JP2017024942A - Carbon nanotube coating film member and method for producing the same - Google Patents
Carbon nanotube coating film member and method for producing the same Download PDFInfo
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Abstract
Description
本発明は、カーボンナノチューブ被膜部材とその製造方法に関する。特に、本発明は、基材の形状に制約を受けにくく、分光反射率の低いカーボンナノチューブ被膜部材とその製造方法に関する。 The present invention relates to a carbon nanotube film member and a method for producing the same. In particular, the present invention relates to a carbon nanotube film member having a low spectral reflectance and a manufacturing method thereof, which is not easily restricted by the shape of a substrate.
放射温度計や光検出器の校正に用いられる黒体空洞や光学機器のバッフル（観測や測定に支障を与える迷光を遮光する部材）の表面は可能な限り反射率が小さい（放射率が大きい）黒色物質で覆われている事が必要である。また、発熱体や放熱板のように輻射熱を放出又は吸収することを目的とする部材の表面も同様な黒色物質で覆われていることが必要であると共に耐熱性も有することが求められる。近年、カーボンナノチューブ（以下、ＣＮＴという）の垂直配向集合体の反射率が非常に小さいことが報告されており、ＣＮＴを黒化膜として応用することが期待されている。ＣＮＴの構成元素である炭素の融点は3000℃以上であるため、耐熱性という点でもＣＮＴは優れた材料である。それゆえ、ＣＮＴを表面に成長させたアルミニウム合金製の基材を地球観測衛星に搭載する黒体光源として利用する事を目的とした様々な開発・評価が行われている事が非特許文献１に報告されている。 The surface of blackbody cavities used for calibration of radiation thermometers and photodetectors and baffles of optical instruments (members that block stray light that interferes with observation and measurement) have as little reflectivity as possible (high emissivity) It must be covered with black material. Further, the surface of a member intended to emit or absorb radiant heat, such as a heating element or a heat radiating plate, needs to be covered with a similar black material and has heat resistance. In recent years, it has been reported that the reflectance of a vertically aligned aggregate of carbon nanotubes (hereinafter referred to as CNT) is very small, and it is expected to apply CNT as a blackening film. Since the melting point of carbon, which is a constituent element of CNT, is 3000 ° C. or higher, CNT is an excellent material in terms of heat resistance. Therefore, various developments and evaluations have been conducted for the purpose of using a base material made of an aluminum alloy with CNTs grown on the surface as a black body light source mounted on an earth observation satellite. Has been reported.
基材表面にＣＮＴ膜を形成する技術の中で最も効率的で商業的に実現する可能性が高い技術としては、鉄系遷移金属を触媒として炭化水素ガスを熱分解してＣＮＴを基材表面に成長させる触媒化学気相成長法（以下、触媒CVD法という）が挙げられる。この方法では、基材自体がＣＮＴの触媒金属を主成分とする合金で無い場合には、CVDの前処理として触媒層となる鉄系遷移金属薄膜を基材表面に形成する必要がある。一般に、上述したような黒化膜を必要とする部材の基材に使われる金属、炭素材料、半導体の多くは触媒金属である鉄系遷移金属とは反応してしまうか、又は基材内部に触媒金属が拡散してしまい、触媒活性が失われてしまう問題が生じる。この問題を解消するため、一般に、金属や炭素材料を基材としてＣＮＴをCVDにより製膜する場合には、触媒層を製膜する前に金属酸化物薄膜からなる触媒担持層を基材上に形成する必要がある。 The technology that forms the CNT film on the surface of the base material is the most efficient and highly likely to be realized commercially. The CNTs are converted into the base material surface by pyrolyzing hydrocarbon gas using iron-based transition metal as a catalyst. And catalytic chemical vapor deposition (hereinafter referred to as catalytic CVD method). In this method, when the base material itself is not an alloy containing a CNT catalyst metal as a main component, it is necessary to form an iron-based transition metal thin film as a catalyst layer on the base material surface as a pretreatment for CVD. In general, most of the metals, carbon materials, and semiconductors used in the base material of the members that require the blackening film as described above react with the iron-based transition metal that is the catalytic metal, or the inside of the base material. The problem arises that the catalytic metal diffuses and the catalytic activity is lost. In order to solve this problem, in general, when a CNT film is formed by CVD using a metal or carbon material as a base material, a catalyst support layer made of a metal oxide thin film is formed on the base material before forming the catalyst layer. Need to form.
触媒層と触媒担持層を成長させることを特徴とするＣＮＴの代表的な製膜方法として、非特許文献２では、スパッタリングにより金属箔上にアルミナ薄膜（触媒担持層）と鉄薄膜（触媒層）を形成した後、エチレンの熱分解を利用したCVD法によりＣＮＴを金属箔上に成長させる手法を報告している。非特許文献３では、カーボンペーパー（炭素繊維複合材の一種）上に電子線蒸着法によりアルミニウムと鉄の２層薄膜を形成した後、アセチレンの熱分解を利用したCVD法によりＣＮＴをカーボンペーパー上に製膜する手法を報告している。非特許文献４では、シリコン基材上に電子線蒸着法によりチタニウムと鉄の２層薄膜を形成した後、アセチレンの熱分解を利用したCVD法によりＣＮＴをシリコン基材上に製膜する手法を報告している。非特許文献３及び４の手法では、基材表面のアルミニウムとチタニウムはいずれもCVDを実施する温度・雰囲気においては鉄よりも酸化しやすい性質を有するため、酸化してアルミナとチタニアとなり鉄触媒の担持層の役割を担うことになる。非特許文献５では、シリコン基材上にスパッタリングにより触媒担持層の前駆体であるアルミニウム薄膜を形成した後、１００℃程度で昇華する鉄化合物であるフェロセン蒸気に基材を暴露させることで鉄薄膜層を形成してからエチレンの熱分解を利用したCVD法によりＣＮＴをシリコン基材上に製膜する手法を報告している。 As a typical CNT film-forming method characterized by growing a catalyst layer and a catalyst support layer, Non-Patent Document 2 discloses an alumina thin film (catalyst support layer) and an iron thin film (catalyst layer) on a metal foil by sputtering. After the formation of CNTs, a method of growing CNTs on a metal foil by a CVD method utilizing the thermal decomposition of ethylene has been reported. In Non-Patent Document 3, a two-layer film of aluminum and iron is formed on carbon paper (a kind of carbon fiber composite material) by electron beam evaporation, and then CNT is deposited on carbon paper by CVD using thermal decomposition of acetylene. The method of film formation is reported. In Non-Patent Document 4, a method of forming a CNT film on a silicon substrate by a CVD method using thermal decomposition of acetylene after forming a two-layer thin film of titanium and iron on the silicon substrate by electron beam evaporation. Reporting. In the methods of Non-Patent Documents 3 and 4, both aluminum and titanium on the surface of the base material are more easily oxidized than iron at the temperature and atmosphere in which CVD is performed. The role of the support layer is assumed. In Non-Patent Document 5, after forming an aluminum thin film that is a precursor of a catalyst support layer on a silicon substrate by sputtering, the substrate is exposed to ferrocene vapor that is an iron compound that sublimes at about 100 ° C. A method for forming a CNT film on a silicon substrate by a CVD method using thermal decomposition of ethylene after forming a layer has been reported.
これら４つの手法は最も一般的に用いられているＣＮＴの製膜法であるが、触媒層や触媒担持層の製膜に電子線蒸着やスパッタリングのような物理気相蒸着（PVD）を用いていることが次に述べるような理由によりＣＮＴの商業的な応用を妨げている。一般にPVDは真空中で処理をおこなう必要があるため製膜できる基材の大きさは使用する真空槽の大きさに依存すると共に膜原料を基材表面に照射させる際に基材自体が遮蔽物となってしまうような複雑な三次元形状を有する物体の表面に製膜することはできないため、このような方法で黒体空洞や天体望遠鏡の内表面等にＣＮＴを製膜することは技術的に困難である。また、一般にPVDを行うための装置の購入・運用には多大なコストが掛かる。これらの問題のため、ＣＮＴを製膜した部材が上述のような用途の市販製品に応用された例はほとんど無い。 These four methods are the most commonly used CNT film formation methods, but physical vapor deposition (PVD) such as electron beam evaporation or sputtering is used to form the catalyst layer and catalyst support layer. This hinders the commercial application of CNTs for the following reasons. In general, PVD needs to be processed in a vacuum, so the size of the substrate that can be formed depends on the size of the vacuum chamber used, and the substrate itself is a shield when the substrate is irradiated with the film material. Since it is impossible to form a film on the surface of an object having a complicated three-dimensional shape, it is technically necessary to form a CNT film on a black body cavity or the inner surface of an astronomical telescope by such a method. It is difficult to. In general, the purchase and operation of a device for performing PVD is very expensive. Because of these problems, there are almost no examples in which a member formed with CNT is applied to a commercial product for the above-mentioned use.
PVDの代わりに低コストのウェットプロセスにより触媒層と触媒担持層を形成することを特徴とするＣＮＴの製膜方法が提案されている。非特許文献６では、10種類の導電性固体試料（高濃度ドーピング処理シリコン、金、銀、銅、アルミニウム、白金、タングステン、窒化チタン、ニクロム合金、鋼）の表面に硝酸アルミニウムと硝酸鉄を混合した水溶液の滴をピペットで落とした後、アルゴンと水素の混合雰囲気下において200℃以上に加熱することで試料表面に触媒担持層となるアルミナ薄膜とＣＮＴの触媒となる鉄薄膜を成長させた後に700℃以上に加熱し、アセチレンの熱分解を利用したCVDによりＣＮＴの製膜を試みた結果、白金以外の試料表面に多層ＣＮＴを成長させることができたことが報告されている。非特許文献７では、非特許文献６とほぼ同様な方法により炭素繊維製の織物の表面にＣＮＴを製膜したことが報告されている。非特許文献６及び７が採用している方法では、基材表面に垂らした溶液に含まれる硝酸アルミニウムと硝酸鉄は200℃以上に加熱されるとそれぞれの酸化物すなわちアルミナとFe2O3に変化してアルミナは触媒担持層の役割を担い、水素を含む還元雰囲気下で更に加熱することによりFe2O3は触媒活性を有する鉄に還元されることで触媒層を形成することを特徴としている。したがって、この方法は雰囲気制御が可能な加熱炉さえあれば基材表面に触媒層とその担持層を製膜可能であるため、複雑な形状の部材表面にＣＮＴを低コストで製膜できる可能性がある。 There has been proposed a CNT film forming method characterized in that a catalyst layer and a catalyst support layer are formed by a low-cost wet process instead of PVD. In Non-Patent Document 6, aluminum nitrate and iron nitrate are mixed on the surface of 10 kinds of conductive solid samples (highly doped silicon, gold, silver, copper, aluminum, platinum, tungsten, titanium nitride, nichrome alloy, steel). After dropping a drop of the aqueous solution with a pipette, by heating to 200 ° C or higher in a mixed atmosphere of argon and hydrogen, after growing an alumina thin film as a catalyst supporting layer and an iron thin film as a CNT catalyst on the sample surface It has been reported that multilayer CNTs can be grown on the surface of a sample other than platinum as a result of attempts to form CNTs by CVD using thermal decomposition of acetylene after heating to 700 ° C. or higher. Non-Patent Document 7 reports that CNTs were formed on the surface of a carbon fiber woven fabric by substantially the same method as in Non-Patent Document 6. In the methods employed in Non-Patent Documents 6 and 7, aluminum nitrate and iron nitrate contained in the solution suspended on the surface of the base material are heated to 200 ° C. or more to form respective oxides, that is, alumina and Fe 2 O 3 . Alumina plays a role as a catalyst support layer, and Fe 2 O 3 is reduced to iron having catalytic activity by further heating in a reducing atmosphere containing hydrogen, thereby forming a catalyst layer. Yes. Therefore, this method can form a catalyst layer and its supporting layer on the surface of the base material as long as there is a heating furnace that can control the atmosphere. There is.
