1312337 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材料，尤其涉及一種奈米碳管絲狀物及其製作 方法。 [先前技術]1312337 IX. Description of the Invention: [Technical Field] The present invention relates to a carbon nanotube material, and more particularly to a carbon nanotube filament and a method of fabricating the same. [Prior technology]
奈米碳管係19讥年由日本科學家飯島澄男教授發現之一種由石墨烯片 卷成之中空管狀物’其具有優異之力學、熱學及電學性質。奈米碳管應用領 域非常廣闊，例如，它可用於製作場效應電晶體、原子力顯微鏡針尖、場發 射電子搶、納米模板等等。然，目前基本上都係於微觀尺度下應用奈米碳管， .操作較困難。故，將奈米碳管組裝成宏觀尺度之結構對於奈米碳管於宏觀領 域之應用具有重要意義。In 19 years, the carbon nanotubes were discovered by a Japanese scientist, Professor Iijima Ichi, a hollow tubular material rolled from graphene sheets, which has excellent mechanical, thermal and electrical properties. The field of carbon nanotubes is very broad, for example, it can be used to make field effect transistors, atomic force microscope tips, field emission electrons, nano templates, and so on. However, at present, it is basically applied to the micro-scale application of carbon nanotubes. The operation is difficult. Therefore, the assembly of carbon nanotubes into a macroscopic scale is of great significance for the application of nanocarbon tubes in the macroscopic field.
Nature, 2002, 419:801, Spinning Continuous CNT Yams 一文中揭露了從一超順排奈米碳管陣列中可以拉出一根連續純奈米碳管 線’這種奈米被官線包括複數於凡得瓦爾力作用下首尾相接之奈米碳管片 段’母個奈米竣官片段具有大致相等之長度，且每個奈米礙管片段由複數相 互平行之奈米碳管束構成》如第一圖所示爲一個從一超順排奈米碳管陣列 拉出一根連續奈米碳管線14之簡單模型。複數奈米碳管片段12於凡得瓦爾 力作用下首尾相接構成連續之奈米碳管線14。然，單根這種奈米碳管線14 之機械強度及韌性等都比較差’例如’拉出一根2〇〇微米寬之線需要〇 1毫 牛頓力’而只要0.5毫牛頓力就可將其折斷。 爲了更好地將這種奈米碟管線應用於宏觀領域，我們將複數根這種奈米 碳管線14錯於一起構成一奈米碳管膜’這種奈米碳管膜找械強度及勤 性等都比單根奈米碳管線要好》然，通常這種奈米碳管膜有錢米寬，卻只 有紐米厚，其表面非常乾淨，表面趙積比非常大，故其具有很強战性， 一旦接觸到其他物體便會粘倾艮難分開，因而大大限製了該種奈米破管膜 於宏觀領域之進一步應用。 、 碳管絲，以及該奈 有鑒於此，提供一種可方便地應用於宏觀領域之奈米 米碳管絲之製作方法實爲必要》 ” 、 【發明内容】 1312337 下面將以具體實施例說明一種可方便地應用於宏觀領域之奈米碳管 絲’以及該奈米碳管絲之製作方法。 ’'a e 一種奈米碳管絲之製作方法’其包括步驟：提供一奈米碳管陣列；採用 一拉伸工具從該奈米碳管陣列拉取一奈米碳管膜；將拉出之奈米碳管膜經由 一有機溶劑浸潤處理後收縮成爲一奈米碳管絲；收集所製得之奈米碳^絲。 一 _種奈求碳管絲，其係由複數根奈米碳管線緊密結合於一起所構 成’其中’所述奈米碳管線包括複數首尾相接之奈来碳管片段，务^奈米碳 管片段具有大致相等之長度，且每個奈米碳管片段由複數相互平行之去 管束構成。 不以、及Nature, 2002, 419:801, Spinning Continuous CNT Yams reveals that a continuous pure nanocarbon pipeline can be pulled from a super-sequential carbon nanotube array. Under the action of Valli, the first and second carbon nanotube fragments of the 'negative nano-manifold segments have approximately equal lengths, and each nano-tube segment consists of a plurality of mutually parallel carbon nanotube bundles. The figure shows a simple model for pulling a continuous nanocarbon line 14 from a super-sequential carbon nanotube array. The plurality of carbon nanotube segments 12 are joined end to end to form a continuous nanocarbon line 14 under the action of van der Waals force. However, the mechanical strength and toughness of a single such carbon nanotube line 14 are relatively poor 'for example, pulling a 2 〇〇 micrometer wide line requires 毫 1 millinewton force' and as long as 0.5 millinewton force It is broken. In order to better apply this nano-disc pipeline to the macroscopic field, we have made a plurality of such nanocarbon pipelines 14 wrong to form a carbon nanotube membrane. Sex and so on are better than single-nano carbon pipelines. Of course, this kind of carbon nanotube film is usually rich in rice, but only thick in neon, its surface is