201125814 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種奈米碳管結構之製備方法。 【先前技#于】 [0002] 奈米碳管（Carbon Nanotube, CNT)係一種由石墨稀片 卷成之中空管狀物，其具有優異之力學、熱學及電學性 質，故具有廣闊之應用領域。由於單根奈米碳管之尺寸 為奈米級，難於進行加工，為便於實際應用，人們嘗試 將複數奈米碳管作為原材料，製成具有較大尺寸之宏觀 結構。該宏觀結構由複數奈米碳管組成，可以係膜狀、 線狀或其他形狀。先前技術中一般將由複數奈米碳管組 成之宏觀膜狀結構稱為奈米破管膜（Carbon Nanotube Film)，將由複數奈米碳管組成之宏觀線狀結構稱為奈 米碳管線（Carbon Nanotube Wire)或奈米碳管線繞 (Carbon Nanotube Cable)。姜開利等人於2008年 11月21日公告之第1303239號台灣發明專利說明書中揭 露了一種從奈米碳管陣列中直接拉取獲得之奈米碳管線 ，這種奈米碳管線具有宏觀尺度且能夠自支撐，其包括 複數在凡德瓦爾力作用下首尾相連之奈米碳管。由於該 奈米碳管線中奈米碳管基本沿同一方向排列，故該奈米 碳管線能夠較好之發揮奈米碳管軸向具有之導電及導熱 等各種優異性質，具有極為廣泛之應用前景。另外，與 上述拉取奈米碳管線相似地，可從奈米碳管陣列中拉取 一奈米碳管膜。 [0003] 先前技術中之奈米碳管陣列一般採用化學氣相沈積法生 099102136 表單編號A0101 第4頁/共37頁 0992004110-0 201125814 Ο Ο [0004]201125814 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a method for preparing a carbon nanotube structure. [Previous Technology #于] [0002] Carbon Nanotube (CNT) is a hollow tube made of graphite flakes. It has excellent mechanical, thermal and electrical properties and therefore has a wide range of applications. Since the size of a single carbon nanotube is nanometer-scale, it is difficult to process. For practical application, it is attempted to use a plurality of carbon nanotubes as a raw material to form a macrostructure having a large size. The macrostructure consists of a plurality of carbon nanotubes and may be in the form of a film, a line or other shape. In the prior art, a macroscopic membrane structure composed of a plurality of carbon nanotubes is generally called a Carbon Nanotube Film, and a macroscopic linear structure composed of a plurality of carbon nanotubes is called a carbon nanotube (Carbon Nanotube). Wire) or Carbon Nanotube Cable. In the Taiwan invention patent specification No. 1303239 published on November 21, 2008 by Jiang Kaili et al., a nanocarbon pipeline obtained by directly pulling from a carbon nanotube array is disclosed, which has a macroscopic scale and Self-supporting, including a plurality of carbon nanotubes connected end to end under the action of Van der Waals force. Since the carbon nanotubes in the nano carbon pipeline are arranged substantially in the same direction, the nanocarbon pipeline can better exert various excellent properties such as conductivity and heat conduction in the axial direction of the carbon nanotube, and has a wide application prospect. . Alternatively, a carbon nanotube membrane can be pulled from the array of carbon nanotubes similarly to the above-described drawn nanocarbon line. [0003] The prior art carbon nanotube arrays are generally produced by chemical vapor deposition. 099102136 Form No. A0101 Page 4 of 37 0992004110-0 201125814 Ο Ο [0004]
[0005] 099102136 長獲得，具體為將一平整之圓形矽片作為基底，一表面 形成一催化劑薄膜，放置於反應爐中加熱，並通入碳源 氣及保護氣體，該碳源氣在矽片表面之催化劑作用下分 解，並在矽片表面生長獲得平面圓形之奈米碳管陣列。 目前用於生長奈米碳管陣列之反應爐通常為管式反應爐 。由於在上述生長過程中，管式反應爐内之氣壓小於爐 外之大氣壓力，管式反應爐之爐壁將承受向内之壓力， 使該管式反應爐之内徑難以做到很大。一般地，當管式 反應爐之直徑為10英寸，長度為2米，内部氣壓為10托（ Torr)時，内外壁壓力差為5萬牛頓。而當管式反應爐之 直徑增加到40英寸時，内外壁壓力差可達到20萬牛頓。 並且，當直徑增加時，由於管式反應爐之爐壁曲率下降 ，其支撐作用也會減弱，使管式反應爐之穩定性和使用 壽命受到影響。 故，當採用圓形矽片作為基底在管式反應爐内生長奈米 碳管陣列時，該圓形矽片之最大直徑受到管式反應爐内 之直徑之限制，使生長於其上之奈米碳管陣列之最大直 徑亦受到限制，從而使從該圓形矽片生長之奈米碳管陣 列中拉取之奈米碳管結構之尺寸，如奈米碳管膜之寬度 、面積或奈米碳管線之長度受到限制。 【發明内容】 有鑒於此，提供一種能夠獲得尺寸較大之奈米碳管結構 之製備方法實為必要。 一種奈米碳管結構之製備方法，其包括以下步驟：提供 一筒狀奈米碳管陣列；採用一拉伸工具與該筒狀奈米碳 表單編號A0101 第5頁/共37頁 0992004110-0 [0006] 201125814 管陣列接觸，從該筒狀奈米碳管陣列中選定一奈米碳管 片段；以及沿該筒狀奈米碳管陣列之徑向方向移動該拉 伸工具遠離該筒狀奈米碳管陣列，拉取該選定之奈米碳 管片段，從而形成一奈米碳管結構，該奈米碳管結構一 端連接該拉伸工具，另一端連接該筒狀奈米碳管陣列， 在拉伸過程中，在所述奈米碳管結構與該筒狀奈米碳管 陣列之連接處，該筒狀奈米碳管陣列之切面與該奈米碳 管結構成一角度，該角度大於等於〇度，小於等於60度。 [0007] 相較於先前技術，由於該奈米碳管陣列為筒狀，故在相 同之先前反應爐中製備之該筒狀奈米碳管陣列比平面奈 米碳管陣列具有更大之尺寸，使從中拉取獲得之奈米碳 管結構也具有更大之尺寸。 【實施方式】 [0008] 以下將結合附圖詳細說明本發明實施例奈米碳管結構之 製備方法。 [0009] 請參閱圖1至圖6，本發明第一實施例提供一種奈米碳管 結構100之製備方法，其包括以下步驟： [0010] 步驟一：提供一筒狀奈米碳管陣列120。 [0011] 步驟二：採用一拉伸工具與該筒狀奈米碳管陣列120接觸 ，從該筒狀奈米碳管陣列120中選定一奈米碳管片段143 〇 [0012] 步驟三：使該拉伸工具沿該筒狀奈米碳管陣列120之徑向 方向移動，並遠離該筒狀奈米碳管陣列120拉取該選定之 奈米碳管片段143，從而形成一奈米碳管結構100，該奈 099102136 表單編號A0101 第6頁/共37頁 0992004110-0 201125814 来碳管結構100—端連接該拉伸工具’另一端連接該筒狀 奈米碳管陣列120，在拉伸過程中，在所述奈米碳管結構 100與該筒狀奈米礙管陣列120之連接處，該筒狀奈米碳 管陣列120之切面與該奈米碳管結構1〇〇成一角度。 [0013] 下面分別對各步驟展開說明。 [0014]首先對步驟一進一步說明。該筒狀奈米碳管陣列12〇係通 過化學氣相沈積法形成於一基底140表面，優選為超順排 Ο 之筒狀奈米碳管陣列12 0。本實施例中，該超順排筒狀奈 Ο 米碳管陣列120之製備方法具體包括： [0015] (a)提供一基底140，該基底140包括至少一枉面； [0016] ( b )在該基底14 0之所述至少一柱面上均勻形成一催化 劑層； [0017] (c)將上述形成有催化劑層之基底140在30(TC〜90〇°c 之空氣中退火約30分鐘~90分鐘； [0018] (d)將基底140置於反應爐中，在森護氣體環境下加熱 到400°C〜900°C，然後通入碳源氣體反應約5分鐘〜30分 鐘，生長得到超順排之筒狀奈米碳管陣列120。 [0019] 該基底140為筒狀體，其外周面可形成所述柱面，其中該 柱面可為圓柱面、橢圓枉面或具有導角之棱柱面，該棱 柱面包括三棱柱面或四棱柱面等；可進一步在筒狀體外 周面筒壁沿筒狀體軸向設置長條狀開口，該長條狀開口 平行於筒狀體之軸向，從而形成轴向具有開口之柱面， 此時該筒狀體之橫截面呈未封閉之圓、橢圓或者圓角多 0992004110-0 099102136 表單編號A0101 第7頁/共37頁 201125814 之 為枝描述’將設有開口（未封閉）和未設有 ，口（封閉）之這兩種情況統稱為筒狀體。且體地 參閱圖在本實施例中，該基底140係截面為圓形之筒 狀體’所述筒狀奈米碳管陣列12〇形成於該筒狀體之外周 面，攸而形成—筒狀奈米碳管陣列120。請參閱圖3 ’該 基底140a可以為具有—平行於筒狀體軸向之開口⑷之未 $閉筒狀體，該筒狀體之橫截面為未封閉之圓形。所述 同狀奈米碳管陣列12〇a形成於該未封閉筒狀體之外周面 ，形成一未封閉之筒狀奈米碳管陣歹,m〇a，即該未封閉 .筒狀奈米碳管陣列12〇3包括一平行於該筒狀奈米碳管 陣列12〇a轴向之開口。請參閱圖4，該基底U〇b也可以 係截面為矩形之筒狀體，該矩形具有圓角144。所述筒狀 奈米碳管陣列12〇b形成於該筒狀體之外周面，形成一封 閉之筒狀奈米碳管陣列12〇13。請參閱圖5，該基底14〇c 還可以為具有一平行於筒狀體轴向之開口 142之未封閉筒 狀體’該筒狀體之截面為未封閉之圓肖_。所述筒狀 奈米碳管陣列120c形成於該未封閉筒狀體之外周面，形 成一未封閉之筒狀奈米碳替陣列120 C ,即該未封閉之筒 狀奈米碳管陣列120c包括一平行於該筒狀奈米碳管陣列 軸向之開口。可以理解，所述基底不限於上述形狀，該 基底之截面也可係橢圓或者具有圓角之其他多邊形等。 [0020]該基底也可以包括但不限於以下形狀，從而得到所述柱 面：該基底可為柱狀體（實心體），該柱狀體外周面形 成所述柱面，其中，與上述筒狀體相似，該柱狀體之橫 截面可以係圓、擴圓或者圓角多邊形，也可進一步在柱 099102136 表單編號A0101 第8頁/共37頁 0992004110-0 201125814 狀體外周面沿軸向設置長條狀溝槽，從而形成轴向具有 缺口之柱面，此時該柱狀體之橫戴面呈未封閉之圓、橢 圓或者圓角多邊形等。 [〇〇21]該基底可選用石英基底、耐高溫破螭基底、P型或N型矽 基底’金屬基底、或選用形成有氧化層之石夕基底，本實 施例中，該基底140優選為一具有較為平滑表面之石英管 Ο 〇 ❹ 〇 [㈤22] 該催化劑層材料可選用鐵（Fe)、鈷（Co)、錄（Ni) 或其任意組合之合金之一，優選為約5奈米厚之鐵催化劑 層。該催化劑層可形成在該石英管之外周面。 [0023] 當所述反應爐為管式反應爐時，該基底140可沿管式反應 爐之軸向設置於該管式反應爐内，即該基底14〇之轴線方 向平行於管式反應爐之軸線方向。進一步地，可通過一 支架支撐該基底140之兩端，該支架可使該基扈140懸於 該反應爐内並可繞該基底140之軸線方向名位旋轉。該碳 源氣可選用乙炔、乙稀、乙烷等，優選為乙炔等化學性 質較活潑之碳氫化合物，保護氣體可選用氮氣、氨氣或 惰性氣體。 [0024] 該筒狀奈米碳管陣列120包括複數奈米碳管，其中，大多 數奈米碳管基本彼此平行且垂直於該基底140表面。該筒 狀奈米碳管陣列120之頂面為與該基底140表面平行之柱 面。通過上述控制生長條件，該筒狀奈米碳管陣列120中 基本不含有雜質，如無定型碳或殘留之催化劑金屬顆粒 等。該筒狀奈米碳管陣列120中之奈米碳管彼此通過凡德 099102136 表單編號A0101 第9頁/共37頁 0992004110-0 201125814 瓦爾力緊密接觸形成陣列。該筒狀奈米碳管陣列120之生 長面積可以與上述基底140面積基本相同。該筒狀奈米碳 管陣列120中之奈米碳管可以至少包括單壁奈米碳管、雙 壁奈米碳管及多壁奈米碳管中之一種。該筒狀奈米碳管 陣列120中奈米碳管之高度為2微米〜10毫米，優選為 100〜900微米。該奈米碳管之直徑為1〜50奈米。 [0025] 其次，對步驟二進一步說明，請參閱圖6，在該步驟中， 該奈米碳管片段143由該筒狀奈米碳管陣列1 20中之一個 或相鄰之複數奈米碳管145組成，該複數奈米碳管145通 過凡德瓦爾力相互作用。該拉伸工具用於選定並拉取該 奈米碳管片段143。該拉伸工具可以為鑷子、夾子、膠帶 或表面具有黏膠之硬質基條。該選定所述奈米碳管片段 143之過程可以係採用鑷子或夾子夾取筒狀奈米碳管陣列 120中之部分奈米碳管145，或者係採用膠帶或基條之黏 膠接觸該筒狀奈米碳管陣列120。 [0026] 具體地，所述拉伸工具可直接沿平行於所述筒狀奈米碳 管陣列120之軸線方向選定所述奈米碳管片段143，請參 閱圖3，當該筒狀奈米碳管陣列120a具有一開口時，所述 拉伸工具可從該筒狀奈米碳管陣列120a靠近開口之邊緣 處沿平行於所述筒狀奈米碳管陣列120a之軸線方向選定 所述奈米碳管片段，從而避免有不參與後續拉伸之奈米 碳管黏結到拉伸工具上，降低所拉伸獲得之奈米碳管結 構100之品質。 [0027] 當該拉伸工具選定之奈米碳管片段143之寬度與所述筒狀 奈米碳管陣列120之軸長度（沿平行於基底140之軸線方 099102136 表單編號A0101 第10頁/共37頁 0992004110-0 201125814 向之尺寸）相同時，該拉伸工具可在後續杈伸之步驟之 後獲得一具有固定寬度之奈米碳管膜或固芩直徑之奈米 碳管線。 剛最後，對步驟三進—步說明。所述徑向指垂直於筒狀奈 米碳管陣列120轴向之方向。