JP2012082077A - Multilayer carbon nanotube aggregate and method for producing the same - Google Patents
Multilayer carbon nanotube aggregate and method for producing the same Download PDFInfo
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- JP2012082077A JP2012082077A JP2010226807A JP2010226807A JP2012082077A JP 2012082077 A JP2012082077 A JP 2012082077A JP 2010226807 A JP2010226807 A JP 2010226807A JP 2010226807 A JP2010226807 A JP 2010226807A JP 2012082077 A JP2012082077 A JP 2012082077A
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- Prior art keywords
- aggregate
- carbon
- mwcnt
- carbon nanotubes
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Landscapes
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Abstract
Description
本発明は、多層カーボンナノチューブ集合体及びその製造方法に関する。 The present invention relates to an aggregate of multi-walled carbon nanotubes and a method for producing the same.
カーボンナノチューブは、高い電気導電性、熱伝導性、機械的強度、可飽和吸収効果という光学非線形性などを有することから、燃料電池、電極、電磁波シールド材、導電性樹脂、電界放出ディスプレイ(FED)用部材、水素を始めとする各種ガスの吸蔵材料、高速光通信用デバイス、レーザー用デバイスなどの機能性材料として、エレクトロニクス、エネルギー、医療など幅広い分野への利用が期待されている。その中でも、工業的な規模で製造、供給されている多層カーボンナノチューブは、樹脂に分散した成形体や、溶媒に分散して基材に塗工した薄膜などカーボンナノチューブ分散体としての利用が、各種用途について検討されている。 Since carbon nanotubes have high electrical conductivity, thermal conductivity, mechanical strength, optical nonlinearity such as saturable absorption effect, etc., fuel cells, electrodes, electromagnetic shielding materials, conductive resins, field emission displays (FED) It is expected to be used in a wide range of fields such as electronics, energy, and medicine as functional materials such as materials for materials, storage materials for various gases such as hydrogen, devices for high-speed optical communication, and devices for lasers. Among them, multi-walled carbon nanotubes manufactured and supplied on an industrial scale can be used as carbon nanotube dispersions such as molded bodies dispersed in resins and thin films dispersed in solvents and coated on substrates. Applications are being studied.
カーボンナノチューブは1本づつ分離した状態で得られることは稀であり、チューブの外径・内径や長さなどの形状、結晶性が異なる複数本からなるカーボンナノチューブ集合体として存在する。カーボンナノチューブ集合体には不純物(カーボンナノチューブ以外の炭素物質、触媒などに由来する炭素以外の元素を含む物質)が含まれている場合も多い。必要に応じて、このようなカーボンナノチューブ集合体を精製し、用途や目的に適合した分散剤、及び分散方法を使って各種媒体に分散させることによりカーボンナノチューブ分散体を得ることができる。 The carbon nanotubes are rarely obtained in a state of being separated one by one, and exist as an aggregate of carbon nanotubes composed of a plurality of tubes having different shapes and crystallinity such as the outer diameter, inner diameter, and length of the tube. In many cases, the aggregate of carbon nanotubes contains impurities (a carbon substance other than carbon nanotubes, a substance containing an element other than carbon derived from a catalyst). If necessary, the carbon nanotube aggregate can be obtained by purifying such a carbon nanotube aggregate and dispersing it in various media using a dispersant and a dispersion method suitable for the purpose and purpose.
カーボンナノチューブ分散体に求められる導電性などの諸機能は、カーボンナノチューブ集合体に含まれる微量不純物、構成する各カーボンナノチューブの形状、及びカーボンナノチューブ集合体の形態などに大きく影響される。分散させるカーボンナノチューブ集合体には、求められる機能を阻害する物質(例えば、金属酸化物などの絶縁体など)が含まれていない、又は極微量しか含まれていないことが好ましい。分散体に含まれるカーボンナノチューブの濃度が同一でも、より導電性や熱伝導性が高まることから、アスペクト比(長さ/外径)が大きいカーボンナノチューブが好ましい。さらに、分散体中でカーボンナノチューブがネットワークを形成し易いことから、カーボンナノチューブは直線性が高いものより屈曲した形状が好ましい。 Various functions such as conductivity required for the carbon nanotube dispersion are greatly influenced by a small amount of impurities contained in the carbon nanotube aggregate, the shape of each carbon nanotube constituting the carbon nanotube aggregate, and the form of the carbon nanotube aggregate. It is preferable that the aggregate of carbon nanotubes to be dispersed does not contain a substance that inhibits a required function (for example, an insulator such as a metal oxide) or contains a very small amount. Even if the concentration of the carbon nanotubes contained in the dispersion is the same, carbon nanotubes having a large aspect ratio (length / outer diameter) are preferable because the conductivity and thermal conductivity are further increased. Furthermore, since the carbon nanotubes easily form a network in the dispersion, the carbon nanotubes are preferably bent rather than highly linear.
一方、各種媒体にカーボンナノチューブを均一かつ安定に分散させるためには、過度に長いカーボンナノチューブは好ましくない。また、過度に凝集しているカーボンナノチューブ集合体も、煩雑な分散処理工程が増えるため好ましくない。 On the other hand, in order to disperse carbon nanotubes uniformly and stably in various media, excessively long carbon nanotubes are not preferable. Also, excessively aggregated carbon nanotube aggregates are not preferable because they increase the number of complicated dispersion processing steps.
カーボンナノチューブ、カーボンナノファイバーなどのナノ炭素繊維を大量に合成する方法としては、CVD法(化学気相成長法)が知られており、工業的に実施されている。 As a method for synthesizing a large amount of nanocarbon fibers such as carbon nanotubes and carbon nanofibers, a CVD method (chemical vapor deposition method) is known and practiced industrially.
触媒微粒子あるいはCVD条件下で触媒微粒子に転化する触媒前駆体、原料炭化水素(ベンゼンやトルエンなど)、水素などのキャリアガスを、反応帯域にガス状で導入して、流動条件下にナノ炭素繊維を成長させる気相流動法による製造方法が開示されている。 Catalyst carbon that is converted into catalyst fine particles or catalyst fine particles under CVD conditions, raw material hydrocarbon (benzene, toluene, etc.), carrier gas such as hydrogen is introduced into the reaction zone in the form of gas, and nanocarbon fiber under flow conditions The manufacturing method by the vapor-phase flow method for growing the substrate is disclosed.
特許文献1には、ベンゼンなどの炭素化合物、フェロセンなどの有機遷移金属化合物、水素などからなる混合ガスを、1050〜1200℃で加熱することにより、直径が100〜200nm、長さが5〜12μmである気相成長炭素繊維が得られることが開示されている。得られる気相成長炭素繊維の直径は100μmを超えており、アスペクト比が大きくても150程度である。そのため、樹脂に対して少量(1質量%など)添加しただけでは所望の機能(導電性など)が得られない場合があった。この気相成長炭素繊維は樹脂に対する分散性が悪いため、所望の機能を得るために、高充填することが困難であった。 In Patent Document 1, a mixed gas composed of a carbon compound such as benzene, an organic transition metal compound such as ferrocene, hydrogen, and the like is heated at 1050 to 1200 ° C. to thereby have a diameter of 100 to 200 nm and a length of 5 to 12 μm. It is disclosed that a vapor-grown carbon fiber can be obtained. The diameter of the vapor-grown carbon fiber obtained is over 100 μm and is about 150 even if the aspect ratio is large. Therefore, the desired function (conductivity etc.) may not be obtained only by adding a small amount (1% by mass etc.) to the resin. Since this vapor-grown carbon fiber has poor dispersibility with respect to the resin, it has been difficult to achieve high filling in order to obtain a desired function.
特許文献2には、ベンゼンなどの炭素化合物、フェロセンなどの有機遷移金属化合物からなる原料液を反応域に噴霧し熱分解反応させて炭素繊維を製造する方法において、3〜30度の噴霧角度で原料溶液を噴霧することを特徴とする気相法炭素繊維の製造方法と、この方法で得られる分岐度が0.15個/μm以上の気相法炭素繊維が開示されている。特許文献1に開示された気相成長炭素繊維より樹脂などへの分散性は向上するものの、満足できるものではなかった。 In Patent Document 2, a method of producing a carbon fiber by spraying a raw material liquid composed of a carbon compound such as benzene and an organic transition metal compound such as ferrocene onto a reaction zone and performing a thermal decomposition reaction, the spray angle is 3 to 30 degrees. A method of producing vapor grown carbon fiber characterized by spraying a raw material solution and a vapor grown carbon fiber having a degree of branching of 0.15 pieces / μm or more obtained by this method are disclosed. Although dispersibility into a resin or the like is improved from the vapor-grown carbon fiber disclosed in Patent Document 1, it is not satisfactory.
触媒活性を有する金属微粒子を、CVD条件下で触媒活性を有しない多孔質担体に担持した固体触媒と炭素含有ガスを接触させてナノ炭素繊維を成長させる製造方法も、多数、開示されている。 A number of production methods for growing nanocarbon fibers by bringing a metal catalyst having catalytic activity into contact with a carbon-containing gas and a solid catalyst supported on a porous carrier having no catalytic activity under CVD conditions are also disclosed.
特許文献3には、気体状炭素含有化合物と、鉄、コバルト、ニッケルなどの金属粒子をアルミナなどの耐火性担体に担持した触媒を接触させることにより、直径が約3.5〜70nm、長さが直径の100倍以上の炭素フィブリルが得られることが記載されている。 Patent Document 3 discloses that a diameter of about 3.5 to 70 nm is obtained by contacting a gaseous carbon-containing compound with a catalyst in which metal particles such as iron, cobalt, and nickel are supported on a refractory carrier such as alumina. Describes that carbon fibrils having a diameter of 100 times or more can be obtained.
非特許文献1には、含浸法により硝酸コバルトを酸化マグネシウムに担持し、乾燥、900℃にて焼成すると(Co、Mg)O固溶体からなる触媒前駆体が得られること、この前駆体を水素で還元することにより得た触媒(コバルト担持量 48質量%)とメタンを900℃で接触させると、多層カーボンナノチューブが得られることが記載されている。 Non-Patent Document 1 discloses that a catalyst precursor composed of a (Co, Mg) O solid solution is obtained when cobalt nitrate is supported on magnesium oxide by an impregnation method, dried and calcined at 900 ° C., and this precursor is hydrogenated. It is described that multi-walled carbon nanotubes can be obtained by contacting a catalyst obtained by reduction (cobalt loading amount 48 mass%) and methane at 900 ° C.
特許文献4には、Fe2O3粉末とAl2O3粉末をモル比1:1で混合し、焼成(1400℃、10h)することにより複合酸化物FeAlO3が得られること、この複合酸化物を水素で還元することにより得た触媒とエチレンを600℃で接触させると、10nm程度の均一な外径を有するカーボンナノファイバー集合体が得られることが開示されている。 Patent Document 4 discloses that a composite oxide FeAlO 3 is obtained by mixing Fe 2 O 3 powder and Al 2 O 3 powder at a molar ratio of 1: 1 and firing (1400 ° C., 10 hours), and this composite oxidation. It is disclosed that when a catalyst obtained by reducing a product with hydrogen is brought into contact with ethylene at 600 ° C., a carbon nanofiber aggregate having a uniform outer diameter of about 10 nm can be obtained.
特許文献5には、担体である水酸化アルミニウムなどの水酸化物、炭酸マグネシウムなどの炭酸塩に、活性金属成分である鉄、コバルト、ニッケルなどを担持させた触媒(活性金属の担持量≦10質量%)と、及び当該触媒を使用した多層カーボンナノチューブの製造方法が開示されている。 Patent Document 5 discloses a catalyst in which an active metal component such as iron, cobalt, nickel or the like is supported on a hydroxide such as aluminum hydroxide or a carbonate such as magnesium carbonate (supported amount of active metal ≦ 10). Mass%) and a method for producing multi-walled carbon nanotubes using the catalyst.
特許文献6には、炭化水素と接触させて多層カーボンナノチューブを製造する触媒としてCoFe2O4(Al2O3)4.5、CoFe2O4(Al2O3)16、CoFe2O4(Al2O3)32などコバルト-鉄複合酸化物を含有する触媒が開示されている。 Patent Document 6 discloses CoFe 2 O 4 (Al 2 O 3 ) 4.5 , CoFe 2 O 4 (Al 2 O 3 ) 16 , and CoFe 2 O 4 as catalysts for producing multi-walled carbon nanotubes by contacting with hydrocarbons. A catalyst containing a cobalt-iron composite oxide such as (Al 2 O 3 ) 32 is disclosed.
特許文献7には、鉄、コバルト、ニッケルなど触媒活性金属を含有する塩、モリブデンなどの助触媒成分を含有する化合物、及びマグネシウムなど担体成分を構成する金属を含有する塩にシュウ酸を添加して得られる共沈を焼成、還元して得られる触媒と、炭素含有ガスを接触させる気相成長炭素繊維の製造方法が開示されている。 In Patent Document 7, oxalic acid is added to a salt containing a catalytic active metal such as iron, cobalt, nickel, a compound containing a promoter component such as molybdenum, and a salt containing a metal constituting the carrier component such as magnesium. A method for producing vapor-grown carbon fibers in which a catalyst obtained by calcining and reducing the coprecipitate obtained in this manner and a carbon-containing gas is brought into contact is disclosed.
特許文献3〜7、非特許文献1に開示されている製造方法により得られる多層カーボンナノチューブなどのナノ炭素繊維集合体には、無機酸化物担体(複合酸化物、固溶体なども含む)に由来するミクロンオーダーの粒径を有する粒子が残存している。そのため、各種媒体に分散し難く、得られる多層カーボンナノチューブ分散体についても、導電性など目的とする機能が充分なレベルまで得られない場合があった。カーボンナノチューブ分散体の機能を上げるために、多量のカーボンナノチューブを分散させようとすると、機械的強度などが低下する場合があった。 Nanocarbon fiber aggregates such as multi-walled carbon nanotubes obtained by the production methods disclosed in Patent Documents 3 to 7 and Non-Patent Document 1 are derived from inorganic oxide carriers (including complex oxides and solid solutions). Particles having a particle size on the order of microns remain. Therefore, it is difficult to disperse in various media, and the obtained multi-walled carbon nanotube dispersion may not be able to obtain a target function such as conductivity to a sufficient level. When a large amount of carbon nanotubes are dispersed in order to improve the function of the carbon nanotube dispersion, mechanical strength and the like may be lowered.
無機酸化物担体に由来する物質を除去するために、フッ化水素酸、硝酸、硫酸、塩酸などの酸や、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウムなどのアルカリ水溶液、過酸化水素などの酸化剤で処理する精製法が知られている。カーボンナノチューブ集合体に含まれる無機酸化物担体を除去するためには、高濃度の薬剤、加熱、長時間の処理といった比較的強い条件を必要とすることが多い。そのためカーボンナノチューブの結晶性が低下したり、グラファイト層の官能基化が生じることがあり、各種媒体に分散したカーボンナノチューブ分散体の特性の低下を引き起こすことがあった。また、酸で処理した場合は、精製工程においてカーボンナノチューブが凝集体を形成し易くなるため、樹脂や溶媒などへの均一に分散することが困難になるという問題もあった。 In order to remove substances derived from the inorganic oxide carrier, acids such as hydrofluoric acid, nitric acid, sulfuric acid and hydrochloric acid, alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide and sodium carbonate, and oxidation such as hydrogen peroxide Purification methods of treating with an agent are known. In order to remove the inorganic oxide carrier contained in the aggregate of carbon nanotubes, relatively strong conditions such as a high concentration of chemicals, heating, and long-time treatment are often required. For this reason, the crystallinity of the carbon nanotubes may be lowered, or the functionalization of the graphite layer may occur, and the characteristics of the carbon nanotube dispersion dispersed in various media may be lowered. In addition, when treated with an acid, the carbon nanotubes easily form aggregates in the purification step, which makes it difficult to uniformly disperse in a resin or a solvent.
