200844041 九、發明說明： 【發明所屬之技術領域】 本發明涉及一種奈米碳管薄膜的製備方法。 【先前技術】 〜卞口令打子豕Ujlma首次發現奈米碳管 (Carbon N—，_以來，以奈米碳管為代表的辆 米材料以其獨特的結構和性質引起了人們極大的關注。近 幾年來’隨著奈米碳管及奈米材料研究的不斷深入，其廣 闊應用前景不斷顯現出來。例如，由於奈米碳管所具有二 獨特的電磁學、弁學、六興 i P 、 學性能等，大量有關其在 原、感測器、新型光學材料、軟鐵磁材料 域的應用研究不斷被報導。 、 呈體㈣係奈轉#實際翻的—觀要形式。 物=Γ炭管薄膜已被研究用作場發射源、光電和生 =、透明導電體、電池電極、吸波材料、水淨4 科、發光材料等。這此岸 尹化材 的f備糾Α 九的基礎’係奈米碳管薄膜 術中’奈米碳管薄膜的製備除可通過 管薄膜的方4包括用奈米破管粉末製備奈米破 法、電料 溶繼滴乾驗、L-B縣、印刷 ^水法’以及濾、膜法等。 ^而上述奈米碳管薄膜的f備方、^ 雜、製備效率較低；_ 的衣備方法的工序較為複 較差，容易破|。° r所製備的奈米碳管薄 膜的韋刃性 有鑒於此，提供_ 間早、效率較高且製備的奈米碳 6 200844041 管薄膜具有很好_性，可以彎曲折疊而Μ破裂的奈米 碳管薄膜的製備方法實為必要。 / ” 【發明内容】 -種奈米碳管薄膜的製備方法’包括：將奈米碳 管原料加人到溶劑中並進行絮化處理獲得奈米碳管 絮狀結構；以及將上述奈米碳管絮狀結構從溶劑中分 離，並對該奈米碳管絮狀結敎型處理以獲得奈米碳 管薄膜。 所述的奈米碳管原料的製備包括以下步驟：提供 奈米石厌官陣列；以及使奈米碳管陣列脫離基底，獲 得奈米碳管原料。 & ▲所述的絮化處理的方法包括超聲波分散處理或 鬲強度擾拌。 所述的溶劑為水或有機溶劑。 所述的分離奈米碳管絮狀結構的方法具體包括 以下步驟：將上述含有奈米碳管絮狀結構的溶劑倒入 放有濾紙的漏斗中；靜置乾燥—段時間從而獲得分離 的奈米碳管絮狀結構。 /斤述的定型處理具體包括以下㈣：將上述奈米 碳管絮狀結構置於m巾；將奈米碳管絮狀結構按 妝預定形狀攤開；施加一定壓力於攤開的奈米碳管絮 狀結構薄膜；以及’將溶劑烘乾或等溶劑自然揮發後 獲得奈米碳管薄膜。 所述的分離和定型處理具體包括以下步驟：提供 200844041 從孔/慮膜及一抽氣漏斗，將上述含有奈米碳爹絮狀 結構的溶劑經過微孔濾膜倒入抽氣漏斗中；抽濾並乾 燥後獲得奈米碳管薄膜。 所述的奈米碳管薄膜為1微米至2毫米。 相較於先前技術，所述的奈米碳管薄膜的製備方 法通過將奈米碳管原料進行絮化處理後使奈米碳管 相互纏繞，具有很好的韌性。而且，該製備方法可在 製備過程中對奈米碳管薄膜的厚度和面密度進行控 制’工序簡單，易於實際應用。 【實施方式】 以下將結合附圖對本發明作進一步之詳細說明。 請參閱圖1，本實施例奈米碳管薄膜的製備方法主 要包括以下步驟·· 步驟一：提供一奈米碳管陣列，優選地，該陣列 為超順排奈米碳管陣列。 本實施例中，奈米碳管陣列的製備方法採用化學 氣相沉積法，其具體步驟包括：（a)提供一平整基底， 該基底可選用p型或N型石夕基底，或選用形成有氧化 層的矽基底，本實施例優選為採用4英寸的矽基底； (b)在基底表面均勻形成一催化劑層，該催化劑層 材料:選用鐵（Fe)、鉛（㈤、鎳（Ni)或其任意組 合的合金之一；（c)將上述形成有催化劑層的基底在 700〜90(TC的空氣中退火約3〇分鐘〜9〇分鐘：⑷將 處理過的基底置於反應爐中，在保護氣體環境下加埶 200844041 到500〜740 C，然後通入碳源氣體反應約5〜3〇分鐘， 生長得到奈米碳管陣列，其高度大於1〇〇微米。該奈 米石反官陣列為多個彼此平行且垂直於基底生長的奈 米石反官形成的純奈米碳管陣列，由於生成的奈米碳管 長度較長，部分奈米碳管會相互纏繞。通過上述控制 生長條件，該超順排奈米碳管陣列中基本不含有雜 質，如無定型碳或殘留的催化劑金屬顆粒等。本實施 例中妷源氣可選用乙炔等化學性質較活潑的碳氫化 口物，保護氣體可選用氮氣、氨氣或惰性氣體。可以 理解的係，本實施例提供的奈米碳管陣列不限於上述 製備方法。 步驟二：使奈米碳管陣列脫離基底，獲得奈米碳 管原料。 本貝知例優运採用刀片或其他工具將奈米碳管從 基底刮落，獲得奈米碳管原料，其中奈米碳管一定程 度上保持相互纏繞的狀態。 步驟三··將上述奈米碳管原料添加到溶劑中並進 行絮化處理獲得奈米碳管絮狀結構。 本實施例中，溶劑可選用水、易揮發的有機溶劑 等。絮化處理可通過採用超聲波分散處理或高強度攪 拌等方法。優選地，本實施例採用超聲波分散1〇〜3〇 刀在里由於奈米石反管具有極大的比表面積，相互纏繞 的奈米碳管之間具有較大的凡德瓦爾力。上述絮化處 理亚不會將奈米碳管原料中的奈米碳管完全分散在 200844041 溶劑中，溶劑中的本 π不水奴官之間通過凡德瓦爾力相互 吸引、纏繞，形成網路狀結構。 ， +步驟將上述奈米碳管絮狀結構從溶劑中分 ί二！對°亥不米蚊管絮狀結構定型處理以獲得奈米碳 本實= 例中’分離奈米碳管絮狀結構的方 f括;了：將上述含有奈米碳管絮狀結構的溶劑 倒入放有慮紙的漏斗中；靜置乾燥一段時間從而 分離的奈米石炭管絮狀結構。請參閱圖2,為置於^氏 上的奈米碳管絮狀結構。可以看 _ ^ 繞成不規則的絮狀結構。 $ ”官相互纏 .定型處理具體包括以下步驟：將上述奈米碳管絮 狀結構置於一容哭中·膝太止山μ 、 疋[力於攤開的奈米碳管絮狀結 ΐ二 碳管絮狀結構中殘留的溶劑供乾或 :、洛劑自然揮發後獲得奈米碳管薄膜。可以理解，本 f施例可通過控制奈㈣管絮狀結構攤片的面積來 :制奈米碳管薄膜的厚度和面密度。攤片的面積越 大，則奈米碳管薄膜的厚度和面密度就越小。本 例中獲得的奈米碳管薄膜的厚度為ι微米至2毫^。 的方另二It離與定型處理步驟也可直接通過抽濾200844041 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for preparing a carbon nanotube film. [Prior Art] ~ 卞 打 豕 豕 Ujlma first discovered the carbon nanotubes (Carbon N-, _, the rice material represented by the carbon nanotubes has attracted great attention due to its unique structure and properties. In recent years, with the deepening of research on carbon nanotubes and nanomaterials, its broad application prospects have been continuously revealed. For example, because of the unique magnetism, dropout, and Liuxing i P, Performance, etc., a large number of applications related to its application in the original, sensor, new optical materials, soft ferromagnetic material fields have been reported., the body (4) is the nai turn # actual turn - view the form. Has been studied as a field emission source, photoelectric and raw =, transparent conductors, battery electrodes, absorbing materials, water