具體地，該拉伸工具沿該筒 狀奈来礙管陣列12〇之徑向方向移動之過程中由於相鄰 之奈米礙管之間存在相互之凡德瓦爾力作用從而使複 Ο 數不米被^首尾相連地被連續拉出，即該奈米碳管結構 〇 100中之奈米碳管連續不斷地從該筒狀奈米碳管陣列12〇 中拉出，進而形成一連續之奈米碳管結構100。另外，由 於所述基底140可活動且可繞其軸向原位旋轉故當所述 拉伸X具在外力之作用下逐漸移動時，所述基底也可 在外力之作用下同時繞其轴向原位旋轉以補償筒狀奈米 厌吕陣列120中奈米碳管之消耗，從而在筒狀奈米碳管陣 列120中之奈米碳管逐漸脫難所述基底14〇。另外，若所 〇 絲底14G固定不峡轉，賴述拉伸工具可在拉伸過程 〇 中隨者奈米碳管逐_離所述基底14 0之同時繞該基底 140逐漸驢拉伸位以確㈣償所述筒狀奈米碳管陣列 120之消耗。該奈米嚷營結構_可以為_奈来碳管膜或 一奈米碳管線。該形成之奈米破管結構咖係奈米碳管線 還係奈米碳管膜由該技伸工具選定之奈米碳管片段143之 寬度決定。 [0029] 此外在拉伸過程巾，在所述奈米碳管結構⑽與該筒狀 奈米破管陣列120之連接處，該筒狀奈米碳管陣列12〇之 切面與該奈米碳管結構1〇〇需成-角度，該角度可大於等 099102136 表單編號A0101 第11灵/共37頁 0992004110-0 201125814 於0度，小於等於60度，優選為大於0度小於等於15度， 本實施例中，該角度為15度。具體為，如果該角度為0° ，所拉出之奈米碳管結構100容易與所述筒狀奈米碳管陣 列120之生長基底140接觸，由於生長基底140可能殘留 有催化劑或無定形碳，這些雜質會吸附到奈米碳管結構 上影響該奈米碳管結構之品質；若角度太大，奈米碳管 結構中奈米碳管片段之間之凡德瓦爾力會變小，使得奈 米碳管片斷結合不牢固，容易破裂。 [0030] 以下將分別就該形成奈米碳管線及奈米碳管膜之兩種情 況進行具體介紹。 [0031] 當該選定之奈米碳管片段之寬度較窄時，可形成一奈米 碳管線。具體地，當該拉伸工具沿該筒狀奈米碳管陣列 120之徑向方向拉取該奈米碳管片段時，與該選定之奈米 碳管片段相鄰之奈米碳管片段通過凡德瓦爾力之作用被 首尾相連地不斷從筒狀奈米碳管陣列120中拉出並形成一 奈米碳管線。 [0032] 另外，當所選定之奈米碳管片段之寬度較寬時，通過拉 伸可形成一寬度較窄之奈米碳管膜，為形成一奈米碳管 線，該過程可進一步包括採用一有機溶劑處理該寬度較 窄之奈米碳管膜，使該奈米碳管膜中之奈米碳管迅速在 聚攏形成所述奈米碳管線。本實施例具體為使該奈米碳 管膜通過該有機溶劑浸潤並彙聚成奈米碳管線後使該有 機溶劑揮發。該有機溶劑為揮發性有機溶劑，如乙醇、 曱醇、丙酮、二氣乙烷或氣仿，本實施例中採用乙醇。 請參閱圖7和圖8，在揮發性有機溶劑揮發時產生之表面 099102136 表單編號Α0101 第12頁/共37頁 0992004110-0 201125814 張力之作用下，該奈米碳管膜中之奈米碳管通過凡德瓦 爾力聚攏，從而形成一非扭轉之奈米碳管線102。 [0033] 該形成奈米碳管線之過程還可進一步包括扭轉所述碳米 管膜，從而使所述奈米碳管膜扭轉成一扭轉之奈米碳管 線，具體可在移動所述拉伸工具之同時，使該拉伸工具 繞拉伸工具之移動方向旋轉該拉伸工具，從而使奈米碳 管膜也隨之旋轉，從而形成一扭轉之奈米碳管線。 〇 [0034] Ο[0005] 099102136 long obtained, specifically, a flat circular bract is used as a substrate, a catalyst film is formed on a surface, placed in a reaction furnace for heating, and a carbon source gas and a shielding gas are introduced, and the carbon source gas is in the crucible. Decomposes under the action of the catalyst on the surface of the sheet, and grows on the surface of the sheet to obtain a planar circular carbon nanotube array. The reactors currently used to grow carbon nanotube arrays are typically tubular reactors. Since the gas pressure in the tubular reactor is less than the atmospheric pressure outside the furnace during the above growth process, the wall of the tubular reactor will be subjected to the inward pressure, making the inner diameter of the tubular reactor difficult to achieve. Generally, when the tubular reactor has a diameter of 10 inches, a length of 2 meters, and an internal gas pressure of 10 Torr, the pressure difference between the inner and outer walls is 50,000 Newtons. When the diameter of the tubular reactor is increased to 40 inches, the pressure difference between the inner and outer walls can reach 200,000 Newtons. Further, when the diameter is increased, since the curvature of the furnace wall of the tubular reactor is lowered, the supporting action is also weakened, and the stability and service life of the tubular reactor are affected. Therefore, when a carbon nanotube array is grown in a tubular reactor using a circular cymbal as a substrate, the maximum diameter of the circular cymbal is limited by the diameter in the tubular reactor, so that it grows on it. The maximum diameter of the carbon nanotube array is also limited, so that the size of the carbon nanotube structure drawn from the carbon nanotube array grown by the circular cymbal, such as the width, area or area of the carbon nanotube membrane The length of the carbon carbon pipeline is limited. SUMMARY OF THE INVENTION In view of the above, it is necessary to provide a method of preparing a carbon nanotube structure having a large size. A method for preparing a carbon nanotube structure, comprising the steps of: providing a cylindrical carbon nanotube array; using a stretching tool and the cylindrical carbon form number A0101, page 5 of 37, 0992004110-0 [0006] 201125814 tube array contact, selecting a carbon nanotube segment from the cylindrical carbon nanotube array; and moving the stretching tool away from the tubular nai in a radial direction of the cylindrical carbon nanotube array An array of carbon nanotubes, the selected carbon nanotube segments are pulled to form a carbon nanotube structure, the carbon nanotube structure is connected at one end to the stretching tool, and the other end is connected to the cylindrical carbon nanotube array. During the stretching process, at the junction of the carbon nanotube structure and the tubular carbon nanotube array, the section of the cylindrical carbon nanotube array is at an angle to the carbon nanotube structure, the angle being greater than It is equal to the degree of twist, less than or equal to 60 degrees. [0007] Compared to the prior art, since the carbon nanotube array is cylindrical, the cylindrical carbon nanotube array prepared in the same previous reactor has a larger size than the planar carbon nanotube array. The carbon nanotube structure obtained from the drawing is also of a larger size. [Embodiment] Hereinafter, a method of preparing a carbon nanotube structure according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings. Referring to FIG. 1 to FIG. 6 , a first embodiment of the present invention provides a method for preparing a carbon nanotube structure 100, which includes the following steps: [0010] Step 1: providing a tubular carbon nanotube array 120 . [0011] Step 2: contacting the tubular carbon nanotube array 120 with a stretching tool, and selecting a carbon nanotube segment 143 from the tubular carbon nanotube array 120 [0012] Step 3: The stretching tool moves in a radial direction of the tubular carbon nanotube array 120, and pulls the selected carbon nanotube segment 143 away from the cylindrical carbon nanotube array 120 to form a carbon nanotube. Structure 100, the Nai 099102136 Form No. A0101 Page 6 / Total 37 Page 0992004110-0 201125814 The carbon tube structure 100-end connection of the stretching tool 'the other end is connected to the cylindrical carbon nanotube array 120 during the stretching process The junction of the tubular carbon nanotube array 120 and the tubular carbon nanotube array 120 are at an angle to the carbon nanotube structure 1 at the junction of the carbon nanotube structure 100 and the tubular nanotube array 120. [0013] The following describes each step separately. [0014] First, step one is further explained. The tubular carbon nanotube array 12 is formed on the surface of a substrate 140 by chemical vapor deposition, preferably a super-arranged cylindrical carbon nanotube array 120. In this embodiment, the method for preparing the super-sequential tubular carbon nanotube array 120 specifically includes: [0015] (a) providing a substrate 140, the substrate 140 including at least one surface; [0016] (b) Forming a catalyst layer uniformly on the at least one cylinder surface of the substrate 140; (c) annealing the substrate 140 on which the catalyst layer is formed in an atmosphere of 30 (TC to 90 ° C