として得られた炭素繊維のＳＥＭ写真を図１１及び図１２にそれぞれ示す。炭素繊維の表面には極めて微細な炭素ナノ構造体が形成されており、照射時間の増加に伴ってその密度及び量が増加している。 The SEM photograph of the carbon fiber obtained as microwave irradiation time 1 minute and 5 minutes is respectively shown in FIG.11 and FIG.12. Very fine carbon nanostructures are formed on the surface of carbon fibers, and the density and amount thereof increase with the increase of irradiation time.
≪実施例３≫
ガラス管の内部を約１００Ｐａのアルゴン雰囲気とし、マイクロ波の照射時間を１分又は５分としたこと以外は実施例１と同様にして、炭素繊維に表面処理を施した。なお、マイクロ波の照射中は発光が認められた。
Example 3
The carbon fibers were surface-treated in the same manner as in Example 1 except that the inside of the glass tube was an argon atmosphere of about 100 Pa, and the microwave irradiation time was 1 minute or 5 minutes. In addition, light emission was recognized during irradiation of a microwave.
マイクロ波の照射時間を１分及び５分として得られた炭素繊維のＳＥＭ写真を図１３及び図１４にそれぞれ示す。炭素繊維の表面には極めて微細な炭素ナノ構造体が形成されており、照射時間の増加に伴ってその密度及び量が増加している。 The SEM photograph of the carbon fiber obtained as microwave irradiation time 1 minute and 5 minutes is respectively shown in FIG.13 and FIG.14. Very fine carbon nanostructures are formed on the surface of carbon fibers, and the density and amount thereof increase with the increase of irradiation time.
≪実施例４≫
ガラス管の内部を約１００Ｐａの窒素雰囲気とし、マイクロ波の照射時間を１分又は５分としたこと以外は実施例１と同様にして、炭素繊維に表面処理を施した。なお、マイクロ波の照射中は発光が認められた。
Example 4
The carbon fibers were surface-treated in the same manner as in Example 1 except that the inside of the glass tube was a nitrogen atmosphere of about 100 Pa and the microwave irradiation time was 1 minute or 5 minutes. In addition, light emission was recognized during irradiation of a microwave.
マイクロ波の照射時間を１分及び５分として得られた炭素繊維のＳＥＭ写真を図１５及び図１６にそれぞれ示す。炭素繊維の表面には極めて微細な炭素ナノ構造体が形成されており、照射時間の増加に伴ってその密度及び量が増加している。 The SEM photograph of the carbon fiber obtained as microwave irradiation time 1 minute and 5 minutes is shown in FIG.15 and FIG.16, respectively. Very fine carbon nanostructures are formed on the surface of carbon fibers, and the density and amount thereof increase with the increase of irradiation time.
≪比較例≫
ガラス管の内部を１０００Ｐａに減圧し、マイクロ波の照射時間を５分としたこと以外は実施例２と同様にして、炭素繊維に表面処理を施した。なお、マイクロ波照射中に発光現象は認められず、紫外線は発生していないものと考えられる。
«Comparative example»
The carbon fibers were subjected to surface treatment in the same manner as in Example 2 except that the inside of the glass tube was depressurized to 1000 Pa and the microwave irradiation time was 5 minutes. Note that no light emission phenomenon is observed during microwave irradiation, and it is considered that no ultraviolet light is generated.
得られた炭素繊維のＳＥＭ写真を図１７に示す。炭素繊維表面は荒れているものの、炭素ナノ構造体の形成は認められない。 The SEM photograph of the obtained carbon fiber is shown in FIG. Although the carbon fiber surface is rough, the formation of carbon nanostructures is not observed.
