JP2011167598A - Catalyst for producing carbon nanocoil, method for producing the nanocoil and carbon nanocoil - Google Patents
Catalyst for producing carbon nanocoil, method for producing the nanocoil and carbon nanocoil Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- 239000000758 substrate Substances 0.000 claims abstract description 87
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 71
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 21
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
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- 238000001354 calcination Methods 0.000 claims description 3
- KKHJTSPUUIRIOP-UHFFFAOYSA-J tetrachlorostannane;hydrate Chemical compound O.Cl[Sn](Cl)(Cl)Cl KKHJTSPUUIRIOP-UHFFFAOYSA-J 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 39
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- 229910052751 metal Inorganic materials 0.000 abstract description 9
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- 208000037998 chronic venous disease Diseases 0.000 description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 27
- 229910020810 Sn-Co Inorganic materials 0.000 description 22
- 229910018757 Sn—Co Inorganic materials 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 20
- 239000011777 magnesium Substances 0.000 description 11
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
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- 229910052718 tin Inorganic materials 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
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- 229910052749 magnesium Inorganic materials 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910018645 Mn—Sn Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OAUNEKQRMZKISO-UHFFFAOYSA-J tetrachlorostannane hexahydrate Chemical compound O.O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl OAUNEKQRMZKISO-UHFFFAOYSA-J 0.000 description 1
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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Abstract
Description
本発明は、炭素原子を螺旋状に巻回成長させた外直径が１０００ｎｍ以下のカーボンナノコイル（以下、ＣＮＣという。）の製造に用いるカーボンナノコイル製造用触媒及びその触媒を用いてＣＮＣを製造する製造方法に関する。 The present invention relates to a catalyst for producing carbon nanocoils used to produce carbon nanocoils (hereinafter referred to as CNC) having an outer diameter of 1000 nm or less in which carbon atoms are spirally wound and grown, and a CNC is produced using the catalyst. It relates to a manufacturing method.
ＣＮＣの合成は、特許文献１〜３等に開示されているように、内部を加熱した反応器内部にアセチレンガス等の炭化水素ガスを流通させ、この炭化水素ガスの中にＣＮＣ製造用触媒を粒子状に分散させ、炭化水素を触媒近傍で分解しながら触媒粒子の表面にカーボンナノコイルを成長させて行われる。カーボンナノコイルはｎｍサイズの線径を有し、長さ数１０μｍのコイル状物質からなるものである。
In the synthesis of CNC, as disclosed in
ＣＮＣを化学気相成長法（ＣＶＤ法）により高効率で合成できる触媒として、非特許文献１に示すように、Ｆｅ−Ｉｎ−Ｓｎ系酸化物が有効であることが既に知られている。
As shown in Non-Patent
ＣＮＣ合成において、例えば、湿式触媒を用いるとき、触媒は触媒金属塩化物及び硝酸塩の水又はエタノール溶液として成長基板上に塗布され、乾燥の後に８００℃付近の高温で酸化処理することにより前駆体が形成される。ＣＶＤ開始時に炭素源であるアセチレンガスが触媒に到達すると同時に還元されて最適な組成や粒径を持つ触媒粒子が形成され、ＣＮＣが基板上に成長していく。 In CNC synthesis, for example, when a wet catalyst is used, the catalyst is applied on the growth substrate as a catalyst metal chloride and nitrate water or ethanol solution, and after drying, the precursor is oxidized at a high temperature around 800 ° C. It is formed. At the start of CVD, acetylene gas as a carbon source reaches the catalyst and is simultaneously reduced to form catalyst particles having an optimal composition and particle size, and the CNC grows on the substrate.
ＣＮＣ合成のとき、ＣＶＤ後の生成物の断面を電子顕微鏡で観察すると、担持材質と成長したＣＮＣとの間には、黒鉛及び触媒金属からなる厚い炭化層が形成される。炭化層の厚さは成長したＣＮＣの長さと同じオーダーにまで達する。 When the cross section of the product after CVD is observed with an electron microscope during the CNC synthesis, a thick carbonized layer made of graphite and catalytic metal is formed between the support material and the grown CNC. The thickness of the carbonized layer reaches the same order as the length of the grown CNC.
しかしながら、かかる炭化層の形成は、ＣＮＣ合成に必要なアセチレンガス等の炭化水素ガスや触媒金属を余分に消費してしまうため、ＣＮＣ合成コストの上昇を招き、また、所要製造時間の無駄を生じ、更に製造効率の低下を招くといった問題を生じていた。 However, the formation of such a carbonized layer consumes an excess of hydrocarbon gas such as acetylene gas and catalytic metal necessary for CNC synthesis, leading to an increase in CNC synthesis cost and waste of required production time. Further, there has been a problem that the production efficiency is lowered.
本発明の目的は、上記課題に鑑み、ＣＮＣ製造過程で生ずる炭化層を低減して、ＣＮＣ合成に必要なアセチレンガス等の炭化水素ガスや触媒金属を余分に消費することなく、製造時間の削減、低コスト化及びＣＮＣ合成効率の向上を図ることのできるカーボンナノコイル製造用触媒、その製造方法及びその製法により製造されたカーボンナノコイルを提供することである。 In view of the above problems, the object of the present invention is to reduce the carbonization layer generated in the CNC production process, and reduce the production time without consuming extra hydrocarbon gas such as acetylene gas and catalyst metal necessary for CNC synthesis. Another object of the present invention is to provide a carbon nanocoil production catalyst capable of reducing the cost and improving the CNC synthesis efficiency, a production method thereof, and a carbon nanocoil produced by the production method.
本発明者らは、上記課題を解決すべく鋭意研究した結果、基板材質と触媒層の界面に予め酸化スズ層からなるバッファー層を形成することによりＣＮＣ合成過程で生ずる炭化層の低減に成功した。
本発明の第１の形態は、基板と、前記基板表面に形成された酸化スズ層と、前記酸化スズ層の表面に形成されたカーボンナノコイル製造用触媒層を少なくとも有するカーボンナノコイル製造用触媒である。
As a result of diligent research to solve the above problems, the present inventors succeeded in reducing the carbonized layer generated in the CNC synthesis process by forming a buffer layer made of a tin oxide layer in advance at the interface between the substrate material and the catalyst layer. .
A first embodiment of the present invention is a carbon nanocoil manufacturing catalyst having at least a substrate, a tin oxide layer formed on the substrate surface, and a carbon nanocoil manufacturing catalyst layer formed on the surface of the tin oxide layer. It is.
本発明の第２の形態は、第１形態において、前記カーボンナノコイル製造用触媒層がＦｅＭｇＳｎ、ＦｅＭｇＳｎＣｏ、ＦｅＭｇＣｏ、ＦｅＩｎＳｎ、ＦｅＩｎＳｎＣｏ、ＦｅＩｎＣｏの1種以上からなるカーボンナノコイル製造用触媒である。 A second aspect of the present invention is the carbon nanocoil manufacturing catalyst according to the first aspect, wherein the carbon nanocoil manufacturing catalyst layer is made of at least one of FeMgSn, FeMgSnCo, FeMgCo, FeInSn, FeInSnCo, and FeInCo.
本発明の第３の形態は、第１又は第２形態において、前記基板が、Ｓｉ、ＳｉＯ２、Ａｌ２Ｏ３、Ｓｉ３Ｎ４の1種以上からなるカーボンナノコイル製造用触媒である。 A third aspect of the present invention is the carbon nanocoil manufacturing catalyst according to the first or second aspect, wherein the substrate is composed of one or more of Si, SiO 2 , Al 2 O 3 , and Si 3 N 4 .
