201202134 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複合結構。 【先前技術】 [0002] 奈米碳管係一種由石墨烯片卷成之中空管狀物。奈米碳 管具有優異之力學、熱學及電學性質，其應用領域非常 廣闊。例如，奈米碳管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、奈米模板等。上述技術 中奈米碳管之應用主要係奈米碳管在微觀尺度上之應用 ® ，操作較困難。故，使奈米碳管具有宏觀尺度之結構並 在宏觀上應用具有重要意義。 [0003] 姜開利等人於2002年成功地從一奈米碳管陣列拉取獲得 一具有宏觀尺度之奈米碳管線，具有請參見文獻“Spin-ning Continuous Carbon Nanotube Yarns” ， Nature，V419，P801。所述奈米碳管線由複數首尾 相連且基本沿同一方向擇優取向排列之奈米碳管組成。 〇 [0004] 然，所述奈米碳管線中之奈米碳管之間之結合力較弱， 故，所述奈米碳管線之機械性能還需進一步提高。 【發明内容】 [0005] 有鑒於此，提供一種具有良好機械性能之奈米碳管複合 結構實為必要。 [0006] —種奈米碳管複合結構，其包括一奈米碳管膜結構及一 石墨結構。所述奈米碳管膜結構具有複數微孔，所述石 墨結構與所述奈米碳管膜結構複合。所述石墨結構包括 099122584 表單編號A0101 第3頁/共27頁 0992039786-0 201202134 複數石墨片段填充在所述複數微孔中。 [0007] 一種奈米碳管複合結構，其包括一奈米碳管膜結構，所 述奈米碳管膜結構具有複數微孔。所述奈米碳管複合結 構進一步包括複數石墨片段填充在所述複數微孔中。該 石墨片段通過碳碳鍵與所述奈米碳管膜結構結合，相鄰 的石墨片段通過碳碳鍵結合。 [0008] 相較於先前技術，所述奈米碳管複合結構在所述奈米碳 管膜結構填充有複數石墨片段，所述複數石墨片段與所 述奈米碳管膜結構複合後能夠增強該奈米碳管結構中奈 米碳管之間的結合力，從而使所述奈米碳管複合結構的 具有優異的機械性能。 【實施方式】 [0009] 以下將結合附圖對本發明作進一步詳細之說明。 [00103 本發明實施例提供一奈米碳管複合結構之製備方法，其 具體包括如下步驟： [0011] 步驟S10，提供一奈米碳管結構，所述奈米碳管結構包括 複數奈米碳管通過凡得瓦力（Van der Waals attractive force) 連接； [0012] 步驟S20，所述奈米碳管結構中複合一聚合物；以及 [0013] 步驟S30，石墨化複合有聚合物之奈米碳管結構，使所述 聚合物石墨化為一石墨結構。 [0014] 在步驟S10中，所述奈米碳管結構為由複數奈米碳管通過 凡得瓦力彼此相連構成之一奈米碳管骨架，所述奈米碳 099122584 表單編號A0101 第4頁/共27頁 0992039786-0 201202134 θ [0015] Ο [0016] s月架可為膜狀結構、線狀結構或者其他形狀之結構。 所述奈米礙管結構為—奈米碳管自支推結構，所謂“自 支撐即該奈米碳管結構無需通過設置於—基體表面， 2緣或者相對端部提供支撐而其未得到支撐之其他部 分能保持自身特定之形狀。由於該自續之奈米碳管結 構中大量之奈米碳管通過凡得瓦力相互吸引從而使該 奈米碳管結構具有特定之形狀，形成-自支#結構。通 常所述自支撐之奈米碳管結構中距離在〇. 2奈米到9奈 米之間之奈米碳管之數量較多，這部分奈米碳管之間具 有較大之凡得瓦力，從，使得所述奈米碳管結構僅通過 凡得瓦力即可形成自支撐結構- 所述奈米碳管結構可包括一奈米碳管膜結構，所述奈米 碳管膜結構為一具有複數微孔之膜狀結構。所述微孔由 複數奈米碳管通過凡得瓦力相互連接而形成，形成所述 微孔之奈米碳管可處於同一平面，也可處於不同平面。 該微孔之尺寸在1奈米到5〇〇奈米之間。所述条米碳管膜 結構之結構不限，僅能形成複數上述微孔即町。優選地 ，所述奈米碳管膜結構可為一自支撐結構，從而該奈米 碳管膜結構可作為所述奈米碳管複合結構之貧架。所謂 “自支撐”即該奈米碳管膜結構無需通過設寰於一基體 表面，也忐保持自身特定之形狀。由於該自支撐之奈米 破管膜結構包括大量之奈米碳管通過凡得瓦力相互吸引 ，從而使該奈米碳管膜結構具有特定之形狀，形成一自 支撐結構。 所述奈米碳管膜結構可包括至少一奈米碳管膜，當所述 099122584 表單編號A0101 第5頁/共27頁 0992039786-0 201202134 奈米碳管膜結構包括複數奈米碳管膜時，該複數奈米碳 管膜層疊設置，相鄰之奈米碳管膜之間通過凡得瓦力相 結合。 [0017] 請參閱圖1，所述奈米碳管膜可為一奈米碳管絮化膜，該 奈米碳管絮化膜為將一奈米碳管原料，如一超順排陣列 ，絮化處理獲得之一自支撐之奈米碳管膜。該奈米碳管 絮化膜包括相互纏繞且均勻分佈之奈米碳管。奈米碳管 之長度大於10微米，優選為200微米到900微米，從而使 奈米碳管相互纏繞在一起。所述奈米碳管之間通過凡得 瓦力相互吸引、分佈，形成網路狀結構。由於該自支撐 之奈米碳管絮化膜中大量之奈米碳管通過凡得瓦力相互 吸引並相互纏繞，從而使該奈米碳管絮化膜具有特定之 形狀，形成一自支撐結構。所述奈米碳管絮化膜各向同 性。所述奈米碳管絮化膜中之奈米碳管為均勻分佈，無 規則排列，形成大量尺寸在1奈米到500奈米之間之間隙 或微孔。所述奈米碳管絮化膜之面積及厚度均不限，厚 度大致在0. 5奈米到100微米之間。 [0018] 所述奈米碳管膜可為一奈米碳管碾壓膜，該奈米碳管碾 壓膜為通過碾壓一奈米碳管陣列獲得之一種具有自支撐 性之奈米碳管膜。該奈米碳管碾壓膜包括均勻分佈之奈 米碳管，奈米碳管沿同一方向或不同方向擇優取向排列 。所述奈米碳管碾壓膜中之奈米碳管相互部分交疊，並 通過凡得瓦力相互吸引，緊密結合，使得該奈米碳管膜 具有很好之柔韌性，可彎曲折疊成任意形狀而不破裂。 且由於奈米碳管碾壓膜中之奈米碳管之間通過凡得瓦力 099122584 表單編號A0101 第6頁/共27頁 0992039786-0 201202134 相互吸引，緊密結合，使奈米碳管碾壓膜為一自支撐之 結構。所述奈米碳管碾壓膜中之奈米碳管與形成奈米碳 管陣列之生長基底之表面形成一夾角卢，其中，yS大於 等於0度且小於等於15度，該夾角/3與施加在奈米碳管陣 列上之壓力有關，壓力越大，該失角越小，優選地，該 奈米碳管碾壓膜中之奈米碳管平行於該生長基底排列。 該奈米碳管碾壓膜為通過碾壓一奈米碳管陣列獲得，依 據碾壓之方式不同，該奈米碳管碾壓膜中之奈米碳管具 有不同之排列形式。具體地，奈米碳管可無序排列；請 Ο 參閱圖2，當沿不同方向碾壓時，奈米碳管沿不同方向擇 優取向排列；當沿同一方向碾壓時，奈米碳管沿一固定 方向擇優取向排列。該奈米碳管碾壓膜中奈米碳管之長 度大於50微米。該奈米碳管碾壓膜之面積與奈米碳管陣 列之尺寸基本相同。該奈米碳管碾壓膜厚度與奈米碳管 陣列之高度以及碾壓之壓力有關，可為0. 5奈米到100微 米之間。可以理解，奈米碳管陣列之高度越大而施加之 壓力越小，則製備之奈米碳管碾壓膜之厚度越大；反之 〇 ，奈米碳管陣列之高度越小而施加之壓力越大，則製備 之奈米碳管碾壓膜之厚度越小。所述奈米碳管碾壓膜之 中之相鄰之奈米碳管之間具有一定間隙，從而在奈米碳 管碾壓膜中形成複數尺寸在1奈米到500奈米之間之間隙 或微孔。 [0019] 所述奈米碳管膜可為一奈米碳管拉膜，且此時所述奈米 碳管膜結構至少包括兩層奈米碳管拉膜。請參見圖3，所 述形成之奈米碳管拉膜係由若干奈米碳管組成之自支撐 099122584 表單編號A0101 第7頁/共27頁 0992039786-0 201202134 結構。所述若干奈米碳管為沿該奈米碳管拉膜之長度方 向擇優取向排列。所述擇優取向係指在奈米碳管拉膜中 大多數奈米碳管之整體延伸方向基本朝同一方向。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 管拉膜之表面。進一步地，所述奈米碳管拉膜中多數奈 米碳管係通過凡得瓦力首尾相連。具體地，所述奈米碳 管拉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得瓦力 首尾相連。當然，所述奈米碳管拉膜中存在少數偏離該 延伸方向之奈米碳管，這些奈米碳管不會對奈米碳管拉 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拉膜不需要大面積之載體支撐，而 僅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，即將該奈米碳管拉膜置於（或固定於）間隔一定 距離設置之兩個支撐體上時’位於兩個支撐'體之間之奈 米碳管拉膜能夠懸空保持自身膜狀狀態。所述自支撐主 要通過奈米碳管拉膜中存在連續之通過凡得瓦力首尾相 連延伸排列之奈米碳管而實現。具體地，所述奈米碳管 拉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，可適當之彎曲；或者並非完全按照延伸方向 上排列，可適當之偏離延伸方向。故，不能排除奈米碳 管拉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。 [0020] 具體地，該奈米碳管拉膜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得瓦力首尾相 099122584 表單編號A0101 第8頁/共27頁 0992039786-0 201202134 連。每一奈米碳管片段由複數相互平行之奈米碳管組成 。該奈米碳管片段具有任意之長度、厚度、均勻性及形 狀。該奈米碳管拉膜具有較好之透光性，可見光透過率 可達到75%以上。 [0021] ❹ 當所述奈米碳管膜結構包括多層奈米碳管拉膜時，相鄰 兩層奈米碳管拉膜中之擇優取向排列之奈米碳管之間形 成一交叉角度α，α大於等於0度小於等於90度（0° a 90°)。請參閱圖4,優選地，為提高所述奈米碳管膜 之強度，所述交叉角度α大致為90度，即相鄰兩層奈米 碳管拉膜中之奈求碳管之排列方向基本垂直，形成一交 叉膜。所述複數奈米碳管拉膜之間或一個奈米碳管拉膜 之中之相鄰之奈米碳管之間具有一定間隙，從而在奈米 碳管結構中形成複數均勻分佈，無規則排列，尺寸在1奈 米到500奈米之間之間隙或微孔。201202134 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a carbon nanotube composite structure. [Prior Art] [0002] A carbon nanotube is a hollow tube rolled from a graphene sheet. Nano carbon tubes have excellent mechanical, thermal and electrical properties and are used in a wide range of applications. For example, carbon nanotubes can be used to make field effect transistors, atomic force microscope tips, field emission electrons, nano templates, and the like. The application of the carbon nanotubes in the above technology is mainly applied to the microscopic scale of the carbon nanotubes of the carbon nanotubes, and the operation is difficult. Therefore, it is important to make the carbon nanotubes have a macroscopic structure and to be applied at a macroscopic level. [0003] Jiang Kaili et al. successfully extracted a nanometer carbon pipeline with a macroscopic scale from a carbon nanotube array in 2002, see the document "Spin-ning Continuous Carbon Nanotube Yarns", Nature, V419, P801. . The nanocarbon pipeline is composed of a plurality of carbon nanotubes connected end to end and arranged in a preferred orientation along the same direction. 