さらに、特許文献3〜7、非特許文献1に開示されているナノ炭素繊維の製造方法は、含浸法や共沈法などによる触媒活性金属含有化合物を無機酸化物担体に担持する工程、非還元性雰囲気で熱処理する工程など煩雑な工程を経る必要があるという短所があった。 Furthermore, the method for producing nanocarbon fibers disclosed in Patent Documents 3 to 7 and Non-Patent Document 1 includes a step of supporting a catalytically active metal-containing compound on an inorganic oxide carrier by an impregnation method or a coprecipitation method, non-reduction There is a disadvantage that it is necessary to go through complicated processes such as a process of heat treatment in a neutral atmosphere.
また、担体を使用しない無担持型触媒と炭素含有ガスを接触させてナノ炭素繊維を成長させる製造方法も知られている。 Also known is a production method in which nanocarbon fibers are grown by bringing a non-supported catalyst not using a carrier into contact with a carbon-containing gas.
特許文献8には、1次粒子の平均粒径が500nm以下の酸化ニッケル、酸化銅などの還元性無機材料粒子、および1次粒子の平均粒径が500nm以下の酸化アルミニウムなどの難還元性無機材料粒子からなる混合粉末(難還元性無機材料粒子が1〜20体積%)である触媒前駆体を、水素雰囲気下、加熱することにより得られる、平均粒径が1μm未満のニッケルなどの金属微粒子、または銅などとの合金微粒子と前記金属微粒子より小さい平均粒径を有する難還元性無機材料粒子からなる炭素繊維合成用触媒、及び本発明触媒を使用した炭素繊維の製造方法が開示されている。本触媒及び本製造方法によって得られる炭素繊維は、平均直径が100〜1000nmで、アスペクト比が100程度であるプレートレット型又はヘリンボーン型カーボンナノファイバーである。特許文献8に開示されているカーボンナノファイバーは、BET法による比表面積が200〜450m2/gと大きいことから、燃料電池用触媒材料としては有用である。しかし、アスペクト比が小さいこと、及びファイバーの外径のバラツキが大きいことから、樹脂や溶媒など各種媒体に分散させて使用した場合、各種媒体に均一に分散し難く、得られるカーボンナノファイバー分散体がナノカーボン材料に期待される特性を十分に発揮できない場合があった。 Patent Document 8 discloses reducible inorganic material particles such as nickel oxide and copper oxide whose primary particles have an average particle size of 500 nm or less, and non-reducible inorganic materials such as aluminum oxide whose primary particles have an average particle size of 500 nm or less. Metal fine particles such as nickel having an average particle size of less than 1 μm, obtained by heating a catalyst precursor, which is a mixed powder composed of material particles (1-20% by volume of non-reducible inorganic material particles) in a hydrogen atmosphere. Also disclosed is a carbon fiber synthesis catalyst comprising fine particles of an alloy with copper or the like and non-reducible inorganic material particles having an average particle size smaller than that of the fine metal particles, and a method for producing carbon fiber using the catalyst of the present invention. . The carbon fiber obtained by the present catalyst and the present production method is a platelet type or herringbone type carbon nanofiber having an average diameter of 100 to 1000 nm and an aspect ratio of about 100. The carbon nanofiber disclosed in Patent Document 8 has a large specific surface area of 200 to 450 m 2 / g by the BET method, and is therefore useful as a fuel cell catalyst material. However, since the aspect ratio is small and the variation in the outer diameter of the fiber is large, it is difficult to uniformly disperse in various media such as resins and solvents. However, there are cases where the properties expected of nanocarbon materials cannot be fully exhibited.
このように、前記した多層カーボンナノチューブは、樹脂や溶媒など各種媒体に分散させた場合、期待される機能を十分に発揮し、かつ添加による悪影響を最小限とするような、満足できる物とは言えなかった。また、多層カーボンナノチューブを担持型触媒を使用して製造する場合は、触媒活性金属の担体への担持など煩雑な工程を必要とするものであった。 As described above, when the above-mentioned multi-walled carbon nanotube is dispersed in various media such as a resin or a solvent, it is a satisfactory product that sufficiently performs the expected function and minimizes the adverse effects of addition. I could not say it. Moreover, when producing multi-walled carbon nanotubes using a supported catalyst, a complicated process such as supporting a catalytically active metal on a carrier is required.
樹脂や溶媒など各種媒体への分散性が良好であり、かつ導電性、熱伝導性、電磁波吸収性などカーボンナノチューブが有する諸機能に優れる分散体を与える多層カーボンナノチューブ、及びその製造方法を提供する。 Provided is a multi-walled carbon nanotube that has a good dispersibility in various media such as a resin and a solvent, and that provides a dispersion having excellent functions such as conductivity, thermal conductivity, and electromagnetic wave absorption, and a method for producing the same. .
本発明者は、上記の課題を解決する為に鋭意研究を重ねた結果、特定の形状(外径、長さ、屈曲度など)からなる多層カーボンナノチューブから構成され、触媒活性金属微粒子が凝集したカーボンナノチューブの外径より大きな径を有する二次粒子、及び触媒担体に由来する無機酸化物微粒子が凝集した10μm以上の二次粒子を含まず、特定範囲の嵩密度を有する多層カーボンナノチューブ集合体は、各種媒体への分散性が良好であり、かつ導電性などに優れる分散体を与えることを見出した。また、このような多層カーボンナノチューブ集合体は、特定の原料化合物を混合、加熱することにより得られる触媒と、炭素含有ガスを接触させることにより、簡便かつ効率的に製造できることを見出した。これらの知見に基づき本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventor is composed of multi-walled carbon nanotubes having a specific shape (outer diameter, length, bending degree, etc.), and the catalytically active metal fine particles are aggregated. An aggregate of multi-walled carbon nanotubes that does not contain secondary particles having a diameter larger than the outer diameter of the carbon nanotubes and secondary particles of 10 μm or more aggregated with inorganic oxide fine particles derived from the catalyst carrier and having a specific range of bulk density The present inventors have found that a dispersion having good dispersibility in various media and having excellent conductivity and the like can be obtained. Further, it has been found that such an aggregate of multi-walled carbon nanotubes can be easily and efficiently produced by contacting a carbon-containing gas with a catalyst obtained by mixing and heating a specific raw material compound. The present invention has been completed based on these findings.
本発明の多層カーボンナノチューブ集合体は、以下の条件(1)〜(5)を満足することを特徴とするものである。 The aggregate of multi-walled carbon nanotubes of the present invention is characterized by satisfying the following conditions (1) to (5).
(1)多層カーボンナノチューブの平均アスペクト比が100〜10000であり、平均外径が10〜150nmであること。 (1) The average aspect ratio of the multi-walled carbon nanotube is 100 to 10,000, and the average outer diameter is 10 to 150 nm.
ただし、多層カーボンナノチューブの平均アスペクト比、平均外径、平均長さは、以下の方法で測定、算出した値である。
a.多層カーボンナノチューブの平均アスペクト比:多層カーボンナノチューブの平均長さ/多層カーボンナノチューブの平均外径
b.多層カーボンナノチューブの平均外径:走査型電子顕微鏡を用いて倍率10000倍以上で10本の多層カーボンナノチューブを観察し、その最も太い部分を測定した値の数平均値
c.多層カーボンナノチューブの平均長さ:走査型電子顕微鏡を用いて倍率1000倍で10本の多層カーボンナノチューブを観察し、長さを測定した値の数平均値
(2)多層カーボンナノチューブの屈曲度が10°以上であること
屈曲度:走査型電子顕微鏡を用いて倍率10000倍以上で観察した任意のカーボンナノチューブ1本について、平均外径の5倍離れた任意の2点A、Bを選び、それぞれの点に接線LA、LBを引いて、接線LA、LBの交点Qの外角を5点測定した値の数平均値
(3)走査型電子顕微鏡により倍率10000倍以上で5視野観察した場合、触媒活性金属微粒子が凝集した、カーボンナノチューブの外径より大きな径の二次粒子が観察されないこと
(4)走査型電子顕微鏡により倍率1000倍で5視野観察した場合、触媒担体に由来する無機酸化物微粒子が凝集した、径が10μm以上の二次粒子が観察されないこと
(5)以下の方法で算出した嵩密度が0.005〜0.25g/cm3であること
カーボンナノチューブ集合体を乾燥した100mlメスシリンダー(最小目盛単位:1ml)に静かに入れ、粉体層の上面を圧密せずに注意深くならし、体積を測定し嵩体積とする。カーボンナノチューブ集合体を取り出して測定した質量を嵩体積で除する。この測定、計算を3回行い、その平均値を嵩密度とする。
However, the average aspect ratio, average outer diameter, and average length of the multi-walled carbon nanotube are values measured and calculated by the following methods.
a. Average aspect ratio of multi-walled carbon nanotubes: average length of multi-walled carbon nanotubes / average outer diameter of multi-walled carbon nanotubes b. Average outer diameter of multi-walled carbon nanotubes: Number average value of values obtained by observing ten multi-walled carbon nanotubes with a scanning electron microscope at a magnification of 10,000 times or more and measuring the thickest part c. Average length of multi-walled carbon nanotubes: 10 multi-walled carbon nanotubes were observed at a magnification of 1000 using a scanning electron microscope, and the number average value of the measured lengths (2) The degree of bending of the multi-walled carbon nanotubes was 10 The degree of bending is not less than °. For any one carbon nanotube observed with a scanning electron microscope at a magnification of 10,000 times or more, two arbitrary points A and B separated by 5 times the average outer diameter are selected, The number average value of the values obtained by drawing the tangent lines LA and LB at the points and measuring the outer angle of the intersection Q of the tangent lines LA and LB at 5 points. (3) catalytic activity when observed in 5 fields with a scanning electron microscope at a magnification of 10,000 times or more No secondary particles with a diameter larger than the outer diameter of the carbon nanotubes observed by aggregation of metal fine particles (4) Observation with a scanning electron microscope at a magnification of 1000 times for 5 fields of view If, inorganic oxide fine particles derived from the catalyst support are aggregated, the size is not observed 10μm or more secondary particles (5) Bulk density was calculated by the following method is in 0.005~0.25g / cm 3 The carbon nanotube aggregate is gently put into a dry 100 ml graduated cylinder (minimum scale unit: 1 ml), and the upper surface of the powder layer is carefully leveled without being compacted, and the volume is measured to obtain a bulk volume. The mass measured by taking out the carbon nanotube aggregate is divided by the bulk volume. This measurement and calculation are performed three times, and the average value is defined as the bulk density.
前記した本発明の多層カーボンナノチューブ集合体の製造方法は、水素ガスと、コバルト及び/又は鉄を含む炭素化合物(A)、並びにマグネシウム及び/又はアルミニウムを含む炭素化合物(B)からなる混合物を加熱することにより得たカーボンナノチューブ製造用触媒と、炭素含有ガスを、500〜900℃で接触させることを特徴とするものである。 In the method for producing an aggregate of multi-walled carbon nanotubes of the present invention described above, a mixture comprising hydrogen gas, a carbon compound (A) containing cobalt and / or iron, and a carbon compound (B) containing magnesium and / or aluminum is heated. The catalyst for producing carbon nanotubes obtained in this manner is brought into contact with the carbon-containing gas at 500 to 900 ° C.
本発明の多層カーボンナノチューブ集合体の製造方法においては、水素ガスと、耐熱性容器に固定して設置したコバルト及び/又は鉄を含む炭素化合物(A)、並びにマグネシウム及び/又はアルミニウムを含む炭素化合物(B)からなる粉体混合物を加熱することにより得たカーボンナノチューブ製造用触媒と、炭素含有ガスを、500〜900℃で接触させることが好ましい。 In the method for producing a multi-walled carbon nanotube aggregate of the present invention, hydrogen gas, a carbon compound (A) containing cobalt and / or iron fixed to a heat-resistant container, and a carbon compound containing magnesium and / or aluminum It is preferable that the carbon nanotube production catalyst obtained by heating the powder mixture comprising (B) and the carbon-containing gas are brought into contact at 500 to 900 ° C.
本発明の多層カーボンナノチューブ集合体の製造方法においては、前記した炭素化合物(A)及び炭素化合物(B)としては、炭素数1〜18のカルボン酸塩(水和物を含む)又は炭酸塩(水和物を含む)が好ましい。 In the method for producing an aggregate of multi-walled carbon nanotubes of the present invention, as the carbon compound (A) and the carbon compound (B), a C1-C18 carboxylate (including hydrate) or carbonate ( Including hydrates).
本発明の多層カーボンナノチューブ集合体の製造方法においては、前記した炭素化合物(A)及び炭素化合物(B)としては、酢酸塩(水和物を含む)又は炭酸塩(水和物を含む)が、さらに好ましい。 In the method for producing an aggregate of multi-walled carbon nanotubes of the present invention, acetate (including hydrate) or carbonate (including hydrate) is used as the carbon compound (A) and carbon compound (B). More preferred.
本発明の多層カーボンナノチューブ集合体の製造方法においては、前記した炭素化合物(A)に含まれる鉄、コバルトと、前記した炭素化合物(B)に含まれるマグネシウム、アルミニウムの化学量論比(Fe+Co)/(Mg+Al)が0.2〜10になるように混合することが好ましい。 In the method for producing an aggregate of multi-walled carbon nanotubes of the present invention, the stoichiometric ratio (Fe + Co) of iron and cobalt contained in the carbon compound (A) and magnesium and aluminum contained in the carbon compound (B). It is preferable to mix so that / (Mg + Al) is 0.2 to 10.
本発明の多層カーボンナノチューブ集合体の製造方法においては、前記した炭素化合物(A)、炭素化合物(B)に加えて、さらに、モリブデン化合物、タングステン化合物、及びバナジウム化合物から選ばれる1種を共存させて、炭素含有ガスと接触させてもよい。 In the method for producing an aggregate of multi-walled carbon nanotubes of the present invention, in addition to the carbon compound (A) and the carbon compound (B), one type selected from a molybdenum compound, a tungsten compound, and a vanadium compound is allowed to coexist. The carbon-containing gas may be contacted.
本発明の多層カーボンナノチューブ集合体の製造方法においては、前記した炭素化合物(A)、炭素化合物(B)に加えて、さらに、リチウム化合物を共存させて、炭素含有ガスと接触させてもよい。 In the method for producing an aggregate of multi-walled carbon nanotubes of the present invention, in addition to the above-described carbon compound (A) and carbon compound (B), a lithium compound may be coexisted and contacted with a carbon-containing gas.
本発明の多層カーボンナノチューブ集合体の製造方法においては、前記した炭素含有ガスとしては、メタン、エタン、プロパン、エチレン、ブタジエン、アセチレン、及び一酸化炭素からなる群から選ばれる少なくとも1種であることが好ましい。 In the method for producing a multi-wall carbon nanotube aggregate of the present invention, the carbon-containing gas is at least one selected from the group consisting of methane, ethane, propane, ethylene, butadiene, acetylene, and carbon monoxide. Is preferred.
本発明の多層カーボンナノチューブ集合体を樹脂や溶媒など各種媒体に分散させた多層カーボンナノチューブ分散体は、経時的な凝集や沈殿が生じ難く、分散性が良好である。また、この多層カーボンナノチューブ分散体(表層に本カーボンナノチューブ分散層を有する積層体、成形体など)は、多層カーボンナノチューブが有する導電性、熱伝導性、電磁波吸収性などの諸機能に優れている。 The multi-walled carbon nanotube dispersion in which the multi-walled carbon nanotube aggregate of the present invention is dispersed in various media such as a resin and a solvent is less likely to aggregate and precipitate over time and has good dispersibility. Moreover, this multi-walled carbon nanotube dispersion (laminated body, molded body, etc. having the present carbon nanotube-dispersed layer on the surface layer) is excellent in various functions such as conductivity, thermal conductivity, electromagnetic wave absorption, etc. possessed by the multi-walled carbon nanotube. .