for about 30 minutes) [0018] (d) The substrate 140 is placed in a reaction furnace, heated to 400 ° C to 900 ° C in a protective atmosphere, and then passed through a carbon source gas for about 5 minutes to 30 minutes to grow. The super-aligned cylindrical carbon nanotube array 120 is obtained. [0019] The substrate 140 is a cylindrical body, and the outer peripheral surface thereof can form the cylindrical surface, wherein the cylindrical surface can be a cylindrical surface, an elliptical surface or a guide a prismatic surface of the corner, the prism surface includes a triangular prism surface or a quadrangular prism surface; and further, an elongated opening may be further disposed in the cylindrical outer circumferential wall along the axial direction of the cylindrical body, the elongated opening parallel to the cylindrical body The axial direction, thereby forming a cylindrical surface having an opening in the axial direction, and the cross section of the cylindrical body is an unclosed circle, an ellipse or Rounded corners 0992004110-0 099102136 Form No. A0101 Page 7 of 37 201125814 Description of the branch 'The two cases of opening (unclosed) and not provided, mouth (closed) are collectively referred to as the cylinder In the present embodiment, the base 140 is a cylindrical tubular body having a circular cross section. The cylindrical carbon nanotube array 12 is formed on the outer peripheral surface of the cylindrical body, and is formed by the cymbal. Cylindrical carbon nanotube array 120. Please refer to Fig. 3 'The base 140a may be an unclosed cylindrical body having an opening (4) parallel to the axial direction of the cylindrical body, the cylindrical body having an unclosed cross section a circular shape. The same shape of the carbon nanotube array 12〇a is formed on the outer peripheral surface of the unsealed cylindrical body to form an unsealed tubular carbon nanotube array, m〇a, that is, the unclosed. The cylindrical carbon nanotube array 12〇3 includes an opening parallel to the axial direction of the tubular carbon nanotube array 12〇a. Referring to FIG. 4, the substrate U〇b may also be a cylindrical body having a rectangular cross section. The rectangle has a rounded corner 144. The cylindrical carbon nanotube array 12〇b is formed on the outer peripheral surface of the cylindrical body to form a closed The cylindrical carbon nanotube array 12〇13. Referring to Fig. 5, the substrate 14〇c may also be an unsealed cylindrical body having an opening 142 parallel to the axial direction of the cylindrical body. The cylindrical carbon nanotube array 120c is formed on the outer peripheral surface of the unsealed cylindrical body to form an unsealed tubular nanocarbon array 120 C, that is, the unclosed The cylindrical carbon nanotube array 120c includes an opening parallel to the axial direction of the cylindrical carbon nanotube array. It is understood that the substrate is not limited to the above shape, and the cross section of the substrate may be elliptical or have other rounded corners. Polygons, etc. [0020] The substrate may also include, but is not limited to, the following shape, thereby obtaining the cylinder: the substrate may be a columnar body (solid body), the columnar outer peripheral surface forming the cylinder surface, wherein Similar to the shape, the cross section of the column can be rounded, rounded or rounded, or further placed in the column 099102136 Form No. A0101 Page 8 / Total 37 Page 0992004110-0 201125814 The strip-shaped groove forms a cylindrical surface having a notch in the axial direction, and at this time, the transverse surface of the columnar body is an unclosed circle, an ellipse or a rounded polygon. [〇〇21] The substrate may be selected from a quartz substrate, a high temperature resistant ruthenium substrate, a P-type or N-type ruthenium substrate, or a ruthenium substrate formed with an oxide layer. In this embodiment, the substrate 140 is preferably A quartz tube having a relatively smooth surface ( ( ( [(5) 22] The catalyst layer material may be selected from iron (Fe), cobalt (Co), recorded (Ni) or any combination thereof, preferably about 5 nm. Thick iron catalyst layer. The catalyst layer may be formed on the outer peripheral surface of the quartz tube. [0023] When the reaction furnace is a tubular reactor, the substrate 140 may be disposed in the tubular reactor along the axial direction of the tubular reactor, that is, the axis direction of the substrate 14 is parallel to the tubular reaction. The direction of the axis of the furnace. Further, the two ends of the substrate 140 can be supported by a bracket which can suspend the base 140 in the reactor and can rotate in the direction of the axis of the substrate 140. The carbon source gas may be selected from the group consisting of acetylene, ethylene, ethane, etc., preferably a chemically active hydrocarbon such as acetylene, and the protective gas may be nitrogen, ammonia or an inert gas. [0024] The cylindrical carbon nanotube array 120 includes a plurality of carbon nanotubes, wherein most of the carbon nanotubes are substantially parallel to each other and perpendicular to the surface of the substrate 140. The top surface of the cylindrical carbon nanotube array 120 is a cylinder parallel to the surface of the substrate 140. The tubular carbon nanotube array 120 contains substantially no impurities such as amorphous carbon or residual catalyst metal particles, etc., by controlling the growth conditions described above. The carbon nanotubes in the tubular carbon nanotube array 120 pass each other through Vander 099102136 Form No. A0101 Page 9 of 37 0992004110-0 201125814 Valli is in close contact to form an array. The growth area of the cylindrical carbon nanotube array 120 may be substantially the same as the area of the substrate 140 described above. The carbon nanotubes in the tubular carbon nanotube array 120 may include at least one of a single-walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube. The height of the carbon nanotubes in the cylindrical carbon nanotube array 120 is from 2 μm to 10 mm, preferably from 100 to 900 μm. The carbon nanotubes have a diameter of 1 to 50 nm. [0025] Next, for further description of step two, please refer to FIG. 6, in which the carbon nanotube segment 143 is formed by one of the cylindrical carbon nanotube arrays 1 20 or adjacent plurality of nanocarbons. The tube 145 is composed of the plurality of carbon nanotubes 145 interacting through the van der Waals force. The stretching tool is used to select and pull the carbon nanotube segment 143. The stretching tool can be a tweezers, a clip, a tape or a hard base strip with a glue on the surface. The process of selecting the carbon nanotube segments 143 may be performed by picking