（２）カーボンナノウォールの生成方法
≪実施例５≫
アルミナボート内に活性炭粉末及び基材（Ａｌ基材、Ｃｕ基材及びＦｅ基材）を配置し、ガラス管の内部を１．４Ｐａのアルゴン雰囲気としてマイクロ波の照射時間を５分としたこと以外は実施例１と同様にして、基材表面にカーボンナノウォールを生成させた。アルミナボート内の活性炭素粉末及び各基材の配置状況を図１８に示す。各基材のサイズは５×５ｍｍとした。なお、マイクロ波の照射中は発光が認められた。
(2) Method of Producing Carbon Nanowall << Example 5 >>
An activated carbon powder and a base material (Al base material, Cu base material and Fe base material) are arranged in an alumina boat, and the inside of the glass tube is made an argon atmosphere of 1.4 Pa and the microwave irradiation time is 5 minutes. In the same manner as in Example 1, carbon nanowalls were formed on the substrate surface. The arrangement | positioning condition of the activated carbon powder and each base material in an alumina boat is shown in FIG. The size of each substrate was 5 × 5 mm. In addition, light emission was recognized during irradiation of a microwave.
処理後の各基材の外観写真を図１９に示す。各基材の表面は黒色化しており、活性炭粉末から分離した炭素が付着したことが確認できる。なお、Ａｌ基材については変形が認められるが、当該変形はマイクロ波照射による昇温が原因であると考えられる。 The external appearance photograph of each base material after a process is shown in FIG. The surface of each substrate is blackened, and it can be confirmed that carbon separated from the activated carbon powder is attached. In addition, although a deformation | transformation is recognized about an Al base material, it is thought that the said deformation | transformation is caused by the temperature rising by microwave irradiation.
Ｃｕ基材から黒色の付着物を剥離させ、ＳＥＭ観察を行った。得られたＳＥＭ写真を図２０に示す。襞状の微細構造体が観察され、カーボンナノウォールが生成していることが確認された。また、Ａｌ基材の表面についてもＳＥＭ写真を行ったところ、図２１に示すように炭素ナノ構造体（カーボンナノウォール）の生成が確認された。 The black deposit was peeled off from the Cu substrate, and SEM observation was performed. The obtained SEM photograph is shown in FIG. A bowl-shaped microstructure was observed, and it was confirmed that carbon nanowalls were formed. Moreover, when the SEM photograph was performed also about the surface of Al base material, as shown in FIG. 21, generation | occurrence | production of the carbon nanostructure (carbon nano wall) was confirmed.
≪実施例６≫
炭素材及び基材をそれぞれ炭素繊維及びＳｉ基材とし、ガラス管の内部を８Ｐａの二酸化炭素雰囲気としてマイクロ波の照射時間を３分としたこと以外は実施例５と同様にして、基材表面にカーボンナノウォールを生成させた。
Example 6
In the same manner as in Example 5 except that the carbon material and the base material are respectively a carbon fiber and a Si base material, and the inside of the glass tube is a carbon dioxide atmosphere of 8 Pa and the irradiation time of the microwave is 3 minutes, Carbon nanowalls were formed.
処理後のＳｉ基材の外観写真を図２２に示す。表面は黒色化しており、炭素が付着したことが確認できる。また、Ｓｉ基材を側面からＳＥＭ観察したところ、図２３に示すように密集したカーボンナノウォールが確認された。 An appearance photograph of the Si substrate after the treatment is shown in FIG. The surface is blackened, and it can be confirmed that carbon is attached. In addition, SEM observation of the Si base material from the side revealed that dense carbon nanowalls were observed as shown in FIG.
≪実施例７≫
基材をガラス基材としたこと以外は実施例６と同様にして、基材表面にカーボンナノウォールを生成させた。
<< Example 7 >>
Carbon nanowalls were formed on the surface of a substrate in the same manner as in Example 6 except that the substrate was a glass substrate.
アルミナボート内の処理後のガラス基材の外観写真を図２４に示す。アルミナボート及びガラス基材の表面は黒色化しており、炭素が付着したことが確認できる。また、ガラス基材の表面をＳＥＭ観察したところ、図２５に示すように密集したカーボンナノウォールが確認された。 An appearance photograph of the glass substrate after the treatment in the alumina boat is shown in FIG. The surfaces of the alumina boat and the glass substrate are blackened, and it can be confirmed that carbon is attached. In addition, SEM observation of the surface of the glass substrate revealed dense carbon nanowalls as shown in FIG.