本発明の製造方法によれば、各種媒体への分散性が良好で、諸機能に優れる分散体を与える多層カーボンナノチューブ集合体を、触媒活性金属の担体への担持などの煩雑な触媒調製工程を経ずに、簡便かつ効率的に製造できる。 According to the production method of the present invention, a complicated catalyst preparation step such as loading a catalytically active metal on a carrier with a multi-walled carbon nanotube aggregate that gives a dispersion excellent in various functions and excellent in various functions can be performed. It can be manufactured easily and efficiently without passing through.
本発明の多層カーボンナノチューブ集合体、及びその製造方法について、以下に詳細に説明する。なお、本発明では、カーボンナノチューブをCNT、多層カーボンナノチューブをMWCNTと略称することがある。 The multi-wall carbon nanotube aggregate of the present invention and the production method thereof will be described in detail below. In the present invention, the carbon nanotube may be abbreviated as CNT, and the multi-walled carbon nanotube may be abbreviated as MWCNT.
1.多層カーボンナノチューブ集合体
本発明の多層カーボンナノチューブ集合体は、触媒金属粒子から成長した特定した範囲の平均アスペクト比(平均長さ/平均外径)、平均外径、及び屈曲した形状を有するMWCNTが不規則に交絡した集合体であること、及び径がミクロンオーダーの粒子を含まないことを特徴としている。
1. Multi-walled carbon nanotube aggregate The multi-walled carbon nanotube aggregate of the present invention comprises an MWCNT having an average aspect ratio (average length / average outer diameter), an average outer diameter, and a bent shape within a specified range grown from catalytic metal particles. It is characterized by being an irregularly entangled aggregate and not containing particles having a diameter of micron order.
本発明のMWCNTは中空であって、構成する黒鉛層がカーボンナノチューブの繊維軸に対して平行であり(カーボンナノチューブの長軸(繊維軸)方向に対する黒鉛結晶のC面の角度が180゜であり)、同心円状に2以上積層している。本発明のMWCNT集合体には、黒鉛結晶のC面の繊維軸方向に対する角度が90゜であるプレートレット型カーボンナノファイバー、及び同角度が0゜より大きく90゜未満であるヘリンボーン型カーボンナノファイバーは、実質的に含まれていない。 The MWCNT of the present invention is hollow, and the constituting graphite layer is parallel to the fiber axis of the carbon nanotube (the angle of the C plane of the graphite crystal with respect to the long axis (fiber axis) direction of the carbon nanotube is 180 °. ), Two or more are concentrically stacked. The MWCNT aggregate of the present invention includes a platelet-type carbon nanofiber having an angle of 90 ° with respect to the fiber axis direction of the C-plane of the graphite crystal, and a herringbone carbon nanofiber having the same angle greater than 0 ° and less than 90 °. Is substantially not included.
本発明のMWCNTの平均アスペクト比は100〜10000であり、かつ平均外径は10〜150nmである。MWCNTの平均アスペクト比としては700〜7500がより好ましく、平均外径としては30〜100nmがより好ましい。MWCNTの平均アスペクト比が100未満である場合は、各種媒体にMWCNT集合体を分散して得られる多層カーボンナノチューブ分散体について、目的とする導電性、熱伝導性などの諸機能が発現し難くなり、10000を超える場合は、媒体によっては分散し難くなることがあるため好ましくない。MWCNTの平均外径が10nm未満であるとMWCNTが凝集し易くなり、150nmを超えるとアスペクト比が大幅に低下し易くなることから好ましくない。 The average aspect ratio of the MWCNT of the present invention is 100 to 10,000, and the average outer diameter is 10 to 150 nm. The average aspect ratio of MWCNT is more preferably 700 to 7500, and the average outer diameter is more preferably 30 to 100 nm. When the average aspect ratio of MWCNT is less than 100, the multi-walled carbon nanotube dispersion obtained by dispersing the MWCNT aggregate in various media is less likely to exhibit various functions such as intended conductivity and thermal conductivity. If it exceeds 10,000, it may be difficult to disperse depending on the medium, which is not preferable. If the average outer diameter of the MWCNT is less than 10 nm, the MWCNT tends to aggregate, and if it exceeds 150 nm, the aspect ratio is likely to be greatly reduced, which is not preferable.
本発明のMWCNTの平均長さとしては5〜100μmが好ましく、10〜100μmがさらに好ましく、30〜100μmが特に好ましい。MWCNTの平均長さが前記範囲にあると、各種媒体に分散して得られる多層カーボンナノチューブ分散体が、目的とするレベルの導電性、熱伝導性などを発現することができる。 The average length of the MWCNT of the present invention is preferably 5 to 100 μm, more preferably 10 to 100 μm, and particularly preferably 30 to 100 μm. When the average length of the MWCNT is within the above range, the multi-walled carbon nanotube dispersion obtained by dispersing in the various media can express the target level of conductivity, thermal conductivity, and the like.
ここで、「MWCNTの外径」は、走査型電子顕微鏡(以下、SEMと略称することがある)を用いて倍率10000倍以上でMWCNT集合体を観察したときの観察視野内におけるMWCNTの最も太い部分を測定した値である。同様にして10本のMWCNTを測定し、その数平均値を「MWCNTの平均外径」とした。一方、「MWCNTの長さ」は、SEMを用いて倍率1000倍でMWCNT集合体を観察したときのMWCNTの軸線長さを測定した値である。倍率1000倍での視野から外れる長さのMWCNTについては、その長さ全てが入る1000倍の別視野像を観察し、長さを測定した。同様にして10本のMWCNTを測定し、その数平均値を「MWCNTの平均長さ」とした。MWCNTの平均アスペクト比(平均長さ/平均外径)は、このようにして算出される平均長さを平均外径で除して算出した。 Here, the “outer diameter of MWCNT” is the thickest MWCNT in the observation field when the MWCNT aggregate is observed at a magnification of 10,000 times or more using a scanning electron microscope (hereinafter sometimes abbreviated as SEM). This is the value measured for the part. Similarly, ten MWCNTs were measured, and the number average value was defined as “average outer diameter of MWCNT”. On the other hand, the “length of MWCNT” is a value obtained by measuring the axial length of the MWCNT when the MWCNT aggregate is observed using a SEM at a magnification of 1000 times. For the MWCNT having a length that deviates from the field of view at a magnification of 1000, a separate field image of 1000 times in which the entire length is included was observed and the length was measured. Similarly, ten MWCNTs were measured, and the number average value was defined as “average length of MWCNT”. The average aspect ratio (average length / average outer diameter) of MWCNT was calculated by dividing the average length thus calculated by the average outer diameter.
本発明のMWCNTの屈曲度は10°以上である。より好ましくは30°以上である。屈曲度が10°未満であると樹脂などに添加しても凝集し易くなり、媒体中でカーボンナノチューブのネットワークを形成し難くなり、目的とする導電性などの機能が十分に発揮できないことがあるため好ましくない。 The bending degree of the MWCNT of the present invention is 10 ° or more. More preferably, it is 30 ° or more. If the degree of flexion is less than 10 °, it tends to aggregate even when added to a resin or the like, it becomes difficult to form a network of carbon nanotubes in the medium, and the intended functions such as conductivity may not be sufficiently exhibited. Therefore, it is not preferable.
ここで、MWCNTの屈曲度は、SEMを用いて倍率10000倍以上で観察した任意のカーボンナノチューブ1本について、平均外径の5倍離れた任意の2点A、Bを選び、それぞれの点に接線La、Lbを引いて、接線La、Lbの交点Qの外角θを5点測定した値の数平均とする(図1参照)。 Here, the degree of flexion of MWCNT is selected from two arbitrary points A and B separated by 5 times the average outer diameter for one arbitrary carbon nanotube observed at a magnification of 10,000 times or more using SEM. By subtracting the tangent lines La and Lb, the outside angle θ of the intersection Q of the tangent lines La and Lb is taken as the number average of the values measured at five points (see FIG. 1).
本発明のMWCNT集合体を、SEMにより倍率10000倍以上で5視野観察した場合、触媒活性金属微粒子が凝集した、カーボンナノチューブの外径より大きな径の二次粒子が観察されない。カーボンナノチューブの外径より大きな径の二次粒子が存在すると、樹脂などへの分散性が低下することがあるため好ましくない。 When the MWCNT aggregate of the present invention is observed by SEM at five fields of view at a magnification of 10,000 times or more, secondary particles having a diameter larger than the outer diameter of the carbon nanotube in which the catalytically active metal fine particles are aggregated are not observed. The presence of secondary particles having a diameter larger than the outer diameter of the carbon nanotube is not preferable because dispersibility in a resin or the like may be deteriorated.
本発明のMWCNT集合体は、SEMにより倍率1000倍で5視野観察した場合、触媒担体に由来する無機酸化物微粒子が凝集した、径が10μm以上の二次粒子が観察されない。触媒担体に由来する無機酸化物微粒子が凝集した、径が10μm以上の二次粒子が存在すると、樹脂などへの分散性が低下し、MWCNT分散体も目的とする導電性などの機能が十分に発揮できないため好ましくない。 When the MWCNT aggregate of the present invention is observed by SEM at five magnifications at a magnification of 1000, secondary particles having a diameter of 10 μm or more in which inorganic oxide fine particles derived from the catalyst support are aggregated are not observed. When secondary particles having a diameter of 10 μm or more in which the inorganic oxide fine particles derived from the catalyst support are aggregated, the dispersibility in a resin or the like is lowered, and the MWCNT dispersion has sufficient functions such as intended conductivity. Since it cannot be demonstrated, it is not preferable.
本発明のMWCNT集合体の嵩密度は0.005〜0.25g/cm3であり、好ましくは、0.01〜0.20g/cm3である。嵩密度が0.005g/cm3未満であると、飛散し易いため取扱いが困難となり、0.25g/cm3を超えると、樹脂などへの分散性が低下するため好ましくない。 The bulk density of the MWCNT assembly of the present invention is 0.005~0.25g / cm 3, preferably from 0.01~0.20g / cm 3. When the bulk density is less than 0.005 g / cm 3, it becomes difficult to handle because easily scattered, exceeds 0.25 g / cm 3, undesirably lowers the dispersibility in a resin.
2.多層カーボンナノチューブ集合体の製造方法
(1)MWCNT製造用触媒の製造方法
水素ガスと、コバルト及び/又は鉄を含む炭素化合物(A)、並びにマグネシウム及び/又はアルミニウムを含む炭素化合物(B)からなる混合物を接触させながら加熱することにより合成する。この時、炭素化合物(A)は分解、還元されて、MWCNT製造触媒の活性成分であるコバルト金属微粒子や鉄金属微粒子が生成する。
2. Production method of multi-walled carbon nanotube aggregate (1) Production method of catalyst for MWCNT production Carbon compound (A) containing hydrogen gas, cobalt and / or iron, and carbon compound (B) containing magnesium and / or aluminum Synthesize by heating the mixture in contact. At this time, the carbon compound (A) is decomposed and reduced to produce cobalt metal fine particles and iron metal fine particles which are active components of the MWCNT production catalyst.
コバルト及び/又は鉄を含む炭素化合物(A)には、コバルトや鉄のカルボン酸塩や炭酸塩、コバルトや鉄に有機配位子が結合したキレート錯体、炭素−金属結合を有する有機金属(コバルト、鉄)化合物などが含まれる。具体的には、酢酸コバルト(II)、プロピオン酸コバルト(II)、酪酸コバルト(II)、吉草酸コバルト(II)、カプロン酸コバルト(II)、エナント酸コバルト(II)、カプリル酸コバルト(II)、2−エチルヘキサン酸コバルト(II)、オレイン酸コバルト(II)、ステアリン酸コバルト(II)、リノール酸コバルト(II)、ナフテン酸コバルト(II)、シュウ酸コバルト(II)、マロン酸コバルト(II)、グルタル酸コバルト(II)、アジピン酸コバルト(II)、マレイン酸コバルト(II)、乳酸コバルト(II)、クエン酸コバルト(II)、安息香酸コバルト(II)、フタル酸コバルト(II)、ケイ皮酸コバルト(II)、サリチル酸コバルト(II)、酢酸鉄(II)、プロピオン酸鉄(II)、酪酸鉄(II)、吉草酸鉄(II)、カプロン酸鉄(II)、エナント酸鉄(II)、カプリル酸鉄(II)、2−エチルヘキサン酸鉄(III)、オレイン酸鉄(III)、ステアリン酸鉄(III)、ナフテン酸鉄、シュウ酸鉄(II)、マロン酸鉄(II)、グルタル酸鉄(II)、アジピン酸鉄(II)、アジピン酸鉄(II)、マレイン酸鉄(II)、乳酸鉄(II)、クエン酸鉄(II)、安息香酸鉄(II)、フタル酸鉄(II)、ケイ皮酸鉄(II)、サリチル酸鉄(II)などのカルボン酸塩及びその水和物;炭酸コバルト(II)、炭酸鉄(II)などの炭酸塩及びその水和物;トリス(アセチルアセトナト)コバルト(III)、ビス(アセチルアセトナト)ジアクアコバルト(II)、トリス(アセチルアセトナト)鉄(III)、ビス(アセチルアセトナト)ジアクア鉄(II)などのキレート錯体;ビス(シクロペンタジエニル)コバルト(II)、オクタカルボニルニコバルト(0)、ビス(シクロペンタジエニル)鉄(II)、ペンタカルボニル鉄(0)などの有機金属化合物が例示できる。 Carbon compounds (A) containing cobalt and / or iron include cobalt and iron carboxylates and carbonates, chelate complexes in which organic ligands are bonded to cobalt and iron, and organic metals having a carbon-metal bond (cobalt). , Iron) compounds and the like. Specifically, cobalt (II) acetate, cobalt (II) propionate, cobalt (II) butyrate, cobalt (II) valerate, cobalt (II) caproate, cobalt (II) enanthate, cobalt caprylate (II) ), Cobalt (II) 2-ethylhexanoate, cobalt (II) oleate, cobalt (II) stearate, cobalt (II) linoleate, cobalt (II) naphthenate, cobalt (II) oxalate, cobalt malonate (II), cobalt glutarate (II), cobalt adipate (II), cobalt maleate (II), cobalt lactate (II), cobalt citrate (II), cobalt benzoate (II), cobalt phthalate (II) ), Cobalt (II) cinnamate, cobalt (II) salicylate, iron (II) acetate, iron (II) propionate, iron (II) butyrate, iron (II) valerate, iron (II) caproate, enanthate Iron (II), iron caprylate (II), iron (III) 2-ethylhexanoate, iron (III) oleate, iron (III) stearate, iron naphthenate, iron (II) oxalate, iron malonate (II), iron (II) glutarate, iron (II) adipate, iron (II) adipate, iron (II) maleate, iron (II) lactate, iron (II) citrate, iron benzoate (II) ), Iron (II) phthalate, iron (II) cinnamate, iron (II) salicylate and other carboxylic acid salts and hydrates thereof; carbonates such as cobalt (II) carbonate and iron (II) carbonate and the like Hydrate: Tris (acetylacetonato) cobalt (III), bis (acetylacetonato) diaquacobalt (II), tris (acetylacetonato) iron (III), bis (acetylacetonato) diaquairon (II) Chelate complexes such as: bis (cyclopentadienyl) cobalt (II), octacarbonyl dicobalt (0), bi (Cyclopentadienyl) iron (II), organometallic compounds such as iron pentacarbonyl (0) can be exemplified.