net 4, luminescent materials, etc. This is the basis of the yin yin material In the tube film, the preparation of the nanotube film can be carried out except that the tube film can be used to prepare the nano-breaking method, the nano-disinfection method, the LB county, the printing method, and the filtration. , membrane method, etc. ^ and the above Nai The m-carbon tube film has a low preparation ratio, low preparation efficiency, and the preparation process of the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Providing _ early, efficient and prepared nanocarbon 6 200844041 tube film has a good _ sex, can be bent and folded Μ ruptured carbon nanotube film preparation method is necessary. / ” [Summary] The preparation method of the carbon nanotube film comprises: adding a carbon nanotube raw material to a solvent and performing a flocculation treatment to obtain a nano carbon tube floc structure; and the above-mentioned nano carbon tube floc structure from the solvent Separating and treating the carbon nanotube flocculent type to obtain a carbon nanotube film. The preparation of the carbon nanotube raw material comprises the following steps: providing a nano-stone array; and making the nanocarbon The tube array is detached from the substrate to obtain a carbon nanotube raw material. & ▲ The method for flocculation treatment includes ultrasonic dispersion treatment or enthalpy strength. The solvent is water or an organic solvent. Tube floc structure method specific package The following steps are included: the above solvent containing the carbon nanotube floc structure is poured into a funnel provided with a filter paper; the drying is allowed to dry for a period of time to obtain a separated carbon nanotube floc structure. Including the following (4): placing the above-mentioned nano carbon tube floc structure on the m towel; spreading the nano carbon tube floc structure in a predetermined shape; applying a certain pressure to the spread of the carbon nanotube floc structure film; 'The solvent is dried or the solvent is naturally volatilized to obtain a carbon nanotube film. The separation and sizing treatment specifically includes the following steps: providing 200844041 from the hole/film and an extraction funnel, the above containing nanocarbon 爹The solvent of the floc structure is poured into the suction funnel through the microporous membrane; the carbon nanotube film is obtained by suction filtration and drying. The carbon nanotube film is 1 micrometer to 2 mm. Compared with the prior art, the preparation method of the carbon nanotube film has excellent toughness by pulverizing the carbon nanotubes by flocculation of the carbon nanotube raw materials. Moreover, the preparation method can control the thickness and the areal density of the carbon nanotube film during the preparation process, and the process is simple and easy to apply. [Embodiment] Hereinafter, the present invention will be further described in detail with reference to the accompanying drawings. Referring to Fig. 1, the preparation method of the carbon nanotube film of the present embodiment mainly comprises the following steps: Step 1: provide a carbon nanotube array, preferably, the array is a super-sequential carbon nanotube array. In this embodiment, the method for preparing the carbon nanotube array adopts a chemical vapor