触媒CVD法によるＣＮＴ製膜においてウェットプロセスを用いて基材表面に触媒層及びに触媒担持層を製膜させる場合、次に述べる２つの問題が生じる。 When forming a catalyst layer and a catalyst support layer on the surface of a substrate using a wet process in the CNT film formation by the catalytic CVD method, the following two problems occur.
触媒層を成長させるためにはウェットプロセス後の基材を水素雰囲気下で加熱して基材表面の酸化鉄を触媒の鉄に還元する処理は必須である。しかしながら、非特許文献６に指摘されているように、水素の存在は白金表面でのＣＮＴの成長を阻害してしまう。さらに、一般に金属の場合、高温の水素雰囲気に晒されると水素が金属原子間に侵入してもろくなる現象（水素脆化）が起きるため、基材を金属とする場合には水素の使用は避けることが望ましい。また、ＣＮＴは原料である炭化水素の熱分解反応によって生じるため、副生成物として水素もしくは水素と酸素が反応して水が生成される。したがって、副生成物である水素の反応系内での濃度が上昇した場合、ルシャトリエの原理から判るように炭化水素の熱分解反応が阻害される方向に反応が進むため、ＣＮＴの成長という観点に立てば水素の導入は熱力学的には不利と考えられる。このような問題を回避するため水素以外の還元ガスとして一酸化炭素を使用することが考えられるが、一酸化炭素は有毒ガスであるため運用時における安全性に問題がある。また、還元ガスを必要とするプロセスは設備の購入・運用に関わるコストの増大を招く。 In order to grow the catalyst layer, it is indispensable to heat the substrate after the wet process in a hydrogen atmosphere to reduce the iron oxide on the surface of the substrate to the iron of the catalyst. However, as pointed out in Non-Patent Document 6, the presence of hydrogen inhibits the growth of CNTs on the platinum surface. Furthermore, in general, in the case of metals, when exposed to a high-temperature hydrogen atmosphere, the phenomenon that hydrogen penetrates between metal atoms becomes brittle (hydrogen embrittlement), so avoid using hydrogen when the substrate is made of metal. It is desirable. In addition, since CNT is generated by a thermal decomposition reaction of hydrocarbon as a raw material, water or hydrogen and oxygen react as a by-product to generate water. Therefore, when the concentration of hydrogen, which is a by-product, increases in the reaction system, the reaction proceeds in a direction that inhibits the thermal decomposition reaction of hydrocarbons as can be seen from the principle of Le Chatelier. The introduction of hydrogen is considered to be disadvantageous in terms of thermodynamics. In order to avoid such problems, it is conceivable to use carbon monoxide as a reducing gas other than hydrogen. However, since carbon monoxide is a toxic gas, there is a problem in safety during operation. In addition, a process that requires a reducing gas causes an increase in costs related to the purchase and operation of equipment.
ウェットプロセスのもう一つの問題点は、触媒前駆体溶液と基材の濡れ性が悪い場合、溶液が表面に不均一に滞留してしまうため、触媒層及び触媒担持層が不均一になってしまい、結果として成長させたＣＮＴ膜も不均一になってしまうことである。非特許文献６及び７に紹介されているウェットプロセスによる表面前処理を用いたＣＮＴの製膜実験では、触媒前駆体溶液はピペットや注射器で基材の非常に小さい範囲にのみ垂らしているだけであり、大面積を有する基材の全面にＣＮＴの製膜が可能であることを実証していない。実際、発明者らは非特許文献６の実験で使われている硝酸鉄と硝酸アルミニウムの混合水溶液に金属板を浸漬させた後にＣＮＴの製膜を試みたが、不均一な膜しか形成できなかった。 Another problem of the wet process is that if the wettability of the catalyst precursor solution and the substrate is poor, the solution stays unevenly on the surface, so the catalyst layer and the catalyst support layer become non-uniform. As a result, the grown CNT film also becomes non-uniform. In the CNT film formation experiment using the surface pretreatment by the wet process introduced in Non-Patent Documents 6 and 7, the catalyst precursor solution is only dropped on a very small area of the substrate with a pipette or a syringe. In addition, it has not been demonstrated that CNT film formation is possible on the entire surface of a substrate having a large area. In fact, the inventors tried to form a CNT film after immersing a metal plate in a mixed aqueous solution of iron nitrate and aluminum nitrate used in the experiment of Non-Patent Document 6, but only a non-uniform film could be formed. It was.
本発明は、上述した問題を解決するものであって、金属や炭素材料の基材に製膜した、分光反射率の低いカーボンナノチューブ被膜部材とその製造方法を提供する。 The present invention solves the above-described problems, and provides a carbon nanotube film member having a low spectral reflectance formed on a metal or carbon material substrate and a method for producing the same.
本発明の一実施形態によると、基材をアルミニウム化合物溶液に浸漬し、前記基材を800℃以上に加熱し、金属錯体蒸気を用いる浮遊触媒輸送式の化学気相成長により、カーボンナノチューブを前記基材の表面に製膜するカーボンナノチューブ被膜部材の製造方法が提供される。 According to one embodiment of the present invention, the carbon nanotubes are immersed in an aluminum compound solution, the substrate is heated to 800 ° C. or more, and the carbon nanotubes are formed by floating catalyst transport chemical vapor deposition using a metal complex vapor. A method of manufacturing a carbon nanotube film member that forms a film on the surface of a substrate is provided.
前記カーボンナノチューブ被膜部材の製造方法において、前記アルミニウム化合物溶液が硝酸アルミニウム溶液であってもよい。 In the method of manufacturing the carbon nanotube film member, the aluminum compound solution may be an aluminum nitrate solution.
前記カーボンナノチューブ被膜部材の製造方法において、前記アルミニウム化合物溶液に浸漬した前記基材を、真空下で800℃以上に加熱してもよい。 In the method for manufacturing the carbon nanotube film member, the base material immersed in the aluminum compound solution may be heated to 800 ° C. or higher under vacuum.
前記カーボンナノチューブ被膜部材の製造方法において、前記基材は、Au、Ag、Cu、Pt、W、Nb、Ta、Mo、V、Pd、Fe、Ni、Co、Cr、Ti、Hf、Zr、Si、Eu、Gd、U及びそれらを主成分とする合金からなる群から選択されてもよい。 In the method of manufacturing a carbon nanotube film member, the base material is Au, Ag, Cu, Pt, W, Nb, Ta, Mo, V, Pd, Fe, Ni, Co, Cr, Ti, Hf, Zr, Si. , Eu, Gd, U, and an alloy containing them as a main component may be selected.
前記カーボンナノチューブ被膜部材の製造方法において、前記基材に無機物微粒子を衝突させて粗面を形成してもよい。 In the method of manufacturing the carbon nanotube film member, a rough surface may be formed by causing inorganic fine particles to collide with the base material.
前記カーボンナノチューブ被膜部材の製造方法において、前記基材は、炭素繊維複合材、等方性黒鉛、ガラス状炭素及び天然黒鉛からなる群から選択されてもよい。 In the method of manufacturing the carbon nanotube film member, the base material may be selected from the group consisting of a carbon fiber composite material, isotropic graphite, glassy carbon, and natural graphite.
また、本発明の一実施形態によると、基材と、前記基材の表面に配置された無機物層と、前記無機物層上に担持された触媒金属微粒子層と、前記触媒金属微粒子層上に配置されたカーボンナノチューブを備え、分光反射率が０．０１以下であるカーボンナノチューブ被膜部材が提供される。 According to one embodiment of the present invention, the substrate, the inorganic layer disposed on the surface of the substrate, the catalyst metal fine particle layer supported on the inorganic layer, and the catalyst metal fine particle layer are disposed. A carbon nanotube film member comprising the carbon nanotubes having a spectral reflectance of 0.01 or less is provided.
前記カーボンナノチューブ被膜部材において、前記基材は、Au、Ag、Cu、Pt、W、Nb、Ta、Mo、V、Pd、Fe、Ni、Co、Cr、Ti、Hf、Zr、Si、Eu、Gd、U及びそれらを主成分とする合金からなる群から選択されてもよい。 In the carbon nanotube film member, the base material is Au, Ag, Cu, Pt, W, Nb, Ta, Mo, V, Pd, Fe, Ni, Co, Cr, Ti, Hf, Zr, Si, Eu, It may be selected from the group consisting of Gd, U and alloys based on them.
前記カーボンナノチューブ被膜部材において、前記基材が粗面を備えてもよい。 In the carbon nanotube film member, the base material may have a rough surface.
前記カーボンナノチューブ被膜部材において、前記基材が炭素繊維複合材、等方性黒鉛、ガラス状炭素及び天然黒鉛からなる群から選択されてもよい。 In the carbon nanotube film member, the base material may be selected from the group consisting of a carbon fiber composite material, isotropic graphite, glassy carbon, and natural graphite.
本発明によると、金属や炭素材料の基材の表面に、その形状に大きな制限を受けることなく、カーボンナノチューブを一様に成長させた分光反射率の低いカーボンナノチューブ被膜部材とその製造方法を提供することができる。分光反射率の低い本発明に係るカーボンナノチューブ被膜部材は、黒体炉、標準反射板、発熱体、放熱板、光学機器のバッフル等に利用することができる。 According to the present invention, a carbon nanotube coating member having a low spectral reflectance, in which carbon nanotubes are uniformly grown on the surface of a metal or carbon material base material without being greatly limited in shape, and a method for producing the same are provided. can do. The carbon nanotube film member according to the present invention having a low spectral reflectance can be used for a black body furnace, a standard reflector, a heating element, a heat radiating plate, a baffle of an optical instrument, and the like.
本発明者らは、上述した問題を解決すべく鋭意検討した結果、ウェットプロセスによる触媒担持層の形成と、金属錯体蒸気を触媒前駆体として用いる浮遊触媒輸送式の化学気相成長法によるカーボンナノチューブ（以下、ＣＮＴという）の合成を組合せることにより、金属や炭素材料の基材の表面に、その形状に大きな制限を受けることなく、カーボンナノチューブを一様に成長させ、分光反射率の低いカーボンナノチューブ被膜部材を得られることを見出した。 As a result of intensive investigations to solve the above-mentioned problems, the inventors of the present invention have formed a catalyst support layer by a wet process and carbon nanotubes by a floating catalyst transport type chemical vapor deposition method using a metal complex vapor as a catalyst precursor. By combining the synthesis of carbon (hereinafter referred to as CNT), carbon nanotubes can be grown uniformly on the surface of the base material of metal or carbon material without being greatly restricted in its shape, and carbon having a low spectral reflectance It has been found that a nanotube-coated member can be obtained.
以下、図面を参照して本発明に係るカーボンナノチューブ被膜部材（以下、ＣＮＴ被膜部材）とその製造方法について説明する。本発明のＣＮＴ被膜部材とその製造方法は、以下に示す実施の形態及び実施例の記載内容に限定して解釈されるものではない。なお、本実施の形態及び後述する実施例で参照する図面において、同一部分又は同様な機能を有する部分には同一の符号を付し、その繰り返しの説明は省略する。 Hereinafter, a carbon nanotube film member (hereinafter referred to as a CNT film member) and a manufacturing method thereof according to the present invention will be described with reference to the drawings. The CNT coated member and the manufacturing method thereof of the present invention are not construed as being limited to the description of the embodiments and examples shown below. Note that in the drawings referred to in this embodiment mode and examples to be described later, the same portions or portions having similar functions are denoted by the same reference numerals, and description thereof is not repeated.
本明細書において、浮遊触媒輸送式の化学気相成長法（以下CVD法という）とは、金属錯体蒸気に基材を暴露させることにより触媒層を形成し、炭素を含有するガスの熱分解によりＣＮＴを合成する方法である。 In this specification, floating catalyst transport type chemical vapor deposition (hereinafter referred to as CVD method) is a method in which a catalyst layer is formed by exposing a substrate to a metal complex vapor and pyrolysis of a gas containing carbon. This is a method of synthesizing CNT.