up a portion of the carbon nanotubes 145 in the tubular carbon nanotube array 120 by using tweezers or clips, or contacting the tube with a tape or a strip of adhesive. Shaped carbon nanotube array 120. Specifically, the stretching tool may directly select the carbon nanotube segment 143 in an axial direction parallel to the cylindrical carbon nanotube array 120, see FIG. 3, when the tubular nanometer When the carbon tube array 120a has an opening, the stretching tool can select the nai from the edge of the tubular carbon nanotube array 120a near the opening along the axis parallel to the cylindrical carbon nanotube array 120a. The carbon nanotube segments are used to prevent the carbon nanotubes that are not involved in the subsequent stretching from sticking to the stretching tool, thereby reducing the quality of the carbon nanotube structure 100 obtained by stretching. [0027] When the width of the carbon nanotube segment 143 selected by the stretching tool is the same as the axial length of the cylindrical carbon nanotube array 120 (along the axis parallel to the substrate 140, 099102136, Form No. A0101, page 10/total 37 pages 0992004110-0 201125814 When the dimensions are the same, the stretching tool can obtain a carbon nanotube membrane having a fixed width or a solid carbon nanotube diameter having a fixed diameter after the subsequent stretching step. Just at the end, step on the steps - step by step. The radial direction is perpendicular to the axial direction of the cylindrical carbon nanotube array 120. Specifically, during the movement of the tensile tool in the radial direction of the tubular array 12, the enthalpy is not caused by the mutual van der Waals force between adjacent nanotubes. The rice is continuously pulled out end to end, that is, the carbon nanotubes in the carbon nanotube structure 〇100 are continuously pulled out from the cylindrical carbon nanotube array 12, thereby forming a continuous Carbon tube structure 100. In addition, since the substrate 140 is movable and can be rotated in its axial direction in the axial direction, when the tensile X is gradually moved by an external force, the substrate can also be axially wound around it under the action of an external force. The in-situ rotation compensates for the consumption of the carbon nanotubes in the tubular nano-rude array 120, so that the carbon nanotubes in the cylindrical carbon nanotube array 120 gradually get out of the substrate 14 〇. In addition, if the bottom of the wire 14G is fixed and not twisted, the drawing tool can gradually stretch the wire around the substrate 140 while the nano carbon tube is separated from the substrate 14 0 in the stretching process. The consumption of the tubular carbon nanotube array 120 is compensated by (4). The nano 嚷 camp structure _ can be a 奈奈碳管膜 or a nano carbon line. The formed nano-tube-breaking structure is also determined by the width of the carbon nanotube film 143 selected by the technique. [0029] Further, in the stretching process towel, at the junction of the carbon nanotube structure (10) and the tubular nanotube array 120, the cylindrical carbon nanotube array 12 is cut into the surface and the nanocarbon The tube structure 1 is not required to be angled, and the angle may be greater than or equal to 099102136. Form number A0101 11th spirit/total 37 pages 0992004110-0 201125814 at 0 degrees, less than or equal to 60 degrees, preferably greater than 0 degrees and less than or equal to 15 degrees, In an embodiment, the angle is 15 degrees. Specifically, if the angle is 0°, the drawn carbon nanotube structure 100 is easily in contact with the growth substrate 140 of the cylindrical carbon nanotube array 120, and the catalyst or amorphous carbon may remain due to the growth substrate 140. These impurities will adsorb to the carbon nanotube structure to affect the quality of the carbon nanotube structure; if the angle is too large, the van der Waals force between the carbon nanotube segments in the carbon nanotube structure will become smaller, making The carbon nanotube segments are not firmly bonded and are easily broken. [0030] The two cases of forming the nanocarbon line and the carbon nanotube film will be specifically described below. [0031] When the width of the selected carbon nanotube segments is narrow, a carbon nanotube line can be formed. Specifically, when the stretching tool pulls the carbon nanotube segment in the radial direction of the cylindrical carbon nanotube array 120, the carbon nanotube segment adjacent to the selected carbon nanotube segment passes The effect of Van der Waals forces is continuously pulled out of the tubular carbon nanotube array 120 end to end and forms a nano carbon line. [0032] In addition, when the width of the selected carbon nanotube segments is wide, a narrow-width carbon nanotube film can be formed by stretching. To form a nanocarbon pipeline, the process may further include adopting The carbon nanotube film having a narrow width is treated by an organic solvent, so that the carbon nanotubes in the carbon nanotube film are rapidly gathered to form the nanocarbon line. Specifically, in this embodiment, the carbon nanotube film is infiltrated by the organic solvent and concentrated into a nanocarbon line to volatilize the organic solvent. The organic solvent is a volatile organic solvent such as ethanol, decyl alcohol, acetone, di-ethane or gas, and ethanol is used in this embodiment. Please refer to Fig. 7 and Fig. 8 for the surface generated when the volatile organic solvent is volatilized. 099102136 Form No. 1010101 Page 12/37 Page 0992004110-0 201125814 The carbon nanotubes in the carbon nanotube membrane under the action of tension A non-twisted nanocarbon line 102 is formed by the van der Waals force gathering. [0033] The process of forming a carbon nanotube line may further include twisting the carbon nanotube film to twist the carbon nanotube film into a twisted nanocarbon line, specifically, moving the stretching tool At the same time, the stretching tool is rotated around the stretching tool in the moving direction of the stretching tool, so that the carbon nanotube film is also rotated to form a twisted nanocarbon line. 〇 [0034] Ο