本発明の第４の形態は、スズ化合物溶液を調製し、前記スズ化合物溶液を基板表面に塗布して乾燥、焼成し、前記基板上に酸化スズ層を形成した中間触媒体を形成し、前記中間触媒体の酸化スズ層の表面にカーボンナノコイル製造用触媒層を形成するカーボンナノコイル製造用触媒の製造方法である。 According to a fourth aspect of the present invention, a tin compound solution is prepared, the tin compound solution is applied to a substrate surface, dried and fired, and an intermediate catalyst body in which a tin oxide layer is formed on the substrate is formed. It is the manufacturing method of the catalyst for carbon nanocoil manufacture which forms the catalyst layer for carbon nanocoil manufacture on the surface of the tin oxide layer of an intermediate catalyst body.
本発明の第５の形態は、第４形態において、前記スズ化合物溶液が、塩化スズ水和物と、水、アルコール又は水及びアルコールとの混合溶液であるカーボンナノコイル製造用触媒の製造方法である。 A fifth aspect of the present invention is a method for producing a catalyst for producing carbon nanocoils according to the fourth aspect, wherein the tin compound solution is a tin chloride hydrate and water, alcohol, or a mixed solution of water and alcohol. is there.
本発明の第６の形態は、第４又は第５の形態において、前記乾燥を１００〜１５０℃で行い、前記焼成を３００〜５００℃の酸化処理で行うカーボンナノコイル製造用触媒の製造方法である。 A sixth aspect of the present invention is a method for producing a catalyst for producing carbon nanocoils according to the fourth or fifth aspect, wherein the drying is performed at 100 to 150 ° C., and the calcination is performed by an oxidation treatment at 300 to 500 ° C. is there.
本発明の第７の形態は、第４、第５又は第６の形態において、前記酸化スズ層の層厚が１０〜１００ｎｍであり、前記カーボンナノコイル製造用触媒層の層厚が１００〜７００ｎｍであるカーボンナノコイル製造用触媒の製造方法である。 According to a seventh aspect of the present invention, in the fourth, fifth or sixth aspect, the tin oxide layer has a thickness of 10 to 100 nm, and the carbon nanocoil production catalyst layer has a thickness of 100 to 700 nm. It is a manufacturing method of the catalyst for carbon nanocoil manufacture which is.
本発明の第８の形態は、第４〜第７のいずれかの形態に係る製造方法により製造した前記中間触媒体及び前記カーボンナノコイル製造用触媒層を形成した基板を反応器内部に設置し、前記反応器内部を加熱して炭化水素ガスを流通させ、この炭化水素ガスの中に前記カーボンナノコイル製造用触媒層を粒子状に分散させ、炭化水素を触媒近傍で分解しながら触媒粒子の表面にカーボンナノコイルを成長させるカーボンナノコイルの製造方法である。 In an eighth aspect of the present invention, a substrate on which the intermediate catalyst body produced by the production method according to any one of the fourth to seventh aspects and the catalyst layer for producing the carbon nanocoil are formed is installed inside a reactor. The inside of the reactor is heated to circulate a hydrocarbon gas, and the catalyst layer for producing the carbon nanocoil is dispersed in the hydrocarbon gas in the form of particles. This is a carbon nanocoil manufacturing method in which carbon nanocoils are grown on the surface.
本発明の第９の形態は、第８の形態に係る製造方法により触媒粒子の表面に成長されたカーボンナノコイルからなることを特徴とするカーボンナノコイルである。 According to a ninth aspect of the present invention, there is provided a carbon nanocoil comprising carbon nanocoils grown on the surface of catalyst particles by the production method according to the eighth aspect.
本発明の第１の形態によれば、基板材質とＣＮＣ製造用触媒層の界面に予め形成した酸化スズ層がバッファー層として機能してＣＮＣ合成過程で生ずる炭化層を低減することができる。従って、ＣＮＣ製造過程で生ずる炭化層を低減できるため、ＣＮＣ合成に必要なアセチレンガス等の炭化水素ガスや触媒金属を余分に消費することなく、製造時間の削減、低コスト化及びＣＮＣ合成効率の向上を図ることができる。 According to the first embodiment of the present invention, the tin oxide layer formed in advance at the interface between the substrate material and the CNC production catalyst layer functions as a buffer layer, and the carbonized layer generated in the CNC synthesis process can be reduced. Accordingly, since the carbonized layer generated in the CNC production process can be reduced, the production time can be reduced, the cost can be reduced, and the CNC synthesis efficiency can be reduced without consuming extra hydrocarbon gas such as acetylene gas and catalyst metal necessary for CNC synthesis. Improvements can be made.
本発明の第２の形態によれば、前記カーボンナノコイル製造用触媒層として、ＦｅＩｎＳｎやＦｅＩｎＣｏのＦｅ−Ｉｎ−Ｓｎ系触媒の他、Ｉｎを安価なＭｇに代替したＦｅ−Ｍｇ−Ｓｎ系触媒のＦｅＭｇＳｎやＦｅＭｇＣｏ、更に、Ｃｏを添加したＦｅ−Ｍｇ−Ｓｎ−Ｃｏ系触媒のＦｅＩｎＳｎＣｏ、ＦｅＭｇＳｎＣｏの1種以上からなるので、より高効率にカーボンナノコイルを製造することが可能になる。 According to the second embodiment of the present invention, as the carbon nanocoil production catalyst layer, Fe—Mn—Sn catalyst in which In is replaced with inexpensive Mg in addition to FeInSn and FeInCo Fe—In—Sn catalysts. Thus, it is possible to manufacture carbon nanocoils with higher efficiency because FeMnSn, FeMgCo, and Fe—Mg—Sn—Co based catalysts FeInSnCo and FeMgSnCo added with Co are added.
本発明の第３の形態によれば、Ｓｉ、ＳｉＯ２、Ａｌ２Ｏ３、Ｓｉ３Ｎ４の1種以上からなるＣＮＣ合成に好適な担持基板上にカーボンナノコイルを高効率に製造することが可能になる。 According to the third aspect of the present invention, carbon nanocoils can be efficiently produced on a support substrate suitable for CNC synthesis comprising one or more of Si, SiO 2 , Al 2 O 3 , and Si 3 N 4. Is possible.
本発明の第４の形態によれば、スズ化合物溶液を調製し、前記スズ化合物溶液を基板表面に塗布して乾燥、焼成し、前記基板上に酸化スズ層を形成した中間触媒体を形成し、前記中間触媒体の酸化スズ層の表面にカーボンナノコイル製造用触媒層を形成するので、基板材質とＣＮＣ製造用触媒層の界面に酸化スズ層をバッファー層として形成でき、ＣＮＣ合成過程で生ずる炭化層を低減することができる。 According to the fourth aspect of the present invention, a tin compound solution is prepared, the tin compound solution is applied to a substrate surface, dried and fired, and an intermediate catalyst body having a tin oxide layer formed on the substrate is formed. The catalyst layer for producing carbon nanocoils is formed on the surface of the tin oxide layer of the intermediate catalyst body, so that the tin oxide layer can be formed as a buffer layer at the interface between the substrate material and the catalyst layer for producing CNC, which is generated in the CNC synthesis process. The carbonized layer can be reduced.