ここで述べる粗面とは、表面に様々な曲率半径を有する屈曲部が無数かつ不規則に存在する表面構造を指し、加熱時に形成される熱酸化膜と金属基材の熱膨張差により膜の無数の屈曲部に微細な割れが生じる。それゆえ、平滑面と比較して粗面に形成された熱酸化膜には、より多くの空隙が存在することになる。そして、それらの空隙に触媒金属が強固に沈着するため、ＣＮＴが基板表面に欠損部無く一様に成長する効果が高まることを見出した。 The rough surface described here refers to a surface structure in which a bend having various radii of curvature exists innumerably and irregularly on the surface, and the film has a difference in thermal expansion between the thermal oxide film formed during heating and the metal substrate. Fine cracks occur in countless bends. Therefore, more voids exist in the thermal oxide film formed on the rough surface compared to the smooth surface. And since catalyst metal deposited firmly in those space | gap, it discovered that the effect that CNT grew uniformly on a substrate surface without a defect part increased.
（実施形態１）
図１は、本発明の一実施形態に係るＣＮＴ被膜部材１００を示す模式図である。ＣＮＴ被膜部材１００は、例えば、基材１１０と、基材１１０の表面に配置された無機物層１２０と、無機物層１２０に担持された触媒金属微粒子層１３０と、触媒金属微粒子層１３０上に配置されたＣＮＴ１５０を備える。
(Embodiment 1)
FIG. 1 is a schematic view showing a CNT coating member 100 according to an embodiment of the present invention. The CNT coating member 100 is, for example, disposed on the substrate 110, the inorganic layer 120 disposed on the surface of the substrate 110, the catalyst metal fine particle layer 130 supported on the inorganic layer 120, and the catalyst metal fine particle layer 130. CNT150.
［カーボンナノチューブ］
本発明により形成されるＣＮＴ１５０は、主に多層カーボンナノチューブ（ＭＷＣＮＴ）であるが、これに限定されるものではない。ＣＮＴ１５０は、触媒金属微粒子層１３０を構成する触媒金属微粒子１３１から、基材１１０の表面に対して概ね垂直に配向して成長すると共に、ＣＮＴ１５０の最上部（表層又は表面）において、先端が無配向となる集合体を形成する。例えば、基材に単層カーボンナノチューブ（ＳＷＣＮＴ）を高密度に垂直配向成長させると、表面はＣＮＴの先端が規則的かつ高密度に配置した構造を形成する。そのような構造規則性を有すると、光干渉効果のため分光反射率の角度異方性が顕著になる懸念がある。一方、本発明に係るＣＮＴ１５０は、ＳＷＣＮＴよりも太いＭＷＣＮＴが比較的低密度に垂直配向している。それゆえ、ＣＮＴ先端の周囲には比較的空間が存在するため、最上部（表層又は表面）は比較的無配向な集合体を形成する。そのような構造の不規則性のため、分光反射率の角度異方性は非常に小さくなる。
[carbon nanotube]
The CNTs 150 formed according to the present invention are mainly multi-walled carbon nanotubes (MWCNTs), but are not limited thereto. The CNT 150 grows from the catalyst metal fine particles 131 constituting the catalyst metal fine particle layer 130 while being oriented substantially perpendicular to the surface of the substrate 110, and the tip is not oriented at the uppermost portion (surface layer or surface) of the CNT 150. To form an aggregate. For example, when single-walled carbon nanotubes (SWCNT) are vertically aligned and grown on a base material at a high density, the surface forms a structure in which the tips of the CNTs are regularly arranged at a high density. With such a structural regularity, there is a concern that the angular anisotropy of the spectral reflectance becomes remarkable due to the optical interference effect. On the other hand, in the CNT 150 according to the present invention, MWCNTs that are thicker than SWCNTs are vertically aligned at a relatively low density. Therefore, since there is a relatively space around the CNT tip, the uppermost part (surface layer or surface) forms a relatively non-oriented aggregate. Due to such structural irregularities, the angular anisotropy of the spectral reflectance is very small.
［基材］
基材１１０の材質は、ＣＮＴの成長温度において溶融しない純金属及び合金、又は炭素材料であり、例えば、ＣＮＴの原料であるアセチレンの熱分解温度（約750℃）において溶融しない純金属及び合金、又は炭素材料である。ＣＮＴをCVD法で製造する場合、ＣＮＴを成長させる基板の材質として、一般にはシリコン基板が用いられる。この理由としては、ＣＮＴはシリコン基板製の電子デバイス上の部材に応用する研究開発が盛んに行われているため、シリコン基板上にＣＮＴを成長させる技術の蓄積が進んでいたことや高温での安定性、平滑で高純度な基板の入手の容易さ等があげられる。
[Base material]
The material of the substrate 110 is a pure metal and alloy that does not melt at the growth temperature of CNT, or a carbon material, for example, a pure metal and alloy that does not melt at the thermal decomposition temperature (about 750 ° C.) of acetylene that is a raw material of CNT, Or it is a carbon material. When manufacturing CNT by the CVD method, a silicon substrate is generally used as a material for a substrate on which CNT is grown. This is because CNTs are actively researched and applied to members on electronic devices made of silicon substrates, and the accumulation of technology for growing CNTs on silicon substrates has progressed. For example, stability and ease of obtaining a smooth and high-purity substrate can be mentioned.
しかし、シリコン基板にＣＮＴを成長させた物体を光学部材として用いることは必ずしも適切ではない。光学部材は一般に温度分布が一定であることが求められるが、シリコン基板は半導体であるため金属と比較して熱伝導率が小さいため、金属基板と比較して温度分布が不均一になる恐れがある。電磁波の放射のために用いられる光学部材は目的とする電磁波を発するために加熱する必要があるが、金属基板であれば通電加熱により容易に温度制御が可能である。また、複雑な形状の光学部材を作製する場合、シリコンよりも金属や炭素材料を素材に用いた方が容易に加工できる。これらの理由から、光学部材を構成する基材は金属又は炭素材料である事が望ましい。 However, it is not always appropriate to use an object obtained by growing CNTs on a silicon substrate as an optical member. Optical members are generally required to have a constant temperature distribution. However, since a silicon substrate is a semiconductor, its thermal conductivity is small compared to a metal, so that the temperature distribution may be non-uniform compared to a metal substrate. is there. An optical member used for electromagnetic wave radiation needs to be heated in order to emit a desired electromagnetic wave, but a metal substrate can be easily temperature controlled by energization heating. Further, when producing an optical member having a complicated shape, it is easier to process a metal or carbon material as a material than silicon. For these reasons, the base material constituting the optical member is preferably a metal or a carbon material.
基材１１０は、ＣＮＴの原料となる炭化水素の熱分解温度においても溶融しない金属又は炭素材料で形成される限り、その材質や形状は特に限定されない。基材１１０に用いる金属は、例えば、Au、Ag、Cu、Pt、W、Nb、Ta、Mo、V、Pd、Fe、Ni、Co、Cr、Ti、Hf、Zr、Si、Eu、Gd、U及びそれらを主成分とする合金からなる群から選択することができる。好ましくは、基材１１０に用いる金属として、Au、Ag、Cu、Pt、W、Nb、Ta、Mo、V、Pd及びそれらを主成分とする合金を用いることができる。また、基材１１０に用いる炭素材料は、炭素繊維複合材、等方性黒鉛、ガラス状炭素及び天然黒鉛からなる群から選択される。 The material and shape of the substrate 110 are not particularly limited as long as the substrate 110 is formed of a metal or a carbon material that does not melt even at the thermal decomposition temperature of the hydrocarbon that is a raw material of CNT. The metal used for the substrate 110 is, for example, Au, Ag, Cu, Pt, W, Nb, Ta, Mo, V, Pd, Fe, Ni, Co, Cr, Ti, Hf, Zr, Si, Eu, Gd, It can be selected from the group consisting of U and alloys based on them. Preferably, Au, Ag, Cu, Pt, W, Nb, Ta, Mo, V, Pd and alloys containing them as main components can be used as the metal used for the substrate 110. The carbon material used for the substrate 110 is selected from the group consisting of a carbon fiber composite material, isotropic graphite, glassy carbon, and natural graphite.
本発明においては、下記に詳述する方法により無機物層１２０及び触媒金属微粒子層１３０を形成することにより、ほぼ任意の材質の金属基材又は炭素材料基材の表面上にＣＮＴ１５０を形成することができる。本発明において、基材１１０は、平板状の基板に限定されず、３次元構造体であってもよい。本発明においては、後述するウェットプロセスにより無機物層１２０を形成するため、３次元構造体の基材を用いても、ＣＮＴ１５０を均一に形成することができる。 In the present invention, by forming the inorganic layer 120 and the catalytic metal fine particle layer 130 by the method described in detail below, the CNT 150 can be formed on the surface of a substantially arbitrary metal substrate or carbon material substrate. it can. In the present invention, the base material 110 is not limited to a flat substrate, and may be a three-dimensional structure. In the present invention, since the inorganic layer 120 is formed by a wet process to be described later, the CNT 150 can be uniformly formed even if a base material of a three-dimensional structure is used.
［無機物層］
無機物層１２０は、触媒金属微粒子層１３０を形成するための触媒金属微粒子１３１を担持させるための足場である。無機物微粒子１２１としては、金属酸化物粒子が好ましく、例えば、アルミナ、ジルコニア、チタニア、ハフニア等を用いることができるが、これらに限定されるものではない。従来技術では、触媒の担持に用いる無機物層は、基材上にスパッタリングで形成するか真空蒸着装置で金属薄膜を蒸着した後に酸化処理を行って酸化物膜を形成する方法が用いられていた。しかし、スパッタリングや蒸着を用いる方法では、３次元構造体の基材表面に無機物層を一様に形成するのは困難である。一方、本発明においては、無機物層１２０は、ウェットプロセスにより形成する。このため、３次元構造体の基材を用いる場合にも、基材１１０の表面に無機物層１２０を一様に形成することができる。また、本発明に係る無機物層１２０は、連続膜ではなく、不連続な膜構造を有する。不連続な無機物層１２０は、ＣＮＴを製膜して基材１１０から剥離しにくく、結果として、均一なＣＮＴの製膜を可能とする。
[Inorganic layer]
The inorganic layer 120 is a scaffold for supporting the catalyst metal fine particles 131 for forming the catalyst metal fine particle layer 130. As the inorganic fine particles 121, metal oxide particles are preferable, and for example, alumina, zirconia, titania, hafnia and the like can be used, but are not limited thereto. In the prior art, a method of forming an oxide film by forming an inorganic layer used for supporting a catalyst by sputtering on a substrate or by depositing a metal thin film with a vacuum deposition apparatus and then performing an oxidation treatment has been used. However, in the method using sputtering or vapor deposition, it is difficult to uniformly form the inorganic layer on the surface of the base material of the three-dimensional structure. On the other hand, in the present invention, the inorganic layer 120 is formed by a wet process. For this reason, also when using the base material of a three-dimensional structure, the inorganic substance layer 120 can be uniformly formed on the surface of the base material 110. In addition, the inorganic layer 120 according to the present invention has a discontinuous film structure, not a continuous film. The discontinuous inorganic layer 120 is difficult to peel CNTs from the substrate 110, and as a result, uniform CNTs can be formed.
［触媒金属微粒子層］
触媒金属微粒子層１３０は、反応系内で炭化水素を熱分解してＣＮＴ１５０を形成するための触媒層である。触媒金属微粒子層１３０は、無機物層１２０に担持された触媒金属微粒子１３１により形成される。本発明においては、金属錯体蒸気を用いる浮遊触媒輸送式CVD法によりＣＮＴ１５０を形成するため、フェロセンやカルボニル鉄等の金属錯体を触媒前駆体に用いる。その他、Coを含む金属錯体であるコバルトセンも触媒前駆体として用いることが可能である。しかし、浮遊触媒輸送式CVD法では、安全性や取り扱いの観点から、触媒金属微粒子１３１の供給源として、フェロセンを好適に用いることができる。浮遊触媒輸送式CVD法の場合、触媒金属微粒子が反応炉全体に拡散するため３次元形状物体の全面に触媒層を形成することが可能であると共に触媒層を炭化水素の熱分解反応の直前に同一の反応炉を用いて効率的に形成することが可能である。
[Catalyst metal fine particle layer]
The catalyst metal fine particle layer 130 is a catalyst layer for thermally decomposing hydrocarbons in the reaction system to form the CNT 150. The catalyst metal fine particle layer 130 is formed by the catalyst metal fine particles 131 supported on the inorganic layer 120. In the present invention, a metal complex such as ferrocene or carbonyl iron is used as a catalyst precursor in order to form CNT 150 by a floating catalyst transport CVD method using a metal complex vapor. In addition, cobaltcene, which is a metal complex containing Co, can also be used as a catalyst precursor. However, in the floating catalyst transport CVD method, ferrocene can be suitably used as a supply source of the catalyst metal fine particles 131 from the viewpoint of safety and handling. In the case of the floating catalyst transport CVD method, the catalyst metal fine particles diffuse throughout the reactor, so that a catalyst layer can be formed on the entire surface of the three-dimensional object and the catalyst layer is immediately before the hydrocarbon pyrolysis reaction. It can be formed efficiently using the same reactor.