deposition method, and the specific steps thereof include: (a) providing a flat substrate, the substrate may be selected from a p-type or N-type stone base substrate, or alternatively formed The ruthenium substrate of the oxide layer is preferably a 4-inch ruthenium substrate in this embodiment; (b) a catalyst layer is uniformly formed on the surface of the substrate, and the catalyst layer material is selected from iron (Fe), lead ((5), nickel (Ni) or One of the alloys of any combination thereof; (c) the substrate on which the catalyst layer is formed is annealed in air of 700 to 90 (TC for about 3 minutes to 9 minutes: (4) the treated substrate is placed in a reaction furnace, Adding 200844041 to 500~740 C in a protective gas atmosphere, and then reacting with a carbon source gas for about 5 to 3 minutes, growing to obtain a carbon nanotube array having a height greater than 1 〇〇 micron. The array is a plurality of pure carbon nanotube arrays formed by a plurality of nano-stones that are parallel to each other and perpendicular to the substrate. Since the length of the formed carbon nanotubes is long, some of the carbon nanotubes are entangled with each other. Condition, the super-shunned nano The tube array contains substantially no impurities, such as amorphous carbon or residual catalyst metal particles, etc. In the present embodiment, the source gas may be a chemically active hydrocarbon port such as acetylene, and the shielding gas may be nitrogen or ammonia. Inert gas. It is understood that the carbon nanotube array provided in this embodiment is not limited to the above preparation method. Step 2: The carbon nanotube array is separated from the substrate to obtain a carbon nanotube raw material. A blade or other tool scrapes the carbon nanotubes from the substrate to obtain a carbon nanotube raw material, wherein the carbon nanotubes are kept entangled to some extent. Step 3· Adding the above carbon nanotube raw materials to the solvent And the flocculation treatment is carried out to obtain a nano carbon tube floc structure. In this embodiment, the solvent may be selected from water, a volatile organic solvent, etc. The flocculation treatment may be carried out by using ultrasonic dispersion treatment or high-strength stirring, etc. Preferably, In this embodiment, ultrasonic dispersion 1〇~3 boring tool is used. Since the nanometer stone has a large specific surface area, the intertwined carbon nanotubes have a large relationship between them. Van der Valli. The above flocculation treatment does not completely disperse the carbon nanotubes in the carbon nanotube raw material in the solvent of 200844041. The π waterless slaves in the solvent attract each other through the van der Waals force. Winding, forming a network-like structure. + Steps to separate the above-mentioned nano-carbon tube floc structure from the solvent! The shaping of the floc structure of the 亥米米米 mosquito tube to obtain the nano-carbon real = in the example Separating the carbon nanotube floc structure; pouring: the above solvent containing the carbon nanotube floc structure into the funnel placed in the paper; standing and drying for a period of time to separate the nano-carbon tube Fig. 2 shows the structure of the carbon nanotubes placed on the surface of the carbon nanotubes. It can be seen that _ ^ is wound into an irregular floc