0004 [0004] However, the bonding force between the carbon nanotubes in the nanocarbon pipeline is weak, so the mechanical properties of the nanocarbon pipeline need to be further improved. SUMMARY OF THE INVENTION [0005] In view of the above, it is necessary to provide a carbon nanotube composite structure having good mechanical properties. [0006] A carbon nanotube composite structure comprising a carbon nanotube membrane structure and a graphite structure. The carbon nanotube membrane structure has a plurality of micropores, and the graphite structure is composited with the carbon nanotube membrane structure. The graphite structure includes 099122584 Form No. A0101 Page 3 of 27 0992039786-0 201202134 A plurality of graphite fragments are filled in the plurality of micropores. [0007] A carbon nanotube composite structure comprising a carbon nanotube membrane structure, the nanocarbon membrane membrane structure having a plurality of micropores. The carbon nanotube composite structure further includes a plurality of graphite segments filled in the plurality of micropores. The graphite fragments are bonded to the carbon nanotube film structure by carbon-carbon bonds, and adjacent graphite fragments are bonded by carbon-carbon bonds. [0008] Compared to the prior art, the carbon nanotube composite structure is filled with a plurality of graphite fragments in the carbon nanotube film structure, and the plurality of graphite fragments can be enhanced after being combined with the carbon nanotube film structure. The bonding force between the carbon nanotubes in the carbon nanotube structure, so that the carbon nanotube composite structure has excellent mechanical properties. [Embodiment] The present invention will be further described in detail below with reference to the accompanying drawings. [00103] Embodiments of the present invention provide a method for preparing a carbon nanotube composite structure, which specifically includes the following steps: [0011] Step S10, providing a carbon nanotube structure, the carbon nanotube structure including a plurality of nano carbon The tube is connected by Van der Waals attractive force; [0012] step S20, compounding a polymer in the carbon nanotube structure; and [0013] step S30, graphitizing the polymer-composited nano The carbon tube structure graphitizes the polymer into a graphite structure. [0014] In step S10, the carbon nanotube structure is composed of a plurality of carbon nanotubes connected to each other by a van der Waals force to form a carbon nanotube skeleton, the nanocarbon 099122584 Form No. A0101 Page 4 / Total 27 pages 0992039786-0 201202134 θ [0015] The s-moon frame may be a film structure, a wire structure or other shape structure. The nano-barrier structure is a self-supporting structure of carbon nanotubes. The so-called "self-supporting, that is, the carbon nanotube structure does not need to be supported on the surface of the substrate, and the two edges or opposite ends provide support without being supported. The other part can maintain its own specific shape. Since a large number of carbon nanotubes in the self-sustaining carbon nanotube structure attract each other by van der Waals force, the carbon nanotube structure has a specific shape, forming - self The structure of the support. Generally, the number of carbon nanotubes in the self-supporting carbon nanotube structure is between 2 nm and 9 nm, and the carbon nanotubes are larger. The van der Waals force, so that the carbon nanotube structure can form a self-supporting structure only by van der Waals force - the carbon nanotube structure can include a carbon nanotube film structure, the nano The carbon tube membrane structure is a membrane-like structure having a plurality of micropores formed by interconnecting a plurality of carbon nanotubes by van der Waals, and the carbon nanotubes forming the micropores can be in the same plane. Can also be in different planes. The size of the micropores is 1 nm. Between 5 nanometers, the structure of the carbon nanotube film structure is not limited, and only a plurality of micropores can be formed. Preferably, the carbon nanotube membrane structure can be a self-supporting structure, thereby The carbon nanotube film structure can be used as a lean frame of the carbon nanotube composite structure. The so-called "self-supporting" means that the carbon nanotube film structure does not need to be placed on a substrate surface, and also maintains its own specific shape. Since the self-supporting nanotube membrane structure comprises a large number of carbon nanotubes attracted to each other by van der Waals force, the carbon nanotube membrane structure has a specific shape to form a self-supporting structure. The carbon nanotube film structure may include at least one carbon nanotube film, when the 099122584 form number A0101 page 5 / 27 pages 0992039786-0 201202134 nano carbon film structure includes a plurality of carbon nanotube films, the plural The carbon nanotube membranes are stacked, and the adjacent carbon nanotube membranes are combined by van der Waals force. [0017] Referring to FIG. 1, the carbon nanotube membrane can be a nano carbon tube flocculation. Membrane, the carbon nanotube flocculation membrane is a carbon nanotube raw material As a super-aligned array, a self-supporting carbon nanotube membrane is obtained by flocculation treatment. The carbon nanotube flocculation membrane comprises carbon nanotubes which are intertwined and uniformly distributed. The length of the carbon nanotubes is greater than 10 micrometers. Preferably, the carbon nanotubes are entangled with each other by 200 micrometers to 900 micrometers. The carbon nanotubes are mutually attracted and distributed by van der Waals forces to form a network-like structure. A large number of carbon nanotubes in the carbon nanotube flocculation membrane are mutually attracted and intertwined by van der Waals force, so that the carbon nanotube flocculation membrane has a specific shape to form a self-supporting structure. The tube flocculation membrane is isotropic. The carbon nanotubes in the carbon nanotube flocculation membrane are uniformly distributed and randomly arranged to form a plurality of gaps or micropores having a size ranging from 1 nm to 500 nm. 5纳米至100微米之间。 