従来、触媒担持層や触媒層を形成するために用いられるスパッタリング装置は、一般に平板状の基材であれば触媒担持層や触媒層を形成することは容易であるが、スパッタリングターゲットや蒸着源と基材の間に障害物が存在するような３次元形状を有する基材の表面に触媒担持層や触媒層を形成するのは困難である。一方、本発明においては、ウェットプロセスによる無機物層１２０の形成と浮遊触媒輸送式の触媒金属微粒子層１３０の形成とを組み合わせることにより、３次元形状を有する基材１１０の表面にＣＮＴ１５０を成長させることができる。 Conventionally, a sputtering apparatus used to form a catalyst supporting layer or a catalyst layer is generally easy to form a catalyst supporting layer or a catalyst layer if it is a flat substrate, It is difficult to form a catalyst support layer or a catalyst layer on the surface of a substrate having a three-dimensional shape in which an obstacle exists between the substrates. On the other hand, in the present invention, the CNT 150 is grown on the surface of the substrate 110 having a three-dimensional shape by combining the formation of the inorganic layer 120 by the wet process and the formation of the floating catalyst transport type catalytic metal fine particle layer 130. Can do.
［光学部材の特性］
本発明に係る光学部材の可視波長域での分光反射率は０．０１以下である。本発明に係る光学部材は、可視波長域での非常に低い分光反射率を有することにより、黒化面として有用である。
[Characteristics of optical members]
The spectral reflectance in the visible wavelength region of the optical member according to the present invention is 0.01 or less. The optical member according to the present invention is useful as a blackened surface by having a very low spectral reflectance in the visible wavelength region.
［光学部材の製造方法］
本発明に係るＣＮＴ被膜部材の製造方法について説明する。図２は、本発明の一実施形態に係るＣＮＴ被膜部材１００の製造方法を示す模式図である。基材１１０を準備する（図２（ａ））。基材１１０は、ＣＮＴの原料となる炭化水素の熱分解温度においても溶融しない金属又は炭素材料で形成される限り、その材質や形状は特に限定されない。基材１１０として炭素材料を用いる場合、金属基材よりもＣＮＴ製膜面の均一性が高くなることを見出した。特に、炭素繊維複合材については非常に濃密なＣＮＴ製膜面が基材全面に形成される。これは、炭素繊維複合材に対する硝酸アルミニウム溶液の濡れ性が金属や他の炭素材料よりも良いためであると考えられる。
[Method for producing optical member]
The manufacturing method of the CNT film member which concerns on this invention is demonstrated. FIG. 2 is a schematic view showing a method for manufacturing the CNT film member 100 according to an embodiment of the present invention. The base material 110 is prepared (FIG. 2 (a)). The material and shape of the substrate 110 are not particularly limited as long as the substrate 110 is formed of a metal or a carbon material that does not melt even at the thermal decomposition temperature of the hydrocarbon that is a raw material of CNT. When using a carbon material as the base material 110, it discovered that the uniformity of the CNT film-forming surface became higher than a metal base material. In particular, for carbon fiber composites, a very dense CNT film surface is formed on the entire surface of the substrate. This is considered to be because the wettability of the aluminum nitrate solution with respect to the carbon fiber composite material is better than that of metal or other carbon materials.
本発明においては、ウェットプロセスにより、基材１１０の表面に無機物層１２０を形成する（図２（ｂ））。この後の工程に用いる浮遊触媒輸送式CVD法では、触媒金属微粒子１３１の触媒活性を維持するためには基材１１０に前もって触媒担持層である無機物層１２０を形成することは不可欠で有る。従来、無機物層１２０の製膜方法には物理気相蒸着（PVD）が用いられていた。それゆえ、ＣＮＴを製膜可能な基材の形状や大きさはPVDの使用にともなう制限を受けていた。本発明者らは、ウェットプロセスを用いて無機物層１２０を形成し、触媒金属微粒子層１３０を金属錯体蒸気への暴露により形成することを発案した。本明細書において、ウェットプロセスによる無機物層１２０の形成は、基材１１０をアルミニウム化合物溶液に浸漬した後に、基材１１０を800℃以上に加熱することにより行う。アルミニウム化合物溶液として、硝酸アルミニウム溶液が好ましい。基材１１０の加熱は、基材の酸化を防ぐため10-3 Pa程度の真空もしくは窒素ガス雰囲気で行うことが好ましい。 In the present invention, the inorganic layer 120 is formed on the surface of the substrate 110 by a wet process (FIG. 2B). In the floating catalyst transport CVD method used in the subsequent steps, in order to maintain the catalytic activity of the catalytic metal fine particles 131, it is indispensable to form the inorganic layer 120 as the catalyst supporting layer on the substrate 110 in advance. Conventionally, physical vapor deposition (PVD) has been used as a method for forming the inorganic layer 120. Therefore, the shape and size of the substrate capable of forming a CNT film have been limited by the use of PVD. The inventors of the present invention have proposed that the inorganic layer 120 is formed using a wet process, and the catalytic metal fine particle layer 130 is formed by exposure to a metal complex vapor. In this specification, the inorganic layer 120 is formed by a wet process by heating the substrate 110 to 800 ° C. or higher after the substrate 110 is immersed in the aluminum compound solution. As the aluminum compound solution, an aluminum nitrate solution is preferable. The substrate 110 is preferably heated in a vacuum of about 10 −3 Pa or a nitrogen gas atmosphere in order to prevent the substrate from being oxidized.
非特許文献６及び７には、硝酸アルミニウム溶液を滴下した基材を200℃に加熱することにより、アルミナからなる触媒担持層が形成されることが記載されている。本発明者らは、硝酸アルミニウム水溶液に浸漬した基材を大気中で約200℃に加熱した後に、上述の浮遊触媒輸送式CVDを行ったが、基材表面にＣＮＴは成長しなかった。これは、200℃で焼成したアルミナ膜が化学的に不安定であるためＣＮＴが成長しなかったためと推察される。 Non-Patent Documents 6 and 7 describe that a catalyst-supporting layer made of alumina is formed by heating a substrate to which an aluminum nitrate solution is dropped to 200 ° C. The present inventors performed the above-mentioned floating catalyst transport CVD after heating a substrate immersed in an aluminum nitrate aqueous solution to about 200 ° C. in the atmosphere, but CNT did not grow on the surface of the substrate. This is presumably because CNT did not grow because the alumina film fired at 200 ° C. was chemically unstable.
硝酸アルミニウムを加熱すると約200℃で化学的に不安定なアルミナ中間相が生成し、温度の上昇に伴い徐々に安定性を増し、約1200℃まで加熱すると安定相であるαアルミナが生成する事が知られている。本発明者らは、化学的に不安定な中間相アルミナはフェロセン蒸気から供給される反応性の高い鉄と容易に化学反応を起こし、鉄微粒子の活性が失われると考えた。硝酸鉄の焼成を利用した従来のウェットプロセスでは、中間相アルミナが存在する温度域では硝酸鉄は反応性の低い酸化鉄として存在し、中間相アルミナと接触しても反応を起こさないためＣＮＴの製膜が可能であったと考えられる。 When aluminum nitrate is heated, a chemically unstable alumina intermediate phase is formed at about 200 ° C, and the stability gradually increases as the temperature rises. When heated to about 1200 ° C, α-alumina, which is a stable phase, is formed. It has been known. The present inventors thought that chemically unstable mesophase alumina easily undergoes a chemical reaction with highly reactive iron supplied from ferrocene vapor, and the activity of the iron fine particles is lost. In the conventional wet process using iron nitrate firing, iron nitrate exists as low-reactivity iron oxide in the temperature range where intermediate phase alumina exists, and it does not react even when it comes into contact with intermediate phase alumina. It is thought that film formation was possible.
そこで、本発明者らは、硝酸アルミニウム溶液に浸漬した基材をより高温で焼成することにより、フェロセン蒸気として供給される鉄微粒子触媒を担持するに耐え得る安定なアルミナ中間相が得られると考えた。ただし、200℃以上の高温で基材を焼成することになると基材の酸化を防ぐ必要があるため、大気中ではなく真空もしくは不活性雰囲気下で加熱する。硝酸アルミニウム溶液に浸漬した基材を焼成する場合、不活性ガス雰囲気より真空条件下の方がＣＮＴ製膜面の均一性を向上させることができる。本発明者らは、無機物層１２０を焼成する温度を繰り返し検討した結果、800℃以上で焼成した基材１１０については浮遊触媒輸送式CVD法によりＣＮＴを製膜可能であることを初めて見出した。 Therefore, the present inventors believe that a stable alumina intermediate phase that can withstand carrying an iron fine particle catalyst supplied as ferrocene vapor can be obtained by firing a substrate immersed in an aluminum nitrate solution at a higher temperature. It was. However, since it is necessary to prevent the base material from being oxidized when the base material is fired at a high temperature of 200 ° C. or higher, it is heated not in the air but in a vacuum or an inert atmosphere. When firing a substrate immersed in an aluminum nitrate solution, the uniformity of the CNT film surface can be improved under vacuum conditions than in an inert gas atmosphere. As a result of repeatedly examining the temperature at which the inorganic layer 120 is fired, the present inventors have found for the first time that the base material 110 fired at 800 ° C. or higher can be formed into a CNT film by the floating catalyst transport CVD method.
本発明においては、浮遊触媒輸送式CVD法により無機物層１２０上に触媒金属微粒子層１３０を形成する（図２（ｃ））。触媒金属微粒子層１３０は、金属錯体を加熱して発生させた触媒金属微粒子１３１を含む蒸気を供給して形成する。例えば、ＣＮＴ１５０を成長させるためのCVD反応炉内に無機物層１２０を形成した基材１１０と触媒前駆体の金属錯体の粉末を設置し、窒素ガス雰囲気下で金属錯体が蒸発する温度まで炉内を加熱する。浮遊した触媒金属微粒子１３１が無機物層１２０上に堆積して触媒金属微粒子層１３０を形成する。このとき、本発明においては、無機物層１２０が基材１１０の表面に不連続に形成された膜構造を有するため、触媒金属微粒子１３１が無機物層１２０の表面に適度に分散して付着し、ＣＮＴ成長に適した不連続な膜構造を有する触媒金属微粒子層１３０を基材表面全体に一様に形成することができる。 In the present invention, the catalyst metal fine particle layer 130 is formed on the inorganic layer 120 by the floating catalyst transport CVD method (FIG. 2C). The catalytic metal fine particle layer 130 is formed by supplying vapor containing catalytic metal fine particles 131 generated by heating a metal complex. For example, a substrate 110 on which an inorganic layer 120 is formed and a powder of a metal complex of a catalyst precursor are placed in a CVD reactor for growing CNT 150, and the inside of the furnace is heated to a temperature at which the metal complex evaporates in a nitrogen gas atmosphere. Heat. The suspended catalytic metal fine particles 131 are deposited on the inorganic layer 120 to form the catalytic metal fine particle layer 130. At this time, in the present invention, since the inorganic layer 120 has a film structure in which the surface of the substrate 110 is discontinuously formed, the catalyst metal fine particles 131 are appropriately dispersed and attached to the surface of the inorganic layer 120. The catalyst metal fine particle layer 130 having a discontinuous film structure suitable for growth can be uniformly formed on the entire surface of the substrate.