本発明の第５の形態によれば、前記スズ化合物溶液が、塩化スズ水和物と、水、アルコール又は水及びアルコールとの混合溶液であるので、湿式法により簡単に酸化スズ層を形成することができ、炭化層の低減を低コストで行うことができる。 According to the fifth aspect of the present invention, since the tin compound solution is a mixed solution of tin chloride hydrate and water, alcohol or water and alcohol, a tin oxide layer is easily formed by a wet method. The carbonized layer can be reduced at a low cost.
本発明の第６の形態によれば、前記乾燥を１００〜１５０℃で行い、前記焼成を３００〜５００℃の酸化処理で行うので、通常の乾燥処理及び酸化処理を用いて炭化層の低減処理を簡易且つ低コストで行うことができる。 According to the sixth aspect of the present invention, since the drying is performed at 100 to 150 ° C. and the baking is performed at an oxidation treatment of 300 to 500 ° C., the carbonized layer reduction treatment is performed using a normal drying treatment and an oxidation treatment. Can be performed easily and at low cost.
本発明の第７の形態は、前記酸化スズ層の層厚が１０〜１００ｎｍであり、前記カーボンナノコイル製造用触媒層の層厚が１００〜７００ｎｍであるので、ＣＮＣ製造過程で簡易にカーボンナノコイル製造用触媒を製造することができる。 In the seventh embodiment of the present invention, the tin oxide layer has a thickness of 10 to 100 nm, and the carbon nanocoil production catalyst layer has a thickness of 100 to 700 nm. A catalyst for coil production can be produced.
本発明の第８の形態によれば、前記中間触媒体及び前記カーボンナノコイル製造用触媒層を形成した基板を反応器内部に設置し、前記反応器内部を加熱して炭化水素ガスを流通させ、この炭化水素ガスの中に前記カーボンナノコイル製造用触媒層を粒子状に分散させ、炭化水素を触媒近傍で分解しながら触媒粒子の表面にカーボンナノコイルを成長させるので、酸化スズ層がバッファー層として機能してＣＮＣ合成過程で生ずる炭化層を低減することができる。しかも、炭化層の低減化によりＣＮＣ合成に必要なアセチレンガス等の炭化水素ガスや触媒金属を余分に消費しなくて済み、また、比較的簡単な酸化スズ層形成工程を付与するだけであり、製造時間の削減、低コスト化及びＣＮＣ合成効率の向上を図ることができる。炭化水素ガスにはアセチレンに限らず、炭化水素ガスである限り特に制限されず、例えば、メタン、エタン、プロパン、ブタンなどのアルカン類、エチレンなどのアルケン類、アセチレン以外のアルキン類等が用いられる。 According to an eighth aspect of the present invention, the substrate on which the intermediate catalyst body and the carbon nanocoil production catalyst layer are formed is installed inside a reactor, and the inside of the reactor is heated to allow hydrocarbon gas to flow. The carbon nanocoil production catalyst layer is dispersed in particles in the hydrocarbon gas, and carbon nanocoils are grown on the surface of the catalyst particles while decomposing hydrocarbons in the vicinity of the catalyst. It can function as a layer and reduce the carbonized layer generated in the CNC synthesis process. In addition, by reducing the carbonized layer, it is not necessary to consume extra hydrocarbon gas such as acetylene gas and catalyst metal necessary for CNC synthesis, and only a relatively simple tin oxide layer forming step is provided. Manufacturing time can be reduced, costs can be reduced, and CNC synthesis efficiency can be improved. The hydrocarbon gas is not limited to acetylene, and is not particularly limited as long as it is a hydrocarbon gas. For example, alkanes such as methane, ethane, propane, and butane, alkenes such as ethylene, and alkynes other than acetylene are used. .
本発明者らの検証実験によれば、酸化スズ層がバッファー層として機能することにより、以下の効果を奏することに基づきＣＮＣ合成効率が向上すると考察される。
１）基板材質と触媒金属との化学反応が抑制され、ＣＮＣ触媒組成がより効果的に調整できた。
２）触媒焼成段階で昇華しやすい低融点のスズをあえて触媒層とは別の酸化スズ層として提供することができ、ＣＶＤ開始時と同時にスズが効果的に気相中に供給され、ＣＮＣ触媒組成の安定化を促進した。
According to the verification experiment of the present inventors, it is considered that the CNC synthesis efficiency is improved based on the following effects by the function of the tin oxide layer as the buffer layer.
1) The chemical reaction between the substrate material and the catalyst metal was suppressed, and the CNC catalyst composition could be adjusted more effectively.
2) Low melting point tin that is easily sublimated in the catalyst calcination stage can be provided as a tin oxide layer separate from the catalyst layer, and tin is effectively supplied into the gas phase at the same time as the start of CVD. Promoted composition stabilization.
本発明の第９の形態によれば、第８の形態に係る製造方法によって製造されることにより、低コスト化に良質のカーボンナノコイル得ることができる。 According to the ninth aspect of the present invention, high-quality carbon nanocoils can be obtained at low cost by being manufactured by the manufacturing method according to the eighth aspect.
以下、本発明の実施形態に係るＣＮＣ製造用触媒を用いたＣＮＣ製造方法を説明する。 Hereinafter, a CNC manufacturing method using a CNC manufacturing catalyst according to an embodiment of the present invention will be described.
図１は本発明の実施形態に係るＣＮＣ合成プロセスを示す。図２はＣＮＣ合成の様子を模式的に示す図である。ＣＮＣ担持基板材料にはアルミナＡｌ２Ｏ３、シリコンＳｉ、酸化シリコンＳｉＯ２、窒化ケイ素Ｓｉ３Ｎ４等を使用する。図２において担持基板材料を用意してからの工程Ａが本実施形態に対応する。 FIG. 1 illustrates a CNC synthesis process according to an embodiment of the present invention. FIG. 2 is a diagram schematically showing the state of CNC synthesis. Alumina Al 2 O 3 , silicon Si, silicon oxide SiO 2 , silicon nitride Si 3 N 4 or the like is used as the CNC supporting substrate material. In FIG. 2, step A after preparing the supporting substrate material corresponds to this embodiment.
ステップＳ１〜Ｓ２は、カーボンナノコイル製造用触媒で形成工程である。上記担持基板材料１上にスズ化合物溶液を基板表面に塗布して乾燥させた後（ステップＳ１）、酸化処理により焼成して基板１上に酸化スズ層２を形成した中間触媒体を形成する（ステップＳ２）。スズ化合物溶液は、四塩化スズ・六水和物を水又はエタノールで溶解して調製される。酸化スズ層２は１０〜１００ｎｍの層厚に形成される。
Steps S <b> 1 to S <b> 2 are steps for forming a carbon nanocoil manufacturing catalyst. After applying a tin compound solution onto the
ステップＳ１の乾燥は１００〜１５０℃の温度で行われ、ステップＳ２の焼成は３００〜５００℃の大気中酸化処理で行われる。スズ化合物溶液の塗布処理はディップコート法やスピンコート法を用いて行われる。 The drying in step S1 is performed at a temperature of 100 to 150 ° C., and the firing in step S2 is performed by an atmospheric oxidation treatment at 300 to 500 ° C. The tin compound solution is applied by a dip coating method or a spin coating method.