structure. $ ” Intertwined. The shaping process specifically includes the following steps: The above-mentioned carbon nanotube floc structure is placed in a crying, knee-toothed mountain μ, 疋 [strengthen the solvent remaining in the flocculent structure of the carbon nanotubes of the carbon nanotubes of the carbon nanotubes or the: The carbon nanotube film is obtained after the natural evaporation of the agent. It can be understood that the present embodiment can control the thickness of the carbon nanotube film and the areal density by controlling the area of the n. The larger the area of the tile, the smaller the thickness and areal density of the carbon nanotube film. The carbon nanotube film obtained in this example has a thickness of from 1 to 2 m. The other side of the It and the setting process can also be directly filtered through the suction
St:: 薄臈’具體包括以下步驟:提供 沾1 “、抽虱漏斗；將上述含有奈米碳管絮狀 、.，。構的溶劑經過微孔遽臈倒入抽氣漏斗中；抽遽並乾 200844041 燥後獲得奈料管薄膜。該微孔_為_表面$滑、 孔徑為0.22微米的濾膜。由於抽濾方式本身將：供 -較大的氣壓作用于奈米碳管絮狀結構，該奈米碳管 絮狀結構經過抽濾會直接形成—均勻的夺：碳“ :。且’由於微孔濾膜表面光滑，該奈米碳管薄膜容 易剝離。 請參閱圖3,本實施例獲得的奈料管薄膜中，由 於奈米碳管相互纏繞，因此具有㈣ 曲折豐成任意形狀而不破裂。 本實施例中奈米碳管薄膜的製備方法具有以下優 點.其-，通過將奈米碳管原料進行絮化處理後使夺 米碳管相互賴，具有很好的㈣；其二，該製備方 法可在製備過程中對奈米石炭管薄膜的厚度和面密度 進行控制，工序簡單，易於實際應用。 綜上所述，本發明確已符合發明專利之要件，遂 依法提出專射請。惟’以上所述者僅為本發明之較 佳實施例’自不能錢限制本案之申請專·圍。舉 凡熟悉本案技藝之人士援依本發明之精神所作之等 效修飾或變化，皆應涵蓋於以下申請專利範圍内。 【圖式簡單說明】 示意圖。 圖1係本發明實施例奈米薄膜的製備方法的流程 圖 片 11 200844041 圖3係本發明實施例獲得的預定形狀的奈_碳管 薄膜的照片。 【主要元件符號說明】 12St:: 臈 臈 ' 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 具体 臈 臈 、 、 、 、 、 、 、 、 、 、 、 、 、 And dried 200844041 to obtain the film of the tube. The microporous_ is a filter with a surface of $slip and a pore size of 0.22 micrometer. Since the suction filtration method itself will be: the larger air pressure acts on the carbon nanotube floc Structure, the carbon nanotube floc structure is directly formed by suction filtration - uniform capture: carbon ":. And because the surface of the microporous membrane is smooth, the carbon nanotube film is easily peeled off. Referring to Fig. 3, in the naphthalmic tube film obtained in this embodiment, since the carbon nanotubes are intertwined with each other, they have (4) zigzag into any shape without cracking. The preparation method of the carbon nanotube film in the embodiment has the following advantages. It has good (4) by subjecting the carbon nanotube raw material to flocculation treatment, and has good (4); second, the preparation The method can control the thickness and the areal density of the nano-carboniferous film during the preparation process, and the process is simple and easy to be practically applied. In summary, the present invention has indeed met the requirements of the invention patent, and 提出 legally proposed special shots. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the application of the case. Equivalent modifications or variations made by those skilled in the art to the spirit of the invention are intended to be included within the scope of the following claims. [Simple description of the diagram] Schematic. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a method for preparing a nano film according to an embodiment of the present invention. Fig. 11 200844041 Fig. 3 is a photograph of a carbon nanotube film of a predetermined shape obtained in an embodiment of the present invention. [Main component symbol description] 12