触媒金属微粒子層１３０が形成された基材１１０に対して、炭化水素を供給し、触媒金属微粒子層１３０上にＣＮＴ１５０を形成する（図２（ｄ））。供給する炭化水素としては、ＣＮＴ１５０を形成可能な公知のものを用いることができ、例えば、アセチレンを好適に用いることができる。アセチレンを供給してＣＮＴ１５０を成長させる場合は、アセチレンの熱分解温度である約750℃まで炉内を加熱してからアセチレンを炉内へ導入するか、アセチレン導入後に炉を約750℃まで加熱すればよい。炉内温度は、用いる炭化水素の熱分解温度に基づいて、任意に設定可能である。このようにして、本発明に係るＣＮＴ被膜部材１００を製造することができる。 Hydrocarbon is supplied to the base material 110 on which the catalytic metal fine particle layer 130 is formed, and CNTs 150 are formed on the catalytic metal fine particle layer 130 (FIG. 2D). As the hydrocarbon to be supplied, a known hydrocarbon capable of forming CNT 150 can be used. For example, acetylene can be preferably used. When acetylene is supplied to grow CNT150, either heat the interior of the furnace to about 750 ° C, which is the thermal decomposition temperature of acetylene, and then introduce acetylene into the furnace, or heat the furnace to about 750 ° C after introducing acetylene. That's fine. The furnace temperature can be arbitrarily set based on the thermal decomposition temperature of the hydrocarbon used. In this way, the CNT coating member 100 according to the present invention can be manufactured.
なお、CVD反応炉内に無機物層１２０を形成した基材１１０と触媒前駆体の金属錯体の粉末を設置し、窒素ガスとアセチレンを供給して750℃まで炉内を加熱すれば、予熱段階（金属錯体としてフェロセンを用いた場合は100℃〜200℃）で金属錯体が昇華し、触媒金属微粒子１３１が無機物層１２０上に堆積して触媒金属微粒子層１３０を形成し、炉内温度が約750℃に達した時点でＣＮＴ１５０を成長させることができる。 In addition, if the substrate 110 on which the inorganic layer 120 is formed in the CVD reactor and the metal powder of the catalyst precursor are placed, and the furnace is heated to 750 ° C. by supplying nitrogen gas and acetylene, the preheating stage ( When ferrocene is used as the metal complex, the metal complex sublimates at 100 ° C. to 200 ° C., and the catalyst metal fine particles 131 are deposited on the inorganic layer 120 to form the catalyst metal fine particle layer 130, and the furnace temperature is about 750. The CNT 150 can be grown when the temperature reaches 0C.
以上説明したように、本発明に係るＣＮＴ被膜部材の製造方法は、ＣＮＴを製膜する基材の材質や形状について従来技術と比較して制限を受けず、三次元形状の物体の表面にＣＮＴを欠損部無く一様に成長させることができる。 As described above, the manufacturing method of the CNT film member according to the present invention is not limited in terms of the material and shape of the base material on which the CNT is formed as compared with the prior art, and the CNT film is formed on the surface of the three-dimensional object. Can be grown uniformly without a defect.
また、本発明に係るＣＮＴ被膜部材の製造方法においては、従来のCVDによるＣＮＴの製造において必要であった還元剤の水素や一酸化炭素を使用する必要が無いため、水素雰囲気下で金属を加熱する際に問題となる金属の水素脆化や有毒ガスである一酸化炭素の使用を避けられる利点がある。特に、水素を使わないことにより、ＣＮＴの生成に際しての副生成物である水素もしくは水の反応炉内での分圧を低い値に維持できるため、熱力学的に炭化水素の分解反応を促進することができる。さらに、本発明に係る光学部材は、可視波長域での分光反射率が０．０１以下であり、高性能のＣＮＴ被膜部材である。 In addition, in the method for producing a CNT coated member according to the present invention, it is not necessary to use hydrogen or carbon monoxide as a reducing agent, which is necessary in the conventional CNT production by CVD, so that the metal is heated in a hydrogen atmosphere. This has the advantage of avoiding the use of carbon monoxide, which is a hydrogen embrittlement and toxic gas, which is a problem. In particular, by not using hydrogen, the partial pressure of hydrogen or water, which is a by-product during the production of CNTs, can be maintained at a low value in the reactor, so that the hydrocarbon decomposition reaction is thermodynamically promoted. be able to. Furthermore, the optical member according to the present invention is a high-performance CNT film member having a spectral reflectance in the visible wavelength region of 0.01 or less.
（実施形態２）
上述したように、金属基材は炭素材料に比してＣＮＴ製膜面の均一性が低くなる傾向にある。これは、金属基材表面の濡れ性が炭素材料に比して低く、無機物層が表面全体に一様に形成されにくいためである。本実施形態においては、金属基材表面の濡れ性を向上させて無機物層を形成する方法について説明する。
(Embodiment 2)
As described above, the metal substrate tends to have lower uniformity of the CNT film surface than the carbon material. This is because the wettability of the surface of the metal substrate is lower than that of the carbon material, and the inorganic layer is difficult to be uniformly formed on the entire surface. In the present embodiment, a method for improving the wettability of the metal substrate surface and forming an inorganic layer will be described.
図３は、本発明の一実施形態に係るＣＮＴ被膜部材２００の模式図を示す。ＣＮＴ被膜部材２００は、ＣＮＴを成長させる面が粗面を有する金属基材２１０と、金属基材２１０の粗面に付着した無機物微粒子２１９で構成される無機物微粒子層２１７と、金属基材２１０の表面に配置され、無機物微粒子２１９を覆う無機物層２２０と、無機物層２２０に担持された触媒金属微粒子２３１で構成される触媒金属微粒子層２３０と、触媒金属微粒子層２３０上に形成されたＣＮＴ１５０を備える。 FIG. 3 is a schematic view of a CNT coating member 200 according to an embodiment of the present invention. The CNT coating member 200 includes a metal substrate 210 having a rough surface on which CNT is grown, an inorganic fine particle layer 217 composed of inorganic fine particles 219 attached to the rough surface of the metal substrate 210, and a metal substrate 210. An inorganic layer 220 disposed on the surface and covering the inorganic fine particles 219, a catalytic metal fine particle layer 230 composed of catalytic metal fine particles 231 supported on the inorganic layer 220, and a CNT 150 formed on the catalytic metal fine particle layer 230 are provided. .
金属錯体蒸気を用いる浮遊触媒輸送式の化学気相成長によりＣＮＴ１５０を成長させるため、触媒担持層である無機物層２２０の形成が必要であるが、金属基材２１０を用いる本実施形態においては、金属基材２１０の表面を粗面化することにより濡れ性を向上させる。本実施形態においては、金属基材２１０の表面の濡れ性が向上することにより、金属基材２１０全体に無機物層２２０が形成され、触媒金属微粒子２３１が金属基材２１０の表面全体に一様に形成される。本実施形態においては、金属基材２１０の表面を粗面化することにより、金属基材表面に一様にＣＮＴ１５０を形成することができる。３次元構造体の基材では、基材表面の濡れ性が低いと基材全体に無機物層を形成するのは困難である。しかし、本実施形態においては、３次元構造体の金属基材を用いても、基材表面に粗面を形成することにより、ＣＮＴ１５０の成長に適した場を提供することができる。 In order to grow the CNT 150 by floating catalyst transport type chemical vapor deposition using a metal complex vapor, it is necessary to form the inorganic material layer 220 which is a catalyst supporting layer. The wettability is improved by roughening the surface of the substrate 210. In this embodiment, by improving the wettability of the surface of the metal substrate 210, the inorganic layer 220 is formed on the entire metal substrate 210, and the catalyst metal fine particles 231 are uniformly distributed on the entire surface of the metal substrate 210. It is formed. In this embodiment, the CNTs 150 can be uniformly formed on the surface of the metal substrate by roughening the surface of the metal substrate 210. In the base material having a three-dimensional structure, it is difficult to form an inorganic layer on the whole base material when the wettability of the base material surface is low. However, in the present embodiment, even when a metal base material having a three-dimensional structure is used, a field suitable for the growth of the CNT 150 can be provided by forming a rough surface on the base material surface.
［粗面］
無機物微粒子２１９は、硬い無機物である金属酸化物、金属窒化物又は金属炭化物からなる。無機物微粒子２１９としては、金属酸化物が好ましく、例えば、アルミナ、ジルコニア、チタニア、ハフニア等を用いることができるが、これらに限定されるものではない。本実施形態において、金属基材２１０の粗面は、例えば、金属基材２１０の表面に上述した金属酸化物等の硬い無機物の微粉末を空力的もしくは投射的な方法で衝突させる処理（微粉末ショット処理）を実施することにより形成することができる。
[Rough surface]
The inorganic fine particles 219 are made of a metal oxide, metal nitride, or metal carbide that is a hard inorganic material. As the inorganic fine particles 219, metal oxides are preferable, and for example, alumina, zirconia, titania, hafnia and the like can be used, but are not limited thereto. In the present embodiment, the rough surface of the metal substrate 210 is, for example, a treatment (fine powder) in which the fine powder of the hard inorganic material such as the metal oxide described above collides with the surface of the metal substrate 210 by an aerodynamic or projection method. It can be formed by performing shot processing.
金属基材２１０の表面に衝突させた無機物微粒子２１９の一部は細かく砕けて金属基材２１０の表面に無数に食い込むため、無機物微粒子２１９を覆う無機物層２２０が金属基材２１０の粗面に形成される。粗面を有する金属基材２１０は濡れ性が向上し、無機物層２２０が金属基材２１０の粗面に形成され、触媒金属微粒子２３１が一様に担持される。また、微粉末ショット処理により金属基材２１０の表面に存在する汚染物質が機械的に削り取られるため、金属基材２１０の表面を清浄にする効果も得られる。また、微粉末ショット処理は真空チャンバー等に金属基材２１０を設置して処理する必要が無いと共に微粉末を射出する方向を処理中に変更することは容易であるため、金属基材２１０の形状や大きさによらず、金属基材２１０の全面に処理を施すことが可能である。 A portion of the inorganic fine particles 219 colliding with the surface of the metal substrate 210 is finely crushed and bites into the surface of the metal substrate 210 innumerably, so that an inorganic layer 220 covering the inorganic fine particles 219 is formed on the rough surface of the metal substrate 210. Is done. The metal substrate 210 having a rough surface has improved wettability, the inorganic layer 220 is formed on the rough surface of the metal substrate 210, and the catalyst metal fine particles 231 are uniformly supported. In addition, since the contaminants present on the surface of the metal substrate 210 are mechanically scraped off by the fine powder shot process, an effect of cleaning the surface of the metal substrate 210 is also obtained. In addition, the fine powder shot process does not need to be performed by installing the metal substrate 210 in a vacuum chamber or the like, and the direction in which the fine powder is injected can be easily changed during the process. Regardless of the size, the entire surface of the metal substrate 210 can be treated.
例えば、アルミナ微粉末の微粉末ショット処理により粗面を形成した場合、走査型電子顕微鏡（以下、SEMとも称す）像で明確な無機物微粒子層２１７が観察されない場合であっても、金属基材２１０の最表面のオージェスペクトルにおいて約1390 eVの位置にAlに対応するピークが検出される。 For example, when a rough surface is formed by a fine powder shot treatment of fine alumina powder, the metal substrate 210 is formed even when a clear inorganic fine particle layer 217 is not observed in a scanning electron microscope (hereinafter also referred to as SEM) image. In the outermost Auger spectrum, a peak corresponding to Al is detected at a position of about 1390 eV.
［光学部材の製造方法］
金属基材２１０に粗面を形成してＣＮＴを一様に製膜したＣＮＴ被膜部材２００の製造方法について説明する。金属基材２１０を準備する（図４（ａ））。金属基材２１０には上述した金属を用いることができるため、詳細な説明は省略する。
[Method for producing optical member]
A manufacturing method of the CNT coating member 200 in which a rough surface is formed on the metal substrate 210 to uniformly form CNTs will be described. A metal substrate 210 is prepared (FIG. 4A). Since the metal mentioned above can be used for the metal base 210, detailed description is abbreviate | omitted.