酸化スズ層２の形成後には、湿式触媒による触媒層の形成が行われる。予め触媒種に応じて調整された触媒溶液が酸化スズ層２上に塗布されて大気中での乾燥が行われる（ステップＳ３）。触媒物質としては、ＦｅＭｇＳｎ、ＦｅＭｇＳｎＣｏ、ＦｅＭｇＣｏ、ＦｅＩｎＳｎ、ＦｅＩｎＣｏ、ＦｅＩｎＳｎＣｏの1種以上を選択的に使用することができる。触媒溶液としては、Ｆｅ、Ｍｇ、Ｓｎ、Ｃｏの塩化物又は硝酸塩の混合エタノール溶液を使用することができ、例えば、ＦｅＭｇＳｎＣｏ触媒の場合には、硝酸鉄、塩化スズ、塩化マグネシウム、塩化コバルトの主成分に水又はエタノールの溶媒を混合した混合溶液により触媒溶液が調製される。
After the
触媒乾燥の後は６００〜１１００℃の温度で大気中での焼成処理が行われ、ＣＮＣ製造用触媒層３が酸化スズ層２上に形成される（ステップＳ４）。例えば、Ｆｅ−（Ｉｎ又はＭｇ）−Ｓｎ系触媒の場合には乾燥処理により粒径３０〜２００ｎｍ程度の酸化物微粒子が生成される。ＣＮＣ製造用触媒層３は１００〜７００ｎｍの層厚に形成される。
After the catalyst is dried, a firing process in the air is performed at a temperature of 600 to 1100 ° C., and a CNC
上記ステップＳ１〜Ｓ４により製造した中間触媒体及びＣＮＣ製造用触媒層を形成した基板１を反応炉（図示せず）内部に導入する（ステップＳ５）。当該反応炉内部はＨｅ、Ａｒ、Ｎ２等の不活性ガスで置換された後、７００℃に昇温される。ついで、加熱反応炉に炭化水素ガス（例えば、アセチレンガス）を流通させることにより（ステップＳ６）、炭化水素ガスの中にＣＮＣ製造用触媒層を粒子状に分散させ、炭化水素を触媒近傍で分解しながら触媒粒子の表面にカーボンナノコイル４を成長させる（ステップＳ７）。
The
本発明との比較のために、図３に従来のＣＮＣ合成プロセスを示す。図２において担持基板材料を用意してからの工程Ｂが従来プロセスに対応する。従来のＣＮＣ合成プロセスでは、図１の合成プロセスと比較して、酸化スズ層の中間触媒体形成工程はなく、触媒溶液の塗布・乾燥（ステップＳ１０）、焼成（ステップＳ１１）、反応炉導入（ステップＳ１２）、アセチレンガス導入（ステップＳ１３）、ＣＮＣ成長（ステップＳ１４）の手順だけで行われる。 For comparison with the present invention, FIG. 3 shows a conventional CNC synthesis process. In FIG. 2, Step B after preparing the supporting substrate material corresponds to the conventional process. In the conventional CNC synthesis process, as compared with the synthesis process of FIG. 1, there is no intermediate catalyst body forming step of the tin oxide layer, application and drying of the catalyst solution (step S10), firing (step S11), introduction of the reactor ( It is performed only by the procedures of step S12), acetylene gas introduction (step S13), and CNC growth (step S14).
従来の合成プロセスでは、図２に示すように、ＣＮＣ合成過程で厚い炭化層５が生じ、その上にＣＮＣ６が成長する。一方、本実施形態に係るＣＮＣ合成プロセスによれば、基板１とＣＮＣ製造用触媒層３の界面に予め形成した酸化スズ層２がバッファー層として機能するため、炭化層を生じず、あるいは大幅に低減することができ、ＣＮＣ４の合成に必要なアセチレンガス等の炭化水素ガスや触媒金属を余分に消費することなく、製造時間の削減、低コスト化及びＣＮＣ合成効率の向上を図ることができる。
In the conventional synthesis process, as shown in FIG. 2, a thick
本実施形態に係るＣＮＣ製造方法及び触媒の優位性につき、以下の実施例及び各種検証実験に基づいて詳述する。
＜実施例１＞
まず、アルミナとシリカ基板を用いて酸化スズ層を形成した。酸化スズ層の作製は、四塩化スズ・五水和物のエタノールもしくはエタノール:水＝１：１溶液０．１〜０．５ｍｏｌ／Ｌ濃度の溶液を滴下して、スピンコート法（１０００〜１５００ｒｐｍ、１５〜４５秒）により塗布、あるいは、０．０２ｍｏｌ／Ｌ濃度の溶液へ含浸して塗布した後１００〜１５０℃で乾燥させ、基板の端に凝集した液滴を吸い取りながら１００〜１５０℃で乾燥させ、更に３００〜５００℃で酸化処理した。触媒には、Ｆｅ−Ｍｇ−Ｓｎ−Ｃｏ系酸化物触媒とＳｎを含まないものを２種類使用した。つまり、夫々の配合比は、Ｆｅ：Ｍｇ：Ｓｎ：Ｃｏ＝１０：１：１：０．５〜１、Ｆｅ：Ｍｇ：Ｃｏ＝１０：１：０．５である。
The superiority of the CNC manufacturing method and catalyst according to the present embodiment will be described in detail based on the following examples and various verification experiments.
<Example 1>
First, a tin oxide layer was formed using an alumina and a silica substrate. The tin oxide layer was prepared by adding dropwise a solution of tin tetrachloride pentahydrate in ethanol or ethanol: water = 1: 1 solution at a concentration of 0.1 to 0.5 mol / L, and spin coating (1000-1500 rpm). 15 to 45 seconds) or impregnated in a solution having a concentration of 0.02 mol / L and dried at 100 to 150 ° C. It was dried and further oxidized at 300 to 500 ° C. As the catalyst, two kinds of Fe-Mg-Sn-Co-based oxide catalyst and Sn-free catalyst were used. That is, each compounding ratio is Fe: Mg: Sn: Co = 10: 1: 1: 0.5-1 and Fe: Mg: Co = 10: 1: 0.5.
図４の（４Ａ）はアルミナ基板上に作製した酸化スズ層のＳＥＭ断層写真を示す。酸化スズ層の厚さ４ａは３０〜６０ｎｍである。図４の（４Ｂ）は焼成後の酸化スズ層上の触媒粒子のＳＥＭ写真である。触媒粒子層の厚さは２５０〜６００ｎｍである。触媒粒子のＳＥＭ写真（４Ｂ）から明らかなように、炭化層が形成されずに触媒粒子が分散している。（４Ｂ）の４ｂは酸化スズ層である。触媒には、Ｆｅ−Ｍｇ−Ｓｎ−Ｃｏ系酸化物触媒と、上記配合のＳｎを含まないものを使用したが、Ｓｎを含まない場合には、塗布厚さが薄くなる傾向にある。なお、ＣＮＣの成長効率には塗布ムラが大きく影響された。
(4A) in FIG. 4 shows a SEM tomographic image of the tin oxide layer produced on the alumina substrate. The
上記の酸化スズ層及び触媒層の形成後、ＣＶＤ法によるＣＮＣ成長を１５分実施した。図５の（５Ａ）は上記実施例において、アルミナ基板上に生成したＣＮＣ試料のＳＥＭ断層写真である。同図（５Ｂ）、（５Ｃ）は夫々、（５Ａ）のＣＮＣ主要部分、アルミナ基板との界面付近のＳＥＭ写真である。この試料におけるアルミナ基板上の酸化スズ層の厚さは約３０ｎｍであり、その上の触媒層の厚さは約２００ｎｍである。 After the formation of the tin oxide layer and the catalyst layer, CNC growth by CVD was performed for 15 minutes. FIG. 5 (5A) is a SEM tomographic image of a CNC sample produced on an alumina substrate in the above example. FIGS. 5B and 5C are SEM photographs of the CNC main portion of 5A and the vicinity of the interface with the alumina substrate, respectively. In this sample, the thickness of the tin oxide layer on the alumina substrate is about 30 nm, and the thickness of the catalyst layer thereon is about 200 nm.