The carbon nanotubes are not limited in area and thickness, the thickness is between about 0.5 nm to 100 microns. [0018] The carbon nanotube film may be a carbon nanotube rolled film, and the carbon nanotube film is a self-supporting nano carbon obtained by rolling a carbon nanotube array. Tube membrane. The carbon nanotube rolled film comprises uniformly distributed carbon nanotubes, and the carbon nanotubes are arranged in the same direction or in different directions. The carbon nanotubes in the carbon nanotube rolled film partially overlap each other and are attracted to each other by the van der Waals force, and the carbon nanotube film has good flexibility and can be bent and folded into Any shape without breaking. And because the carbon nanotubes in the carbon nanotube rolled film pass through the van der Waals force 099122584 Form No. A0101 Page 6 / Total 27 Page 0992039786-0 201202134 mutual attraction, close combination, so that the carbon nanotubes are crushed The membrane is a self-supporting structure. The carbon nanotubes in the carbon nanotube rolled film form an angle with the surface of the growth substrate forming the carbon nanotube array, wherein yS is greater than or equal to 0 degrees and less than or equal to 15 degrees, and the angle/3 is The pressure applied to the array of carbon nanotubes is related. The greater the pressure, the smaller the angle of loss. Preferably, the carbon nanotubes in the carbon nanotube rolled film are aligned parallel to the growth substrate. The carbon nanotube rolled film is obtained by rolling a carbon nanotube array, and the carbon nanotubes in the carbon nanotube rolled film have different arrangements depending on the manner of rolling. Specifically, the carbon nanotubes can be arranged in disorder; please refer to Figure 2. When rolling in different directions, the carbon nanotubes are arranged in different orientations; when rolled in the same direction, the carbon nanotubes are along A fixed orientation is preferred. The length of the carbon nanotubes in the carbon nanotube rolled film is greater than 50 microns. The area of the carbon nanotube rolled film is substantially the same as the size of the carbon nanotube array. The thickness of the carbon nanotube film is related to the height of the carbon nanotube array and the pressure of the rolling, and may be between 0.5 nm and 100 μm. It can be understood that the greater the height of the carbon nanotube array and the lower the pressure applied, the greater the thickness of the prepared carbon nanotube rolled film; conversely, the smaller the height of the carbon nanotube array and the applied pressure The larger the diameter, the smaller the thickness of the prepared carbon nanotube rolled film. a gap between adjacent carbon nanotubes in the carbon nanotube film, thereby forming a plurality of gaps between 1 nm and 500 nm in the carbon nanotube film Or micropores. [0019] The carbon nanotube film may be a carbon nanotube film, and at this time, the carbon nanotube film structure comprises at least two layers of carbon nanotube film. Referring to Fig. 3, the formed carbon nanotube film is self-supporting composed of a plurality of carbon nanotubes. 099122584 Form No. A0101 Page 7 of 27 0992039786-0 201202134 Structure. The plurality of carbon nanotubes are arranged in a preferred orientation along the length of the carbon nanotube film. The preferred orientation means that the overall extension direction of most of the carbon nanotubes in the carbon nanotube film is 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 film 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 few carbon nanotubes in the carbon nanotube film that deviate from the extending direction. These carbon nanotubes do not constitute an obvious alignment of the majority of the carbon nanotubes in the carbon nanotube film. influences. The self-supporting carbon nanotube film does not need a large-area carrier support, but only provides support force on both sides, and can be suspended in the whole to maintain its own film state, that is, the carbon nanotube film is placed (or When fixed on the two supports arranged at a certain distance, the carbon nanotube film between the two support bodies can be suspended to maintain its own film state. The self-supporting is mainly achieved by the presence of a continuous carbon nanotube in the carbon nanotube film which is continuously extended by van der Waals. Specifically, the majority of the carbon nanotubes extending substantially in the same direction in the carbon nanotube film are not absolutely linear and may be appropriately bent; or are not completely aligned in the extending direction, and may be appropriately deviated from the extending direction. . Therefore, it is not possible to exclude partial contact between the carbon nanotubes juxtaposed in the majority of the carbon nanotubes which are substantially extended in the same direction. [0020] Specifically, the carbon nanotube film comprises a plurality of continuous and aligned carbon nanotube segments. The plurality of carbon nanotube segments are connected by van der Waals end-to-end phase 099122584 Form No. A0101 Page 8 of 27 0992039786-0 201202134. Each carbon nanotube segment consists of a plurality of carbon nanotubes that are parallel to each other. The carbon nanotube segments have any length, thickness, uniformity and shape. The carbon nanotube film has good light transmittance and the visible light transmittance can reach more than 75%. [0021] ❹ When the carbon nanotube membrane structure comprises a multi-layered carbon nanotube film, a preferred angle between the adjacent two layers of carbon nanotube film forming a cross angle α is formed between the carbon nanotubes , α is greater than or equal to 0 degrees and less than or equal to 90 degrees (0° a 90°). Referring to FIG. 4, preferably, in order to increase the strength of the carbon nanotube film, the intersection angle α is approximately 90 degrees, that is, the arrangement direction of the carbon tubes in the adjacent two layers of carbon nanotube film Basically vertical, forming a cross film. There is a gap between the adjacent carbon nanotube film or between adjacent carbon nanotubes in a carbon nanotube film, thereby forming a plurality of uniform distributions in the carbon nanotube structure, without rules Arranged, with a size between 1 nm and 500 nm or a micropore.