金属基材２１０の少なくともＣＮＴを製膜する面に粗面２１５を形成して、金属基材２１０の粗面２１５上に無機物微粒子層２１７を形成する（図４（ｂ））。金属基材２１０の表面を粗面２１５にすることにより、金属基材２１０の表面の濡れ性が向上する。 A rough surface 215 is formed on at least a surface of the metal substrate 210 on which CNT is formed, and an inorganic fine particle layer 217 is formed on the rough surface 215 of the metal substrate 210 (FIG. 4B). By making the surface of the metal substrate 210 rough, the wettability of the surface of the metal substrate 210 is improved.
粗面２１５を形成した金属基材２１０を硝酸アルミニウム溶液に浸漬する。硝酸アルミニウム溶液には、溶媒として、例えば、水や、アセトン、エタノールのような有機溶媒を用いることができる。硝酸アルミニウム溶液に浸漬した金属基材２１０を、CVD反応炉内に配置し、真空もしくは不活性雰囲気下で、800℃以上で焼成する。これにより、ＣＮＴを製膜する金属基材２１０の表面に無機物層２２０が形成される（図４（ｃ））。本実施形態においては、無機物微粒子２１９を覆う無機物層２２０が金属基材２１０の粗面２１５に形成される。これにより、触媒金属微粒子２３１が金属基材２１０の表面に欠損部無く一様に沈着することができる。 The metal substrate 210 on which the rough surface 215 is formed is immersed in an aluminum nitrate solution. In the aluminum nitrate solution, for example, water, an organic solvent such as acetone or ethanol can be used as a solvent. A metal substrate 210 immersed in an aluminum nitrate solution is placed in a CVD reactor and baked at 800 ° C. or higher in a vacuum or an inert atmosphere. Thereby, the inorganic layer 220 is formed on the surface of the metal substrate 210 on which the CNTs are formed (FIG. 4C). In the present embodiment, an inorganic layer 220 covering the inorganic fine particles 219 is formed on the rough surface 215 of the metal substrate 210. As a result, the catalyst metal fine particles 231 can be uniformly deposited on the surface of the metal substrate 210 without any defects.
浮遊触媒輸送式CVD法により、無機物層２２０上に触媒金属微粒子層２３０を形成する（図４（ｄ））。また、触媒金属微粒子層２３０が形成された金属基材２１０に対して、炭化水素を供給し、触媒金属微粒子層２３０上にＣＮＴ１５０を形成する（図４（ｅ））。浮遊触媒輸送式CVD法による触媒金属微粒子層２３０の形成方法及びＣＮＴ１５０の製膜方法については上述したため、詳細な説明は省略する。 A catalytic metal fine particle layer 230 is formed on the inorganic layer 220 by a floating catalyst transport CVD method (FIG. 4D). Further, hydrocarbons are supplied to the metal base 210 on which the catalytic metal fine particle layer 230 is formed, and CNTs 150 are formed on the catalytic metal fine particle layer 230 (FIG. 4E). Since the method for forming the catalytic metal fine particle layer 230 and the method for forming the CNT 150 by the floating catalyst transport CVD method have been described above, detailed description thereof will be omitted.
本実施形態においては、濡れ性が低い金属基材を用いる場合にも、金属基材の表面を粗面化することにより濡れ性を向上させ、ＣＮＴを一様に成長させることができる。従来、CVD法によるＣＮＴの製造において、水素や一酸化炭素は触媒金属の酸化を防ぐことで触媒活性を維持するために導入される。本実施形態においては、浮遊触媒輸送式CVD法を用いることにより、CVD反応炉に還元剤を導入せずに、ＣＮＴ１５０を成長させることができる。 In the present embodiment, even when a metal substrate having low wettability is used, wettability can be improved by roughening the surface of the metal substrate, and CNTs can be grown uniformly. Conventionally, in the production of CNTs by the CVD method, hydrogen or carbon monoxide is introduced to maintain catalytic activity by preventing oxidation of the catalytic metal. In this embodiment, by using the floating catalyst transport CVD method, the CNT 150 can be grown without introducing a reducing agent into the CVD reactor.
以上説明したように、本発明に係るＣＮＴ被膜部材の製造方法は、ＣＮＴを製膜する基材の材質や形状について従来技術と比較して制限を受けず、三次元形状の物体の表面にＣＮＴを欠損部無く一様に成長させることができる。 As described above, the manufacturing method of the CNT film member according to the present invention is not limited in terms of the material and shape of the base material on which the CNT is formed as compared with the prior art, and the CNT film is formed on the surface of the three-dimensional object. Can be grown uniformly without a defect.
また、本発明に係るＣＮＴ被膜部材は濡れ性が低い金属基材を用いても、可視波長域での分光反射率が０．０１以下であり、高性能のＣＮＴ被膜部材である。 Further, the CNT coated member according to the present invention is a high-performance CNT coated member having a spectral reflectance of 0.01 or less in the visible wavelength region even when a metal substrate having low wettability is used.
本発明に係る光学部材について、具体例を挙げて、さらに説明する。 The optical member according to the present invention will be further described with specific examples.
ＣＮＴの触媒前駆体としてフェロセンを用い、原料の炭化水素ガスとしてアセチレンを用いた。金属基材としてAu、Ag、Cu、Pt、W、Nb、Ta、Mo、V及びPdを用い、炭素材料として炭素繊維複合材、等方性黒鉛及びガラス状炭素からなる、厚さ0.2〜1 mmの基板から長方形（40 ×5 mm）又は円盤形状（φ43〜45）の基材を放電加工機やフライス盤により切り出した。なお、本発明においては、基材を切り出す手段については特に限定されない。また、複雑な３次元形状の物体表面への製膜の可否を確かめるため、外径3 mm、内径2.6 mmで長さ40 mmのチューブ形状のタングステン試験片を作製した。金属試料については、同一材質に対して複数の試験片を作製した。 Ferrocene was used as the catalyst precursor of CNT, and acetylene was used as the raw material hydrocarbon gas. Au, Ag, Cu, Pt, W, Nb, Ta, Mo, V, and Pd are used as the metal base material, and the carbon material is made of carbon fiber composite material, isotropic graphite, and glassy carbon. A rectangular (40 × 5 mm) or disk-shaped (φ43 to 45) base material was cut out from an mm substrate by an electric discharge machine or a milling machine. In the present invention, the means for cutting out the substrate is not particularly limited. In addition, in order to confirm the possibility of film formation on the surface of a complex three-dimensional object, a tube-shaped tungsten test piece having an outer diameter of 3 mm, an inner diameter of 2.6 mm and a length of 40 mm was prepared. For the metal sample, a plurality of test pieces were prepared for the same material.
［粗面の形成］
金属基材については、微粉末ショット処理により、粗面を形成した。無機物微粒子として、粒番号が#60のアルミナ微粉末を用い、エアーブラスト装置（株式会社不二製作所、ニューマブラスター、型番：SGF-4(B)型）に装填して基材の全表面に対して微粉末ショット処理を行った。使用したエアーブラスト装置は、コンプレッサを用いて0.9 MPの高圧空気を１分間に約0.55 m3噴出させ、アルミナ微粉末を約140 m/sの速度で基材の表面に吹き付けて粗面を形成した。
[Rough surface formation]
About the metal base material, the rough surface was formed by the fine powder shot process. Alumina fine powder with particle number # 60 is used as inorganic fine particles and loaded into an air blasting device (Fuji Seisakusho, Pneumatic Blaster, model number: SGF-4 (B) type) on the entire surface of the substrate Then, a fine powder shot treatment was performed. Air blast device used was formed a 0.9 MP high pressure air is about 0.55 m 3 ejected per minute, rough surface by spraying the surface of the base material of alumina powder at a rate of approximately 140 m / s using a compressor did.
図５に、使用した無機物微粒子（アルミナ粉）の電子顕微鏡（SEM）像を示す。図５のスケールと粒子画像の比較から判るように、無機物微粒子の粒径は主として10〜40 μm程度であった。 FIG. 5 shows an electron microscope (SEM) image of the used inorganic fine particles (alumina powder). As can be seen from the comparison of the scale and particle image in FIG. 5, the particle size of the inorganic fine particles was mainly about 10 to 40 μm.
［ウェットプロセスによる無機物層の形成］
無機物層を形成するため、触媒担持層前駆体溶液には和光純薬工業株式会社が製造した塩基性硝酸アルミニウム溶液を用いた。塩基性硝酸アルミニウム溶液はウェットバインダーとも呼ばれ、硝酸アルミニウムの水溶液である。使用した溶液の硝酸アルミニウム濃度は約3.9 mol/lであり、加熱することにより1 mlの溶液から0.190〜0.204 gのアルミナ（Al2O3）を生成可能である。
[Formation of inorganic layer by wet process]
In order to form the inorganic layer, a basic aluminum nitrate solution manufactured by Wako Pure Chemical Industries, Ltd. was used as the catalyst support layer precursor solution. The basic aluminum nitrate solution is also called a wet binder and is an aqueous solution of aluminum nitrate. The concentration of aluminum nitrate in the solution used is about 3.9 mol / l, and 0.190 to 0.204 g of alumina (Al 2 O 3 ) can be produced from 1 ml of the solution by heating.
試験片を上述の溶液に約30分間浸漬した。溶液中の試験片表面に気泡が付着した場合には、超音波洗浄器を用いて浸漬中の試験片に振動を加えて気泡を除去した。その後、大気中で自然乾燥させた後、雰囲気制御可能な加熱炉やホットプレートにより試験片を850〜900℃に加熱して約10分間保持して、基材表面にアルミナからなる無機物層を形成した。焼成時の雰囲気には、基材の酸化を防ぐため10-3 Pa程度の真空もしくは窒素ガス雰囲気のいずれかを選択した。 The specimen was immersed in the above solution for about 30 minutes. When bubbles adhered to the surface of the test piece in the solution, the bubbles were removed by applying vibration to the immersed test piece using an ultrasonic cleaner. Then, after naturally drying in the air, the test piece is heated to 850-900 ° C with a furnace or hot plate that can control the atmosphere and held for about 10 minutes to form an inorganic layer made of alumina on the substrate surface did. As the atmosphere during firing, either a vacuum of about 10 −3 Pa or a nitrogen gas atmosphere was selected to prevent oxidation of the substrate.
（無機物層の微細構造観察）
上述の方法により製膜したアルミナからなる無機物層の微細構造を分析するため、無機物層を形成した基材表面に対して、走査電子顕微鏡（SEM）による微細形状観察と走査式オージェ電子分光装置によるアルミニウムの面分布分析を行った。使用した走査式オージェ電子分光装置はアルバック・ファイ製の型式PHI-710であり、電子銃加速電圧と電流はそれぞれ20 kVと1 nAに設定した。この装置のオージェ電子空間分解能は約8 nmであり、面分布空間分解能は約4 nm/stepである。
(Fine structure observation of inorganic layer)
In order to analyze the fine structure of the inorganic layer made of alumina formed by the above-mentioned method, the surface of the substrate on which the inorganic layer is formed is observed with a fine shape by a scanning electron microscope (SEM) and by a scanning Auger electron spectrometer. Surface distribution analysis of aluminum was performed. The scanning Auger electron spectrometer used was a model PHI-710 made by ULVAC-PHI, and the electron gun acceleration voltage and current were set to 20 kV and 1 nA, respectively. The Auger electron spatial resolution of this device is about 8 nm, and the surface distribution spatial resolution is about 4 nm / step.