炭素化合物(A)としては、取り扱い易いことから、室温で固体である炭素化合物が好ましい。 The carbon compound (A) is preferably a carbon compound that is solid at room temperature because it is easy to handle.
炭素化合物(A)が室温で固体である場合は、一次粒子の平均粒径が0.001〜30μmである粉体が好ましい。一次粒子の平均粒径としては、0.01〜3μmがより好ましい。 When the carbon compound (A) is solid at room temperature, a powder having an average primary particle size of 0.001 to 30 μm is preferable. As an average particle diameter of a primary particle, 0.01-3 micrometers is more preferable.
また、炭素化合物(A)としては、入手し易いことから、コバルトや鉄の炭素数1〜18のカルボン酸塩や炭酸塩及びそれらの水和物が好ましく、酢酸塩や炭酸塩及びそれらの水和物が、特に好ましい。 Moreover, since it is easy to obtain as a carbon compound (A), C1-C18 carboxylate, carbonate, and those hydrates of cobalt and iron are preferable, and acetate, carbonate, and those water are preferable. Japanese products are particularly preferred.
酢酸コバルト(II)、炭酸コバルト(II)、酢酸鉄(II)、炭酸鉄(II)及びそれらの水和物は、市販品をそのまま使用できる。 Commercially available products can be used as they are for cobalt (II) acetate, cobalt (II) carbonate, iron (II) acetate, iron (II) carbonate and their hydrates.
マグネシウム及び/又はアルミニウムを含む炭素化合物(B)としては、マグネシウムやアルミニウムのカルボン酸塩や炭酸塩、マグネシウムやアルミニウムに有機配位子が結合したキレート錯体、炭素−金属結合を有する有機金属(マグネシウム、アルミニウム)化合物などが含まれる。具体的には、酢酸マグネシウム、プロピオン酸マグネシウム、酪酸マグネシウム、吉草酸マグネシウム、カプロン酸マグネシウム、エナント酸マグネシウム、カプリル酸マグネシウム、2−エチルヘキサン酸マグネシウム、オレイン酸マグネシウム、ステアリン酸マグネシウム、ナフテン酸マグネシウム、シュウ酸マグネシウム、マロン酸マグネシウム、グルタル酸マグネシウム、アジピン酸マグネシウム、アジピン酸マグネシウム、マレイン酸マグネシウム、乳酸マグネシウム、クエン酸マグネシウム、安息香酸マグネシウム、フタル酸マグネシウム、ケイ皮酸マグネシウム、サリチル酸マグネシウム、塩基性蟻酸アルミニウム、塩基性酢酸アルミニウム、塩基性酪酸アルミニウム、塩基性カプリル酸アルミニウム、塩基性2−エチルヘキサン酸アルミニウム、塩基性ステアリン酸アルミニウム、ナフテン酸アルミニウム、塩基性乳酸アルミニウム、塩基性アルミニウムグリシネートなどのカルボン酸塩及びその水和物;塩基性炭酸マグネシウム、塩基性炭酸アルミニウムなどの炭酸塩及びその水和物;ビス(アセチルアセトナト)マグネシウム、トリス(アセチルアセトナト)アルミニウムなどのキレート錯体などが例示できる。 Examples of the carbon compound (B) containing magnesium and / or aluminum include magnesium and aluminum carboxylates and carbonates, chelate complexes in which an organic ligand is bonded to magnesium and aluminum, and organic metals having a carbon-metal bond (magnesium). , Aluminum) compounds and the like. Specifically, magnesium acetate, magnesium propionate, magnesium butyrate, magnesium valerate, magnesium caproate, magnesium enanthate, magnesium caprylate, magnesium 2-ethylhexanoate, magnesium oleate, magnesium stearate, magnesium naphthenate, Magnesium oxalate, magnesium malonate, magnesium glutarate, magnesium adipate, magnesium adipate, magnesium maleate, magnesium lactate, magnesium citrate, magnesium benzoate, magnesium phthalate, magnesium cinnamate, magnesium salicylate, basic formic acid Aluminum, basic aluminum acetate, basic aluminum butyrate, basic aluminum caprylate, basic 2-ethylhex Carboxylic acid salts and hydrates such as aluminum nitrate, basic aluminum stearate, aluminum naphthenate, basic aluminum lactate and basic aluminum glycinate; carbonates such as basic magnesium carbonate and basic aluminum carbonate and the like Hydrates; chelate complexes such as bis (acetylacetonato) magnesium and tris (acetylacetonato) aluminum can be exemplified.
炭素化合物(B)としては、取り扱い易いことから、室温で固体である炭素化合物が好ましい。 The carbon compound (B) is preferably a carbon compound that is solid at room temperature because it is easy to handle.
炭素化合物(B)が室温で固体である場合は、一次粒子の平均粒径が0.001〜30μmである粉体が好ましい。一次粒子の平均粒径としては、0.01〜7μmがより好ましい。 When the carbon compound (B) is solid at room temperature, a powder having an average primary particle size of 0.001 to 30 μm is preferable. As an average particle diameter of a primary particle, 0.01-7 micrometers is more preferable.
また、炭素化合物(B)としては、入手し易いことから、マグネシウムやアルミニウムの炭素数1〜18のカルボン酸塩や炭酸塩及びそれらの水和物が好ましい。マグネシウムやアルミニウムの酢酸塩や炭酸塩及びそれらの水和物が、特に好ましい。 Moreover, since it is easy to obtain as a carbon compound (B), the C1-C18 carboxylate and carbonate of magnesium and aluminum, and those hydrates are preferable. Particularly preferred are magnesium and aluminum acetates and carbonates and their hydrates.
酢酸マグネシウム、塩基性炭酸マグネシウム、塩基性酢酸アルミニウム、塩基性炭酸アルミニウム、及びそれらの水和物は、市販品をそのまま使用できる。 Commercially available products can be used as they are for magnesium acetate, basic magnesium carbonate, basic aluminum acetate, basic aluminum carbonate, and hydrates thereof.
炭素化合物(A)と炭素化合物(B)の具体例としては、酢酸コバルト(II)・4水和物−酢酸マグネシウム・4水和物、酢酸鉄(II)−酢酸マグネシウム・4水和物、酢酸コバルト(II)・4水和物−塩基性酢酸アルミニウム水和物、酢酸鉄(II)−塩基性酢酸アルミニウム水和物、塩基性炭酸コバルト(II)水和物−酢酸マグネシウム・4水和物、炭酸鉄(II)−酢酸マグネシウム・4水和物、塩基性炭酸コバルト(II)水和物−塩基性酢酸アルミニウム水和物、炭酸鉄(II)−塩基性酢酸アルミニウム水和物などが挙げられる。 Specific examples of the carbon compound (A) and the carbon compound (B) include cobalt acetate (II) tetrahydrate-magnesium acetate tetrahydrate, iron acetate (II) -magnesium acetate tetrahydrate, Cobalt acetate (II) tetrahydrate-basic aluminum acetate hydrate, iron acetate (II) -basic aluminum acetate hydrate, basic cobalt carbonate (II) hydrate-magnesium acetate tetrahydrate Iron carbonate (II) -magnesium acetate tetrahydrate, basic cobalt carbonate (II) hydrate-basic aluminum acetate hydrate, iron carbonate (II) -basic aluminum acetate hydrate, etc. Can be mentioned.
炭素化合物(A)及び炭素化合物(B)の使用量は特に限定されないが、炭素化合物(A)に含まれる鉄、コバルトと、炭素化合物(B)に含まれるマグネシウム、アルミニウムの化学量論比(Fe+Co)/(Mg+Al)が0.2〜10になるように調整することが好ましい。さらに好ましくは、化学量論比(Fe+Co)/(Mg+Al)は0.4〜6である。化学量論比(Fe+Co)/(Mg+Al)が0.2未満であると、MWCNTの成長速度が減少し、得られたMWCNTの各種媒体への分散性も低下するため好ましくない。化学量論比(Fe+Co)/(Mg+Al)が10を超えると、MWCNTの成長速度が減少するため好ましくない。 The amount of carbon compound (A) and carbon compound (B) used is not particularly limited, but the stoichiometric ratio of iron and cobalt contained in carbon compound (A) to magnesium and aluminum contained in carbon compound (B) ( It is preferable to adjust so that Fe + Co) / (Mg + Al) is 0.2-10. More preferably, the stoichiometric ratio (Fe + Co) / (Mg + Al) is 0.4-6. When the stoichiometric ratio (Fe + Co) / (Mg + Al) is less than 0.2, the growth rate of MWCNT is decreased, and the dispersibility of the obtained MWCNT in various media is also not preferable. If the stoichiometric ratio (Fe + Co) / (Mg + Al) exceeds 10, the growth rate of MWCNT decreases, which is not preferable.
炭素化合物(A)及び炭素化合物(B)からなる混合物を水素ガスと接触させる際に、共存させてもよいモリブデン化合物、タングステン化合物、バナジウム化合物としては、モリブデン酸、リンモリブデン酸アンモニウム、ヘプタモリブデン酸ヘキサアンモニウム、ビス(アセチルアセトナト)ジオキソモリブデン(VI)、塩化モリブデン(V)、酸化モリブデン(VI)、メタタングステン酸アンモニウム、パラタングステン酸アンモニウム、塩化タングステン(VI)、酸化タングステン(VI)、メタバナジン酸アンモニウム、塩化バナジウム(IV)、酸化バナジウム(V)などが例示できる。好ましくは、ヘプタモリブデン酸ヘキサアンモニウム、メタタングステン酸アンモニウム、パラタングステン酸アンモニウム、メタバナジン酸アンモニウムであり、市販品をそのまま使用できる。 The molybdenum compound, tungsten compound, and vanadium compound that may coexist when the mixture of the carbon compound (A) and the carbon compound (B) is brought into contact with hydrogen gas include molybdic acid, ammonium phosphomolybdate, and heptamolybdic acid. Hexaammonium, bis (acetylacetonato) dioxomolybdenum (VI), molybdenum chloride (V), molybdenum oxide (VI), ammonium metatungstate, ammonium paratungstate, tungsten chloride (VI), tungsten oxide (VI), Examples thereof include ammonium metavanadate, vanadium chloride (IV), and vanadium oxide (V). Preferred are hexaammonium heptamolybdate, ammonium metatungstate, ammonium paratungstate, and ammonium metavanadate, and commercially available products can be used as they are.
モリブデン化合物、タングステン化合物、バナジウム化合物の使用量は、各化合物に含まれるモリブデン、タングステン、バナジウムと、炭素化合物(A)に含まれる鉄、コバルトの化学量論比(Mo+W+V)/(Fe+Co)が0.05〜0.3になるように混合する。モリブデン、タングステン、バナジウムを少量添加することにより、触媒活性金属である鉄微粒子やコバルト微粒子の凝集を抑制するため、外径が大きいMWCNTの成長を抑制する。鉄を含む炭素化合物(A)と、炭素化合物(B)からなる混合物を使用して本発明の製造方法を実施すると、外径が異なる2種類のMWCNT(外径:約40〜70nm、約100〜140nm)が成長する。この混合物にモリブデン化合物を添加すると、外径が100nm以上のMWCNTは成長しない。 The amount of molybdenum compound, tungsten compound and vanadium compound used is 0 in the stoichiometric ratio (Mo + W + V) / (Fe + Co) of molybdenum, tungsten and vanadium contained in each compound and iron and cobalt contained in the carbon compound (A). Mix to 0.05-0.3. By adding a small amount of molybdenum, tungsten, or vanadium, the growth of MWCNT having a large outer diameter is suppressed in order to suppress the aggregation of iron fine particles and cobalt fine particles that are catalytically active metals. When the production method of the present invention is carried out using a mixture comprising a carbon compound (A) containing iron and a carbon compound (B), two types of MWCNTs having different outer diameters (outer diameter: about 40 to 70 nm, about 100 ˜140 nm). When a molybdenum compound is added to this mixture, MWCNT having an outer diameter of 100 nm or more does not grow.
炭素化合物(A)及び炭素化合物(B)からなる触媒前駆体を水素ガスと接触させる際に、共存させてもよいリチウム化合物としては、炭酸リチウム、シュウ酸リチウム、酢酸リチウムなどが例示でき、市販品をそのまま使用できる。 Examples of the lithium compound that may coexist when the catalyst precursor composed of the carbon compound (A) and the carbon compound (B) is brought into contact with hydrogen gas include lithium carbonate, lithium oxalate, and lithium acetate. The product can be used as it is.
リチウム化合物の使用量は、リチウム化合物に含まれるリチウムと、炭素化合物(A)に含まれる鉄、コバルトの化学量論比Li/(Fe+Co)が0.05〜0.3になるように混合する。より好ましい化学量論比Li/(Fe+Co)は0.05〜0.1である。リチウムを少量添加することにより、触媒活性成分である鉄やコバルト微粒子の凝集を抑制し、外径が大きいMWCNTの成長を抑制する。鉄を含む炭素化合物(A)、炭素化合物(B)、及びリチウム化合物からなる混合物を使用して本発明の製造方法を実施すると、外径が100nm以上のMWCNTは成長しない。また、MWCNTの成長速度も増大させる。 The amount of lithium compound used is mixed so that the stoichiometric ratio Li / (Fe + Co) of lithium contained in the lithium compound and iron and cobalt contained in the carbon compound (A) is 0.05 to 0.3. . A more preferable stoichiometric ratio Li / (Fe + Co) is 0.05 to 0.1. By adding a small amount of lithium, aggregation of iron and cobalt fine particles as catalytic active components is suppressed, and growth of MWCNT having a large outer diameter is suppressed. When the production method of the present invention is carried out using a mixture comprising a carbon compound (A) containing iron, a carbon compound (B), and a lithium compound, MWCNT having an outer diameter of 100 nm or more does not grow. It also increases the growth rate of MWCNT.
炭素化合物(A)、炭素化合物(B)、必要に応じて添加するモリブデン化合物、タングステン化合物、バナジウム化合物、リチウム化合物などは混合して使用する。混合しないで使用すると、カーボンナノチューブの成長速度が大きく低下するため好ましくない。混合しようとする化合物が室温で全て粉体である場合は、公知の乾式又は湿式法により、各種の混合装置(容器回転型、容器固定型など)を使用して混合し、炭素化合物(A)、炭素化合物(B)及びモリブデン化合物などの任意添加物からなる混合物(以下、触媒前駆体と呼称することがある)を得る。 A carbon compound (A), a carbon compound (B), a molybdenum compound added as necessary, a tungsten compound, a vanadium compound, a lithium compound, and the like are mixed and used. Use without mixing is not preferable because the growth rate of the carbon nanotubes is greatly reduced. When the compounds to be mixed are all powders at room temperature, they are mixed using various mixing apparatuses (container rotation type, container fixed type, etc.) by a known dry or wet method, and carbon compound (A) Then, a mixture (hereinafter sometimes referred to as a catalyst precursor) composed of optional additives such as a carbon compound (B) and a molybdenum compound is obtained.
また、触媒前駆体は、混合しようとする化合物を適当な溶媒に溶解、又は分散させた溶液や分散液の形態でもよい。溶媒としては、触媒前駆体と反応せず、溶解又は分散できるものであれば特に限定されないが、水、メタノール、エタノール、プロパノールなどのアルコール類、シクロヘキサン、ベンゼン、トルエンなどの炭化水素が挙げられる。少量の水と低級アルコールとの混合溶媒が好ましい。 The catalyst precursor may be in the form of a solution or dispersion in which the compound to be mixed is dissolved or dispersed in an appropriate solvent. The solvent is not particularly limited as long as it does not react with the catalyst precursor and can be dissolved or dispersed, and examples thereof include water, alcohols such as methanol, ethanol, and propanol, and hydrocarbons such as cyclohexane, benzene, and toluene. A mixed solvent of a small amount of water and a lower alcohol is preferred.