[0022] G 所述奈米碳管結構可包括至少一奈米碳管線結構，當所 述奈米碳管結構包括複數奈米碳管線結構時，所述複數 奈米碳管線可相互平行、纏繞或編織設置。所述奈米碳 管線結構包括至少一奈米碳管線，所述奈米碳管線包括 複數奈米碳管通過凡得瓦力相互連接且基本沿所述奈米 碳管線之軸向延伸。當所述奈米碳管線結構包括複數奈 米碳管線時，所述複數奈米碳管線可相互平行或纏繞設 置。所述奈米碳管線之結構不限，優選地，所述奈米碳 管線為一自支撐結構。所謂“自支撐”即該奈米碳管線 無需通過設置於一基體表面，也能保持自身特定之形狀 。由於該自支撐之奈米碳管線中大量之奈米碳管通過凡 099122584 表單編號Α0101 第9頁/共27頁 0992039786-0 201202134 之 =力9互❿從而使讀奈米集結構具有特定 料—自捕結構。通常，所料米碳管線中之 二=之間具有較大之凡得瓦力，從而使得所述奈米 :=構僅通過凡得瓦力即可形成所越自支撑結構。 二結構包括複數奈米碳管線時，所述複 線可相互平行或纏繞設置 碳管線同過凡得〖力連接。 [0023] 所述奈米碳管線可為將 線結構，所述奈米碳管_ Is _過處理形成之 機溶劑浸潤處理或職轉處·包括用揮發性有 浸潤處理可通過試管將 _發性有機溶劑 面浸潤整個4心在奈米碳管拉膜表 米故官拉棋，或者 一膜之固定框架整個浸人盛有有機 浸潤。該揮發性有機溶劑為乙醇、甲酵劑之合 烧或氣仿’本實施射 醇、㈣、二氣乙 硐乙知。所述有機溶劑在揮發 軸料w管减_誠所述奈米碳 吕線。請參閱圖5,通過揮發性有機溶劑浸潤處理所得到 之奈米破管線為—非扭轉之奈㈣管線，該非扭轉之奈 未碳官線包括複數沿Μ碳管線長度方向排列之奈来碳 s ’、體地該非扭轉之奈米碳管線包括複數奈米碳管 通過凡付瓦力首尾相連且沿奈米後管線韩向擇優取向排 列所述機械扭轉處理可通過採用一機械力將所述奈米 碳管拉錢端沿相反方向扭轉。請參閱圖6 ，通過機械扭 轉處理而得到之奈米碳管線為—扭轉之奈米破管線，該 扭轉之奈米後管線包括複數繞奈米礙管線軸向螺旋排列 099122584 表單編號Α0101 第1〇頁/共27頁 0992039786-0 201202134 之奈米碳管。具體地，該扭轉之奈米碳管線包括複數奈 米碳管通過凡得瓦力首尾相連且沿奈米碳管線輪向呈螺 旋狀延伸。可以理解，也可對獲得之奈米碳管拉膜同時 或者依次進行有機溶劑揮發性有機溶劑浸潤處理或機械 扭轉處理來獲得所述扭轉之奈米碳管線。 [0024] Ο 在步驟S20中’所述奈米碳管結構中複合所述聚合物之方 法不限，僅能夠使所述聚合物與所述奈米碳管結構中之 複數奈米碳管複合，並在所述複數奈米碳管與聚合物之 間形成複數共價鍵即可。具體地，使所述奈米碳管結構 複合有聚合物之方參寸進一步包括如下步驟：S21，將所 述奈米碳管結構浸潤在一聚合物溶液中以與所述聚合物 複合。 。 [0025] ❹ 在步驟S21中，所述聚合物溶液可通過將所述聚合物直接 熔融或將所述聚合物溶解於一溶劑而得到。在本實施例 中，所述聚合物溶液通過將該聚合物溶解於—有機^容劑 而得到。所述聚合物之種類與性質不限，可根據實際需 求而選擇。所述聚合物可包括聚丙烯腈（polyae_ rylonitrile，PAN)、聚乙烯醇（p〇lyVinyl alc〇_ hoi, PVA)、聚丙烯（Polypropylene，pp)、聚苯 乙烯（Polystyrene，PS)、聚氣乙烯（p〇lyvinyl_ chlorid，PVC)及聚對苯二甲酸乙二酯（p〇lyethyl_ ene terephthalate，PET)中之任意一種或任旁、組合 。所述聚合物之聚合度也可根據實際操作而選擇。優選 地，所述聚合物之聚合度在1500到3500之間，從而使得 所述聚合物既可被溶解’又可與奈米碳管又保持—定之 099122584 表單编號Α0101 第11頁/共27頁 0992039786-0 201202134 浸潤性。所述聚合物溶液中之聚合物之品質百分比根據 聚合物及有機溶劑之不同而不同，通常，所述聚合物溶 液中之聚合物之品質百分比大致在1%到9%之間。所述有 機溶劑用於溶解所述聚合物，並能夠與所述奈米碳管浸 潤，從而能夠使所述聚合物充分複合到所述奈米碳管結 構中甚至複合到所述奈米碳管結構中之奈米碳管内部。 優選地，所述有機溶劑在能能溶解所述聚合物之同時， 還具有較大之表面張力。具體地，可選擇表面張力大於 20毫牛每米且對奈米碳管之接觸角小於90度之有機溶劑 。所述有機溶劑可包括二曱基亞礙（Dimethyl Sulph-oxide，DMSO)、二甲基甲醯胺（0111161±71?〇〇13111-ide，DMF)、2,5-二曱基口夫咕（2,5-dimethyl furan )及 N -甲基0 比咯烧 _(N-methyl-2-pyrrolidone， NMP)中之任意一種或組合。由於所述有機溶劑之溶解能 力根據聚合物之不同而不同，故，所述有機溶劑之選擇 還需根據具體之聚合物而選擇。譬如，當所述聚合物為 聚乙烯醇時，所述有機溶劑可選擇二甲基亞砜。所述二 甲基亞砜之表面張力大致為43. 54毫牛每米且對奈米碳管 之接觸角大致為110度。所述有機溶劑對奈米碳管之接觸 角越小，所述聚合物對所述奈米碳管結構之浸潤性越好 ，所述聚合物與所述奈米碳管結構結合越緊密。所述有 機溶劑之表面張力越大，所述聚合物對所述奈米碳管結 構之浸潤性越好，使所述奈米碳管結構收縮之能力越強 ，所述聚合物與所述奈米碳管結構結合越緊密。 [0026] 當所述奈米碳管結構為奈米碳管膜結構時，所述聚合物 099122584 表單編號A0101 第12頁/共27頁 0992039786-0 201202134[0022] G The carbon nanotube structure may include at least one nanocarbon pipeline structure, and when the carbon nanotube structure includes a plurality of nanocarbon pipeline structures, the plurality of carbon nanotube pipelines may be parallel to each other and entangled Or weave settings. The nanocarbon line structure includes at least one nanocarbon line including a plurality of carbon nanotubes interconnected by van der Waals and extending substantially axially along the carbon nanotube line. When the nanocarbon line structure includes a plurality of carbon nanotube lines, the plurality of carbon nanotube lines may be disposed in parallel or wound with each other. The structure of the nanocarbon pipeline is not limited, and preferably, the nanocarbon pipeline is a self-supporting structure. The so-called "self-supporting" means that the nanocarbon pipeline can maintain its own specific shape without being disposed on a surface of a substrate. Since the large number of carbon nanotubes in the self-supporting nanocarbon pipeline pass through the 099122584 form number Α0101 page 9/27 page 0992039786-0 201202134 = force 9 mutual enthalpy, so that the read nano set structure has a specific material - Self-trapping structure. Typically, there is a greater Van der Waals force between the two of the metered carbon lines, such that the nano:= structure forms the self-supporting structure only by van der Waals. When the two structures include a plurality of carbon nanotubes, the double wires may be arranged in parallel or wound with each other. [0023] The nano carbon pipeline may be a wire structure, the carbon nanotube _ Is _ over-processed solvent infiltration treatment or turnover; including the use of volatile infiltration treatment can be passed through the test tube The organic solvent surface infiltrates the entire 4 cores in the carbon nanotubes to pull the film, and the entire frame is fixed with an organic infiltration. The volatile organic solvent is a combination of ethanol or a fermenting agent or a gas-like imitation of the alcohol, (4), and a second gas. The organic solvent is reduced in the volatilization of the axon tube. Referring to FIG. 5, the nano-crushed pipeline obtained by the volatile organic solvent infiltration treatment is a non-twisted nep (four) pipeline, and the non-twisted nai carbon no-carbon line includes a plurality of nanocarbons arranged along the length direction of the tantalum carbon pipeline. The non-twisted nanocarbon pipeline includes a plurality of carbon nanotubes connected end to end by a wattage force and arranged in a preferred orientation along the nanometer pipeline. The mechanical torsion treatment can be performed by using a mechanical force. The carbon tube pull end is