図６には、炭素繊維複合材の表面に窒素雰囲気中（（ａ）及び（ｂ））と真空中（（ｃ）及び（ｄ））の異なる条件において焼成した触媒担持層のSEM像の比較を示している。像（ａ）及び像（ｃ）は倍率2万倍のSEM像であり、表面には数ミクロン程度の角張ったタイル形状のアルミナが点在し、その間の領域を細かい粒子状のアルミナが無数に分散している事が判る。像（ｂ）及び像（ｄ）は、粒子状のアルミナが分散している領域を10万倍に拡大したSEM像である。真空中で焼成した基材表面には窒素雰囲気中で焼成した基材表面のアルミナ粒子よりも微細な粒径（数〜数十 nm）のアルミナ粒子が分散している事が判明した。 FIG. 6 shows a comparison of SEM images of the catalyst support layers fired on the surface of the carbon fiber composite material under different conditions in a nitrogen atmosphere ((a) and (b)) and in a vacuum ((c) and (d)). Is shown. Image (a) and image (c) are SEM images at a magnification of 20,000 times, and the surface is dotted with angular tile-shaped alumina of several microns, and there are innumerable fine particulate alumina in the area between them. You can see that they are dispersed. The image (b) and the image (d) are SEM images obtained by enlarging the region where the particulate alumina is dispersed by a factor of 100,000. It was found that alumina particles having a finer particle diameter (several to several tens of nm) were dispersed on the surface of the substrate fired in vacuum than the alumina particles fired in a nitrogen atmosphere.
図７には、ガラス状炭素基材の表面に窒素雰囲気中と真空中の異なる条件で焼成した触媒担持層のSEM像とオージェ電子分光分析（AES）による触媒担持層の最表面におけるアルミニウム面分布の比較を示している。像（ｂ）の白点は、窒素雰囲気中において焼成した触媒担持層表面におけるアルミニウムの存在を示し、像（ｄ）の白点は真空中において焼成した触媒担持層表面におけるアルミニウムの存在を示す。それぞれの像の左側に示す同じ領域を撮影したSEM像（（ａ）と（ｃ））において白く表示される領域がアルミナに対応することが判る。両者のSEM像（（ａ）及び（ｃ））とアルミニウム面分布（（ｂ）及び（ｄ））の比較から、窒素雰囲気中で焼成した触媒担持層の大部分が連続膜状のアルミナに覆われているのに対して、真空中で焼成した触媒担持層は30〜100 nmの粒子状のアルミナが分散している不連続構造である事が判明した。 FIG. 7 shows the SEM image of the catalyst support layer calcined on the surface of the glassy carbon substrate under different conditions in a nitrogen atmosphere and vacuum, and the aluminum surface distribution on the outermost surface of the catalyst support layer by Auger electron spectroscopy (AES). Shows a comparison. The white point in the image (b) indicates the presence of aluminum on the surface of the catalyst support layer fired in a nitrogen atmosphere, and the white point in the image (d) indicates the presence of aluminum on the surface of the catalyst support layer fired in a vacuum. It can be seen that in the SEM images ((a) and (c)) obtained by photographing the same region shown on the left side of each image, the region displayed in white corresponds to alumina. From the comparison of both SEM images ((a) and (c)) and aluminum surface distributions ((b) and (d)), most of the catalyst-supported layer calcined in a nitrogen atmosphere was covered with continuous film-like alumina. In contrast, the catalyst support layer fired in vacuum was found to have a discontinuous structure in which particulate alumina of 30 to 100 nm was dispersed.
以上の観察結果から、真空中で製膜したアルミナ膜は不連続膜となり、窒素雰囲気中で製膜したアルミナ膜は連続膜になる傾向があることが判明した。 From the above observation results, it was found that an alumina film formed in a vacuum tends to be a discontinuous film, and an alumina film formed in a nitrogen atmosphere tends to be a continuous film.
［浮遊触媒輸送式CVDによるＣＮＴの製膜］
試験片表面に触媒担持層を製膜した後、株式会社マイクロフェーズ社製の小型ＣＮＴ合成装置MPCNT-Premiumを用いてフェロセンを触媒前駆体とする浮遊触媒輸送式CVD法によるＣＮＴの製膜を行った。この合成装置は、フェロセンを昇華させる金属リボン発熱体と基材を載せて直接加熱する炭素繊維複合材発熱体が内蔵された試料チャンバーとチャンバー内の雰囲気を制御するためのロータリーポンプと各種のガス供給ラインで構成されており、製膜中の基材の温度は放射温度計で測定することができる。
[CNT film formation by floating catalyst transport CVD]
After forming the catalyst support layer on the surface of the test piece, CNTs were formed by the floating catalyst transport CVD method using ferrocene as the catalyst precursor using the small CNT synthesizer MPCNT-Premium manufactured by Microphase Co., Ltd. It was. This synthesizer is equipped with a metal ribbon heating element for sublimating ferrocene, a sample chamber containing a carbon fiber composite heating element that directly heats the substrate, a rotary pump for controlling the atmosphere in the chamber, and various gases. It comprises a supply line, and the temperature of the substrate during film formation can be measured with a radiation thermometer.
炭素繊維複合材発熱体上に試験片を置くと共に金属リボン発熱体近傍のるつぼにフェロセン粉末を挿入し、試料チャンバー内に窒素を導入後、ロータリーポンプでチャンバー内を真空にする作業を3回繰り返した。その後、体積比で１：２のアセチレンと窒素の混合ガスを導入し、チャンバー内のゲージ圧を-0.085 Paとした。その後、炭素繊維複合材発熱体を加熱して試料を約380℃の温度に上昇させた後、金属リボン発熱体を加熱してフェロセンを昇華させた。フェロセン蒸気がチャンバー内に充満した事を確認した後、炭素繊維複合材発熱体を更に加熱し試料温度を約780℃に上昇させた後、その温度で約5分間保持し試験片表面にＣＮＴを成長させた。 Place the test piece on the carbon fiber composite heating element, insert ferrocene powder into the crucible near the metal ribbon heating element, introduce nitrogen into the sample chamber, and then evacuate the chamber with a rotary pump three times. It was. Thereafter, a mixed gas of acetylene and nitrogen at a volume ratio of 1: 2 was introduced, and the gauge pressure in the chamber was set to -0.085 Pa. Thereafter, the carbon fiber composite heating element was heated to raise the sample to a temperature of about 380 ° C., and then the metal ribbon heating element was heated to sublimate ferrocene. After confirming that the ferrocene vapor was filled in the chamber, the carbon fiber composite heating element was further heated to raise the sample temperature to about 780 ° C., and then held at that temperature for about 5 minutes, and CNT was placed on the surface of the test piece. Grown up.
［ＣＮＴ製の黒化膜の観察］
実施例に用いた13種類全ての基材に対してＣＮＴから構成される黒化膜が形成されることを確認した。金属と炭素材料の基材に成長させた黒化膜の均一性を比較すると、炭素材料の黒化膜の方が均一であった。特に、炭素繊維複合材に関しては試験片全面に濃密に黒色物質が成長することを確認した。図８は黒化膜の製膜前（ａ）と製膜後（ｂ）の炭素繊維複合材の写真を示す。黒化膜の製膜により炭素繊維の筋や織り目が全く見えなくなってしまったことが判る。金属に関しては、基材表面を微粉末ショット処理により粗面化した基材の方が黒化膜の均一性が向上する効果が得られた。
[Observation of CNT black film]
It was confirmed that a blackened film composed of CNTs was formed on all 13 types of base materials used in the examples. Comparing the uniformity of the black film grown on the metal and carbon material substrates, the black film of the carbon material was more uniform. In particular, with respect to the carbon fiber composite material, it was confirmed that the black substance grew densely on the entire surface of the test piece. FIG. 8 shows photographs of the carbon fiber composite material before (a) and after (b) film formation of the blackened film. It can be seen that the carbon fiber streaks and textures are completely invisible due to the formation of the blackened film. Regarding the metal, the effect of improving the uniformity of the blackened film was obtained when the base material was roughened by a fine powder shot process.
図９に、黒化膜を製膜した2本のタングステンチューブの写真を示す。チューブ（ａ）の基材表面は通常の切削面のままとし、チューブ（ｂ）の基材外表面は粉末ショット処理により粗面化処理を行った。両者の外観を比較すると、チューブ（ａ）は左側の端が黒化されていない状態であるが、チューブ（ｂ）はほぼ全面が黒化されていることが判る。なお、両チューブ試料ともチューブ内面は黒化されていたことから、本発明に係るＣＮＴ被膜部材の製造方法が３次元物体表面へのＣＮＴの製膜に有効であることが示された。 FIG. 9 shows a photograph of two tungsten tubes formed with a blackened film. The base material surface of the tube (a) was left as a normal cutting surface, and the outer surface of the base material of the tube (b) was roughened by powder shot processing. Comparing the appearances of the two, it can be seen that the left end of the tube (a) is not blackened, but the entire surface of the tube (b) is blackened. In addition, since the tube inner surface was blackened in both tube samples, it was shown that the manufacturing method of the CNT coating member according to the present invention is effective for forming CNT on the three-dimensional object surface.
また、真空中と窒素雰囲気中の２種類の条件で触媒担持層を形成した基材表面に製膜した黒化面の均質性を比較した結果、窒素雰囲気中で触媒担持層を製膜した基材の黒化膜は所々基材から剥離して均一性が悪くなる傾向があった。前述したように窒素雰囲気中で形成したアルミナ膜は連続膜になる傾向があることを考慮すると、そのことが製膜したＣＮＴ製の黒化膜の剥離及び不均一性に関わっていると考えられる。触媒担持層であるアルミナ膜が連続膜である場合、基材とアルミナとの熱膨張差によりＣＮＴの製膜中にアルミナ膜がひび割れて剥離すると考えられる。したがって、均一性が良好なＣＮＴ製の黒化膜を形成するためには、触媒担持層前駆体溶液を基材にディップコートした後に焼成する際の雰囲気には真空を選択すべきであることが判明した。 In addition, as a result of comparing the homogeneity of the blackened surface formed on the surface of the base material on which the catalyst supporting layer was formed under two conditions in a vacuum and in a nitrogen atmosphere, the base on which the catalyst supporting layer was formed in a nitrogen atmosphere The blackened film of the material tended to peel off from the substrate in some places and the uniformity was poor. Considering that the alumina film formed in the nitrogen atmosphere tends to be a continuous film as described above, this is considered to be related to the peeling and non-uniformity of the formed CNT blackening film. . When the alumina film as the catalyst supporting layer is a continuous film, it is considered that the alumina film is cracked and peeled during the CNT film formation due to the difference in thermal expansion between the base material and alumina. Therefore, in order to form a black film made of CNT with good uniformity, vacuum should be selected as the atmosphere when firing after dip-coating the catalyst support layer precursor solution on the substrate. found.
［SEMによるＣＮＴ膜の観察］
製膜したＣＮＴ製の黒化膜の表面をSEMにより観察した結果を図１０〜２２に示す。図１０〜２２において、（ａ）は倍率250倍のSEM像を示し、（ｂ）は（ａ）の中心部にある白抜きの丸で囲まれた部分について倍率7万倍のSEM像を示す。
[Observation of CNT film by SEM]
The result of having observed the surface of the formed black film made from CNT by SEM is shown in FIGS. 10-22, (a) shows an SEM image at a magnification of 250 times, and (b) shows an SEM image at a magnification of 70,000 times for a portion surrounded by a white circle at the center of (a). .
図１０は、銅（Cu）基材を用いた実施例を示す。図１１は、銀（Ag）基材を用いた実施例を示す。図１２は、金（Au）基材を用いた実施例を示す。図１３は、白金（Pt）基材を用いた実施例を示す。図１４は、タングステン（W）基材を用いた実施例を示す。図１５は、ニオブ（Nb）基材を用いた実施例を示す。図１６は、タンタル（Ta）基材を用いた実施例を示す。図１７は、モリブデン（Mo）基材を用いた実施例を示す。図１８は、バナジウム（V）基材を用いた実施例を示す。図１９は、パラジウム（Pd）基材を用いた実施例を示す。図２０は、等方性黒鉛基材を用いた実施例を示す。図２１は、ガラス状炭素基材を用いた実施例を示す。図２２は、炭素繊維複合材基材を用いた実施例を示す。 FIG. 10 shows an embodiment using a copper (Cu) substrate. FIG. 11 shows an example using a silver (Ag) substrate. FIG. 12 shows an example using a gold (Au) substrate. FIG. 13 shows an example using a platinum (Pt) substrate. FIG. 14 shows an embodiment using a tungsten (W) substrate. FIG. 15 shows an embodiment using a niobium (Nb) substrate. FIG. 16 shows an example using a tantalum (Ta) substrate. FIG. 17 shows an example using a molybdenum (Mo) substrate. FIG. 18 shows an example using a vanadium (V) substrate. FIG. 19 shows an example using a palladium (Pd) substrate. FIG. 20 shows an example using an isotropic graphite substrate. FIG. 21 shows an example using a glassy carbon substrate. FIG. 22 shows an example using a carbon fiber composite substrate.