触媒前駆体と接触させる水素ガスには、炭化水素ガス及び窒素ガスなどの不活性ガスから選ばれる少なくとも1種のガスが含まれていてもよい。含有可能な炭化水素ガスは特に限定されないが、メタン、エタン、プロパン、ブテン、イソブテン、ブタジエン、エチレン、シクロペンタン、シクロヘキサン、プロピレン、アセチレン、ベンゼン、トルエン、キシレン、エチレン、クメン、ナフタレン、アントラセンなどが挙げられる。水素混合ガスの場合、混合ガス中の水素ガス含量は5容量%以上であることが好ましい。水素ガス含量が5容量%未満である場合は、触媒活性成分であるコバルトや鉄金属粒子の生成が不十分であり、MWCNTの成長速度が低下するため好ましくない。 The hydrogen gas brought into contact with the catalyst precursor may contain at least one gas selected from an inert gas such as a hydrocarbon gas and a nitrogen gas. The hydrocarbon gas that can be contained is not particularly limited, but methane, ethane, propane, butene, isobutene, butadiene, ethylene, cyclopentane, cyclohexane, propylene, acetylene, benzene, toluene, xylene, ethylene, cumene, naphthalene, anthracene, etc. Can be mentioned. In the case of a hydrogen mixed gas, the hydrogen gas content in the mixed gas is preferably 5% by volume or more. When the hydrogen gas content is less than 5% by volume, the production of cobalt and iron metal particles, which are catalytically active components, is insufficient, which is not preferable because the growth rate of MWCNT decreases.
触媒前駆体の設置形態、水素ガスとの接触方法、及び反応装置は特に限定されないが、公知の形態、方法、反応装置が利用できる。例えば、触媒前駆体が粉体混合物である場合は、設置形態としては、縦型又は横型の反応管に、触媒前駆体を石英製、アルミナ製などの耐熱性容器に固定して設置する固定床方式、ガスなどで流動するように設置して流動床方式(気泡型、噴流型)などが挙げられる。固定床または流動床とした触媒前駆体と、所定温度で、水素ガスを流通、接触させる。また、触媒前駆体が溶液や分散液である場合は、耐熱性多孔質基板に塗布して水素ガスを流通させる方法、スプレーなどで水素ガス雰囲気中に噴霧する方法などが挙げられる。 The installation form of the catalyst precursor, the method of contacting with hydrogen gas, and the reaction apparatus are not particularly limited, but known forms, methods, and reaction apparatuses can be used. For example, when the catalyst precursor is a powder mixture, the installation form is a fixed bed in which the catalyst precursor is fixed to a heat-resistant container made of quartz or alumina in a vertical or horizontal reaction tube. Examples include a fluidized bed method (bubble type, jet type) that is installed so as to flow with a gas or the like. Hydrogen gas is circulated and brought into contact with the catalyst precursor in a fixed bed or fluidized bed at a predetermined temperature. In addition, when the catalyst precursor is a solution or a dispersion, there are a method in which the catalyst precursor is applied to a heat-resistant porous substrate and hydrogen gas is circulated, a method in which spraying is performed in a hydrogen gas atmosphere by spraying, and the like.
触媒前駆体を設置した反応器に、水素ガスを流通させることにより接触させる。水素ガスの流量としては、10〜3000sccm(Standard Cubic Centimeter per Minutes)が好ましい。流量が10sccm未満である場合は、金属への還元速度が大幅に低下するため好ましくない。流量が3000sccmを超えても特に優位性はなく、ガス温が低下することもあるため好ましくない。 Contact is made by circulating hydrogen gas through a reactor in which the catalyst precursor is installed. The flow rate of hydrogen gas is preferably 10 to 3000 sccm (Standard Cubic Centimeter per Minutes). A flow rate of less than 10 sccm is not preferable because the reduction rate to metal is greatly reduced. Even if the flow rate exceeds 3000 sccm, there is no particular advantage, and the gas temperature may be lowered.
室温、常圧にて水素ガスを流通後、10〜45℃/分で400〜750℃まで昇温して、触媒前駆体の分解、還元を行うことにより、MWCNT製造用触媒を調製する。400℃未満の場合は、炭素化合物(A)に含まれるコバルトや鉄が金属に還元され難く、触媒の調製に長時間を必要とするため好ましくない。一方、750℃を超える場合は、還元された金属粒子が凝集して粒径が大きくなり表面積が大幅に低下して、MWCNTの成長速度が減少するため好ましくない。昇温速度が10℃/分未満の場合は、還元された金属粒子が凝集して触媒金属粒子の粒径が増大する結果、平均直径が100nmを超えたアスペクト比が小さいMWCNTが生成し易くなるため好ましくない。昇温速度が45℃/分を超える場合は、金属への還元が不十分となることがあるため好ましくない。 After flowing hydrogen gas at room temperature and normal pressure, the temperature is raised to 400 to 750 ° C. at 10 to 45 ° C./min, and the catalyst precursor is decomposed and reduced to prepare a catalyst for MWCNT production. When the temperature is lower than 400 ° C., cobalt and iron contained in the carbon compound (A) are difficult to be reduced to metal, and it takes a long time to prepare the catalyst, which is not preferable. On the other hand, when the temperature is higher than 750 ° C., the reduced metal particles are aggregated to increase the particle size, the surface area is greatly reduced, and the growth rate of MWCNT is decreased. When the rate of temperature increase is less than 10 ° C./min, the reduced metal particles are aggregated to increase the particle size of the catalyst metal particles. As a result, MWCNT having an average diameter exceeding 100 nm and a small aspect ratio are easily generated. Therefore, it is not preferable. When the rate of temperature rise exceeds 45 ° C./min, reduction to metal may be insufficient, which is not preferable.
(2)多層カーボンナノチューブ集合体の製造方法
本発明で使用するMWCNT製造用触媒は、MWCNT製造装置とは異なる装置で調製し、分離して使用してもよい。しかし、触媒活性が低下し難く、触媒分離など煩雑な工程が不要なことから、MWCNT製造装置で触媒を製造し、そのまま多層カーボンナノチューブ集合体を製造することが好ましい。以下、MWCNT製造装置で調製した触媒を、そのまま使用してMWCNTを製造する場合について説明する。
(2) Manufacturing method of multi-walled carbon nanotube aggregate The catalyst for MWCNT production used in the present invention may be prepared by an apparatus different from the MWCNT production apparatus and used separately. However, since the catalyst activity is difficult to decrease and a complicated process such as catalyst separation is unnecessary, it is preferable to produce a catalyst with an MWCNT production apparatus and produce a multi-walled carbon nanotube aggregate as it is. Hereinafter, the case where MWCNT is manufactured using the catalyst prepared by the MWCNT manufacturing apparatus as it is will be described.
炭素含有ガスと接触させる所定温度に達したら水素ガスの供給を停止し、炭素含有ガスに替えてMWCNT集合体の製造を続ける。 When a predetermined temperature to be brought into contact with the carbon-containing gas is reached, the supply of hydrogen gas is stopped, and the production of the MWCNT aggregate is continued in place of the carbon-containing gas.
MWCNT製造用触媒と接触させる炭素含有ガスとしては、特に限定されないが、メタン、エタン、プロパン、ブテン、イソブテン、ブタジエン、エチレン、シクロペンタン、シクロヘキサン、エチレン、プロピレン、アセチレン、ベンゼン、トルエン、キシレン、クメン、ナフタレン、アントラセンなどの炭化水素、メタノール、エタノール、プロパノールなどのアルコール類、ホルムアルデヒド、アセトアルデヒド、アセトンなどのアルデヒド・ケトン類などが例示でき、2種以上を混合して使用してもよい。揮発油、灯油なども使用できる。これらの中で、炭素含有ガスとしては、メタン、エタン、プロパン、エチレン、ブタジエン、アセチレン及び一酸化炭素が好ましい。 The carbon-containing gas to be brought into contact with the catalyst for MWCNT production is not particularly limited, but methane, ethane, propane, butene, isobutene, butadiene, ethylene, cyclopentane, cyclohexane, ethylene, propylene, acetylene, benzene, toluene, xylene, cumene Examples thereof include hydrocarbons such as naphthalene and anthracene, alcohols such as methanol, ethanol and propanol, and aldehydes and ketones such as formaldehyde, acetaldehyde and acetone, and a mixture of two or more may be used. Volatile oil and kerosene can also be used. Among these, methane, ethane, propane, ethylene, butadiene, acetylene, and carbon monoxide are preferable as the carbon-containing gas.
炭素含有ガスと、前記(1)の方法で調製した、コバルト、並びにマグネシウム又はアルミニウムを含む触媒を使用する場合は、炭素含有ガスと、500〜750℃で接触させる。接触温度が500℃未満の場合は、カーボンナノチューブが成長し難く、750℃を超える場合も、その成長速度が低下するため好ましくない。 When using a carbon-containing gas and a catalyst containing cobalt and magnesium or aluminum prepared by the above method (1), the catalyst is brought into contact with the carbon-containing gas at 500 to 750 ° C. When the contact temperature is less than 500 ° C., the carbon nanotubes are difficult to grow, and when the contact temperature exceeds 750 ° C., the growth rate is lowered, which is not preferable.
炭素含有ガスの流量としては、10〜3000sccmが好ましい。流量が10sccm未満である場合は、カーボンナノチューブの成長速度が大幅に低下するため好ましくない。流量が3000sccmを超えても特に優位性はなく、ガス温が低下することもあるため好ましくない。 The flow rate of the carbon-containing gas is preferably 10 to 3000 sccm. A flow rate of less than 10 sccm is not preferable because the growth rate of the carbon nanotubes is greatly reduced. Even if the flow rate exceeds 3000 sccm, there is no particular advantage, and the gas temperature may be lowered.
炭素含有ガスと、前記(1)の方法で調製した、鉄、並びにマグネシウム又はアルミニウムを含む触媒を使用する場合は、炭素含有ガスと、650〜900℃で接触させる。接触温度が650℃未満の場合は、カーボンナノチューブが成長し難く、900℃を超える場合も、その成長速度が低下し、得られるMWCNTの平均外径が100nmを大きく超え、アスペクト比が低下するため好ましくない。 When using a carbon-containing gas and a catalyst containing iron and magnesium or aluminum prepared by the method (1), the catalyst is brought into contact with the carbon-containing gas at 650 to 900 ° C. When the contact temperature is less than 650 ° C., the carbon nanotubes are difficult to grow, and when the contact temperature exceeds 900 ° C., the growth rate decreases, the average outer diameter of the obtained MWCNT greatly exceeds 100 nm, and the aspect ratio decreases. It is not preferable.
本発明の方法により製造された多層カーボンナノチューブ集合体は、その用途や要求される機能に応じて、以下のような後処理を行ってもよい。 The aggregate of multi-walled carbon nanotubes produced by the method of the present invention may be subjected to the following post-treatment depending on its application and required function.
黒鉛層の結晶性を上げるため、アルゴンなどの不活性ガス雰囲気にて、2000〜2800℃で熱処理を行ってもよい。 In order to increase the crystallinity of the graphite layer, heat treatment may be performed at 2000 to 2800 ° C. in an inert gas atmosphere such as argon.
MWCNT集合体の用途、及び要求特性によっては、触媒に由来する微量の鉄、コバルト金属微粒子、マグネシウム化合物、及びアルミニウム化合物を徹底的に除去するため、硝酸、塩酸、硫酸、酢酸などの酸、及びこれらの混酸で処理したり、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウムなどのアルカリ水溶液で処理してもよい。 Depending on the use and required characteristics of the MWCNT aggregate, an acid such as nitric acid, hydrochloric acid, sulfuric acid, acetic acid, and the like may be used to thoroughly remove trace amounts of iron, cobalt metal fine particles, magnesium compound, and aluminum compound derived from the catalyst. You may process with these mixed acids, or you may process with alkaline aqueous solutions, such as sodium hydroxide, potassium hydroxide, and sodium carbonate.
MWCNT集合体を樹脂や溶媒など各種媒体に分散させて使用する場合は、媒体への分散性を向上させるため、超音波照射、ボールミリング、キャビテーションの利用などの物理的方法や、硝酸やフッ化水素酸などの酸化性物質を接触させる化学的方法を適宜組み合わせて、MWCNTを適当な長さに切断することが好ましい。 When using MWCNT aggregates dispersed in various media such as resins and solvents, in order to improve the dispersibility in the media, physical methods such as ultrasonic irradiation, ball milling, use of cavitation, nitric acid or fluoride It is preferable to cut the MWCNT to an appropriate length by appropriately combining chemical methods for contacting an oxidizing substance such as hydroacid.
嵩密度が小さい本発明のMWCNT集合体が飛散し難いようにし、取扱い易くするため、真空加圧機などで圧縮処理してもよい。 In order to make the MWCNT aggregate of the present invention having a small bulk density difficult to be scattered and easy to handle, it may be compressed by a vacuum pressurizer or the like.
本発明の多層カーボンナノチューブ集合体は、樹脂、セラミックスなどへの分散性が良好なので、高含量、かつ高分散のMWCNT分散体を与える。 Since the multi-wall carbon nanotube aggregate of the present invention has good dispersibility in resins, ceramics and the like, a high-content and high-dispersion MWCNT dispersion is obtained.
MWCNT分散体としては、溶媒に分散させたMWCNT分散液、分散液を塗工する方法などにより得られるMWCNT分散膜、樹脂に顔料など他の添加剤とともに分散させたMWCNT分散マスターバッチ、マスターバッチを成形したMWCNT分散成形体などを挙げることができる。 Examples of the MWCNT dispersion include MWCNT dispersion liquid dispersed in a solvent, MWCNT dispersion film obtained by a method of applying the dispersion liquid, MWCNT dispersion master batch and master batch dispersed in resin together with other additives such as pigments. Examples thereof include a molded MWCNT dispersion molded body.
次に、実施例を示し、更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 Next, examples will be shown and described in more detail, but the present invention is not limited to these examples.
〔1〕多層カーボンナノチューブ、及び多層カーボンナノチューブ集合体の状態は、以下の走査型電子顕微鏡により、倍率1000倍又は10000倍で観察した。MWCNTの平均アスペクト比、平均外径、平均長さ、屈曲度は、画像より測定した。
走査型電子顕微鏡:品名:JEOL JEM 5500LV(日本電子(株))
〔2〕ラマンスペクトルは、以下の装置により測定した。
レーザーラマン分光装置:NRS−3300(日本分光(株))
〔3〕多層カーボンナノチューブの成長量は、「成長後の重量」から、別途測定した「触媒前駆体還元終了時(触媒)の重量」を差し引くことにより算出した。
〔4〕カーボンナノチューブ集合体を乾燥した100mlメスシリンダー(最小目盛単位:1ml)に静かに入れ、粉体層の上面を圧密せずに注意深くならし、体積を測定し嵩体積とする。カーボンナノチューブ集合体を取り出して測定した質量を嵩体積で除する。この測定、計算を3回行い、その平均値を嵩密度とした。
〔5〕MWCNT水性分散液の基板への塗布には、簡易型引張圧縮試験機(商標:“プッシュプルスタンド”、型式:SV−3、メーカー:(株)今田製作所)を利用して、浸漬法により所定の基材へ塗布した。
〔6〕調製したMWCNT水性分散液の状態は、目視により、凝集、沈殿の有無について経時的に観察した。分散液の状態は、凝集、沈殿がない状態が1カ月以上継続するものを○、1〜3週間継続するものを△、分散液を調製した翌日までに凝集、沈殿が発生するものを×と表示した。
基板上に形成したMWCNT分散膜の状態については、目視により観察した。
〔7〕MWCNT分散膜の表面抵抗率は、抵抗率計(商標:“LORESTA−IP”、型式:MCP−T250、メーカー:三菱化学(株))を使用して、4探針法(電極間距離:5mm、温度:25℃、湿度:15%RH)により測定した。
[1] The state of multi-walled carbon nanotubes and aggregates of multi-walled carbon nanotubes was observed at a magnification of 1000 times or 10,000 times with the following scanning electron microscope. The average aspect ratio, average outer diameter, average length, and bending degree of MWCNT were measured from images.