very clean, and the surface Zhaoji ratio is very large, so it is very strong. The warfare, once exposed to other objects, will be difficult to separate, thus greatly limiting the further application of the nano-barrier film in the macroscopic field. In view of the above, it is necessary to provide a method for producing a nanometer carbon nanotube wire which can be conveniently applied to a macroscopic field, and [invention] 1312337. A specific embodiment will be described below. It can be conveniently applied to the nano carbon wire in the macroscopic field and the manufacturing method of the carbon nanotube wire. ''ae A method for producing a carbon nanotube wire' which comprises the steps of: providing a carbon nanotube array; A carbon nanotube film is drawn from the carbon nanotube array by using a stretching tool; the drawn carbon nanotube film is infiltrated by an organic solvent and shrinks into a nano carbon tube filament; Nano carbon wire. A kind of carbon fiber, which is composed of a plurality of nano carbon pipelines tightly combined together to form 'the' of the nano carbon pipeline including a plurality of first and last carbon nanotubes The segments, the carbon nanotube segments have substantially equal lengths, and each of the carbon nanotube segments is composed of a plurality of bundles that are parallel to each other.
所述奈米碳管絲之製作方法’藉由將從一奈来碳管陣列拉出之奈米碳管 膜經由-有機鋪浸潤處理再收集即可，簡單胳^所述奈米碳管絲由複^ 根奈米碳管線緊密及合於一起所構成，其十，所述奈米碳管 相接之奈米碳管片段，每個奈米碳管片段具有大致相等之長度，且每個奈米 碳管片段由複數相互平行之奈米碳管束構成。該奈米碳管絲表面體積比小， 無粘性’且具有良好之機械強度及動性，能方便地應用於宏觀之複數領域。 【實施方式】 下面將結合附圖對本發明實施例作進一步詳細說明。 本實施例所提供之一種奈米碳管絲之製作方法，包括以下步称：提供一 奈米碳管陣列’採用一拉伸工具從該奈米碳管陣列拉取一奈米碳管媒；將拉 出之奈米碳管膜經由一有機溶劑浸潤處理後收縮成爲一奈米碳管絲；收集所 製得之奈米碳管絲。 ” 請參閱第二圖至第五圖，以下將具體介紹各個步驟： (1)提供一奈米碳管陣列20»優選的，該奈米碳管陣列20為超順排奈米 碳營陣列。本實施例採用化學氣相沈積法生長該超順排奈米碳管陣列2〇之 方法’可參見中國大陸專利申請公開第02134760.3號》該超順排奈米碳管 陣列20之生長方法主要包括步驟：（a)提供一平滑基底，該基底可選用ρ型 或η型石夕基底，⑹於該基底上沈積一催化劑層，該催化劑層之材質可選用 鐵(Fe)、鈷(Co)、鎳(Ni)或其合金之-；（c)將沈積有催化劑層4底於保 護氣體中以300~400°C溫度進行退火處理’時間約爲1〇小時；將退火處 7 1312337 理後之沈積有催化劑層之絲加熱至500~70(rc，通入碳源氣與保護氣體之 混合氣體，控製該碳源氣之流速，使催化劑與環境之溢度差為5(rc以上，控 製該混合氣體之麵比’使碳源氣之分壓彳谈施，妓5〜3Q分鐘，奈米碳 管陣列將錄底長出》其中’碳源氣爲破氫化合物，可爲乙炔 、乙烷等，優 選用乙炔’該保護氣體爲惰性紐或氮氣。由上述方法製得唄排奈米碳 :陣列20 +之奈米碳管呈束狀密集排列，具有很高从面密度，且奈米碳 管束之間存在很強之破瓦爾力，其不僅直徑大小分佈比較集中，而且直徑 大小幾乎相同。 ⑵採用一拉伸工具從該奈米碳管陣列20中拉取一奈米碳管膜24。其可 | 按以·^方法操作：⑷壯述奈米碳管陣列2〇中遵定一包括複數奈米碳管束 之$米碳管片段；（b)使用拉伸工具，如鑷子，沿起始拉力方向拉伸該奈米 碳管片段二在該拉伸過程中，奈米碳管片段於拉力作用下沿拉力方向伸長之 同’奈米碳管片段兩端將由於凡得瓦爾力之作用而首尾相接地連接於一 起，從而形成一連續之奈米碳管線22，該奈米碳管線22類條第一圖模型 中之奈米碳管線14。反復拉轉數次，使拉出續數根奈米碟管線22麵 米碳管膜24»這種新拉出來之奈米碳管膜24有數微米 厚、難米寬’如第三圖所示即爲本實施例中新拉出之奈米礙管膜24之獅 照片。 冷(3)將拉出之奈米碳管膜24經由一有機溶劑浸潤處理後收縮成爲一奈米 > 碳管絲30 »具體操作如下：於奈米碳管膜24之一側斜上方放置一第一容器 40 ’其用於盛裝處理奈米碳管膜24之有機溶劑5〇。該有機溶劑5〇爲挥發随 有2劑’如乙醇、甲醇、丙酮、二氣乙紐氣仿，本實施例中採用乙醇。 該谷器40具有-流道42，該流道42有一通孔44，用於給奈米碳管膜24供 有機溶劑。如第四圖所示爲流道42於其通孔糾處之截面圖。將所述奈 碳管f 24收攏並使其穿過所述通孔鈕。有機溶劑5〇從流道42流出，同時 將奈米碳管賴麟道42之it孔連續拉伸丨，使奈純魏％於流道42 之通孔44處被有機溶劑5〇浸潤。當然，亦可不用收搬奈米碳管膜以，直接 用-個可使該奈米碳管膜24穿取可浸潤該奈米碳管膜24之裝置。於流道 42之通孔44下方放置一第二容器6〇 ’用於盛裝遺漏之有機溶劑。將奈米碳 8 1312337 管膜24經揮發性有機溶劑50浸潤處理後，將該奈米碳管膜24拉過該通孔 44時，於揮發；·生有機溶劑50表面張力作用下，奈米碳管膜24收縮成直徑爲 20~30微米之奈米碳官絲30。如第五圖所示即爲所製得之奈米碳管絲加之 SEM照片°該奈米破官絲30係由複數根奈米碳管線緊密結合於一起所構成， 其中，所述奈米碳管線缺複數首尾相接之奈米碳管片段，每個奈米碳管片 段具有大且軸絲碳管版由複數相互平行之奈米碳管束 構成。