該奈米碳管線包括複數奈米碳管通過凡德瓦爾力首尾相 連。具體地，該奈米碳管線包括複數連續且定向排列之 奈米碳管片段。該複數奈米碳管片段通過凡德瓦爾力首 尾相連。每一奈米碳管片段包括複數相互平行之奈米碳 管，該複數相互平行之奈米碳管通過凡德瓦爾力緊密結 合。該奈米碳管片段具有任意之長度、厚度、均勻性及 形狀。該奈米碳管線長度不限，直徑與所形成之筒狀奈 米碳管陣列120之軸長度有關，當該筒狀奈米碳管陣列 120之軸長度為400寸時，該奈米碳管線之直徑可達300 微米。請參閱圖7，當該奈米碳管線為非扭轉之奈米碳管 線時包括複數基本平行於所述奈米碳管線長度方向排列 之奈米碳管。請參閱圖8，當該奈米碳管線為扭轉之奈米 碳管線時包括複數繞該奈米碳管線軸向螺旋排列之奈米 碳管。 [0035] 當選定之奈米碳管片段之寬度較寬時，可形成一奈米碳 管膜。具體地，當該拉伸工具沿該筒狀奈米碳管陣列120 之徑向方向拉取該奈米碳管片段時，一連續之奈米碳管 膜便從奈米碳管陣列中拉出。 099102136 表單編號Α0101 第13頁/共37頁 0992004110-0 201125814 [0036] 請參閱圖9，所述奈米碳管膜係由若干奈米碳管組成之自 支撐結構。所述若干奈米碳管為沿同一方向擇優取向排 列。所述擇優取向係指在奈米碳管膜中大多數奈米碳管 之整體延伸方向基本朝同一方向。而且，所述大多數奈 米碳管之整體延伸方向基本平行於奈米碳管膜之表面。 進一步地，所述奈米碳管膜中多數奈米碳管係通過凡德 瓦爾力首尾相連。具體地，所述奈米碳管膜中基本朝同 一方向延伸之大多數奈米碳管中每一奈米碳管與在延伸 方向上相鄰之奈米碳管通過凡德瓦爾力首尾相連。當然 ，所述奈米碳管膜中存在少數隨機排列之奈米碳管，這 些奈米碳管不會對奈米碳管膜中大多數奈米碳管之整體 取向排列構成明顯影響。所述自支撐為奈米碳管膜不需 要大面積之載體支撐，而只要相對兩邊提供支撐力即能 整體上懸空而保持自身膜狀狀態，即將該奈米碳管膜置 於（或固定於）間隔一固定距離設置之兩個支撐體上時 ，位於兩個支撐體之間之奈米碳管膜能夠懸空保持自身 膜狀狀態。所述自支撐主要通過奈米碳管膜中存在連續 之通過凡德瓦爾力首尾相連延伸排列之奈米碳管而實現 〇 [0037] 具體地，所述奈米碳管膜中基本朝同一方向延伸之多數 奈米碳管，並非絕對之直線狀，可以適當之彎曲；或者 並非完全沿延伸方向排列，可以適當之偏離延伸方向。 故，不能排除奈米碳管膜之基本朝同一方向延伸之多數 奈米碳管中並列之奈米碳管之間可能存在部分接觸。 [0038] 具體地，請參閱圖6，所述奈米碳管膜包括複數連續且定 099102136 表單編號A0101 第14頁/共37頁 0992004110-0 201125814 向排列之奈米碳管片段143。該複數奈米碳管片段143通 過凡德瓦爾力首尾相連。每一奈米碳管片段143包括複數 相互平行之奈米碳管145，該複數相互平行之奈米碳管 145通過凡德瓦爾力緊密結合。該奈米碳管片段143具有 任意之長度、厚度、均勻性及形狀。該奈米碳管膜中之 奈米碳管14 5沿同一方向擇優取向排列。所述奈米碳管膜 之厚度為0.5奈米〜100微米，最大寬度與所述筒狀奈米碳 管陣列120之軸長度相等。該奈米碳管膜106之比表面積 大於100平方米每克。該奈米碳管膜具有較好之透光性， 可見光透過率可以達到75%以上。 [0039] 請參閱圖10，本發明第二實施例提供一種奈米碳管結構 200之製備方法，該方法具體包括以下步驟： [0040] 步驟一：提供一筒狀奈米碳管陣列220。 [0041] 步驟二：預處理該筒狀奈米碳管陣列220，使在該筒狀奈 米碳管陣列220之表面形成至少一凹槽22，該至少一凹槽 2 2可將該筒狀奈米碳管陣列分割成至少一子奈米碳管陣 列。 [0042] 步驟三：採用一拉伸工具接觸該子奈米碳管陣列，從該 子奈米碳管陣列中選定一寬度與該子奈米碳管陣列之寬 度相同之奈米碳管片段。 [0043] 步驟四：使拉伸工具沿該筒狀奈米碳管陣列220之徑向方 向移動並遠離該筒狀奈米碳管陣列220，拉取該選定之奈 米碳管片段，從而形成一奈米碳管結構200，該奈米碳管 結構200—端連接該拉伸工具，另一端連接該子奈米碳管 099102136 表單編號 A0101 第 15 頁/共 37 頁 0992004110-0 201125814 陣列，在技伸過程中，在所述奈米碳管結構200與該子奈 乂炭貧陣列之連接處，該筒狀奈米碳管陣列之切面與該 不米碳管結構構成一角度，該角度大於等於〇度小於 於60度。 ' [0044] [0045] [0046] [0047] 099102136 下面分別對各步驟展開說明。 本^施例中之步驟—與步驟四與上述第—實施例之步驟 一 v驟二完全相同，在此將不再贅述以下將僅對步驟 二和步驟三進行說明。 首先，對步驟二進一步說明。 本實施例中，為獲得實際需求尺寸之奈米碳管結構2〇〇， 可將所述筒狀奈米碳管陣列22〇分割成至少一個具有—預 2尺寸之子奈米碳管陣列。即可根據實際需要奈米碳管 轉⑽之尺寸，將筒狀奈米碳管陣列22G分割成具有預 ^尺寸之子奈米碳管陣列，從該具有預定尺寸之子奈米、 碳管陣列中便可拉伸出所述實際需求尺寸之奈米碳管結 獅〇。具體地，採用鐳射刻姓之方法在所述筒狀奈米碳 s陣列22G之表面加工形成至少_凹槽22，該至少一凹槽 22可將所㈣狀奈米碳管陣··職至少_個子太^ 碳管陣列，該子奈⑽管_具有_狀尺寸。如所:、 成之至少一凹槽22沿該筒狀奈米碳管陣列220之軸向螺旋 延伸，從而將該筒狀奈米碳管陣列22〇分割成至少一呈連 續之螺旋_繞在基底24G表面之帶狀子奈⑼管陣列， 或者該至少-凹槽環繞該筒狀奈米碳管陣列22〇，從而將 該筒狀奈米碳管陣列220分割成至少兩個筒狀子奈米碳管 表單編號A0101 第16頁/共37頁 0992004110-0 201125814 陣歹。 七成所述g ψ罗 王緣疑形之帶狀子奈米碳管陣列之方法具體為： sl〇l，囡〜> 疋筒狀奈米碳管陣列220連同基底240。 S!〇2，摇桩 恢1供一可移動之鐳射器。 戈=s射器包括固體鐳射器、液體鐳射器、氣體鐳射器 Ο Ο [0048] [0049] [0050] [0051] 導體鐳射器。本實施例中，所述鐳射器為二氧化碳 身士器。玲ίί*、 。厅述鐳射器之移動方法不限，可以通過外力移 動錯射器使其H固定路郷動，也可料過其他方 :移動Αβ射器。本實施例中，該二氧化竣鐳射器之錯射 光束之照射路徑通過電腦程式控制，將確定好筒狀奈米 碳&陣列220中所需要形成之螺旋帶之圖形和位置等資料 登錄電腦程式中。 [0052] 0 0 S103，移動該鐳射器使鐳射光束照射該筒狀奈米碳管陣 列220，使筒狀奈米碳管陣列220中被鐳射處理過之部分 形成一凹槽22，該凹槽22在所述筒狀奈米碳管陣列22〇上 沿該筒狀奈米碳管陣列2 2 0之軸向螺旋延伸。 [0053] 經過上述鐳射處理，凹槽22處奈米碳管之高度小於1〇〇微 米。且該凹槽22可使中間未被鐳射處理之筒狀奈米碳管 陣列220也被分割成具有一固定寬度之呈連續之螺旋形纏 繞在基底240表面之帶狀子奈米碳管陣列。 [0054] 上述被形成之呈螺旋形之帶狀子奈米碳管陣列之寬度可 通過控制由凹槽22構成之螺旋線之螺旋角大小加以控制 。本實施例中，所述呈螺旋形之帶狀子奈米碳管陣列寬 099102136 表單編號Α0101 第17頁/共37頁 0992004110-0 201125814 度為1英寸。 [0055] 所採用之鐳射光束為波長為1 064奈米之紅光鐳射光束、 波長為10640奈米之二氧化碳鐳射光束或波長為532奈米 之綠光鐳射光束。所述鐳射光束之掃描速度為50毫米/秒 至150毫米/秒。所述鐳射光束之功率密度優選地為5x10Ί 瓦/平方米至5χ109瓦/平方米。本實施例中，採用波長為 1 054奈米之紅外鐳射光束，該紅外鐳射光束之掃描速度 為100毫米/秒，功率密度為lxlO8瓦/平方米。 [0056] 鐳射照射過程中，由於鐳射光束所具有之高能量被奈米 碳管吸收，產生之高溫將處於鐳射照射路徑處之奈米碳 管全部或部分燒蝕，從而在筒狀奈米碳管陣列220中形成 預定深度和距離之凹槽22。鐳射處理後奈米碳管之高度 會降低，當被鐳射處理後之奈米碳管之高度小於100微米 時，則該部分奈米碳管就無法參與後續之拉伸過程。以 拉伸獲得一奈米碳管膜為例，即只要被鐳射處理後之奈 米碳管之高度小於100微米，就可保證所製備之奈米碳管 膜具有一致之寬度。但若要所製備之奈米碳管膜不僅寬 度一致，且奈米碳管膜中奈米碳管之密度分佈均勻，則 凹槽22處被處理後之奈米碳管之高度不可太低，其應大 於1微米。這係因為，在後續之拉膜步驟中，僅有凹槽22 處之奈米碳管具有一固定高度才可保持對與其相鄰之奈 米碳管之凡德瓦爾力之作用。故在拉膜過程中，與凹槽 22相鄰之奈米碳管之消耗速度同不與凹槽22相鄰之奈米 碳管消耗速度基本相同，從而保證所得之膜之寬度一致 性以及奈米碳管膜中奈米碳管之均勻性。如果凹槽22處 099102136 表單編號A0101 第18頁/共37頁 201125814 之奈米碳管高度太低，該凹槽22中奈米碳管對與其相鄰 之並未被鐳射處理之奈米碳管就會沒有凡德瓦爾力作用 ，故，與凹槽22相鄰之奈米碳管之消耗速度將大於不與 • 凹槽22相鄰之奈米碳管消耗速度。如此在拉膜過程中使 筒狀奈米碳管陣列220中消耗奈米碳管之邊界線呈弧形， 則使所製備之奈米碳管膜不僅寬度不一致，而奈米碳管 膜中奈米碳管之密度也不一致。故，通過控制鐳射之功 率以及和描速度荨參.數以使鐳射處理過之凹槽Μ中之奈 ^ 米碳管之高度範圍為卜100微米。優選地，凹槽22中之奈 〇 米碳管之高度為5〇-丨⑽微米。本實施例中，所述凹槽 中之奈米碳管之高度為100微米。 [0057]所述凹槽22之寬度優選之大於筒狀奈米碳管陣列22〇中奈 米碳管之高度。這係因為，在拉臈過程中，位於凹槽22 之另一側之奈米碳管有可能傾倒從而跨過凹槽22之間隙 參與到位於螺旋狀凹槽22之間之奈米碳管之拉膜過程中 〇 。這將會導致獲取之奈米破管膜之寬度不-致。本實施 Q 例中，奈米碳管陣列中之奈米碳管之高度為200微米，故 控制凹槽22之寬度為250微米。 [0058]可以理解，該採用鐳射處理筒狀奈米碳管陣列22〇之製備 方法還可以為固定鐳射裝置，移動筒狀奈米碳管陣列22〇 使鐳射照射該筒狀奈米碳管陣列220之方法，其具體包括 以下步驟：提供一固定之鐘射器，該鐳射器在一固定區 域形成一錯射抑描區，使筒狀奈米碳管陣列220連同基底 240以一固定之速度經過該鐳射掃描區，使筒狀奈米碳管 陣列220表面形成一由凹槽22構成之螺旋線。 099102136 表單編號A0101 第19頁/共37頁 〇99 201125814 [0059] 此外，也可在該筒狀奈米碳管陣列2 2 0之表面刻蝕兩條以 上由凹槽22構成之相互間隔且平行排列之螺旋線，形成 兩個以上之螺旋形帶狀子奈米碳管陣列，從而可在該處 理後之奈米碳管陣列上同時拉出兩個以上之奈米碳管結 構。 [0060] 所述將筒狀奈米碳管陣列2 2 0採用鐳射刻蝕之方法刻蝕成 複數具有固定軸長度之圓筒形之子奈米碳管陣列與上述 方法基本相同，在此將不再贅述。 [0061] 其次，對步驟三進一步說明。 [0062] 具體地，該步驟中，本實施例與第一實施例之區別在於 ，在第一實施例中，若拉伸工具選擇之奈米碳管片段143 之寬度小於所述基底140之長度時，雖然初始被選定之奈 米碳管片段143之寬度一固定，然由於在拉伸過程中所選 定之奈米碳管片段143之邊緣處之奈米碳管與其附近之奈 米碳管之間存在凡德瓦爾力，故在拉伸過程中，這些與 選定之奈米碳管片段143中之奈米碳管相鄰之奈米碳管也 會由於凡德瓦爾力之相互作用而陸續被拉出，從而使得 奈米碳管膜之寬度並不等於所選定之奈米碳管片段143之 寬度，或奈米碳管線也並不具有固定之直徑。而係在拉 伸過程中，奈米碳管膜之寬度或奈米碳管線之直徑逐漸 增大。 [0063] 為獲得具有固定寬度之奈米碳管膜或固定直徑之奈米碳 管線，上述第一實施例可採用拉伸工具直接選定一寬度 與筒狀奈米碳管陣列120之軸向長度相同之奈米碳管片段 099102136 表單編號A0101 第20頁/共37頁 0992004110-0 201125814 。而本實施例中可採用所述拉伸工具在該呈螺旋形帶狀 子奈米碳管陣列上選定一寬度與該螺旋形帶狀子奈米碳 管陣列寬度相同之奈米碳管片段’或在上述被加工成之 複數具有固定軸長度之圓筒形子奈米碳管陣列之其中之 一個中選定一寬度與該加工後之圓筒形子奈米碳管陣列 軸長度相同之奈米破管片段，從而在拉伸過程中拉伸獲 得一具有固定寬度之奈米碳管臈和具有固定直徑之奈米 碳管線，可見，本實施例中，可根據實際.需要奈米碳管 ^ 結構2〇〇之尺寸，將筒狀奈米碳管陣列220分割成具有預 定尺寸之子奈米碳管陣列’從該具有預定尺寸之子奈米 碳管陣列中拉伸出所述實際需求尺寸之奈米碳管結構2〇〇 [0064]由於本發明之基底包括柱面，用於生長奈米碳管陣列， 其具有較大之表面積’與平面基底比較，在相同之反應 爐中’可充分利用反應爐内之空間，生長出較大尺寸之 Q 奈米碳管陣列，從而使從該奈米碳管陣列中拉取獲得之 Q 奈米碳管膜具有較大之面積，尤其軸向全尺寸拉取膜時 可以獲得較大之具有固定尺寸之膜，可以用於製備大尺 寸之產品，而拉取獲得之奈米碳管線具有較大之直徑或 長度。 [0065] 综上所述，本發明確已符合發明專利之要件，遂依法提 出專利申請。惟，以上所述者僅為本發明之較佳實施方 式，自不能以此限制本案之申請專利範圍。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。 099102136 表單編號Α0101 第21頁/共37頁 〇! 201125814 【圖式簡單說曰为】 [0066] 圖1係本發明第一實施例中從筒狀奈米碳管陣列中拉伸獲 得一奈米碳管膜之過程示意圖。 [0067] 圖2係本發明第一實施例形成於圓形筒狀體外周面之筒狀 奈米碳管陣列垂直於筒狀體轴向之剖視示意圖。 [0068] 圖3係本發明第一實施例形成於具有開口之圓形筒狀體外 周面之筒狀奈米碳管陣列垂直於筒狀體軸向之剖視示意 圖。 [0069] 圖4係本發明第一實施例形成於具有導角之矩形筒狀體外 周面之筒狀奈米碳管陣列垂直於筒狀體軸向之剖視示意 圖。 [0070] 圖5係本發明第一實施例形成於具有開口和導角之矩形筒 狀體外周面之筒狀奈米碳管陣列垂直於筒狀體軸向之剖 視不意圖。 [0071] 圖6係本發明第一實施例一奈米碳管片段之結構示意圖。 [0072] 圖7係本發明第一實施例非扭轉之奈米碳管線之掃描電鏡 照片。 [0073] 圖8係本發明第一實施例扭轉之奈米碳管線之掃描電鏡照 片。 [0074] 圖9係本發明第一實施例奈米碳管膜之掃描電鏡照片。 [0075] 圖1 0係本發明第二實施例從具有螺旋形帶狀子奈米碳管 陣列中拉伸獲得一奈米碳管線之過程示意圖。 【主要元件符號說明】 099102136 表單編號A0101 第22頁/共37頁 0992004110-0 201125814 [0076] 奈米碳管結構：100，200 [0077] 筒狀奈米碳管陣列：120，120a，120b，120c，220 [0078] 凹槽：22 [0079] 基底：140，140a，140b，140c，240 [0080] 開口 ： 142 [0081] 奈米碳管片段：143The nanocarbon pipeline includes a plurality of carbon nanotubes connected end to end by Van der Waals force. Specifically, the nanocarbon pipeline includes a plurality of continuous and aligned carbon nanotube segments. The plurality of carbon nanotube segments are connected end to end by Van der Valli. Each of the carbon nanotube segments includes a plurality of mutually parallel carbon nanotubes, and the plurality of mutually parallel carbon nanotubes are tightly bonded by van der Waals force. The carbon nanotube segments have any length, thickness, uniformity, and shape. The length of the nano carbon line is not limited, and the diameter is related to the length of the shaft of the formed tubular carbon nanotube array 120. When the length of the cylindrical carbon nanotube array 120 is 400 inches, the carbon line is It can be up to 300 microns in diameter. Referring to Figure 7, when the nanocarbon line is a non-twisted carbon nanotube line, a plurality of carbon nanotubes arranged substantially parallel to the length of the nanocarbon line are included. Referring to Figure 8, when the nanocarbon line is a twisted nanocarbon line, a plurality of carbon nanotubes axially arranged around the nanocarbon line are included. [0035] When the width of the selected carbon nanotube segments is wide, a carbon nanotube film can be formed. Specifically, when the stretching tool pulls the carbon nanotube segments in the radial direction of the cylindrical carbon nanotube array 120, a continuous carbon nanotube film is pulled out from the carbon nanotube array. . 