Scanning electron microscope: Product name: JEOL JEM 5500LV (JEOL Ltd.)
[2] The Raman spectrum was measured by the following apparatus.
Laser Raman spectrometer: NRS-3300 (JASCO Corporation)
[3] The growth amount of the multi-walled carbon nanotubes was calculated by subtracting the “weight at the end of reduction of the catalyst precursor (catalyst)” separately measured from the “weight after growth”.
[4] The carbon nanotube aggregate is gently put into a dry 100 ml graduated cylinder (minimum scale unit: 1 ml), and the upper surface of the powder layer is carefully leveled without being compacted, and the volume is measured to obtain a bulk volume. The mass measured by taking out the carbon nanotube aggregate is divided by the bulk volume. This measurement and calculation were performed three times, and the average value was defined as the bulk density.
[5] Applying MWCNT aqueous dispersion to the substrate using a simple tensile and compression tester (trademark: “push-pull stand”, model: SV-3, manufacturer: Imada Manufacturing Co., Ltd.) It was applied to a predetermined substrate by the method.
[6] The state of the prepared MWCNT aqueous dispersion was observed with time for the presence or absence of aggregation and precipitation. The state of the dispersion is ◯ when the state in which there is no aggregation or precipitation continues for 1 month or longer, △ if it lasts for 1 to 3 weeks, and × if the state in which aggregation or precipitation occurs by the next day after the dispersion is prepared. displayed.
The state of the MWCNT dispersed film formed on the substrate was visually observed.
[7] The surface resistivity of the MWCNT dispersed film is determined by a four-probe method (between electrodes) using a resistivity meter (trademark: “LORESTA-IP”, model: MCP-T250, manufacturer: Mitsubishi Chemical Corporation). Distance: 5 mm, temperature: 25 ° C., humidity: 15% RH).
MWCNT集合体の製造に用いた反応装置の概略を図2に示す。反応装置は、原料供給系、石英反応管、電気炉、排気系から構成されている。石英反応管の直径は50mm、長さは900mmであり、電気炉は開閉式抵抗加熱炉であり、長さは600mmである。図2中、1は石英反応管などの耐熱性反応管を、2は電気炉を、3は石英ボートを、4はMWCNTを、5は触媒(コバルト及び/又は鉄を含む炭素化合物(A)並びにマグネシウム及び/又はアルミニウムを含む炭素化合物(B)からなる混合物の水素還元物)を表す。 An outline of the reaction apparatus used for the production of the MWCNT aggregate is shown in FIG. The reaction apparatus includes a raw material supply system, a quartz reaction tube, an electric furnace, and an exhaust system. The quartz reaction tube has a diameter of 50 mm and a length of 900 mm. The electric furnace is an open / close resistance heating furnace and has a length of 600 mm. In FIG. 2, 1 is a heat-resistant reaction tube such as a quartz reaction tube, 2 is an electric furnace, 3 is a quartz boat, 4 is MWCNT, and 5 is a catalyst (a carbon compound (A) containing cobalt and / or iron). And a hydrogen reduction product of a mixture comprising a carbon compound (B) containing magnesium and / or aluminum.
(実施例1)
酢酸コバルト・4水和物(平均粒径:1μm)と塩基性酢酸アルミニウム水和物(アルミナ含量13質量%;平均粒径:0.5μm)の化学量論比(Co/Al)が4になるように乳鉢を使って混合することにより触媒前駆体を得た。触媒前駆体である混合粉体1gを石英ボート内に設置し、石英ボートを石英反応管中に挿入した。反応管に窒素ガスを300sccmで10分間流して置換し、さらに、水素ガスに切り替えて500sccmで10分間流すことにより、水素ガスに置換した。水素ガスの供給を保持したまま、550℃まで約25℃/分で昇温することにより、触媒前駆体を還元した。750℃に到達後、水素ガスをメタンガスに切り替え、500sccmで流し続けた。30分後、メタンガスを窒素ガス(300sccm)に切り替えて室温まで冷却後、石英反応管から石英ボートを取り出した。
Example 1
The stoichiometric ratio (Co / Al) of cobalt acetate tetrahydrate (average particle size: 1 μm) and basic aluminum acetate hydrate (alumina content 13 mass%; average particle size: 0.5 μm) is 4. The catalyst precursor was obtained by mixing using a mortar. 1 g of the mixed powder as a catalyst precursor was placed in a quartz boat, and the quartz boat was inserted into a quartz reaction tube. The reaction tube was purged with nitrogen gas at 300 sccm for 10 minutes, and further replaced with hydrogen gas by switching to hydrogen gas and flowing at 500 sccm for 10 minutes. While maintaining the supply of hydrogen gas, the catalyst precursor was reduced by raising the temperature to 550 ° C. at about 25 ° C./min. After reaching 750 ° C., the hydrogen gas was switched to methane gas and kept flowing at 500 sccm. After 30 minutes, the methane gas was switched to nitrogen gas (300 sccm) and cooled to room temperature, and then the quartz boat was taken out of the quartz reaction tube.
CNT集合体の生成量は1.806gであり、嵩密度は0.02g/cm3であった。 The production amount of CNT aggregates was 1.806 g, and the bulk density was 0.02 g / cm 3 .
得られたCNT集合体のラマンスペクトルを図14に示した。図14から明らかなように、単層カーボンナノチューブに特有の200〜600cm−1にはピークがないので、得られたカーボンナノチューブは単層ではなくMWCNTであった。 The Raman spectrum of the obtained CNT aggregate is shown in FIG. As apparent from FIG. 14, since there is no peak at 200 to 600 cm −1 peculiar to single-walled carbon nanotubes, the obtained carbon nanotubes were not single-walled but MWCNT.
得られたCNT集合体の倍率10000倍でのSEM画像を図3に、倍率1000倍でのSEM画像を図4に示した。MWCNTの平均外径は40nm、平均長さは100μmであり、屈曲度は55°であった。触媒活性金属微粒子が凝集したCNTの外径より大きな二次粒子や、触媒担体に由来する無機酸化物微粒子が凝集した径が10μm以上の二次粒子は観察されなかった。わかり難いが、図3に見られる粒子状の塊は、カーボンナノチューブが丸まったものであった。 An SEM image of the obtained CNT aggregate at a magnification of 10,000 times is shown in FIG. 3, and an SEM image at a magnification of 1000 times is shown in FIG. The average outer diameter of MWCNT was 40 nm, the average length was 100 μm, and the degree of bending was 55 °. Secondary particles larger than the outer diameter of the CNT aggregated with the catalytically active metal fine particles, or secondary particles with an aggregated diameter of the inorganic oxide fine particles derived from the catalyst support of 10 μm or more were not observed. Although it is difficult to understand, the particulate lump seen in FIG. 3 is a rounded carbon nanotube.
以下に従い、得られたMWCNT水性分散液を調製し、ガラス基板上にMWCNT分散膜を形成し、表面抵抗率を測定した。“アルミゾル−10A” (商標;川研ファインケミカル(株)製;アルミナ水和物10質量%)15.5g、3-グリシドキシプロピルトリメトキシシラン1.55g、N−(2−アミノエチル)エタノールアミン0.025g、アルミニウムモノアセチルアセトネートビス(エチルアセトアセテート)0.025g、メタノール5.6g、及びエタノール13.5gからなる分散液を調製する。この分散液に、2質量%になるように、得られたMWCNT集合体を添加し、家庭用ミキサー(品番:SM−R22、メーカー:三洋電機(株))で5分間攪拌(回転数:11850rpm)することにより、MWCNT水性分散液を調製した。 According to the following, the obtained MWCNT aqueous dispersion was prepared, an MWCNT dispersion film was formed on a glass substrate, and the surface resistivity was measured. “Aluminum sol-10A” (trademark; manufactured by Kawaken Fine Chemical Co., Ltd .; 10% by mass of alumina hydrate) 15.5 g, 1.55 g of 3-glycidoxypropyltrimethoxysilane, N- (2-aminoethyl) ethanol A dispersion is prepared consisting of 0.025 g amine, 0.025 g aluminum monoacetylacetonate bis (ethyl acetoacetate), 5.6 g methanol, and 13.5 g ethanol. The obtained MWCNT aggregate was added to this dispersion so as to be 2% by mass, and the mixture was stirred for 5 minutes with a home mixer (product number: SM-R22, manufacturer: Sanyo Electric Co., Ltd.) (rotation speed: 11850 rpm). MWCNT aqueous dispersion was prepared.
得られたMWCNT水性分散液を室温に放置したが、1カ月経過しても沈澱及び凝集が発生しないことが確認された。 The obtained MWCNT aqueous dispersion was allowed to stand at room temperature, but it was confirmed that precipitation and aggregation did not occur even after one month.
このMWCNT水性分散液をガラス基板上にディップコート(引き上げ速度:557mm/min)し、乾燥(空気雰囲気、120℃、15分)、焼成(空気雰囲気、300℃、15分)することにより、MWCNT分散膜を得た。焼成後のMWCNT分散膜の表面抵抗率は、102〜103Ω/□であった。 This MWCNT aqueous dispersion is dip-coated on a glass substrate (pulling speed: 557 mm / min), dried (air atmosphere, 120 ° C., 15 minutes), and fired (air atmosphere, 300 ° C., 15 minutes) to give MWCNT. A dispersion film was obtained. The surface resistivity of the MWCNT dispersed film after firing was 10 2 to 10 3 Ω / □.
以上の結果を、表1に示した。 The above results are shown in Table 1.
(実施例2)
コバルトとマグネシウムの化学量論比(Co/Mg)が4になるように、塩基性酢酸アルミニウム水和物を酢酸マグネシウム・4水和物(平均粒径:1μm)に変更した以外は、実施例1と同様にしてMWCNT集合体を製造した。また、実施例1と同様にして、MWCNT水性分散液、及び分散膜を調製した。
(Example 2)
Except that the basic aluminum acetate hydrate was changed to magnesium acetate tetrahydrate (average particle size: 1 μm) so that the stoichiometric ratio of cobalt to magnesium (Co / Mg) was 4, Example In the same manner as in Example 1, a MWCNT aggregate was produced. Further, in the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were prepared.
MWCNTの平均外径、平均長さ、屈曲度、成長量、MWCNT集合体の成長量、嵩密度、分散液の状態、分散膜の表面抵抗率などを表1にまとめた。 Table 1 summarizes the average outer diameter, average length, bending degree, growth amount, growth amount of MWCNT aggregate, bulk density, dispersion state, surface resistivity of the dispersion film, and the like.
(実施例3)
コバルトとマグネシウムの化学量論比(Co/Mg)を1に変更した以外は、実施例2と同様にしてMWCNT集合体を製造した。また、実施例1と同様にして、MWCNT水性分散液、及び分散膜を調製した。
(Example 3)
A MWCNT aggregate was produced in the same manner as in Example 2 except that the stoichiometric ratio of cobalt and magnesium (Co / Mg) was changed to 1. Further, in the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were prepared.
MWCNTの平均外径、平均長さ、屈曲度、成長量、MWCNT集合体の成長量、嵩密度、分散液の状態、分散膜の表面抵抗率などを表1にまとめた。 Table 1 summarizes the average outer diameter, average length, bending degree, growth amount, growth amount of MWCNT aggregate, bulk density, dispersion state, surface resistivity of the dispersion film, and the like.
(実施例4)
コバルトとマグネシウムの化学量論比(Co/Mg)を10に変更した以外は、実施例2と同様にしてMWCNT集合体を製造した。また、実施例1と同様にして、MWCNT水性分散液、及び分散膜を調製した。
Example 4
A MWCNT aggregate was produced in the same manner as in Example 2 except that the stoichiometric ratio of cobalt and magnesium (Co / Mg) was changed to 10. Further, in the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were prepared.
MWCNTの平均外径、平均長さ、屈曲度、成長量、MWCNT集合体の成長量、嵩密度、分散液の状態、分散膜の表面抵抗率などを表1にまとめた。 Table 1 summarizes the average outer diameter, average length, bending degree, growth amount, growth amount of MWCNT aggregate, bulk density, dispersion state, surface resistivity of the dispersion film, and the like.
(実施例5)
コバルトとマグネシウムの化学量論比(Co/Mg)を0.2に変更した以外は、実施例2と同様にしてMWCNT集合体を製造した。また、実施例1と同様にして、MWCNT水性分散液、及び分散膜を調製した。
(Example 5)
A MWCNT aggregate was produced in the same manner as in Example 2 except that the stoichiometric ratio of cobalt and magnesium (Co / Mg) was changed to 0.2. Further, in the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were prepared.
MWCNTの平均外径、平均長さ、屈曲度、成長量、MWCNT集合体の成長量、嵩密度、分散液の状態、分散膜の表面抵抗率などを表1にまとめた。 Table 1 summarizes the average outer diameter, average length, bending degree, growth amount, growth amount of MWCNT aggregate, bulk density, dispersion state, surface resistivity of the dispersion film, and the like.
(実施例6)
鉄とアルミニウムの化学量論比(Fe/Al)が4になるように、酢酸マグネシウム・4水和物を塩基性酢酸アルミニウム水和物に変更した以外は、実施例1と同様にしてCNT集合体を製造した。
(Example 6)
CNT assembly in the same manner as in Example 1 except that magnesium acetate tetrahydrate was changed to basic aluminum acetate hydrate so that the stoichiometric ratio of iron to aluminum (Fe / Al) was 4. The body was manufactured.
CNT集合体の生成量は2.202gであり、嵩密度は0.04g/cm3であった。 The production amount of the CNT aggregate was 2.202 g, and the bulk density was 0.04 g / cm 3 .
得られたカーボンナノチューブ集合体のラマンスペクトルを図15に示す。図15から明らかなように、単層カーボンナノチューブに特有の200〜600cm−1にはピークがなかったので、得られたカーボンナノチューブは単層ではなくMWCNTであった。 FIG. 15 shows the Raman spectrum of the obtained carbon nanotube aggregate. As is clear from FIG. 15, since there was no peak at 200 to 600 cm −1 peculiar to single-walled carbon nanotubes, the obtained carbon nanotubes were not single-walled but MWCNT.
得られたカーボンナノチューブ集合体の倍率10000倍でのSEM画像を図5に、倍率1000倍でのSEM画像を図6に示した。 An SEM image of the obtained carbon nanotube aggregate at a magnification of 10,000 times is shown in FIG. 5, and an SEM image at a magnification of 1000 times is shown in FIG.
外径が異なる2種類のMWCNT(平均外径70nm×平均長さ100μm、平均外径140nm×平均長さ100μm)が得られた。いずれも、屈曲度は50°であった。触媒活性金属微粒子が凝集したCNTの外径より大きな二次粒子や、触媒担体に由来する無機酸化物微粒子が凝集した径が10μm以上の二次粒子は観察されなかった。わかり難いが、図5に見られる粒子状の塊は、カーボンナノチューブが丸まったものであった。 Two types of MWCNTs having different outer diameters (average outer diameter 70 nm × average length 100 μm, average outer diameter 140 nm × average length 100 μm) were obtained. In all cases, the degree of bending was 50 °. Secondary particles larger than the outer diameter of the CNT aggregated with the catalytically active metal fine particles, or secondary particles with an aggregated diameter of the inorganic oxide fine particles derived from the catalyst support of 10 μm or more were not observed. Although it is difficult to understand, the particulate lump seen in FIG. 5 is a rounded carbon nanotube.