本実施例によれば、炭化層が生成されず、基板根元から直接ＣＮＣを成長させることができる。従って、ＣＶＤ法によるＣＮＣ成長が従来の合成プロセスと比較して約３倍の成長速度で行われた。成長速度の高速化によって、触媒組成比を調製することにより、触媒塗布量が従来の５０％以下にすることが可能になる。 According to the present embodiment, the carbonized layer is not generated, and the CNC can be grown directly from the base of the substrate. Therefore, the CNC growth by the CVD method was performed at a growth rate about three times that of the conventional synthesis process. By adjusting the catalyst composition ratio by increasing the growth rate, the catalyst coating amount can be reduced to 50% or less of the conventional amount.
図６及び図７は従来の合成プロセスによる合成例を示すＳＥＭ写真である。この従来例はアルミナ基板にＦｅ−Ｍｇ−Ｓｎ−Ｃｏ系酸化物触媒を用いて、実施例１と同様に、１５分間ＣＶＤにより合成した場合である。図６は焼成後のアルミナ基板上の触媒粒子を示すＳＥＭ写真である。図７の（７Ａ）及び（７Ｂ）は、夫々、触媒塗布厚さを約１８０ｎｍとした場合のＣＮＣ写真、断層写真である。図７の（７Ｃ）及び（７Ｄ）は、夫々、触媒塗布厚さを約６５０ｎｍとした場合のＣＮＣ写真、断層写真である。図７の（７Ｂ）及び（７Ｄ）から分かるように、ＣＮＣが成長していない炭化層（（７Ｂ）の７ｅ参照）がアルミナ基板上に生成されている。炭化層の厚さはＣＮＣ高さと同程度の大きさまで形成されている。これがＣＶＤ開始時に基板界面付近の触媒組成に変化を与えてしまい、ＣＮＣ成長開始を遅延させ、アセチレンガスや触媒材料の浪費を生ずる原因となっている。一方、実施例１では、酸化スズ層のバッファー機能によりＣＮＣが成長していない層がなくなり、高速ＣＮＣ成長を可能にした。 6 and 7 are SEM photographs showing examples of synthesis by a conventional synthesis process. This conventional example is a case where an Fe—Mg—Sn—Co-based oxide catalyst is used for an alumina substrate and synthesized by CVD for 15 minutes in the same manner as in Example 1. FIG. 6 is an SEM photograph showing the catalyst particles on the alumina substrate after firing. (7A) and (7B) in FIG. 7 are a CNC photograph and a tomographic photograph, respectively, when the catalyst coating thickness is about 180 nm. (7C) and (7D) in FIG. 7 are a CNC photograph and a tomographic photograph, respectively, when the catalyst coating thickness is about 650 nm. As can be seen from (7B) and (7D) of FIG. 7, a carbonized layer (see 7e of (7B)) on which no CNC has grown is formed on the alumina substrate. The thickness of the carbonized layer is formed to the same size as the CNC height. This changes the catalyst composition in the vicinity of the substrate interface at the start of CVD, delays the start of CNC growth, and causes waste of acetylene gas and catalyst material. On the other hand, in Example 1, the layer in which the CNC was not grown disappeared due to the buffer function of the tin oxide layer, and high-speed CNC growth was enabled.
＜実施例２＞
図８の（８Ａ）は実施例１と同様にして、アルミナ基板上に厚さ約３０ｎｍの酸化スズ層、厚さ約５００ｎｍのＦｅ−Ｍｇ−Ｓｎ−Ｃｏ系触媒層を形成したときのＣＮＣ断層写真である。同図（８Ｂ）は、同種の触媒を使用したときの、酸化スズ層を形成しない従来法による場合のＳＥＭ写真である。この実施例では、ＣＶＤ処理開始から１５分間においてＣＮＣの高さＨが７５μｍまで、従来より３倍の速度で成長した。
<Example 2>
(8A) in FIG. 8 shows a CNC tomography when a tin oxide layer having a thickness of about 30 nm and a Fe—Mg—Sn—Co based catalyst layer having a thickness of about 500 nm are formed on an alumina substrate in the same manner as in Example 1. It is a photograph. FIG. 8B is an SEM photograph in the case of using a conventional method in which a tin oxide layer is not formed when the same type of catalyst is used. In this example, in 15 minutes from the start of the CVD process, the CNC height H was increased to 75 μm and grew at a rate three times that of the conventional method.
図９及び図１０は実施例２の拡大ＳＥＭ写真である。図１０の（１０Ａ）は基板を剥がした状態でのＣＮＣ根元部分を示し、同図（１０Ｂ）、（１０Ｃ）は夫々、（１０Ａ）の部分拡大写真である。この拡大写真からＣＮＣが根元まで視認でき、基板表面に成長していることが確認できた。
上記の実施例１及び２から、酸化スズ層を介在させることによる合成効率の向上の要因は以下の理由によると考察される。
１）基板材質と触媒金属との化学反応がバッファー層により抑制され、ＣＮＣ触媒組成がより効果的に調整できた。
２）触媒焼成段階では昇華しやすい低融点のスズをあえて触媒層とは別の酸化スズ層として提供することにより、ＣＶＤ開始と同時にスズが効果的に機相中を介して供給され、ＣＮＣ触媒組成の安定化を促進したことによる。
9 and 10 are enlarged SEM photographs of Example 2. FIG. (10A) in FIG. 10 shows the CNC root portion in a state where the substrate is peeled off, and (10B) and (10C) are partially enlarged photographs of (10A). From this enlarged photograph, the CNC was visible to the root, and it was confirmed that it was growing on the substrate surface.
From the above Examples 1 and 2, it is considered that the cause of the improvement in the synthesis efficiency by interposing the tin oxide layer is due to the following reason.
1) The chemical reaction between the substrate material and the catalyst metal was suppressed by the buffer layer, and the CNC catalyst composition could be adjusted more effectively.
2) By providing tin with a low melting point, which is easily sublimated at the catalyst firing stage, as a tin oxide layer separate from the catalyst layer, tin is effectively supplied via the inside of the machine at the same time as the start of CVD. This is because the stabilization of the composition was promoted.