該奈米碳官絲30表面體積比小，無點性，且具有良好之機械強度及 勃性，能方便地應用於宏觀之各個領域The method for preparing the carbon nanotube wire can be collected by infiltrating the carbon nanotube film pulled out from the carbon nanotube array, and the nano carbon tube wire can be simply collected. The carbon nanotubes are closely combined and combined, and the carbon nanotube segments of the carbon nanotubes are connected to each other, and each of the carbon nanotube segments has substantially the same length, and each The carbon nanotube segments are composed of a plurality of carbon nanotube bundles that are parallel to each other. The carbon nanotube wire has a small surface volume ratio, no viscosity, and has good mechanical strength and dynamic properties, and can be conveniently applied to the macroscopic plural field. [Embodiment] Hereinafter, embodiments of the present invention will be further described in detail with reference to the accompanying drawings. A method for fabricating a carbon nanotube wire provided in this embodiment includes the following step: providing a carbon nanotube array of 'using a stretching tool to pull a carbon nanotube medium from the carbon nanotube array; The drawn carbon nanotube film is infiltrated by an organic solvent and then shrunk into a nano carbon tube filament; the obtained nano carbon tube filament is collected. Referring to the second to fifth figures, the various steps will be specifically described below: (1) Providing a carbon nanotube array 20» Preferably, the carbon nanotube array 20 is a super-shunned carbon carbon array. The method for growing the super-sequential carbon nanotube array 2 by chemical vapor deposition in the present embodiment is described in the Chinese Patent Application Publication No. 02134760.3. The growth method of the super-sequential carbon nanotube array 20 mainly includes Step: (a) providing a smooth substrate, the substrate may be selected from a p-type or n-type stone substrate, (6) depositing a catalyst layer on the substrate, the catalyst layer may be made of iron (Fe), cobalt (Co), Nickel (Ni) or its alloy - (c) The catalyst layer 4 is deposited in a shielding gas and annealed at a temperature of 300 to 400 ° C for about 1 hour; the annealing portion is 7 1312337 The wire deposited with the catalyst layer is heated to 500~70 (rc, a mixed gas of carbon source gas and shielding gas is introduced, and the flow rate of the carbon source gas is controlled, so that the difference between the catalyst and the environment is 5 (rc or more, control) The surface ratio of the mixed gas is 'the partial pressure of the carbon source gas, 妓5~3Q , the carbon nanotube array will record the bottom of the "where the carbon source gas is a hydrogen-blocking compound, which can be acetylene, ethane, etc., preferably acetylene, the protective gas is inert or nitrogen. The raft is prepared by the above method. Nano carbon: Array 20 + nano carbon tubes are densely arranged in bundles, with high surface density, and there is a strong breaking force between the carbon nanotube bundles, which not only has a large diameter distribution, but also a diameter. The size is almost the same. (2) A carbon nanotube film 24 is pulled from the carbon nanotube array 20 by a stretching tool. It can be operated according to the method: (4) the carbon nanotube array 2 Aligning a carbon nanotube segment comprising a plurality of carbon nanotube bundles; (b) stretching