２・・・マイクロ波発生装置、
４・・・ガラス管、
６・・・アルミナボート、
８・・・炭素繊維、
１０・・・ガス流入口、
１２・・・ガス流出口、
２０・・・炭素ナノ構造体。
2 ... microwave generator,
4 ・ ・ ・ Glass tube,
6 ・ ・ ・ Alumina boat,
8 ... carbon fiber,
10 ・ ・ ・ gas inlet,
12 ・ ・ ・ gas outlet,
20: Carbon nanostructure.
Claims (13)
前記マイクロ波によって前記ガスの励起状態を誘導し、
前記ガスの発光過程で発生する紫外線で前記炭素繊維のＣ＝Ｃ結合を切断すること、
を特徴とする炭素繊維の表面改質方法。 The carbon fibers are irradiated with microwaves by irradiating the carbon fibers with microwaves in a gas atmosphere,
Inducing an excited state of the gas by the microwave;
Breaking the C = C bond of the carbon fiber with ultraviolet light generated in the light emission process of the gas;
Method of surface modification of carbon fiber characterized by
を特徴等する請求項１に記載の炭素繊維の表面改質方法。 The gas comprises at least one of air, argon, helium, nitrogen and carbon dioxide;
The surface modification method of the carbon fiber according to claim 1, characterized in that
を特徴とする請求項１又は２に記載の炭素繊維の表面改質方法。 The carbon fiber is a staple fiber,
The surface modification method of the carbon fiber according to claim 1 or 2 characterized by
を特徴とする請求項１〜３のいずれかに記載の炭素繊維の表面改質方法。 The carbon fiber is a milled fiber,
The surface modification method of the carbon fiber according to any one of claims 1 to 3, characterized in that
前記炭素ナノ構造体に金属元素が含まれないこと、
を特徴とする炭素繊維。 The surface is coated with a carbon nanostructure having a graphene structure,
That the carbon nanostructure does not contain a metal element,
Carbon fiber characterized by
を特徴とする請求項５に記載の炭素繊維。 The carbon nanostructure is a carbon nanotube and / or a carbon nanowall,
The carbon fiber according to claim 5, characterized in that
を特徴とする請求項５又は６に記載の炭素繊維。 Being a staple fiber,
The carbon fiber according to claim 5 or 6, characterized in that
を特徴とする請求項５〜７のいずれかに記載の炭素繊維。 Being a milled fiber,
The carbon fiber according to any one of claims 5 to 7, characterized in that
を特徴とする請求項５〜８のいずれかに記載の炭素繊維。 The carbon nanostructure includes graphene oxide,
The carbon fiber according to any one of claims 5 to 8, characterized by
前記マイクロ波によって前記ガスの励起状態を誘導し、
前記ガスの発光過程で発生する紫外線で前記炭素材のＣ＝Ｃ結合を切断し、
前記炭素材から分離してプラズマ化した炭素を原料として、前記基材の表面にカーボンナノウォールを生成させること、
を特徴とするカーボンナノウォールの生成方法。 The carbon material and the base material are irradiated with microwaves in a gas atmosphere to microwave heat the carbon material and the base material,
Inducing an excited state of the gas by the microwave;
The C す る C bond of the carbon material is broken by ultraviolet light generated in the light emission process of the gas,
Generating carbon nanowalls on the surface of the substrate, using carbon separated from the carbon material and converted into plasma as a raw material,
A method of producing carbon nanowalls characterized by
を特徴とする請求項１０に記載のカーボンナノウォールの生成方法。 The gas contains at least one of air, argon, nitrogen and carbon dioxide;
The method for producing carbon nanowalls according to claim 10, characterized in that
を特徴とする請求項１０又は１１に記載のカーボンナノウォールの生成方法。 The carbon material is carbon fiber,
The method for producing a carbon nanowall according to claim 10 or 11, characterized in that
を特徴とする請求項１０〜１２のうちのいずれかに記載のカーボンナノウォールの生成方法。 The carbon nanowall does not contain a metal element,
The method for producing a carbon nanowall according to any one of claims 10 to 12, characterized in that
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