099102136 Form No. Α0101 Page 13 of 37 0992004110-0 201125814 [0036] Referring to Figure 9, the carbon nanotube membrane is a self-supporting structure composed of a number of carbon nanotubes. The plurality of carbon nanotubes are arranged in a preferred orientation along the same direction. The preferred orientation means that the majority of the carbon nanotubes in the carbon nanotube film extend substantially in the same direction. Moreover, the overall extension direction of the majority of the carbon nanotubes is substantially parallel to the surface of the carbon nanotube film. Further, most of the carbon nanotubes in the carbon nanotube membrane are connected end to end by van der Waals force. Specifically, each of the carbon nanotubes of the majority of the carbon nanotubes extending substantially in the same direction in the carbon nanotube film is connected end to end with the carbon nanotubes adjacent in the extending direction by van der Waals force. Of course, there are a small number of randomly arranged carbon nanotubes in the carbon nanotube film, and these carbon nanotubes do not significantly affect the overall orientation of most of the carbon nanotubes in the carbon nanotube film. The self-supporting carbon nanotube film does not require a large-area carrier support, but can maintain a self-membrane state as long as the supporting force is provided on both sides, that is, the carbon nanotube film is placed (or fixed on) When the two supports are disposed at a fixed distance, the carbon nanotube film located between the two supports can be suspended to maintain the self-membrane state. The self-supporting is mainly achieved by the presence of a continuous carbon nanotube in the inner surface of the carbon nanotube film extending through the van der Waals force. [0037] Specifically, the carbon nanotube film is substantially in the same direction Most of the carbon nanotubes that extend are not absolutely linear and can be bent properly; or they are not completely aligned in the direction of extension and can be appropriately offset from the direction of extension. Therefore, it is not possible to exclude that there may be partial contact between the carbon nanotubes juxtaposed in the majority of the carbon nanotube membranes extending in the same direction. [0038] Specifically, referring to FIG. 6, the carbon nanotube film includes a plurality of consecutive and fixed 099102136 Form No. A0101 Page 14 of 37 0992004110-0 201125814 Arranged carbon nanotube segments 143. The plurality of carbon nanotube segments 143 are connected end to end by Van der Valli. Each of the carbon nanotube segments 143 includes a plurality of mutually parallel carbon nanotubes 145 which are tightly coupled by van der Waals forces. The carbon nanotube segments 143 have any length, thickness, uniformity, and shape. The carbon nanotubes 14 5 in the carbon nanotube film are arranged in a preferred orientation in the same direction. The carbon nanotube film has a thickness of from 0.5 nm to 100 μm and a maximum width equal to the axial length of the cylindrical carbon nanotube array 120. The carbon nanotube film 106 has a specific surface area greater than 100 square meters per gram. The carbon nanotube film has good light transmittance, and the visible light transmittance can reach 75% or more. [0039] Referring to FIG. 10, a second embodiment of the present invention provides a method for preparing a carbon nanotube structure 200. The method specifically includes the following steps: [0040] Step 1: providing a cylindrical carbon nanotube array 220. [0041] Step 2: pretreating the tubular carbon nanotube array 220 to form at least one groove 22 on the surface of the cylindrical carbon nanotube array 220, the at least one groove 2 2 may be cylindrical The carbon nanotube array is divided into at least one sub-carbon nanotube array. [0042] Step 3: contacting the sub-carbon nanotube array with a stretching tool, and selecting a carbon nanotube segment having the same width as the sub-carbon nanotube array from the array of sub-carbon nanotubes. [0043] Step 4: moving the stretching tool along the radial direction of the tubular carbon nanotube array 220 and away from the cylindrical carbon nanotube array 220, and pulling the selected carbon nanotube segments to form a carbon nanotube structure 200, the carbon nanotube structure is connected at 200-end to the stretching tool, and the other end is connected to the sub-nanocarbon tube 099102136 Form No. A0101 Page 15 of 37 0992004110-0 201125814 Array, at During the stretching process, at the junction of the carbon nanotube structure 200 and the sub-nanocarbon lean array, the cut surface of the cylindrical carbon nanotube array forms an angle with the carbon nanotube structure, and the angle is greater than Is equal to less than 60 degrees. [0047] [0047] 099102136 The following is a description of each step. The steps in the embodiment are the same as those in the fourth step of the above-mentioned first embodiment, and the second step and the third step will be described below. First, the second step is further explained. In this embodiment, in order to obtain the carbon nanotube structure 2 of the actual required size, the cylindrical carbon nanotube array 22 can be divided into at least one sub-carbon nanotube array having a pre-size of 2 carbon nanotubes. The tubular carbon nanotube array 22G can be divided into a sub-carbon nanotube array having a pre-size according to the actual size of the carbon nanotube transfer (10), from the nanometer and carbon tube array having a predetermined size. The carbon nanotubes of the actual required size can be stretched out. Specifically, the surface of the tubular nanocarbon s array 22G is processed by a laser engraving method to form at least a recess 22, and the at least one recess 22 can at least have a (four) shaped carbon nanotube array. _ a child too ^ carbon tube array, the child (10) tube _ has a _ size. As shown, at least one groove 22 is spirally extended along the axial direction of the cylindrical carbon nanotube array 220, thereby dividing the cylindrical carbon nanotube array 22 into at least one continuous spiral_around An array of strip-shaped sub-nanotubes (9) on the surface of the substrate 24G, or the at least-groove surrounding the cylindrical array of tubular carbon nanotubes 22, thereby dividing the tubular carbon nanotube array 220 into at least two cylindrical sub-nano Carbon Pipe Form No. A0101 Page 16 of 37 Page 0992004110-0 201125814 The method of the seventy-sixth said g-roof of the suspected strip-shaped carbon nanotube array is specifically: sl〇l, 囡~> The cylindrical carbon nanotube array 220 together with the substrate 240. S!