twisted in the opposite direction. Referring to FIG. 6, the nano carbon pipeline obtained by the mechanical torsion treatment is a twisted nano-breaking pipeline, and the twisted nano-rear pipeline includes a plurality of twisted nanometer impediment pipelines. The axial spiral arrangement is 099122584. Form No. 1010101 Page / Total 27 pages 0992039786-0 201202134 Nano carbon tube. Specifically, the twisted nanocarbon pipeline includes a plurality of carbon nanotubes connected end to end by van der Waals force and spirally extending along the direction of the nanocarbon pipeline. It is to be understood that the twisted nanocarbon line can also be obtained by simultaneously or sequentially performing an organic solvent volatile organic solvent wetting treatment or a mechanical torsion treatment on the obtained carbon nanotube film. [0024] 方法 In step S20, the method of compounding the polymer in the carbon nanotube structure is not limited, and only the polymer can be composited with a plurality of carbon nanotubes in the carbon nanotube structure. And forming a complex covalent bond between the plurality of carbon nanotubes and the polymer. Specifically, the aspect in which the carbon nanotube structure is compounded with the polymer further comprises the step of: S21, impregnating the carbon nanotube structure in a polymer solution to compound with the polymer. . [0025] ❹ In step S21, the polymer solution can be obtained by directly melting the polymer or dissolving the polymer in a solvent. In this embodiment, the polymer solution is obtained by dissolving the polymer in an organic solvent. The type and nature of the polymer are not limited and can be selected according to actual needs. The polymer may include polyacrylonitrile (PAN), polyvinyl alcohol (p〇lyVinyl alc〇_hoi, PVA), polypropylene (Polypropylene, pp), polystyrene (PS), polygas. Either or any combination or combination of ethylene (p〇lyvinyl_ chlorid, PVC) and polyethylene terephthalate (PET). The degree of polymerization of the polymer can also be selected according to the actual operation. Preferably, the degree of polymerization of the polymer is between 1500 and 3500, such that the polymer can be both dissolved and maintained with the carbon nanotubes - 099122584 Form No. 101 0101 Page 11 of 27 Page 0992039786-0 201202134 Infiltration. The percentage by mass of the polymer in the polymer solution varies depending on the polymer and the organic solvent. Generally, the percentage of the polymer in the polymer solution is approximately between 1% and 9%. The organic solvent is used to dissolve the polymer and is capable of being wetted with the carbon nanotubes, thereby enabling the polymer to be sufficiently compounded into the carbon nanotube structure or even composited to the carbon nanotube Inside the carbon nanotubes in the structure. Preferably, the organic solvent has a large surface tension while being capable of dissolving the polymer. Specifically, an organic solvent having a surface tension of more than 20 mN per meter and a contact angle to a carbon nanotube of less than 90 degrees can be selected. The organic solvent may include Dimethyl Sulph-oxide (DMSO), dimethylformamide (0111161±71?〇〇13111-ide, DMF), 2,5-diinyl ketone Any one or combination of (2,5-dimethyl furan) and N-methyl-2-pyrrolidone (NMP). Since the dissolving power of the organic solvent varies depending on the polymer, the selection of the organic solvent is also selected depending on the specific polymer. For example, when the polymer is polyvinyl alcohol, the organic solvent may be selected from dimethyl sulfoxide. The surface tension of the dimethyl sulfoxide is approximately 43.54 milli-Nilometers per meter and the contact angle to the carbon nanotubes is approximately 110 degrees. The smaller the contact angle of the organic solvent to the carbon nanotubes, the better the wettability of the polymer to the carbon nanotube structure, and the closer the polymer is bonded to the carbon nanotube structure. The greater the surface tension of the organic solvent, the better the wettability of the polymer to the carbon nanotube structure, the stronger the ability to shrink the structure of the carbon nanotube, the polymer and the naphthalene The tighter the carbon nanotube structure is combined. [0026] When the carbon nanotube structure is a carbon nanotube film structure, the polymer 099122584 Form No. A0101 Page 12 of 27 0992039786-0 201202134
[0027] ❹ [0028] [0029] 099122584 溶液浸潤所述奈米碳管膜結構後，部分聚合物溶液將滲 透到所述奈米碳管膜結構之微孔中並與所述奈米碳管膜 結構中之奈米碳管接觸。所述聚合物溶液中之有機溶劑 蒸發後，其中之聚合物將與所述奈米碳管接觸緊密接觸 並形成共價鍵。且，當所述聚合物溶液填滿所述微孔後 ，還可在所述奈米碳管膜結構相對之兩個表面形成兩層 聚合物溶液層。所述聚合物溶液層中之有機溶劑蒸發後 ，兩層聚合物層將形成在所述兩個表面並將所述奈米碳 管膜結構夾持其中，形成一層狀結構。 當所述奈米碳管結構包括至少一奈米碳管線結構時，所 述聚合物溶液滲透在所述奈米碳管線結構十之間隙中， 並與該奈米碳管線結構中之奈米碳管浸潤。所述聚合物 溶液中之有機溶劑蒸發後，所述聚合物溶液中之聚合物 將纏繞或包覆所述奈米碳管線結構中首尾相連之奈米碳 管形成複數聚合物纖維，或填滿所述奈米碳管線結構中 之間隙，形成一個整體之聚合物結構。 在步驟S20中，也可通過原位聚合之方式使所述奈米碳管 結構複合有聚合物。具體地，使所述奈米碳管結構複合 有聚合物之方法可進一步包括如下步驟：S1 21，將所述 奈米碳管結構浸潤在一聚合物單體溶液中；以及S122， 使該聚合物單體產生聚合反應，該聚合物單體聚合反應 後成為聚合物與所述奈米碳管結構複合。 在步驟S121及S122中，所述聚合物單體可包括丙烯腈、 乙烯醇、丙烯、苯乙烯、氯乙烯或對苯二甲酸乙二酯。 所述聚合物單體經過聚合後生成聚丙烯腈、聚乙烯醇、 表單編號A0101 第13頁/共27頁 0992039786-0 201202134 聚丙烯、聚苯乙烯、聚氯乙烯或聚對苯二曱酸乙二酯。 [0030] 聚合物單體在同一有機溶劑中之溶解度要大於該聚合物 單體對應之聚合物在該有機溶劑中之溶解度。故，通過 原位聚合之方式使所述奈米碳管結構複合有聚合物之方 法，相對於將奈米碳管結構直接浸潤在所述聚合物溶液 中使所述聚合物與所述奈米碳管結構複合之方法，能夠 使所述聚合物之選擇範圍更廣。 [0031] 在步驟S30中，所述石墨化之方法不限，僅能夠使複合在 奈米碳管結構之聚合物形成石墨結構，且不破壞所述奈 米碳管結構即可。具體之，所述石墨化之方法可包括如 下步驟： [0032] S31，將所述複合有聚合物之奈米碳管結構在空氣中加熱 使所述聚合物進行預氧化；以及 [0033] S32，將預氧化後之聚合物放置於一真空環境或惰性氣體 環境高溫石墨化。 [0034] 在步驟S31中，所述預氧化之溫度大致在200度到300度 之間。 [0035] 在步驟S32中，所述真空環境或惰性氣體環境用於獲得低 氧或絕氧環境，從而使得所述奈米碳管結構在高溫時不 被氧化。當選擇真空環境時，所述真空環境中之大氣壓 小於5*1(Γ2帕，優選地，所述真空環境中之大氣壓小於 5*10_5帕。當選擇惰性氣體環境時，所述惰性氣體包括 氬氣、氮氣等。 099122584 表單編號Α0101 第14頁/共27頁 0992039786-0 201202134 [0036] ❹ 所述複合在奈米碳管結構中之聚合物在石墨化過程中去 掉大.Ρ刀之I、4及氧，形成所述石墨結構。且在石墨 化過程中石墨結構與奈米碳管結構之_成有複數碳碳 鍵’使所t墨結構與奈㈣管結構複合形成所述奈米 碳官複合結構。収碳碳軌可通過魏所述共價鍵而 形成，也可通過在高溫時使石墨結構中之子與奈米 碳管結構中之雙原子晶格重組時而形成。