実施例1と同様にして、MWCNT水性分散液、及び分散膜を得た。得られたMWCNT水性分散液を室温において放置したが、1カ月経過しても沈澱及び凝集が発生しないことが確認された。焼成後のMWCNT分散膜の表面抵抗率は、101〜102Ω/□であった。 In the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were obtained. The obtained MWCNT aqueous dispersion was allowed to stand at room temperature, but it was confirmed that precipitation and aggregation did not occur even after one month. The surface resistivity of the MWCNT dispersion film after firing was 10 1 to 10 2 Ω / □.
以上の結果を、表1に示した。 The above results are shown in Table 1.
(実施例7)
酢酸鉄(II)と酢酸マグネシウム・4水和物の化学量論比(Fe/Mg)が4になるように、塩基性酢酸アルミニウム水和物を酢酸マグネシウム・4水和物に変更した以外は、実施例6と同様にしてMWNTs集合体を製造した。また、実施例1と同様にして、MWCNT水性分散液、及び分散膜を調製した。
(Example 7)
Except for changing the basic aluminum acetate hydrate to magnesium acetate tetrahydrate so that the stoichiometric ratio (Fe / Mg) of iron (II) acetate and magnesium acetate tetrahydrate is 4. MWNTs aggregates were produced in the same manner as in Example 6. Further, in the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were prepared.
実施例6と同様な、外径が異なる2種類のMWCNTが得られた。MWCNTの平均外径、平均長さ、屈曲度、成長量、MWCNT集合体の成長量、嵩密度、分散液の状態、分散膜の表面抵抗率などを表1に示した。 Similar to Example 6, two types of MWCNTs having different outer diameters were obtained. Table 1 shows the average outer diameter, average length, bending degree, growth amount, growth amount of the MWCNT aggregate, bulk density, state of the dispersion, surface resistivity of the dispersion film, and the like.
(実施例8)
酢酸鉄(II)と酢酸マグネシウム・4水和物の化学量論比(Fe/Mg)を1.1に変更した以外は、実施例7と同様にしてMWCNT集合体を製造した。また、実施例1と同様にして、MWCNT水性分散液、及び分散膜を調製した。
(Example 8)
A MWCNT aggregate was produced in the same manner as in Example 7, except that the stoichiometric ratio (Fe / Mg) of iron (II) acetate and magnesium acetate tetrahydrate was changed to 1.1. Further, in the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were prepared.
実施例6と同様な、外径が異なる2種類のMWCNTが得られた。MWCNTの平均外径、平均長さ、屈曲度、成長量、MWCNT集合体の成長量、嵩密度、分散液の状態、分散膜の表面抵抗率などを表1に示した。 Similar to Example 6, two types of MWCNTs having different outer diameters were obtained. Table 1 shows the average outer diameter, average length, bending degree, growth amount, growth amount of the MWCNT aggregate, bulk density, state of the dispersion, surface resistivity of the dispersion film, and the like.
(実施例9)
酢酸鉄(II)と酢酸マグネシウム・4水和物の化学量論比(Fe/Mg)を10に変更した以外は、実施例7と同様にしてMWCNT集合体を製造した。また、実施例1と同様にして、MWCNT水性分散液、及び分散膜を調製した。
Example 9
A MWCNT aggregate was produced in the same manner as in Example 7, except that the stoichiometric ratio (Fe / Mg) of iron (II) acetate and magnesium acetate tetrahydrate was changed to 10. Further, in the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were prepared.
実施例6と同様な、外径が異なる2種類のMWCNTが得られた。MWCNTの平均外径、平均長さ、屈曲度、成長量、MWCNT集合体の成長量、嵩密度、分散液の状態、分散膜の表面抵抗率などを表1に示した。 Similar to Example 6, two types of MWCNTs having different outer diameters were obtained. Table 1 shows the average outer diameter, average length, bending degree, growth amount, growth amount of the MWCNT aggregate, bulk density, state of the dispersion, surface resistivity of the dispersion film, and the like.
(実施例10)
酢酸鉄(II)と酢酸マグネシウム・4水和物の化学量論比(Fe/Mg)を0.2に変更した以外は、実施例7と同様にしてMWCNT集合体を製造した。また、実施例1と同様にして、MWCNT水性分散液、及び分散膜を調製した。
(Example 10)
A MWCNT aggregate was produced in the same manner as in Example 7 except that the stoichiometric ratio (Fe / Mg) of iron (II) acetate and magnesium acetate tetrahydrate was changed to 0.2. Further, in the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were prepared.
実施例6と同様な、外径が異なる2種類のMWCNTが得られた。MWCNTの平均外径、平均長さ、屈曲度、成長量、MWCNT集合体の成長量、嵩密度、分散液の状態、分散膜の表面抵抗率などを表1に示した。 Similar to Example 6, two types of MWCNTs having different outer diameters were obtained. Table 1 shows the average outer diameter, average length, bending degree, growth amount, growth amount of the MWCNT aggregate, bulk density, state of the dispersion, surface resistivity of the dispersion film, and the like.
(実施例11)
触媒前駆体を、鉄、アルミニウム、及びモリブデンの化学量論比(Fe/Al/Mo)が4/1/1になるように調製した酢酸鉄(II)、塩基性酢酸アルミニウム、及びモリブデン酸からなる混合粉体0.5gに変更した以外は、実施例6と同様にしてMWCNT集合体を製造した。また、実施例1と同様にして、MWCNT水性分散液、及び分散膜を調製した。
(Example 11)
A catalyst precursor was prepared from iron (II) acetate, basic aluminum acetate, and molybdic acid prepared so that the stoichiometric ratio (Fe / Al / Mo) of iron, aluminum, and molybdenum was 4/1/1. A MWCNT aggregate was produced in the same manner as in Example 6 except that the mixed powder was changed to 0.5 g. Further, in the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were prepared.
走査型電子顕微鏡で観察したところ、外径が細いMWCNT(平均外径40nm×平均長さ100μm)のみが得られた。MWCNTの平均外径、平均長さ、屈曲度、成長量、MWCNT集合体の成長量、嵩密度、分散液の状態、分散膜の表面抵抗率などを表1に示した。 When observed with a scanning electron microscope, only MWCNT (average outer diameter 40 nm × average length 100 μm) having a small outer diameter was obtained. Table 1 shows the average outer diameter, average length, bending degree, growth amount, growth amount of the MWCNT aggregate, bulk density, state of the dispersion, surface resistivity of the dispersion film, and the like.
(実施例12)
触媒前駆体を、鉄、アルミニウム、およびリチウムの化学量論比(Fe/Al/Li)が4/1/0.4になるように調製した酢酸鉄(II)、塩基性酢酸アルミニウム、及び酢酸リチウムからなる混合粉体1.0gに変更した以外は、実施例6と同様にしてMWCNTを製造した。また、実施例1と同様にして、MWCNT水性分散液、及び分散膜を調製した。
(Example 12)
The catalyst precursor was prepared with iron (II) acetate, basic aluminum acetate, and acetic acid prepared such that the stoichiometric ratio of iron, aluminum, and lithium (Fe / Al / Li) was 4/1 / 0.4 MWCNT was produced in the same manner as in Example 6 except that the mixed powder was changed to 1.0 g of lithium. Further, in the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were prepared.
走査型電子顕微鏡で観察したところ、外径が細いMWCNT(平均外径70nm×平均長さ200μm)のみが得られた。また、カーボンナノチューブの成長速度が増大した。 When observed with a scanning electron microscope, only MWCNT (average outer diameter 70 nm × average length 200 μm) having a small outer diameter was obtained. In addition, the growth rate of carbon nanotubes increased.
MWCNTの平均外径、平均長さ、屈曲度、成長量、MWCNT集合体の成長量、嵩密度、分散液の状態、分散膜の表面抵抗率などを表1に示した。 Table 1 shows the average outer diameter, average length, bending degree, growth amount, growth amount of the MWCNT aggregate, bulk density, state of the dispersion, surface resistivity of the dispersion film, and the like.
(比較例1)
触媒前駆体を酢酸コバルト・4水和物に、触媒前駆体と水素ガスとの接触最高温度及びメタンガスとの接触温度を650℃に変更した以外は、実施例1と同様にしてMWCNT集合体を製造した。カーボンナノチューブは成長しておらず、酢酸コバルト・4水和物が還元分解されたコバルト金属粒子の凝集体が観察された。
(Comparative Example 1)
A MWCNT aggregate was prepared in the same manner as in Example 1 except that the catalyst precursor was changed to cobalt acetate tetrahydrate, and the contact temperature between the catalyst precursor and hydrogen gas and the contact temperature with methane gas were changed to 650 ° C. Manufactured. Carbon nanotubes were not grown, and an aggregate of cobalt metal particles in which cobalt acetate tetrahydrate was reduced and decomposed was observed.
(比較例2)
触媒前駆体を酢酸コバルト・4水和物に、水素ガスをメタンガスに、メタンガスとの接触温度を650℃に変更した以外は、実施例1と同様にしてMWCNT集合体を製造した。カーボンナノチューブは成長しておらず、酢酸コバルト・4水和物が還元分解されたコバルト金属粒子の凝集体が観察された。
(Comparative Example 2)
A MWCNT aggregate was produced in the same manner as in Example 1 except that the catalyst precursor was changed to cobalt acetate tetrahydrate, the hydrogen gas was changed to methane gas, and the contact temperature with the methane gas was changed to 650 ° C. Carbon nanotubes were not grown, and an aggregate of cobalt metal particles in which cobalt acetate tetrahydrate was reduced and decomposed was observed.
(比較例3)
酢酸マグネシウム・4水和物を酸化マグネシウムに変更した以外は、実施例2と同様にしてMWCNT集合体を製造した。カーボンナノチューブは成長していなかった。
(Comparative Example 3)
A MWCNT aggregate was produced in the same manner as in Example 2 except that magnesium acetate tetrahydrate was changed to magnesium oxide. Carbon nanotubes were not growing.
(比較例4)
酢酸コバルト・4水和物を酸化コバルト(II)に変更した以外は、実施例2と同様にしてMWCNT集合体を製造した。カーボンナノチューブは成長していなかった。
(Comparative Example 4)
A MWCNT aggregate was produced in the same manner as in Example 2 except that cobalt acetate tetrahydrate was changed to cobalt (II) oxide. Carbon nanotubes were not growing.
(比較例5)
酢酸コバルト・4水和物を酸化コバルト(II)に、酢酸マグネシウム・4水和物を酸化マグネシウムに変更した以外は、実施例2と同様にしてMWCNT集合体を製造した。カーボンナノチューブは成長していなかった。
(Comparative Example 5)
A MWCNT aggregate was produced in the same manner as in Example 2, except that the cobalt acetate tetrahydrate was changed to cobalt (II) oxide and the magnesium acetate tetrahydrate was changed to magnesium oxide. Carbon nanotubes were not growing.
(比較例6)
触媒前駆体を酢酸鉄(II)に変更した以外は、実施例6と同様にしてMWCNT集合体を製造した。カーボンナノチューブは成長しておらず、酢酸鉄(II)が還元分解された鉄金属粒子の凝集体が観察された。
(Comparative Example 6)
A MWCNT aggregate was produced in the same manner as in Example 6 except that the catalyst precursor was changed to iron (II) acetate. Carbon nanotubes were not grown, and aggregates of iron metal particles in which iron (II) acetate was reduced and decomposed were observed.
(比較例7)
触媒前駆体を酢酸鉄(II)に、水素ガスをメタンガスに変更した以外は、実施例6と同様にしてMWCNT集合体を製造した。カーボンナノチューブは成長しておらず、酢酸鉄(II)が還元分解された鉄金属粒子の凝集体が観察された。
(Comparative Example 7)
A MWCNT aggregate was produced in the same manner as in Example 6 except that the catalyst precursor was changed to iron (II) acetate and the hydrogen gas was changed to methane gas. Carbon nanotubes were not grown, and aggregates of iron metal particles in which iron (II) acetate was reduced and decomposed were observed.
(比較例8)
酢酸マグネシウム・4水和物を酸化マグネシウムに変更した以外は、実施例7と同様にしてMWCNT集合体を製造した。
(Comparative Example 8)
A MWCNT aggregate was produced in the same manner as in Example 7, except that magnesium acetate tetrahydrate was changed to magnesium oxide.
CNT集合体の生成量は0.489gであり、嵩密度は0.565g/cm3であった。 The amount of CNT aggregate produced was 0.489 g, and the bulk density was 0.565 g / cm 3 .
ラマンスペクトルの測定から、得られたカーボンナノチューブはMWCNTであった。 From the measurement of Raman spectrum, the obtained carbon nanotube was MWCNT.
得られたCNT集合体の倍率10000倍で観察したSEM画像を図7に、1000倍でのSEM画像を図8に示した。外径が異なる2種類のMWCNT(平均外径70nm×平均長さ5μm、平均外径140nm×平均長さ5μm)が得られた。いずれも、屈曲度は15°であった。径が10μm以上の酸化マグネシウムに由来する粒子が観察された。 An SEM image of the obtained CNT aggregate observed at a magnification of 10,000 times is shown in FIG. 7, and an SEM image at 1000 times is shown in FIG. Two types of MWCNTs having different outer diameters (average outer diameter 70 nm × average length 5 μm, average outer diameter 140 nm × average length 5 μm) were obtained. In all cases, the degree of bending was 15 °. Particles derived from magnesium oxide having a diameter of 10 μm or more were observed.
実施例1と同様にして、MWCNT水性分散液、及び分散膜を調製した。得られたMWNTs水性分散液を室温に放置したが、翌日には凝集して沈殿物が生成していた。
比較例8で得られたMWCNTは媒体への分散性が悪く、作成したMWCNT分散膜の表面抵抗値も、やや高いものであった。
In the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were prepared. The obtained aqueous dispersion of MWNTs was allowed to stand at room temperature, but the next day, it aggregated and a precipitate was formed.
The MWCNT obtained in Comparative Example 8 was poorly dispersible in the medium, and the surface resistance value of the prepared MWCNT dispersed film was somewhat high.
MWCNTの平均外径、平均長さ、屈曲度、成長量、MWCNT集合体の成長量、嵩密度、分散液の状態、分散膜の表面抵抗率などを表2に示した。 Table 2 shows the average outer diameter, average length, bending degree, growth amount, growth amount of the MWCNT aggregate, bulk density, dispersion state, surface resistivity of the dispersion film, and the like.
(比較例9)
酢酸鉄(II)をα−酸化鉄(III)に変更した以外は、実施例7と同様にしてMWCNT集合体を製造した。カーボンナノチューブは成長していなかった。
(Comparative Example 9)
A MWCNT aggregate was produced in the same manner as in Example 7, except that iron (II) acetate was changed to α-iron oxide (III). Carbon nanotubes were not growing.
(比較例10)
酢酸コバルト・4水和物を酢酸ニッケル・4水和物(平均粒径:3μm)に変更した以外は、実施例1と同様にしてMWCNT集合体を製造した。
(Comparative Example 10)
A MWCNT aggregate was produced in the same manner as in Example 1 except that cobalt acetate tetrahydrate was changed to nickel acetate tetrahydrate (average particle size: 3 μm).
得られたCNT集合体の嵩密度は0.41g/cm3であり、成長量は0.158gであった。 The bulk density of the obtained CNT aggregate was 0.41 g / cm 3 and the growth amount was 0.158 g.
ラマンスペクトルの測定から、得られたカーボンナノチューブはMWCNTであった。 From the measurement of Raman spectrum, the obtained carbon nanotube was MWCNT.