〇2, rocking pile Recovery 1 for a movable laser. Ge = s emitter includes solid laser, liquid laser, gas laser Ο Ο [0049] [0050] [0051] Conductor laser. In this embodiment, the laser is a carbon dioxide body. Ling ίί*, . The moving method of the laser is not limited. The H-fixed path can be moved by the external force to move the erector, or it can be expected to move the Αβ-ray. In this embodiment, the illumination path of the staggered beam of the ceria laser is controlled by a computer program, and the data and the position of the spiral band formed in the tubular carbon carbon array 220 are determined to be registered in the computer. In the program. [0052] 0 0 S103, moving the laser to irradiate the laser beam to the tubular carbon nanotube array 220, so that the laser-treated portion of the cylindrical carbon nanotube array 220 forms a groove 22, the groove 22 is spirally extended along the axial direction of the cylindrical carbon nanotube array 2 2 2 on the cylindrical carbon nanotube array 22 . [0053] After the above laser treatment, the height of the carbon nanotubes at the groove 22 is less than 1 〇〇 micrometer. The recess 22 allows the cylindrical carbon nanotube array 220, which is not laser-processed in the middle, to be further divided into a strip-shaped sub-carbon nanotube array having a constant width and spirally wound around the surface of the substrate 240. [0054] The width of the spiral-shaped ribbon-shaped carbon nanotube array formed above can be controlled by controlling the magnitude of the helix angle of the spiral formed by the groove 22. In this embodiment, the spiral strip-shaped sub-carbon nanotube array width is 099102136. Form number Α0101 Page 17 of 37 0992004110-0 201125814 The degree is 1 inch. [0055] The laser beam used is a red laser beam having a wavelength of 1,064 nm, a carbon dioxide laser beam having a wavelength of 10,640 nm, or a green laser beam having a wavelength of 532 nm. The scanning speed of the laser beam is from 50 mm/sec to 150 mm/sec. The power density of the laser beam is preferably 5 x 10 watts/square meter to 5 χ 109 watts/square meter. In this embodiment, an infrared laser beam having a wavelength of 1 054 nm is used, and the scanning speed of the infrared laser beam is 100 mm/sec, and the power density is lxlO8 watt/m 2 . [0056] During the laser irradiation process, since the high energy of the laser beam is absorbed by the carbon nanotube, the high temperature generated is ablated or partially ablated by the carbon nanotube at the laser irradiation path, thereby being in the cylindrical nanocarbon A groove 22 of a predetermined depth and distance is formed in the tube array 220. After the laser treatment, the height of the carbon nanotubes is lowered. When the height of the carbon nanotubes after laser treatment is less than 100 μm, the portion of the carbon nanotubes cannot participate in the subsequent stretching process. For example, a carbon nanotube film obtained by stretching can be used to ensure that the prepared carbon nanotube film has a uniform width as long as the height of the carbon nanotube after the laser treatment is less than 100 μm. However, if the prepared carbon nanotube film is not only uniform in width, and the density distribution of the carbon nanotubes in the carbon nanotube film is uniform, the height of the carbon nanotube after the treatment at the groove 22 is not too low. It should be greater than 1 micron. This is because, in the subsequent film drawing step, only the carbon nanotubes at the grooves 22 have a fixed height to maintain the effect on the van der Waals force of the carbon nanotubes adjacent thereto. Therefore, during the film drawing process, the carbon nanotubes adjacent to the groove 22 are consumed at the same speed as the carbon nanotubes not adjacent to the groove 22, thereby ensuring the uniformity of the obtained film width and The uniformity of the carbon nanotubes in the carbon nanotube film. If the height of the carbon nanotubes in the groove 22 is 099102136, the number of the carbon nanotubes on the form number A0101, page 18/37, 201125814 is too low, the carbon nanotubes in the groove 22 are adjacent to the carbon nanotubes that are not laser treated. There will be no Van der Waals force, so the carbon nanotubes adjacent to the groove 22 will consume more than the carbon nanotubes that are not adjacent to the groove 22. Thus, in the process of pulling the film, the boundary line of the carbon nanotubes in the tubular carbon nanotube array 220 is curved, so that the prepared carbon nanotube film is not only inconsistent in width, but the carbon nanotube film is in the middle. The density of carbon nanotubes is also inconsistent. Therefore, by controlling the power of the laser and the speed of the drawing, the height of the carbon nanotubes in the laser-treated groove is 100 micrometers. Preferably, the height of the carbon nanotubes in the recess 22 is 5 〇 - 丨 (10) microns. In this embodiment, the height of the carbon nanotubes in the grooves is 100 μm. The width of the recess 22 is preferably greater than the height of the carbon nanotubes in the tubular carbon nanotube array 22 . This is because, during the pulling process, the carbon nanotubes on the other side of the groove 22 are likely to be poured to participate in the carbon nanotubes located between the spiral grooves 22 across the gap of the grooves 22. In the process of pulling the film. This will result in the width of the acquired nanotube membrane being unacceptable. In the present example Q, the height of the carbon nanotubes in the carbon nanotube array was 200 μm, so the width of the control groove 22 was 250 μm. [0058] It can be understood that the preparation method of the laser-processed tubular carbon nanotube array 22 can also be a fixed laser device, and the cylindrical tubular carbon nanotube array 22 is moved to irradiate the cylindrical carbon nanotube array with laser light. The method of 220, specifically comprising the steps of: providing a fixed clock injector that forms a misdirected depression zone in a fixed area such that the tubular carbon nanotube array 220 and the substrate 240 are at a fixed speed Through the laser scanning zone, a spiral line formed by the recess 22 is formed on the surface of the cylindrical carbon nanotube array 220. 