the carbon nanotube segment 2 along a starting tensile force using a stretching tool, such as a tweezers, during the stretching process, the nanometer The carbon tube fragments are elongated in the tensile direction under the action of the tensile force, and the two ends of the carbon nanotube segments are connected end to end due to the action of the van der Waals force, thereby forming a continuous nano carbon line 22, which Nano carbon tube in the first model of the 22 carbon strips 14. Repeatedly pulling several times to pull out a number of nano-disc pipelines 22 face carbon tube film 24» This newly pulled nano carbon tube film 24 has a few micrometers thick, difficult rice width ' as shown in the third figure Shown is the photograph of the lion of the newly pulled nano tube film 24 in the present embodiment. The cold (3) shrinks the drawn carbon nanotube film 24 by an organic solvent and shrinks into a nanometer> The carbon tube wire 30 is specifically operated as follows: a first container 40 is placed obliquely above one side of the carbon nanotube film 24 for holding the organic solvent 5 处理 for treating the carbon nanotube film 24. The organic solvent 5 〇 In the present embodiment, ethanol is used for volatilization with two doses such as ethanol, methanol, acetone, and dioxyne. The trough 40 has a flow passage 42 having a through hole 44 for The carbon nanotube film 24 is supplied with an organic solvent. As shown in the fourth figure, a cross-sectional view of the flow path 42 at its through hole is shown. The carbon nanotubes f 24 are gathered and passed through the through-hole knobs. The organic solvent 5 流出 flows out from the flow channel 42 while the inner pores of the carbon nanotubes of the lyon 42 are continuously stretched, so that the neats are infiltrated by the organic solvent 5 at the through holes 44 of the flow channel 42. Of course, it is also possible to use the carbon nanotube film without the retraction, and the carbon nanotube film 24 can be directly used to pass through the device capable of infiltrating the carbon nanotube film 24. A second container 6'' is placed under the through hole 44 of the flow path 42 for containing the missing organic solvent. After the nano carbon 8 1312337 film 24 is infiltrated by the volatile organic solvent 50, the carbon nanotube film 24 is pulled through the through hole 44 to volatilize; · under the surface tension of the organic solvent 50, the nanometer The carbon tube film 24 is shrunk into a nano carbon official silk 30 having a diameter of 20 to 30 μm. As shown in the fifth figure, the SEM photograph of the prepared nano carbon tube wire is formed. The nano broken official silk 30 is composed of a plurality of nano carbon lines which are closely combined together, wherein the nano carbon is formed. The pipeline lacks a plurality of carbon nanotube segments that are connected end to end. Each carbon nanotube segment has a large and the carbon nanotube plate is composed of a plurality of carbon nanotube bundles that are parallel to each other. The nano-carbon official silk 30 has a small surface volume ratio, no dot, and has good mechanical strength and boring property, and can be conveniently applied to various fields of macroscopic purposes.