次に、酸化スズ層の研究過程で、酸化スズ層の厚さによる生成物の変化が認められた。図１１は、アルミナ基板上に厚さの異なる層形成を行い、その上にＦｅ−Ｍｇ−Ｃｏ系触媒層（Ｆｅ：Ｍｇ：Ｃｏ＝１０：１：０．５）を厚さ約２００ｎｍ形成して１５分ＣＶＤ処理したとき成長したＣＮＣのＳＥＭ写真である。同図（１１Ａ）は約３０ｎｍの酸化スズ層を形成したときであり、このときのＣＮＣ１１ｃは約３０μｍに成長した。一方、同図（１１Ｂ）は約８ｎｍの酸化スズ層を形成したときであり、このときのＣＮＣは約１２μｍの繊維状の物質１１ｅの上に約１７μｍＣＮＣ１１ｅが成長しただけであった。
Next, in the research process of the tin oxide layer, changes in the product due to the thickness of the tin oxide layer were observed. In FIG. 11, layers having different thicknesses are formed on an alumina substrate, and an Fe—Mg—Co based catalyst layer (Fe: Mg: Co = 10: 1: 0.5) is formed on the alumina substrate to a thickness of about 200 nm. It is the SEM photograph of CNC grown when CVD processing for 15 minutes. FIG. 11A shows a case where a tin oxide layer having a thickness of about 30 nm was formed. At this time, the
ＣＶＤ１５分処理における酸化スズ層の厚さがＣＮＣ成長に与える影響ないしその依存性を検証するために各種条件を変えて実験した。
図１２はＦｅ−Ｍｇ−Ｃｏ系触媒層（Ｆｅ：Ｍｇ：Ｃｏ＝１０：１：０．５；Ｓｎなし）によるＣＮＣ成長高さの影響を調べた結果をまとめた表である。
図１３はＦｅ−Ｍｇ−Ｓｎ−Ｃｏ系触媒層（Ｆｅ：Ｍｇ：Ｓｎ：Ｃｏ＝１０：１：１：０．５）によるＣＮＣ成長高さの影響を調べた結果をまとめた表である。図１２及び図１３において、触媒層の厚さを４種類（３００〜５００ｎｍ；２００〜３００ｎｍ；８０〜１２０ｎｍ；Ｓｎコートなし）に分類している。また、Ｓｎ層の厚さを４段階（８０±３０μｍ、６０±３０μｍ、４０±３０μｍ、０〜６０μｍ）に変えている。図表における×、△は夫々、ＣＮＣの未成長、低収率を示す。図表中の上段の数値がＣＮＣ又は繊維状の生成物の高さ（μｍ）を示し、下段が炭化層の厚さ（μｍ）を示す。
In order to verify the influence or dependency of the thickness of the tin oxide layer on the CNC growth in the CVD 15-minute treatment, various experiments were performed under various conditions.
FIG. 12 is a table summarizing the results of examining the influence of the CNC growth height on the Fe—Mg—Co based catalyst layer (Fe: Mg: Co = 10: 1: 0.5; no Sn).
FIG. 13 is a table summarizing the results of examining the influence of the CNC growth height by the Fe—Mg—Sn—Co based catalyst layer (Fe: Mg: Sn: Co = 10: 1: 1: 0.5). 12 and 13, the thickness of the catalyst layer is classified into four types (300 to 500 nm; 200 to 300 nm; 80 to 120 nm; no Sn coating). Further, the thickness of the Sn layer is changed in four steps (80 ± 30 μm, 60 ± 30 μm, 40 ± 30 μm, 0 to 60 μm). In the chart, “x” and “Δ” indicate CNC ungrown and low yield, respectively. The upper value in the chart indicates the height (μm) of the CNC or fibrous product, and the lower value indicates the thickness (μm) of the carbonized layer.
この検証実験によれば、Ｆｅ−Ｍｇ−Ｃｏ系触媒層の場合には、炭化層は完全になくならなかったが、Ｆｅ−Ｍｇ−Ｓｎ−Ｃｏ系触媒層をそのまま基板上に担持させたときよりもＣＮＣ成長速度が１．５倍以上になった。また、酸化スズ層を予め４０〜６０ｎｍ作製しておくことにより、Ｆｅ−Ｍｇ−Ｓｎ−Ｃｏ系触媒を３００〜６００ｎｍ担持したとき、Ｆｅ−Ｍｇ−Ｓｎ−Ｃｏ系触媒を直接担持させたときよりも炭化層を低減することができる。 According to this verification experiment, in the case of the Fe—Mg—Co based catalyst layer, the carbonized layer did not disappear completely, but when the Fe—Mg—Sn—Co based catalyst layer was supported on the substrate as it was. CNC growth rate more than 1.5 times. In addition, by preparing a tin oxide layer in advance in a thickness of 40 to 60 nm, when a Fe—Mg—Sn—Co based catalyst is supported at 300 to 600 nm, compared to when a Fe—Mg—Sn—Co based catalyst is directly supported. Also, the carbonized layer can be reduced.
アルミナ基板に変えて窒化物基板（Ｓｉ３Ｎ４）を使用して酸化スズ層の形成による効果を検証した。触媒には、Ｆｅ−Ｍｇ−Ｓｎ−Ｃｏ系触媒（Ｆｅ：Ｍｇ：Ｓｎ：Ｃｏ＝１０：１：１：０．５）を使用し、３００〜５００ｎｍの層厚にした。図１４は窒化物基板におけるＣＶＤ１５分処理の結果を示すＳＥＭ写真である。図１４の（１４Ａ）及び（１４Ｂ）は酸化スズ層を形成した場合であり、同図（１４Ｃ）及び（１４Ｄ）は酸化スズ層を形成しない場合である。（１４Ａ）及び（１４Ｃ）では、Ｈｅを２３０ｓｃｃｍ、アセチレンＣ２Ｈ２を３０ｓｃｃｍ反応炉に供給した。（１４Ｂ）及び（１４Ｄ）では、Ｈｅを４６０ｓｃｃｍ、アセチレンＣ２Ｈ２を６０ｓｃｃｍ反応炉に供給した。この検証実験によれば、Ｓｎコートしたとき酸化シリコン基板と同様のＣＮＣ成長が確認できた。また、反応ガスの流速を上げるとＣＮＣ形状が安定化し、炭化層も減少した（（１４Ａ）及び（１４Ｂ）参照）。 A nitride substrate (Si 3 N 4 ) was used instead of the alumina substrate to verify the effect of forming the tin oxide layer. As the catalyst, an Fe—Mg—Sn—Co based catalyst (Fe: Mg: Sn: Co = 10: 1: 1: 0.5) was used, and the layer thickness was 300 to 500 nm. FIG. 14 is an SEM photograph showing the result of the CVD 15-minute treatment on the nitride substrate. (14A) and (14B) of FIG. 14 are cases where a tin oxide layer is formed, and (14C) and (14D) of the same figure are cases where a tin oxide layer is not formed. In (14A) and (14C), He was supplied to a 230 sccm reactor and acetylene C 2 H 2 was supplied to a 30 sccm reactor. In (14B) and (14D), 460 sccm of He and acetylene C 2 H 2 were supplied to the 60 sccm reactor. According to this verification experiment, the same CNC growth as that of the silicon oxide substrate was confirmed when Sn coating was performed. Moreover, when the flow rate of the reaction gas was increased, the CNC shape was stabilized and the carbonized layer was reduced (see (14A) and (14B)).