099102136 Form No. A0101 Page 19 of 37 〇99 201125814 [0059] In addition, two or more grooves 20 may be etched on the surface of the cylindrical carbon nanotube array 220 to be spaced apart from each other and parallel. The spirals are arranged to form two or more spiral strip-shaped sub-carbon nanotube arrays, so that more than two carbon nanotube structures can be simultaneously pulled out on the treated carbon nanotube array. [0060] The cylindrical carbon nanotube array 220 is etched into a plurality of cylindrical sub-carbon nanotube arrays having a fixed axial length by laser etching, which is substantially the same as the above method, and will not be used here. Let me repeat. [0061] Next, step 3 is further explained. Specifically, in this step, the difference between the present embodiment and the first embodiment is that, in the first embodiment, if the width of the carbon nanotube segment 143 selected by the stretching tool is smaller than the length of the substrate 140 At the time, although the width of the initially selected carbon nanotube segment 143 is fixed, the carbon nanotube at the edge of the selected carbon nanotube segment 143 during the stretching process is adjacent to the carbon nanotube in the vicinity thereof. There is a van der Waals force, so during the stretching process, these carbon nanotubes adjacent to the carbon nanotubes in the selected carbon nanotube segments 143 will also be successively affected by the interaction of Van der Waals forces. The pull is such that the width of the carbon nanotube film is not equal to the width of the selected carbon nanotube segment 143, or the nanocarbon line does not have a fixed diameter. In the stretching process, the width of the carbon nanotube film or the diameter of the carbon nanotube line gradually increases. [0063] In order to obtain a carbon nanotube membrane having a fixed width or a fixed diameter nanocarbon pipeline, the first embodiment described above may directly select a width and an axial length of the cylindrical carbon nanotube array 120 by using a stretching tool. The same carbon nanotube segment 099102136 Form number A0101 Page 20 / Total 37 page 0992004110-0 201125814. In this embodiment, the stretching tool can be used to select a carbon nanotube segment having the same width as the spiral ribbon-shaped carbon nanotube array on the spiral ribbon-shaped carbon nanotube array. Or selecting a nanometer having the same length as the length of the processed cylindrical sub-carbon nanotube array axis in one of the plurality of cylindrical sub-carbon nanotube arrays having the fixed shaft length processed as described above The tube fragment is broken, thereby stretching to obtain a carbon nanotube having a fixed width and a nano carbon line having a fixed diameter during the stretching process. It can be seen that, in this embodiment, the carbon nanotube can be required according to the actual situation. Dimensions of the structure 2, the cylindrical carbon nanotube array 220 is divided into sub-carbon nanotube arrays having a predetermined size, and the actual required size is drawn from the array of sub-carbon nanotubes having a predetermined size Carbon nanotube structure 2〇〇 [0064] Since the substrate of the present invention comprises a cylinder surface for growing a carbon nanotube array, it has a larger surface area 'comparable to the planar substrate and can be fully utilized in the same reactor In the reactor Space, a larger size Q carbon nanotube array is grown, so that the Q carbon nanotube film obtained from the carbon nanotube array has a larger area, especially when the axial full size is pulled. It is possible to obtain a larger film having a fixed size, which can be used to prepare a large-sized product, and the nano carbon line obtained by drawing has a larger diameter or length. [0065] In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is filed according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by persons skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims. 099102136 Form No. Α0101 Page 21 of 37 2011! 201125814 [Illustration of the Drawings] [0066] FIG. 1 is a first embodiment of the present invention, which is stretched from a cylindrical carbon nanotube array to obtain a nanometer. Schematic diagram of the process of carbon nanotube film. 2 is a schematic cross-sectional view showing a cylindrical carbon nanotube array formed on a circular cylindrical outer peripheral surface of the first embodiment of the present invention perpendicular to the axial direction of the cylindrical body. 3 is a cross-sectional schematic view showing a cylindrical carbon nanotube array formed on a circular cylindrical outer peripheral surface having an opening perpendicular to the axial direction of the cylindrical body according to the first embodiment of the present invention. 4 is a cross-sectional view showing a cylindrical carbon nanotube array formed on a rectangular cylindrical outer peripheral surface having a lead angle perpendicular to the axial direction of the cylindrical body in the first embodiment of the present invention. 5 is a cross-sectional view of a cylindrical carbon nanotube array formed on a rectangular cylindrical outer peripheral surface having an opening and a lead angle perpendicular to the axial direction of the cylindrical body in the first embodiment of the present invention. 6 is a schematic structural view of a carbon nanotube segment according to a first embodiment of the present invention. 7 is a scanning electron micrograph of a non-twisted nanocarbon pipeline of a first embodiment of the present invention. 8 is a scanning electron microscope photograph of a twisted nanocarbon line according to a first embodiment of the present invention. 9 is a scanning electron micrograph of a carbon nanotube film according to a first embodiment of the present invention. 10 is a schematic view showing a process of stretching a nanocarbon line from a spiral ribbon-shaped sub-carbon nanotube array according to a second embodiment of the present invention. [Main component symbol description] 099102136 Form No. A0101 Page 22 / Total 37 0992004110-0 201125814 [0076] Carbon nanotube structure: 100,200 [0077] Cylindrical carbon nanotube array: 120, 120a, 120b, 120c, 220 [0078] Groove: 22 [0079] Substrate: 140, 140a, 140b, 140c, 240 [0080] Opening: 142 [0081] Carbon nanotube segment: 143
[0082] 圓角：144 [0083] 奈米碳管：145[0082] Round Corner: 144 [0083] Nano Carbon Tube: 145
099102136 表單編號A0101 第23頁/共37頁 0992004110-0099102136 Form No. A0101 Page 23 of 37 0992004110-0