(4)收集所製得之奈米碳管絲30。具體爲採用電機7〇將該奈米碳管絲 30卷到線轴80上即可。當然亦可採用手工將其卷到雜上，使其可方便地 於宏觀領域進一步應用。 當然，可以理解，亦可以將拉取出來之雜奈求碳管膜完全浸敝有機 溶劑内使其浸’潤後從該有機溶劑中取出，於該有機溶劑面張力作用下， 該奈米碳魏亦可_成_奈米碳魏，再工具將該奈練管絲卷 起收集即可。 综城述’本辦月確已符合發明專利要件，麦依法提出專利中請。惟， 以讲述者僅為本發明之較佳實施例，舉凡熟悉本案技藝之人士，於援贴 案發明精神所作之等效雜或變化，皆應包含於以下之申請專圍之内。 【圖式簡單說明】 第一圖係先前技術中從一超順排奈米碳管陣列拉出一根連續奈米碳管 線之模型圖》 第二圖係本發明實施例製作奈米碳管絲之過程示意圖。 第二圖係本發明實施例中奈米碳管膜之SEM照片。 第四圖係本發明實施例中第一容器之流道於其通孔處之截面圖。 第五圖係本發明實施例所製得之奈米碳管絲之S£M照片。 【主要元件符號說明】 ' 10'20 奈米碳管片段 12 14、22 奈米碳管膜 24 30 第一容器 40 奈米碳管陣列 奈米碳管線 奈米碳管絲 9 1312337 流道 42 通孔 44 有機溶劑 50 第二容器 60 電機 70 線軸 80 10(4) The obtained carbon nanotube wire 30 was collected. Specifically, the carbon nanotube wire 30 can be wound onto the bobbin 80 by using a motor 7?. Of course, it can also be rolled onto the hand by hand, making it easy to further apply in the macroscopic field. Of course, it can be understood that the extracted carbon nanotube film can be completely immersed in an organic solvent to be immersed and then taken out from the organic solvent, and the nanocarbon is subjected to the surface tension of the organic solvent. Wei can also _ into _ nano carbon Wei, and then the tool can be rolled up and collected. The comprehensive city said that the office has indeed met the requirements of the invention patent, and the patent is filed in accordance with the law. However, the narrator is only a preferred embodiment of the present invention, and any equivalents or variations made by those skilled in the art of the present invention should be included in the following application. BRIEF DESCRIPTION OF THE DRAWINGS The first figure is a model drawing of a continuous nanocarbon line drawn from a super-sequential carbon nanotube array in the prior art. The second figure is a carbon nanotube wire produced by the embodiment of the present invention. Schematic diagram of the process. The second figure is a SEM photograph of a carbon nanotube film in an embodiment of the present invention. The fourth figure is a cross-sectional view of the flow path of the first container in the through hole at the embodiment of the present invention. The fifth drawing is a photograph of the S£M of the carbon nanotube wire produced in the examples of the present invention. [Main component symbol description] '10'20 carbon nanotube segment 12 14, 22 carbon nanotube film 24 30 first container 40 carbon nanotube array nano carbon pipe nano carbon tube wire 9 1312337 channel 42 Hole 44 organic solvent 50 second container 60 motor 70 spool 80 10