図１５は触媒にＦｅ−Ｉｎ−Ｓｎ−Ｃｏ系触媒（Ｆｅ：Ｉｎ：Ｓｎ：Ｃｏ＝１０：１：１：０．５）を使用し、基板に酸化シリコンを使用してＣＮＣ成長させたときのＳＥＭ写真である。図１５の（１５Ａ）、（１５Ｂ）は夫々、酸化スズ層を形成しない場合と、形成する場合（本発明の製造方法による場合）を示す。酸化スズ層を形成する場合には、炭化層が６〜８μｍ生じ、ＣＮＣは３０〜４０μｍ成長した。Ｓｎコートなし（１５Ａ）ではほとんど炭化層のみであり、厚さも３０μｍあった。 FIG. 15 shows a case where an Fe—In—Sn—Co-based catalyst (Fe: In: Sn: Co = 10: 1: 1: 0.5) is used as a catalyst, and silicon oxide is used as a substrate for CNC growth. It is a SEM photograph of. (15A) and (15B) of FIG. 15 show the case where the tin oxide layer is not formed and the case where it is formed (in the case of the manufacturing method of the present invention), respectively. In the case of forming a tin oxide layer, a carbonized layer was formed at 6 to 8 μm, and a CNC was grown at 30 to 40 μm. Without Sn coating (15A), there was almost only a carbonized layer and the thickness was 30 μm.
図１６は基板に酸化シリコンを使用し、更にＳｎコート処理をしてＣＮＣ成長させたときのＳＥＭ写真である。図１６の（１６Ａ）は触媒にＦｅ−Ｉｎ−Ｓｎ−Ｃｏ系触媒（Ｆｅ：Ｉｎ：Ｓｎ：Ｃｏ＝１０：１：１：０．５）を使用したとき、（１６Ｂ）は触媒にＳｎを含まないＦｅ−Ｉｎ−Ｃｏ系触媒（Ｆｅ：Ｉｎ：Ｓｎ：Ｃｏ＝１０：１：０．５）を使用したときの１５分ＣＶＤ処理した結果を示す。酸化スズ層を形成することにより、いずれの場合も、炭化層が減少し、ＣＮＣ成長効率の向上が確認された。 FIG. 16 is an SEM photograph when silicon oxide is used for the substrate and Sn coating is further performed for CNC growth. (16A) in FIG. 16 shows that when a Fe—In—Sn—Co based catalyst (Fe: In: Sn: Co = 10: 1: 1: 0.5) is used as the catalyst, (16B) shows Sn as the catalyst. The result of having performed CVD processing for 15 minutes when using the Fe-In-Co type catalyst (Fe: In: Sn: Co = 10: 1: 0.5) which does not contain is shown. By forming a tin oxide layer, the carbonization layer decreased in any case, and the improvement of CNC growth efficiency was confirmed.
図１７は触媒にＦｅ−Ｉｎ−Ｓｎ−Ｃｏ系触媒（Ｆｅ：Ｉｎ：Ｓｎ：Ｃｏ＝１０：１：１：０．５）を使用し、基板にアルミナを使用し、更にＳｎコートの厚さを変えてＣＮＣ成長させたときのＳＥＭ写真である。図１７の（１７Ａ）、（１７Ｂ）及び（１７Ｃ）は夫々、酸化スズ層なし、薄めの酸化スズ層を形成した場合、厚めの酸化スズ層を形成した場合である。図１８は図１７の場合と同様に、触媒にＦｅ−Ｉｎ−Ｓｎ−Ｃｏ系触媒（Ｆｅ：Ｉｎ：Ｓｎ：Ｃｏ＝１０：１：１：０．５）を使用し、基板に酸化シリコンを使用し、更にＳｎコートの厚さを変えてＣＮＣ成長させたときのＳＥＭ写真である。図１８の（１８Ａ）、（１８Ｂ）及び（１８Ｃ）は夫々、酸化スズ層なし、薄めの酸化スズ層を形成した場合、厚めの酸化スズ層を形成した場合である。図１９は図１７及び図１８の場合と同様に、触媒にＦｅ−Ｉｎ−Ｓｎ系触媒を使用し、配合比をＦｅ：Ｉｎ：Ｓｎ＝１０：１：１にした場合である。
図１７〜図１９による実験によれば、少なくとも、ＣＮＣ成長速度の向上及びＣＮＣ成長の高密度化を確認することができた。
FIG. 17 shows the case where a Fe—In—Sn—Co based catalyst (Fe: In: Sn: Co = 10: 1: 1: 0.5) is used as the catalyst, alumina is used as the substrate, and the thickness of the Sn coat is further increased. It is a SEM photograph when changing CNC and growing CNC. (17A), (17B) and (17C) in FIG. 17 are the cases where a tin oxide layer is not formed, a thin tin oxide layer is formed, and a thick tin oxide layer is formed. As in the case of FIG. 17, FIG. 18 uses a Fe—In—Sn—Co based catalyst (Fe: In: Sn: Co = 10: 1: 1: 0.5) as a catalyst and silicon oxide on the substrate. It is a SEM photograph when it is used, and also the thickness of Sn coat was changed and CNC was grown. (18A), (18B), and (18C) in FIG. 18 are the cases where the tin oxide layer is not formed, the thin tin oxide layer is formed, and the thick tin oxide layer is formed. FIG. 19 shows the case where an Fe—In—Sn catalyst is used as the catalyst and the blending ratio is Fe: In: Sn = 10: 1: 1 as in the case of FIGS. 17 and 18.
According to the experiments shown in FIGS. 17 to 19, at least an improvement in the CNC growth rate and an increase in the density of the CNC growth could be confirmed.
触媒のＳｎ含有有無についても酸化スズ層の効果を検証した。図２０はＳｎを含まない触媒（Ｆｅ：Ｉｎ：Ｃｏ＝１０：１：０．５）を薄く（約１００ｎｍ）塗布して担持させた基板を、Ｓｎを含む触媒を担持させた別の基板と一緒にＣＶＤ処理したときのＣＮＣのＳＥＭ写真である。この比較結果から図２０の矢印に示すように、Ｓｎを含まない触媒を担持させた基板に、別の基板からＳｎがＣＶＤ開始後にも気相中を拡散していき当該基板のＦｅと合金化することが確認できた。 The effect of the tin oxide layer was also verified on the presence or absence of Sn in the catalyst. FIG. 20 shows a substrate on which a catalyst containing no Sn (Fe: In: Co = 10: 1: 0.5) is applied thinly (about 100 nm) and supported on another substrate on which a catalyst containing Sn is supported. It is a SEM photograph of CNC when CVD processing is carried out together. From the comparison result, as shown by the arrow in FIG. 20, Sn diffuses in the gas phase from another substrate even after the start of CVD on the substrate carrying the catalyst not containing Sn and alloyed with Fe of the substrate. I was able to confirm.
次に、Ｓｎコート有無の違いによるＣＮＣ成長初期過程をアルミナ基板で観察した。図２１の（２１Ａ）は酸化スズ層を設けた場合のＣＶＤ処理開始３秒後のＳＥＭ写真である。図２１の（２１Ｂ）及び（２１Ｃ）は酸化スズ層を設けない場合のＣＶＤ処理開始３秒後のＳＥＭ写真である。Ｓｎコートしたときには、触媒層との界面付近の細かい粒子は消滅し、触媒粒子の隙間やアルミナ基板の隙間に析出物が見られた。一方、Ｓｎコートをしない場合には、ＣＮＣでなく、直径１０ｎｍ程度のカーボンナノチューブ（ＣＮＴ）が成長した。
Next, the initial stage of CNC growth depending on the presence or absence of Sn coating was observed on an alumina substrate. (21A) in FIG. 21 is an
図２２は図２１のＣＮＣ処理におけるＣＶＤ処理開始１０秒後のＳＥＭ写真である。図２３は図２２のＣＶＤ処理前のＳＥＭ断層写真である。
ＣＶＤ処理前の触媒担持基板は５０〜１００ｎｍの触媒粒子が凝集しており多孔質状態になっている。ＣＶＤ処理開始して１０秒経過したとき、触媒層と担持基板との界面に細いＣＮＴが多数成長している。
FIG. 22 is an
The catalyst-carrying substrate before the CVD treatment is in a porous state in which catalyst particles of 50 to 100 nm are aggregated. When 10 seconds have passed since the start of the CVD process, many thin CNTs grow on the interface between the catalyst layer and the carrier substrate.