全ての倍率250倍のSEM像は、表面には繊維状の物体無秩序に存在することを示しており、倍率7万倍のSEM像から繊維状の物質の直径は概ね5 nm〜50 nm程度であることが判る。黒色物質は炭素から構成されている事を考慮すると、直径の大きさから繊維状の物質は多層CNTと考えられる。 All SEM images with a magnification of 250 times show that there is a fibrous object disorder on the surface. From the SEM images with a magnification of 70,000 times, the diameter of the fibrous material is approximately 5 nm to 50 nm. I know that there is. Considering that the black material is composed of carbon, the fibrous material is considered to be multi-walled CNT due to the size of the diameter.
［TEMによるＣＮＴの観察］
成長した繊維状物質が多層ＣＮＴであることを透過電子顕微鏡（TEM）により確認した。等方性黒鉛と炭素繊維複合材の基材に成長させた繊維状物質をそれぞれ基材から削り取り分散処理を行った上でTEMによる観察を行った。使用したTEMは日立ハイテクノロジーズ製の型式H-9000NARであり、観察時の加速電圧は200 kVに設定した。図２３に、等方性黒鉛材に成長させた黒色物質の倍率205万倍のTEM像を示す。（ａ）〜（ｄ）において、4〜17層のグラフェンを有する直径6〜20 nmの多層CNTが存在していることが判明した。
[Observation of CNT by TEM]
It was confirmed by transmission electron microscope (TEM) that the grown fibrous material was multi-walled CNT. The fibrous materials grown on the base material of isotropic graphite and carbon fiber composite were each scraped off from the base material and subjected to dispersion treatment, and then observed by TEM. The TEM used was a model H-9000NAR manufactured by Hitachi High-Technologies, and the acceleration voltage during observation was set to 200 kV. FIG. 23 shows a TEM image of a black material grown on an isotropic graphite material at a magnification of 2,050,000. In (a) to (d), it was found that multi-wall CNTs having a diameter of 6 to 20 nm and having 4 to 17 layers of graphene exist.
図２４に、炭素繊維複合材に成長させたＣＮＴの倍率205万倍のTEM像を示す。（ａ）〜（ｃ）において、4〜9層のグラフェンを有する直径5.5〜10 nmの多層CNTが存在していることが判明した。フェロセンを触媒前駆体、アセチレンを原料ガスとして用いた場合、直径が5〜30 nmとなる多層CNTが生成しやすいことが予想されたが、実施例は経験的な予想と合致した。 FIG. 24 shows a TEM image of CNT grown at a carbon fiber composite material at a magnification of 2,050,000. In (a) to (c), it was found that multi-wall CNTs having a diameter of 5.5 to 10 nm and having 4 to 9 layers of graphene exist. When ferrocene was used as a catalyst precursor and acetylene was used as a raw material gas, it was expected that multi-walled CNTs having a diameter of 5 to 30 nm were likely to be produced, but the examples were consistent with empirical expectations.
［分光反射率の測定］
実施例のＣＮＴ被膜部材について、可視域における分光反射率測定を行った。光源付き積分球と回折格子型マルチチャネル分光器を用いて試料と２％標準反射板の半球拡散分光反射強度の比較測定を行い、可視波長域（400〜800 nm）における垂直分光反射率を決定した。炭素繊維複合材（CC）、等方性黒鉛（IG）、タングステン（W）基材に成長させた黒化面の可視域における分光反射率の測定結果を図２５に示す。この図より、黒化面はいずれも0.01以下と非常に低い反射率の値を示しており、黒化面として非常に優れている事が判明した。
[Measurement of spectral reflectance]
About the CNT film member of an Example, the spectral reflectance measurement in a visible region was performed. Using an integrating sphere with a light source and a diffraction grating type multi-channel spectrometer, comparative measurements of the hemispherical diffuse spectral reflection intensity of the sample and 2% standard reflector are performed to determine the vertical spectral reflectance in the visible wavelength range (400-800 nm). did. FIG. 25 shows the measurement results of the spectral reflectance in the visible region of the blackened surface grown on the carbon fiber composite material (CC), isotropic graphite (IG), and tungsten (W) substrate. From this figure, it was found that all the blackened surfaces showed very low reflectance values of 0.01 or less, and that the blackened surface was very excellent.
炭素繊維複合材を素材とする基材にＣＮＴが製膜されたことから、ＣＮＴが炭素繊維から直接成長するかどうかを実験により検証した。図２６は、PAN系炭素繊維上に本発明に係るＣＮＴ被膜部材の製造方法により製膜したＣＮＴのSEM像である。（ａ）は倍率500倍のSEM像であり、（ｂ）は（ａ）の像の丸で囲んだ部分の倍率5000倍のSEM像である。本発明に係るＣＮＴ被膜部材の製造方法により、無機物層を形成することでPAN系炭素繊維の全面にＣＮＴと思われる繊維状の物質が成長することが明らかとなった。 Since CNTs were formed on a substrate made of a carbon fiber composite material, it was verified by experiments whether CNTs grew directly from carbon fibers. FIG. 26 is an SEM image of CNTs formed on a PAN-based carbon fiber by the method for manufacturing a CNT coating member according to the present invention. (A) is an SEM image with a magnification of 500 times, and (b) is an SEM image with a magnification of 5000 times in a portion surrounded by a circle in the image of (a). By the method for producing a CNT coated member according to the present invention, it has been clarified that a fibrous substance that seems to be CNT grows on the entire surface of the PAN-based carbon fiber by forming an inorganic layer.
PAN系炭素繊維に成長した繊維状の物質が多層ＣＮＴであることをTEMにより確認した。図２７は、PAN系炭素繊維上に製膜したＣＮＴのTEM像ある。加速電圧200 kV、倍率205万倍、倍率精度10 %で観察した。（ａ）〜（ｃ）のTEM像から、直径10〜24 nmで6〜23層の多層CNTが形成されたことが明らかとなった。 It was confirmed by TEM that the fibrous material grown on the PAN-based carbon fiber was a multilayer CNT. FIG. 27 is a TEM image of CNTs formed on PAN-based carbon fibers. The observation was performed at an acceleration voltage of 200 kV, a magnification of 2,050,000, and a magnification accuracy of 10%. From the TEM images of (a) to (c), it was revealed that 6 to 23 multilayer CNTs were formed with a diameter of 10 to 24 nm.
［粗面化処理の効果の検証］
本発明に係るＣＮＴ被膜部材の製造方法における粗面化処理の効果を検証した。処理ｂとして、微粉末ショット処理を行わずウェットプロセスによる無機物層の形成のみ行った後にＣＮＴを製膜した。処理ｃとして、微粉末ショット処理後にＣＮＴを製膜した。処理ｄとして、微粉末ショット処理後にウェットプロセスによる無機物層の形成を行った後にＣＮＴを製膜した。
[Verification of the effect of surface roughening]
The effect of the roughening treatment in the method for producing a CNT coated member according to the present invention was verified. As the treatment b, a fine powder shot treatment was not performed, and only an inorganic layer was formed by a wet process, and then a CNT film was formed. As treatment c, a CNT film was formed after the fine powder shot treatment. As the treatment d, an inorganic layer was formed by a wet process after the fine powder shot treatment, and then a CNT film was formed.
図２８は、処理ｂ〜ｄによりタングステン製の基材に製膜したＣＮＴ膜の状態を示す写真である。図の上半分には3個の平面状試験片に対して処理した後の基材の写真を配しており、図の下半分には2本のチューブ状基材に対して処理した後の基材の写真を配している。この図から、処理ｂでは、平面板などの単純な形状の基材の場合でも、所々、ＣＮＴの成長具合にムラが発生した事が判る。処理ｃでは、平面板などの単純な形状の基材の場合にはムラ無くＣＮＴを表面に製膜できるが、３次元形状の表面を有するチューブ状基材等の場合にはＣＮＴが一様に成長せずにムラが発生することがあると言える。処理ｄでは、平面板もチューブのような複雑な３次元形状の基材表面に対してもムラ無く一様にＣＮＴを成長させることができた。なお、処理ｂ〜ｄで生成したＣＮＴのミクロ構造（SEMやTEMでの観察結果）に明確な違いは観察されなかった。 FIG. 28 is a photograph showing the state of the CNT film formed on a tungsten substrate by treatments b to d. The upper half of the figure shows a photograph of the substrate after processing on three flat specimens, and the lower half of the figure shows the result after processing on two tubular substrates. A photo of the substrate is provided. From this figure, it can be seen that in the process b, unevenness occurred in the growth of CNTs in some cases even in the case of a simple base material such as a flat plate. In the process c, CNTs can be formed on the surface without unevenness in the case of a simple substrate such as a flat plate, but in the case of a tube-like substrate having a three-dimensional surface, the CNTs are uniformly formed. It can be said that unevenness may occur without growing. In the treatment d, CNTs were able to grow uniformly on the surface of the base plate having a complicated three-dimensional shape such as a flat plate and a tube. In addition, a clear difference was not observed in the microstructure (observation result by SEM and TEM) of CNT produced | generated by process bd.
本発明に係るカーボンナノチューブ被膜部材は、カーボンナノチューブが一様に被膜され、分光反射率が低いため、計測・試験機器、加熱装置、放熱部材、光学機器等の分野で利用可能である。 The carbon nanotube film member according to the present invention is uniformly coated with carbon nanotubes and has a low spectral reflectance, and thus can be used in the fields of measurement / test equipment, heating devices, heat radiation members, optical equipment, and the like.
１００：ＣＮＴ被膜部材、１１０：基材、１１５：粗面、１２０：無機物層、１２１：無機物微粒子、１３０：触媒金属微粒子層、１３１：触媒金属微粒子、１５０：ＣＮＴ、２００：ＣＮＴ被膜部材、２１０：金属基材、２１５：粗面、２１７：無機物微粒子層、２１９：無機物微粒子、２２０：無機物層、２３０：触媒金属微粒子層、２３１：触媒金属微粒子 100: CNT coating member, 110: substrate, 115: rough surface, 120: inorganic layer, 121: inorganic fine particle, 130: catalytic metal fine particle layer, 131: catalytic metal fine particle, 150: CNT, 200: CNT coating member, 210 : Metal substrate, 215: rough surface, 217: inorganic fine particle layer, 219: inorganic fine particle, 220: inorganic fine layer, 230: catalytic metal fine particle layer, 231: catalytic metal fine particle
Claims (10)
前記基材を800℃以上に加熱し、
金属錯体蒸気を用いる浮遊触媒輸送式の化学気相成長により、カーボンナノチューブを前記基材の表面に製膜することを特徴とするカーボンナノチューブ被膜部材の製造方法。 Immerse the substrate in the aluminum compound solution,
Heating the substrate to 800 ° C. or higher,
A method for producing a carbon nanotube-coated member, comprising depositing carbon nanotubes on the surface of the substrate by chemical vapor deposition using a floating catalyst transport method using a metal complex vapor.
前記基材の表面に配置された無機物層と、
前記無機物層上に担持された触媒金属微粒子層と、
前記触媒金属微粒子層上に配置されたカーボンナノチューブと、
を備え、
分光反射率が０．０１以下であることを特徴とするカーボンナノチューブ被膜部材。 A substrate;
An inorganic layer disposed on the surface of the substrate;
A catalytic metal fine particle layer supported on the inorganic layer;
Carbon nanotubes disposed on the catalyst metal fine particle layer;
With
A carbon nanotube film member having a spectral reflectance of 0.01 or less.
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