得られたCNT集合体の倍率10000倍で観察したSEM画像を図9に、1000倍でのSEM画像を図10に示した。図9から、MWCNTの平均外径は70nm、平均長さは5μmであり、屈曲度は20°であった。径が10μm以上の触媒担体に由来する粒子が存在し、その上からカーボンナノチューブが成長していることがわかる。 FIG. 9 shows an SEM image of the obtained CNT aggregate observed at a magnification of 10,000 times, and FIG. 10 shows an SEM image at a magnification of 1000 times. From FIG. 9, the average outer diameter of MWCNT was 70 nm, the average length was 5 μm, and the degree of bending was 20 °. It can be seen that there are particles derived from the catalyst carrier having a diameter of 10 μm or more, and the carbon nanotubes are grown thereon.
実施例1と同様にして、MWCNT水性分散液、及び分散膜を調製した。得られたMWNTs水性分散液を室温に放置したが、翌日には凝集して沈殿物が生成していた。
比較例10で得られたMWCNTは媒体への分散性が悪く、作成したMWCNT分散膜の表面抵抗値も、やや高いものであった。
In the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were prepared. The obtained aqueous dispersion of MWNTs was allowed to stand at room temperature, but the next day, it aggregated and a precipitate was formed.
The MWCNT obtained in Comparative Example 10 was poorly dispersible in the medium, and the surface resistance value of the prepared MWCNT dispersed film was somewhat high.
MWCNTの平均外径、平均長さ、屈曲度、成長量、MWCNT集合体の成長量、嵩密度、分散液の状態、分散膜の表面抵抗率などを表2に示した。 Table 2 shows the average outer diameter, average length, bending degree, growth amount, growth amount of the MWCNT aggregate, bulk density, dispersion state, surface resistivity of the dispersion film, and the like.
(比較例11)
水素キャリアガスを用いてフェロセン(2.5質量%)/トルエン溶液をスプレーで供給し、MWCNT集合体を製造した。まず、スプレー気化器および石英反応管中に窒素ガスを300sccmで供給し、10分間置換した。引き続き、電気炉により石英反応管全体を1100℃に昇温した(昇温速度25℃/1分)。その後、水素キャリアガスを1000sccmでスプレー気化器に供給した。スプレー気化器により液滴化したフェロセン(2.5質量%)/トルエン溶液を1100℃に加熱された反応管に供給した。30分間成長を行い、成長終了後石英反応管へのフェロセン/トルエン溶液の供給を停止し、窒素ガスを300sccm供給した。石英反応管の温度が650℃まで降温した後、電気炉を開放し、室温まで冷却した。石英反応管が室温まで冷却後、反応管内の触媒を含むMWCNT集合体を回収した。
(Comparative Example 11)
A ferrocene (2.5% by mass) / toluene solution was supplied by spraying using a hydrogen carrier gas to produce an MWCNT aggregate. First, nitrogen gas was supplied at 300 sccm into the spray vaporizer and the quartz reaction tube and replaced for 10 minutes. Subsequently, the entire quartz reaction tube was heated to 1100 ° C. by an electric furnace (temperature increase rate: 25 ° C./1 minute). Thereafter, hydrogen carrier gas was supplied to the spray vaporizer at 1000 sccm. A ferrocene (2.5% by mass) / toluene solution dropletized by a spray vaporizer was supplied to a reaction tube heated to 1100 ° C. The growth was performed for 30 minutes. After the growth was completed, the supply of the ferrocene / toluene solution to the quartz reaction tube was stopped, and 300 sccm of nitrogen gas was supplied. After the temperature of the quartz reaction tube was lowered to 650 ° C., the electric furnace was opened and cooled to room temperature. After the quartz reaction tube was cooled to room temperature, the MWCNT aggregate containing the catalyst in the reaction tube was recovered.
得られたCNT集合体の嵩密度は0.2g/cm3であり、成長量は50gであった。 The bulk density of the obtained CNT aggregate was 0.2 g / cm 3 and the growth amount was 50 g.
ラマンスペクトルの測定から、得られたカーボンナノチューブはMWCNTであった。 From the measurement of Raman spectrum, the obtained carbon nanotube was MWCNT.
得られたCNT集合体の倍率10000倍で観察したSEM画像を図11に、1000倍でのSEM画像を図12に示した。MWCNTの平均外径は100nm、平均長さは30μmであり、ほぼ直線状に成長していた。なお、図11、12に見られる白い塊は、無定形炭素である。 The SEM image observed at a magnification of 10,000 times of the obtained CNT aggregate is shown in FIG. 11, and the SEM image at 1000 times is shown in FIG. MWCNT had an average outer diameter of 100 nm and an average length of 30 μm, and was growing almost linearly. In addition, the white lump seen in FIGS. 11 and 12 is amorphous carbon.
実施例1と同様にして、MWCNT水性分散液、及び分散膜を得た。得られたMWCNT水性分散液を室温において放置したが、1週間後には凝集して沈澱物が生成していた。比較例11で得られたMWCNTは媒体への分散性に劣るものであった。
MWCNTの平均外径、平均長さ、屈曲度、成長量、MWCNT集合体の成長量、嵩密度、分散液の状態、分散膜の表面抵抗率などを表2に示した。
In the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were obtained. The obtained MWCNT aqueous dispersion was allowed to stand at room temperature, but after one week, it aggregated and a precipitate was formed. The MWCNT obtained in Comparative Example 11 was inferior in dispersibility in the medium.
Table 2 shows the average outer diameter, average length, bending degree, growth amount, growth amount of the MWCNT aggregate, bulk density, dispersion state, surface resistivity of the dispersion film, and the like.
(比較例12)
酢酸鉄を硝酸鉄・9水和物、酢酸マクネシウム・4水和物を硝酸マグネシウム・4水和物に変更した以外は、実施例2と同様にしてMWCNT集合体を製造した。カーボンナノチューブは成長していなかった。
(Comparative Example 12)
A MWCNT aggregate was produced in the same manner as in Example 2 except that the iron acetate was changed to iron nitrate nonahydrate and the magnesium acetate tetrahydrate was changed to magnesium nitrate tetrahydrate. Carbon nanotubes were not growing.
(比較例13)
触媒前駆体を、鉄、マグネシウム、無水クエン酸、蒸留水の化学量論比(Fe/Mg/無水クエン酸/水)が0.56/1/1/111になるようにして硝酸鉄9水和物、硝酸マグネシウム6水和物、無水クエン酸、および蒸留水を混合し、完全に溶解させた。この水溶液を120℃で8時間乾燥し固体粉末化した。この粉末を大気中700℃で5時間焼成することにより、触媒前駆体とした。この触媒前駆体の数量を0.3gに変更した以外は、実施例7と同様にしてMWCNTを製造した。なお、Feの化学量論比を0.56以上にすると、カーボンナノチューブは、ほとんど成長しなかった。
(Comparative Example 13)
The catalyst precursor was iron, magnesium, anhydrous citric acid, distilled water 9 iron so that the stoichiometric ratio (Fe / Mg / anhydrous citric acid / water) was 0.56 / 1/1/111. The hydrate, magnesium nitrate hexahydrate, anhydrous citric acid, and distilled water were mixed and completely dissolved. This aqueous solution was dried at 120 ° C. for 8 hours to form a solid powder. This powder was calcined in the atmosphere at 700 ° C. for 5 hours to obtain a catalyst precursor. MWCNT was produced in the same manner as in Example 7 except that the amount of the catalyst precursor was changed to 0.3 g. When the stoichiometric ratio of Fe was 0.56 or more, the carbon nanotubes hardly grew.
得られたCNT集合体の嵩密度は0.4g/cm3であり、成長量は0.493gであった。 The bulk density of the obtained CNT aggregate was 0.4 g / cm 3 and the growth amount was 0.493 g.
ラマンスペクトルの測定から、得られたカーボンナノチューブはMWCNTであった。 From the measurement of Raman spectrum, the obtained carbon nanotube was MWCNT.
得られたCNT集合体の倍率1000倍でのSEM画像を図13に示した。MWCNTの平均外径は70nm、平均長さは5μmであり、屈曲度は20°であった。径が10μm以上の触媒担体に由来する粒子が観察され、その上からCNTが成長していることがわかる。 An SEM image of the obtained CNT aggregate at a magnification of 1000 is shown in FIG. MWCNT had an average outer diameter of 70 nm, an average length of 5 μm, and a degree of bending of 20 °. Particles derived from a catalyst carrier having a diameter of 10 μm or more are observed, and it can be seen that CNTs grow from the particles.
実施例1と同様にして、MWCNT水性分散液、及び分散膜を得た。得られたMWCNT水性分散液を室温において放置したが、1週間後には凝集して沈澱物が生成していた。 In the same manner as in Example 1, an MWCNT aqueous dispersion and a dispersion film were obtained. The obtained MWCNT aqueous dispersion was allowed to stand at room temperature, but after one week, it aggregated and a precipitate was formed.
比較例13で得られたMWCNTは媒体への分散性に劣るものであった。
MWCNTの平均外径、平均長さ、屈曲度、成長量、MWCNT集合体の成長量、嵩密度、分散液の状態、分散膜の表面抵抗率などを表2に示した。
The MWCNT obtained in Comparative Example 13 was inferior in dispersibility in the medium.
Table 2 shows the average outer diameter, average length, bending degree, growth amount, growth amount of the MWCNT aggregate, bulk density, dispersion state, surface resistivity of the dispersion film, and the like.
本発明の多層カーボンナノチューブ集合体は、樹脂、セラミックスなどの基材、マトリックスに、導電性、熱伝導性、難燃性、電磁波遮蔽性など、本来有するカーボンナノチューブの機能を、効果的に与えることができる。 The multi-wall carbon nanotube aggregate of the present invention effectively imparts the functions of carbon nanotubes inherently, such as conductivity, thermal conductivity, flame retardancy, and electromagnetic wave shielding properties, to a substrate and matrix such as resin and ceramics. Can do.
そのため、静電塗装用導電性プライマー、各種半導体部品の加工、移送、保管中における静電気による破壊を防止するための電気・電子部品用容器及びシート、各種電子・電気製品(家電用、車両用、通信用など;電子・電気回路、導電性;熱伝導性、電磁波遮蔽性、難燃性を要求される熱伝導性シートなどの部材・部品)、磁気記録媒体(オーディオテープ、ビデオテープなど;帯電防止)、表示デバイス(液晶ディスプレイ、有機ELディスプレイ、タッチパネルなど;表面の帯電防止、透明導電膜)、画像記録材料(電子写真用、インクジェット記録用、感熱記録用、熱現像用、ハロゲン化銀写真用フィルム・シート;帯電防止)などに利用できる。 Therefore, conductive primer for electrostatic coating, processing and transfer of various semiconductor parts, containers and sheets for electrical and electronic parts to prevent destruction due to static electricity during storage, various electronic and electrical products (for home appliances, vehicles, For communication, etc .; electronic / electrical circuit, conductivity; thermal conductivity, electromagnetic wave shielding properties, members and parts such as heat conductive sheets that require flame resistance, magnetic recording media (audio tape, video tape, etc.); charging Prevention), display devices (liquid crystal display, organic EL display, touch panel, etc .; antistatic surface, transparent conductive film), image recording materials (for electrophotography, inkjet recording, thermal recording, thermal development, silver halide photography) Film / sheet; antistatic).
1 耐熱性反応管
2 電気炉
3 石英ボート
4 MWCNT
5 触媒(コバルト及び/又は鉄を含む炭素化合物(A)、並びにマグネシウム及び/又はアルミニウムを含む炭素化合物(B)からなる混合物の水素還元物)
1 Heat-resistant reaction tube 2 Electric furnace 3 Quartz boat 4 MWCNT
5. Catalyst (hydrogen reduction product of a mixture comprising a carbon compound (A) containing cobalt and / or iron and a carbon compound (B) containing magnesium and / or aluminum)
Claims (9)
(1)多層カーボンナノチューブの平均アスペクト比が100〜10000であり、平均外径が10〜150nmであること。ただし、多層カーボンナノチューブの平均アスペクト比、平均外径、平均長さは、以下の方法で測定、算出した値である。
a.多層カーボンナノチューブの平均アスペクト比:多層カーボンナノチューブの平均長さ/多層カーボンナノチューブの平均外径
b.多層カーボンナノチューブの平均外径:走査型電子顕微鏡を用いて倍率10000倍以上で10本の多層カーボンナノチューブを観察し、その最も太い部分を測定した値の数平均値
c.多層カーボンナノチューブの平均長さ:走査型電子顕微鏡を用いて倍率1000倍で10本の多層カーボンナノチューブを観察し、長さを測定した値の数平均値
(2)多層カーボンナノチューブの屈曲度が10°以上であること
屈曲度:走査型電子顕微鏡を用いて倍率10000倍以上で観察した任意のカーボンナノチューブ1本について、平均外径の5倍離れた任意の2点A、Bを選び、それぞれの点に接線LA、LBを引いて、接線LA、LBの交点Qの外角を5点測定した値の数平均値。
(3)走査型電子顕微鏡により倍率10000倍以上で5視野観察した場合、触媒活性金属微粒子が凝集した、カーボンナノチューブの外径より大きな径の二次粒子が観察されないこと
(4)走査型電子顕微鏡により倍率1000倍で5視野観察した場合、触媒担体に由来する無機酸化物微粒子が凝集した、径が10μm以上の二次粒子が観察されないこと
(5)以下の方法で算出した嵩密度が0.005〜0.25g/cm3であること
カーボンナノチューブ集合体を乾燥した100mlメスシリンダー(最小目盛単位:1ml)に静かに入れ、粉体層の上面を圧密せずに注意深くならし、体積を測定し嵩体積とする。カーボンナノチューブ集合体を取り出して測定した質量を嵩体積で除する。この測定、計算を3回行い、その平均値を嵩密度とする。 An aggregate of multi-walled carbon nanotubes characterized by satisfying the following conditions (1) to (5):
(1) The average aspect ratio of the multi-walled carbon nanotube is 100 to 10,000, and the average outer diameter is 10 to 150 nm. However, the average aspect ratio, average outer diameter, and average length of the multi-walled carbon nanotube are values measured and calculated by the following methods.
a. Average aspect ratio of multi-walled carbon nanotubes: average length of multi-walled carbon nanotubes / average outer diameter of multi-walled carbon nanotubes b. Average outer diameter of multi-walled carbon nanotubes: Number average value of values obtained by observing ten multi-walled carbon nanotubes with a scanning electron microscope at a magnification of 10,000 times or more and measuring the thickest part c. Average length of multi-walled carbon nanotubes: 10 multi-walled carbon nanotubes were observed at a magnification of 1000 using a scanning electron microscope, and the number average value of the measured lengths (2) The degree of bending of the multi-walled carbon nanotubes was 10 The degree of bending is not less than °. For any one carbon nanotube observed with a scanning electron microscope at a magnification of 10,000 times or more, two arbitrary points A and B separated by 5 times the average outer diameter are selected, Number average value of values obtained by drawing tangent lines LA and LB at points and measuring the outer angle of intersection Q of tangent lines LA and LB at five points.
(3) When five fields of view are observed with a scanning electron microscope at a magnification of 10,000 times or more, secondary particles having a diameter larger than the outer diameter of the carbon nanotube are not observed. (2) No secondary particles having a diameter of 10 μm or more are aggregated, and the bulk density calculated by the following method is 0.00. 005 to 0.25 g / cm 3 Gently put the aggregate of carbon nanotubes into a dry 100 ml graduated cylinder (minimum scale unit: 1 ml) and carefully measure the volume of the powder layer without consolidating the upper surface. The bulk volume. The mass measured by taking out the carbon nanotube aggregate is divided by the bulk volume. This measurement and calculation are performed three times, and the average value is defined as the bulk density.
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