所述後碳鍵包 括在碳碳原子間形成之sp2*sp3鍵。具體地，所述碳碳 鍵包括在碳-以子間形叙sp2或sp3鍵。在奈米碳管複 合結構中’由於所述奈米碳管結構為-自支揮結構，該 奈米碳管結構為由複數奈米碳管制凡得瓦力相互連接 形成之奈米碳營骨架’而所边石墨給構則填充在該奈米 碳管骨架中，且通過碳碳鍵及凡得瓦力與所述奈米碳管 骨架緊密結合。 [0037] Ο 所述石墨結構之具體形態與石墨北時之具體工藝有關。 譬如，高溫石墨化之溫度通常在2000度以上，為達到不 同之石墨化效果，加熱到所述萆度之時間可根據實際需 要而選擇。當加熱速度較快時，所述聚合物容易石墨化 為石墨片段。所述石墨片段包括至少一石墨稀（ Graphene) ’當所述石墨片段包括複數石墨烯時，所述 複數石墨稀之間通過碳碳鍵結合。所述碳碳鍵包括在碳一 碳原子間形成之sp2或sp3鍵。具體地，所述碳碳鍵包括 在碳-碳原子間形成之sp2或sp3鍵。當加熱速度較緩慢時 ，所述聚合物容易石墨化為石墨纖維。所述石墨纖維為 所述聚合物纖維去掉大部分之氮、氫及氧而形成。所述 099122584 表單編號A0101 第15頁/共27頁 0992039786-0 201202134 石墨纖維又稱高模量碳纖維，該石墨纖維為分子結構已 石墨化、含碳量在99%以上具有層狀六方晶格石墨結構之 纖維。 [0038] 所述石墨結構之具體形態還與所述奈米碳管結構之結構 有關。當所述奈米碳管結構包括複數微孔時，所述聚合 物容易石墨化為複數石墨片段。當所述奈米碳管結構包 括複數首尾相連且基本沿同一方向延伸之複數奈米碳管 時，所述聚合物容易石墨化為複數石墨纖維。 [0039] 具體地，當所述奈米碳管結構包括至少一奈米碳管膜結 構時，填充在所述奈米碳管膜結構微孔中之聚合物被石 墨化為石墨片段。相鄰之石墨片段之間通過碳碳結合從 而形成所述石墨結構。填充在所述奈米碳管膜結構之微 孔中之石墨片段並不一定能完全填滿所述微孔，通常， 所述複數石墨片段附著在奈米碳管之管壁上或包覆於奈 米碳管之部分表面，且通過碳碳鍵與所述奈米碳管結合 。即，由所述奈米碳管膜結構與石墨結構複合形成之奈 米碳管複合結構基本由奈米碳管與石墨片段組成，所述 奈米碳管與所述石墨片段通過碳碳鍵及凡得瓦力結合。 [0040] 當所述奈米碳管膜結構相對之兩個表面具有兩層聚合物 層時，所述聚合物層在石墨化後在該奈米碳管膜結構兩 側形成兩層石墨層，從而形成一具有層狀結構之奈米碳 管複合結構。且，填充在所述奈米碳管膜結構兩側之石 墨片段與分佈在該奈米碳管膜結構兩側之石墨片段通過 碳碳鍵結合形成一整體結構。此時，所述奈米碳管膜結 構可被所述石墨結構完全包覆，複合在所述石墨結構之 099122584 表單編號A0101 第16頁/共27頁 0992039786-0 201202134 内部。故，從宏觀上看，所述石墨結構為一海綿狀結構 ，且將所述奈米碳管膜結構包埋其中。或者說，該複數 奈米碳管以自支撐之奈米碳管膜結構之形式設置於該石 墨結構中，且所述石墨結構與所述複數奈米碳管通過凡 得瓦力及碳碳鍵相結合。 [0041] 所述奈米碳管複合結構包括由複數奈米碳管形成之奈米 碳管膜結構及填充在該奈米碳管膜結構中之複數石墨片 段。所述複數奈米碳管之間除了用凡得瓦力結合之外， 還可通過所述石墨片段緊密結合，從而增加了所述複數 奈米碳管之間之結合力，提高了所述奈米碳管複合結構 之機械性能。而所述石墨片段與所述奈米碳管結構具有 較小之密度且均為碳素材料，故，由複數石墨片段與複 數奈米碳管複合形成之奈米碳管複合結構具有密度小、 耐腐蝕、耐潮等優點。 [0042] 當所述奈米碳管結構包括至少一奈米碳管攀結構時，所 述聚合物既可通過石墨化為複數石墨片段，又可石墨化 為複數石墨纖維。具體地，如果在石墨化之方法中，通 過快速加熱之方式進行石墨化，所述聚合物將被石墨化 為複數石墨片段。所述石墨片段與所述奈米碳管線結構 通過碳碳鍵結合形成奈米碳管複合結構。而如果在石墨 化之方法中，通過缓慢加熱之方式進行石墨化，則所述 聚合物將被石墨化為複數石墨纖維。所述石墨纖維與所 述奈米碳管通過凡得瓦力及碳碳鍵結合。所述石墨纖維 結構中之複數石墨纖維之間通過碳碳鍵或凡得瓦力相互 結合，並形成一個整體結構。 099122584 表單編號A0101 第17頁/共27頁 0992039786-0 201202134 [0043] [0044] [0045] 在同π米碳管線中之複數奈米碳管基本沿奈米碳管線 1向延伸’故’纏繞或包覆所述複數奈米碳管之石墨 纖維也基本沿所述奈米碳管線之軸向延伸。具體地當 所述奈米碳管線中之複數奈米碳管通過凡得瓦力首尾相 連且基本沿奈米碳管線軸向呈螺旋狀延伸，則所述石墨 纖維也基本沿奈米碳;I*妹向呈螺㈣延伸。當所述奈 米碳管，中之複數奈米碳管通過凡得瓦力首尾相連且沿 奈米碳官線軸向擇優取向排列，則所述石墨纖維也基本 沿所述奈米碳管線轴向擇優取向排列。在同一奈米碳管 線或奈米碳管線結蟫中之石墨纖維即可通過凡得瓦力結 合也可通過碳碳鍵結合，優選地，在同—奈米碳管線中 之石墨纖維通過碳碳鍵結合〇 所述奈米碳管複合結構也可看作0墨織維及奈米碳管 兩種碳素材料複合而成。具體地，所述奈米碳管複合結 攝玎包括複數石墨纖維，每一石墨纖維均包覆或纏繞有 旅數首尾相連之奈米碳管。所述旅敢_米碳管通過凡得 瓦力首尾相連且沿該石墨纖雉軸命延伸。所述複數石墨 殲維可相互平行、纏繞或編織設f。所述複數石墨纖維 之間可通過凡得瓦力或碳破鍵結合办成所述石墨纖維結 構。 所述奈米碳管複合結構包括由複數奈米噥管形成之奈米 碳管線結構及分佈在該奈米碳管線結樽中之石墨纖維。 所述複數奈米碳管之間除了用凡得瓦力結合之外，還可 通過所述石墨纖維緊密結合，也而’ 了所述複數奈米 破管之間之結合力，提高了所述条米嗲官複合結構之機 099122584 #單蝙號A0101 第18頁/共27頁 0992039786-0 201202134 能’尤其械高沿所述奈米碳管線結構轴向方向之 機械性能。而所述石墨纖維與所述奈米碳管結構具有較 小之密度且均為普材料，故，由複數石墨纖維與複數 不米碳管複合形叙奈米碳料合結構具有密度小、耐 腐蝕、耐潮等優點。[0027] [0029] 099122584 After the solution infiltrates the carbon nanotube membrane structure, a portion of the polymer solution will penetrate into the micropores of the carbon nanotube membrane structure and interact with the carbon nanotubes The carbon nanotubes in the membrane structure are in contact. After the organic solvent in the polymer solution is evaporated, the polymer therein will be in intimate contact with the carbon nanotube and form a covalent bond. Moreover, after the polymer solution fills the micropores, two layers of polymer solution may be formed on opposite surfaces of the carbon nanotube film structure. After the organic solvent in the polymer solution layer is evaporated, two polymer layers will be formed on the two surfaces and the carbon nanotube film structure is sandwiched therein to form a layered structure. When the carbon nanotube structure comprises at least one nanocarbon pipeline structure, the polymer solution penetrates into the gap between the nano carbon pipeline structure and the nanocarbon in the nanocarbon pipeline structure Tube infiltration. After the organic solvent in the polymer solution is evaporated, the polymer in the polymer solution will wrap or coat the carbon nanotubes connected end to end in the nanocarbon pipeline structure to form a plurality of polymer fibers, or fill up The gaps in the nanocarbon line structure form a unitary polymer structure. In step S20, the carbon nanotube structure may also be compounded with a polymer by in-situ polymerization. Specifically, the method of compounding the carbon nanotube structure with a polymer may further include the steps of: S1 21, impregnating the carbon nanotube structure in a polymer monomer solution; and S122, the polymerization The monomer generates a polymerization reaction, and the polymer monomer is polymerized to form a polymer complex with the carbon nanotube structure. In steps S121 and S122, the polymer monomer may include acrylonitrile, vinyl alcohol, propylene, styrene, vinyl chloride or ethylene terephthalate. The polymer monomer is polymerized to form polyacrylonitrile, polyvinyl alcohol, Form No. A0101, Page 13 of 27, 0992039786-0 201202134 Polypropylene, Polystyrene, Polyvinyl Chloride or Poly(terephthalic Acid) Diester. [0030] The solubility of the polymer monomer in the same organic solvent is greater than the solubility of the polymer corresponding to the polymer monomer in the organic solvent. Therefore, the method of compounding the carbon nanotube structure with a polymer by in-situ polymerization is performed by directly impregnating the carbon nanotube structure in the polymer solution to make the polymer and the nanometer. The carbon tube structure composite method enables a wider selection of the polymer. [0031] In the step S30, the method of graphitization is not limited, and only the polymer compounded in the carbon nanotube structure can be formed into a graphite structure without destroying the carbon nanotube structure. Specifically, the method of graphitization may include the following steps: [0032] S31, heating the polymerized carbon nanotube structure in air to pre-oxidize the polymer; and [0033] S32 The pre-oxidized polymer is placed in a vacuum environment or an inert gas atmosphere for high temperature graphitization. [0034] In step S31, the pre-oxidation temperature is approximately between 200 and 300 degrees. [0035] In step S32, the vacuum environment or the inert gas environment is used to obtain a low oxygen or anaerobic environment such that the carbon nanotube structure is not oxidized at a high temperature. When a vacuum environment is selected, the atmospheric pressure in the vacuum environment is less than 5*1 (Γ2 Pa, preferably, the atmospheric pressure in the vacuum environment is less than 5*10_5 Pa. When an inert gas environment is selected, the inert gas includes argon. Gas, nitrogen, etc. 099122584 Form No. 1010101 Page 14 of 27 0992039786-0 201202134 [0036] ❹ The polymer compounded in the carbon nanotube structure is removed during the graphitization process. 