図２４はＳｎコート処理して上記触媒を担持させたアルミナ基板を用いた場合のＣＶＤ開始後１分のＳＥＭ写真である。図２５は同様にＳｎコート処理しない場合のＳＥＭ写真である。
ＣＶＤ開始から１分経過した段階では、ＣＮＣが３〜６μｍに成長し始め、触媒粒子の隙間にＣＮＴが成長していく。Ｓｎコートした場合は、しない場合よりもＣＮＴの密度が小さくなる傾向にある。
FIG. 24 is a SEM photograph of 1 minute after the start of CVD in the case of using an alumina substrate on which the above catalyst is supported by Sn coating. FIG. 25 is an SEM photograph in the case where Sn coating is not performed in the same manner.
At the stage where 1 minute has elapsed from the start of CVD, the CNC begins to grow to 3 to 6 μm, and CNT grows in the gaps between the catalyst particles. When Sn coating is performed, the density of CNTs tends to be smaller than when Sn coating is not performed.
触媒含有元素と基板材質の関係も酸化スズ層の有無の観点で検証した。
図２６はＦｅ−Ｍｇ−Ｓｎ−Ｃｏ系触媒とＦｅ−Ｉｎ−Ｓｎ−Ｃｏ系触媒につき、各種基板とＳｎコートの有無との関係をまとめた表である。同表において、×は２０〜３０μｍ以上の炭化層が形成されたことを、△は８〜１５μｍ程度の炭化層が形成されたことを示す。また、符号○は、炭化層はやや軽減するかあるいは低減しないが（割合にして４０％〜０％）、ＣＮＣ成長長さ及び密度の向上が見られたことを表す。特に、符号◎は、炭化層を大幅に軽減且つＣＮＣ成長長さ及び密度が顕著に向上したことを表す。Ｍｇ系とＩｎ系触媒との比較でいえば、Ｍｇ系触媒における酸化スズ層の効果が一層大きい。
The relationship between the catalyst-containing element and the substrate material was also verified from the viewpoint of the presence or absence of a tin oxide layer.
FIG. 26 is a table summarizing the relationship between various substrates and the presence or absence of Sn coating for Fe—Mg—Sn—Co based catalysts and Fe—In—Sn—Co based catalysts. In the table, × indicates that a carbonized layer of 20 to 30 μm or more is formed, and Δ indicates that a carbonized layer of about 8 to 15 μm is formed. Moreover, the symbol “◯” indicates that although the carbonized layer is somewhat reduced or not reduced (40% to 0% as a ratio), the CNC growth length and density are improved. In particular, the symbol “◎” indicates that the carbonized layer is greatly reduced and the CNC growth length and density are remarkably improved. In comparison between the Mg-based catalyst and the In-based catalyst, the effect of the tin oxide layer in the Mg-based catalyst is even greater.
本発明は、上記実施形態や変形例に限定されるものではなく、本発明の技術的思想を逸脱しない範囲における種々変形例、設計変更などをその技術的範囲内に包含するものであることは云うまでもない。 The present invention is not limited to the above-described embodiments and modifications, and includes various modifications and design changes within the technical scope without departing from the technical idea of the present invention. Needless to say.
本発明によれば、ＣＮＣ製造用触媒担持材質の表面改質に好適なＣＮＣ製造用触媒を提供することができる。特に、各種担持材質のうち炭化層の形成が顕著であるアルミナ基板の場合にも、炭化層の低減化を実現できるので、比較的安価なアルミナ基板を用いて高効率且つ低コストで良質のカーボンナノコイルを製造することができる。本発明に係るＣＮＣ製造方法により製造されたＣＮＣは、高伝導性、バネ的な機械特性、電磁波活性に優れており、ＧＨｚ電磁波遮蔽（吸収）材、透明電極膜、制震材料等に好適である。 ADVANTAGE OF THE INVENTION According to this invention, the catalyst for CNC manufacture suitable for the surface modification of the catalyst support material for CNC manufacture can be provided. In particular, even in the case of an alumina substrate, in which the formation of a carbonized layer is remarkable among various support materials, it is possible to reduce the carbonized layer. Nanocoils can be manufactured. The CNC manufactured by the CNC manufacturing method according to the present invention is excellent in high conductivity, spring-like mechanical properties, and electromagnetic wave activity, and is suitable for GHz electromagnetic wave shielding (absorption) materials, transparent electrode films, vibration control materials, and the like. is there.
１ 基板
２ 酸化スズ層
３ 触媒層
４ ＣＮＣ
５ 炭化層
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001192204A (en) * | 1999-12-31 | 2001-07-17 | Yoshikazu Nakayama | Method for manufacturing carbon nano-coil |
| JP2001310130A (en) * | 2000-04-29 | 2001-11-06 | Yoshikazu Nakayama | Method for producing indium-tin-iron catalyst for forming carbon nanocoil |
| WO2004105940A1 (en) * | 2003-05-29 | 2004-12-09 | Japan Science And Technology Agency | Catalyst for preparing carbon nanocoil, method for preparation thereof, method for preparing carbon nanocoil and carbon nanocoil |
| JP2007252982A (en) * | 2006-03-20 | 2007-10-04 | Osaka Industrial Promotion Organization | Catalyst particle for manufacturing carbon nanocoil, its manufacturing method and method for manufacturing carbon nanocoil |
| JP2009018234A (en) * | 2007-07-10 | 2009-01-29 | Osaka Prefecture Univ | Catalyst and method for producing carbon nano-coil |
| WO2010005118A1 (en) * | 2008-07-10 | 2010-01-14 | 財団法人大阪産業振興機構 | Catalyst for producing carbon nanocoil and process for producing carbon nanocoil using the catalyst |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001192204A (en) * | 1999-12-31 | 2001-07-17 | Yoshikazu Nakayama | Method for manufacturing carbon nano-coil |
| JP2001310130A (en) * | 2000-04-29 | 2001-11-06 | Yoshikazu Nakayama | Method for producing indium-tin-iron catalyst for forming carbon nanocoil |
| WO2004105940A1 (en) * | 2003-05-29 | 2004-12-09 | Japan Science And Technology Agency | Catalyst for preparing carbon nanocoil, method for preparation thereof, method for preparing carbon nanocoil and carbon nanocoil |
| JP2007252982A (en) * | 2006-03-20 | 2007-10-04 | Osaka Industrial Promotion Organization | Catalyst particle for manufacturing carbon nanocoil, its manufacturing method and method for manufacturing carbon nanocoil |
| JP2009018234A (en) * | 2007-07-10 | 2009-01-29 | Osaka Prefecture Univ | Catalyst and method for producing carbon nano-coil |
| WO2010005118A1 (en) * | 2008-07-10 | 2010-01-14 | 財団法人大阪産業振興機構 | Catalyst for producing carbon nanocoil and process for producing carbon nanocoil using the catalyst |
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