4 and oxygen, forming the graphite structure, and in the graphitization process, the graphite structure and the carbon nanotube structure have a plurality of carbon-carbon bonds, and the t-ink structure and the naphthalene structure are combined to form the nanocarbon. The composite carbon structure can be formed by the covalent bond described by Wei, or by recombining the child in the graphite structure with the diatomic lattice in the carbon nanotube structure at a high temperature. The carbon bond includes a sp2*sp3 bond formed between carbon carbon atoms. Specifically, the carbon-carbon bond includes a sp2 or sp3 bond in the carbon-to-sub-intern. In the carbon nanotube composite structure, The carbon nanotube structure is a self-supporting structure, the carbon nanotube The structure is a nanocarbon camp skeleton formed by interconnecting a plurality of nano-carbons to control the van der Waals force, and the graphite structure is filled in the carbon nanotube skeleton, and is bonded by carbon-carbon bonds and van der Waals. The carbon nanotube skeleton is tightly bonded. [0037] The specific morphology of the graphite structure is related to a specific process of graphite north. For example, the temperature of high temperature graphitization is usually above 2000 degrees, in order to achieve different graphitization effects. The time of heating to the temperature may be selected according to actual needs. When the heating rate is fast, the polymer is easily graphitized into graphite fragments. The graphite segment includes at least one graphite (as described) When the graphite segment comprises a plurality of graphenes, the plurality of graphites are diluted by carbon-carbon bonds. The carbon-carbon bonds include sp2 or sp3 bonds formed between carbon-carbon atoms. Specifically, the carbon-carbon bonds are included in a sp2 or sp3 bond formed between carbon-carbon atoms. When the heating rate is slow, the polymer is easily graphitized into graphite fibers. The graphite fibers remove most of the nitrogen and hydrogen from the polymer fibers. Formed. 099122584 Form No. A0101 Page 15 / Total 27 Page 0992039786-0 201202134 Graphite fiber is also called high modulus carbon fiber. The graphite fiber has a molecular structure that has been graphitized and has a layered hexagonal carbon content of 99% or more. a fiber of a lattice graphite structure. [0038] The specific form of the graphite structure is also related to the structure of the carbon nanotube structure. When the carbon nanotube structure includes a plurality of micropores, the polymer is easy to be graphite. The plurality of graphite segments are formed. When the carbon nanotube structure comprises a plurality of carbon nanotubes connected end to end and extending substantially in the same direction, the polymer is easily graphitized into a plurality of graphite fibers. [0039] Specifically, when the carbon nanotube structure includes at least one carbon nanotube film structure, the polymer filled in the micropores of the carbon nanotube film structure is graphiteized into graphite fragments. The graphite structure is formed by carbon-carbon bonding between adjacent graphite segments. The graphite fragments filled in the micropores of the carbon nanotube membrane structure do not necessarily completely fill the micropores. Usually, the plurality of graphite fragments are attached to the wall of the carbon nanotube or coated with A portion of the surface of the carbon nanotube is bonded to the carbon nanotube by a carbon-carbon bond. That is, the carbon nanotube composite structure formed by the composite of the carbon nanotube film structure and the graphite structure is basically composed of a carbon nanotube and a graphite segment, and the carbon nanotube and the graphite segment pass through a carbon-carbon bond. Get the combination of Wahli. [0040] when the carbon nanotube film structure has two polymer layers on opposite surfaces, the polymer layer forms two graphite layers on both sides of the carbon nanotube film structure after graphitization. Thereby, a carbon nanotube composite structure having a layered structure is formed. Further, the graphite fragments filled on both sides of the carbon nanotube film structure and the graphite fragments distributed on both sides of the carbon nanotube film structure are bonded by carbon-carbon bonds to form a unitary structure. At this time, the carbon nanotube film structure may be completely coated by the graphite structure and composited inside the graphite structure 099122584 Form No. A0101 Page 16 of 27 0992039786-0 201202134. Therefore, from a macroscopic point of view, the graphite structure is a sponge-like structure, and the carbon nanotube film structure is embedded therein. In other words, the plurality of carbon nanotubes are disposed in the graphite structure in the form of a self-supporting carbon nanotube film structure, and the graphite structure and the plurality of carbon nanotubes pass the van der Waals and carbon-carbon bonds. Combine. [0041] The carbon nanotube composite structure includes a carbon nanotube film structure formed of a plurality of carbon nanotubes and a plurality of graphite segments filled in the carbon nanotube film structure. In addition to being combined with van der Waals force, the plurality of carbon nanotubes can be tightly bonded by the graphite fragments, thereby increasing the bonding force between the plurality of carbon nanotubes and improving the naphthalene Mechanical properties of the carbon nanotube composite structure. The graphite segment and the carbon nanotube structure have a small density and are both carbon materials. Therefore, the carbon nanotube composite structure formed by combining the plurality of graphite segments and the plurality of carbon nanotubes has a small density. Corrosion resistance, moisture resistance and other advantages. [0042] When the carbon nanotube structure includes at least one carbon nanotube structure, the polymer can be graphitized into a plurality of graphite fragments and graphitized into a plurality of graphite fibers. Specifically, if graphitization is carried out by rapid heating in the method of graphitization, the polymer will be graphitized into a plurality of graphite fragments. The graphite segment and the nanocarbon pipeline structure are combined by carbon-carbon bonds to form a carbon nanotube composite structure. Whereas in the method of graphitization, graphitization is carried out by slow heating, the polymer will be graphitized into a plurality of graphite fibers. The graphite fibers are bonded to the carbon nanotubes by van der Waals and carbon-carbon bonds. The plurality of graphite fibers in the graphite fiber structure are bonded to each other by a carbon-carbon bond or a van der Waals force, and form a unitary structure. 099122584 Form No. A0101 Page 17 of 27 0992039786-0 201202134 [0044] [0045] The plurality of carbon nanotubes in the same π-meter carbon pipeline are substantially entangled along the nanocarbon pipeline 1 Or the graphite fibers covering the plurality of carbon nanotubes also extend substantially along the axial direction of the nanocarbon line. Specifically, when the plurality of carbon nanotubes in the nanocarbon pipeline are connected end to end by van der Waals force and extend substantially spirally along the axial direction of the nanocarbon pipeline, the graphite fiber is also substantially along the nanocarbon; * The sister extends to the snail (four). When the carbon nanotubes of the carbon nanotubes are connected end to end by van der Waals force and arranged in an axially preferred orientation along the nano carbon official line, the graphite fibers are also substantially along the axis of the nanocarbon pipeline. Arrange to the preferred orientation. Graphite fibers in the same nanocarbon pipeline or nanocarbon pipeline crucible can be bonded by van der Waals force or by carbon-carbon bond. Preferably, the graphite fiber in the same-nano carbon pipeline passes carbon and carbon. The key combination of the carbon nanotube composite structure can also be regarded as a composite of two carbon materials of 0 ink woven and carbon nanotube. Specifically, the carbon nanotube composite composite comprises a plurality of graphite fibers, each of which is coated or wound with a carbon nanotube connected end to end. The brigade-meter carbon tube is connected end to end by van der Waals force and extends along the axis of the graphite fiber. The plurality of graphites may be parallel, entangled or woven with each other. The graphite fiber structure can be formed by combining van der Waals force or carbon breaking bond between the plurality of graphite fibers. The carbon nanotube composite structure includes a nanocarbon pipeline structure formed by a plurality of nanotube tubes and graphite fibers distributed in the crucible of the nanocarbon pipeline. In addition to being combined with van der Waals force, the plurality of carbon nanotubes can be tightly bonded by the graphite fibers, and the bonding force between the plurality of nanotubes can be improved. The machine of the composite structure of the line 0 0 099122584 #单 蝙号 A0101 page 18 / a total of 27 pages 0992039786-0 201202134 can 'specially high mechanical properties along the axial direction of the nanocarbon pipeline structure. The graphite fiber and the carbon nanotube structure have a small density and are all general materials. Therefore, the composite material of the plurality of graphite fibers and the plurality of carbon nanotubes has a low density and resistance. Corrosion, moisture resistance and other advantages.
刚综上所述，本糾確已符合發料狀要件，遂依法提 出專利中n以上所述者僅為本發明之較佳實施例 ’自不能以此限财案之申請專職圍。舉凡習知本案 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】 —\ ' ?:;卞·:、 [0047] 圖1為一奈米碳管絮化膜之掃描電鏡照片。 [0048] 圖2為一奈米碳管礙壓膜之掃描電鏡照片。 [^049]圖3為一奈米碳管拉膜之掃描電鏡照片：。 [0050] 圖4為一奈米碳管交又膜之掃描電鏡照片。As mentioned above, this correction has been consistent with the requirements of the issue, and the patents mentioned above are only the preferred embodiment of the present invention. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims. [Simple description of the drawing] —\ ' ?:;卞·:, [0047] Figure 1 is a scanning electron micrograph of a carbon nanotube flocculation film. 2 is a scanning electron micrograph of a carbon nanotube barrier film. [^049] Figure 3 is a scanning electron micrograph of a carbon nanotube film: [0050] FIG. 4 is a scanning electron micrograph of a carbon nanotube cross-film.
[0〇51]圖5為一非扭轉之奈米碳管線之掃描電鏡照片。 [0052] 圖6為一扭;轉之奈米碳管線之掃描電鏡照片。 【主要元件符號說明】 [0053] 無： 099122584 表單編號Α0101 第19頁/共27頁 0992039786-0[0〇51] Figure 5 is a scanning electron micrograph of a non-twisted nanocarbon pipeline. [0052] FIG. 6 is a scanning electron micrograph of a twisted, reversed carbon carbon line. [Main component symbol description] [0053] None: 099122584 Form number Α0101 Page 19 of 27 0992039786-0