TWI494264B - Carbon nanotube composite structure and method for making same - Google Patents
Carbon nanotube composite structure and method for making same Download PDFInfo
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本發明涉及一種奈米碳管複合結構及其製備方法。 The invention relates to a carbon nanotube composite structure and a preparation method thereof.
從1991年日本科學家飯島澄男首次發現奈米碳管(Carbon Nanotube,CNT)以來，以奈米碳管為代表的奈米材料以其獨特的結構和性質引起了人們極大的關注。近幾年來，隨著奈米碳管及奈米材料研究的不斷深入，其廣闊應用前景不斷顯現出來。例如，由於奈米碳管所具有的獨特的電磁學、光學、力學、化學性能等，使其在場發射電子源、超薄平面顯示器、陰極電極、生物感測器等領域具有廣泛的應用前景。 Since the first discovery of carbon nanotubes (CNTs) by Japanese scientist Iijima Iman in 1991, nanomaterials represented by carbon nanotubes have attracted great attention due to their unique structure and properties. In recent years, with the deepening of research on carbon nanotubes and nanomaterials, its broad application prospects have been continuously revealed. For example, due to the unique electromagnetic, optical, mechanical, and chemical properties of carbon nanotubes, it has broad application prospects in fields such as field emission electron sources, ultra-thin flat panel displays, cathode electrodes, and biosensors. .
特別地，奈米碳管與其他材料例如金屬、半導體或者聚合物等的複合可以實現材料的優勢互補或加強。奈米碳管具有較大的長徑比和中空的結構，具有優異的力學性能、電學性能、光學性能等，其在複合材料中，可以對複合材料起到增強作用，使得複合材料具有較好的化學和機械性能。奈米碳管複合材料的研究已經成為一個極為重要的領域。 In particular, the composite of carbon nanotubes with other materials such as metals, semiconductors or polymers can complement or enhance the advantages of the materials. The carbon nanotubes have a large aspect ratio and a hollow structure, and have excellent mechanical properties, electrical properties, optical properties, etc., and in the composite material, the composite material can be enhanced to make the composite material better. Chemical and mechanical properties. Research on carbon nanotube composites has become an extremely important area.
先前技術中，宏觀的奈米碳管及其複合結構主要有奈米碳管線及其複合結構。然而，先前技術並沒有揭示一種具有空心管狀結構的奈米碳管複合結構及其製備方法。 In the prior art, the macroscopic carbon nanotubes and their composite structures mainly include nano carbon pipelines and composite structures thereof. However, the prior art does not disclose a carbon nanotube composite structure having a hollow tubular structure and a preparation method thereof.
有鑒於此，提供一種具有宏觀尺寸且具有空心結構的奈米碳管複合結構及其製備方法實為必要。 In view of the above, it is necessary to provide a carbon nanotube composite structure having a macroscopic size and a hollow structure and a preparation method thereof.
一種奈米碳管複合結構，該奈米碳管複合結構係由複數個奈米碳管及聚合物材料複合而成的一個管狀複合結構，其中，該奈米碳管複合結構中的奈米碳管之間通過凡得瓦力緊密相連並形成複數個間隙，所述聚合物材料填充於所述奈米碳管之間的間隙或包覆於所述奈米碳管表面。 A carbon nanotube composite structure, wherein the carbon nanotube composite structure is a tubular composite structure composed of a plurality of carbon nanotubes and a polymer material, wherein the nano carbon in the carbon nanotube composite structure The tubes are closely connected by van der Waals and form a plurality of gaps, and the polymer material is filled in a gap between the carbon nanotubes or coated on the surface of the carbon nanotubes.
一種奈米碳管複合結構，其中，該奈米碳管複合結構係一個管狀複合結構，包括一管壁及由管壁圍成的中空的軸心，該奈米碳管複合結構的管壁係由通過凡得瓦力緊密結合的複數個奈米碳管及一聚合物材料組成，其中，該奈米碳管複合結構中的奈米碳管之間形成複數個間隙，所述聚合物材料填充於所述奈米碳管之間的間隙或包覆於所述奈米碳管表面。 A carbon nanotube composite structure, wherein the carbon nanotube composite structure is a tubular composite structure comprising a pipe wall and a hollow axis surrounded by the pipe wall, the pipe wall system of the carbon nanotube composite structure Composed of a plurality of carbon nanotubes and a polymer material closely combined by van der Waals force, wherein a plurality of gaps are formed between the carbon nanotubes in the carbon nanotube composite structure, and the polymer material is filled a gap between the carbon nanotubes or coated on the surface of the carbon nanotube.
一種奈米碳管複合結構的製備方法，包括：提供一線狀支撐體，以及至少一奈米碳管膜或至少一奈米碳管線；將所述至少一奈米碳管膜或至少一奈米碳管線纏繞在所述線狀支撐體表面；將一聚合物材料與所述纏繞於該線狀支撐體表面的奈米碳管膜或奈米碳管線複合；以及移除所述線狀支撐體，形成一奈米碳管複合結構。 A method for preparing a carbon nanotube composite structure, comprising: providing a linear support body, and at least one carbon nanotube film or at least one nano carbon line; and the at least one carbon nanotube film or at least one nanometer a carbon line is wound around the surface of the linear support; a polymer material is compounded with the carbon nanotube film or the nanocarbon line wound on the surface of the linear support; and the linear support is removed Forming a carbon nanotube composite structure.
與先前技術相較，本發明的奈米碳管複合結構係由至少一奈米碳管膜或至少一奈米碳管線與一聚合物材料構成的。該奈米碳管複合結構係一個空心的管狀複合結構，具有質量輕、熱容小，無黏性，強度高以及封閉性能良好等特性，能方便地應用於宏觀的複 數個領域。所述奈米碳管複合結構的製作方法，通過將一奈米碳管膜或至少一奈米碳管線直接纏繞於一線狀支撐體結構表面，然後將一聚合物材料與纏繞於該線狀支撐體表面的奈米碳管膜或或奈米碳管線複合，最後移除該線狀支撐體製備而成，該方法簡單、易行。 Compared to the prior art, the carbon nanotube composite structure of the present invention is composed of at least one carbon nanotube film or at least one nano carbon line and a polymer material. The carbon nanotube composite structure is a hollow tubular composite structure, which has the characteristics of light weight, small heat capacity, no viscosity, high strength and good sealing performance, and can be conveniently applied to macroscopic complexes. Several fields. The carbon nanotube composite structure is prepared by directly winding a carbon nanotube film or at least one nano carbon line on a surface of a linear support structure, and then winding a polymer material around the linear support. The surface of the carbon nanotube film or the nano carbon line is composited, and finally the linear support is removed, and the method is simple and easy.
10‧‧‧基底 10‧‧‧Base
12‧‧‧奈米碳管陣列 12‧‧‧Nano Carbon Tube Array
14‧‧‧奈米碳管拉膜 14‧‧‧Nano carbon tube film
20‧‧‧供給單元 20‧‧‧Supply unit
22‧‧‧支撐座 22‧‧‧ Support
24‧‧‧線軸 24‧‧‧ spool
28‧‧‧導向軸 28‧‧‧Guide axis
30‧‧‧包覆單元 30‧‧‧Wrap unit
32‧‧‧驅動機構 32‧‧‧ drive mechanism
322‧‧‧第一電機 322‧‧‧First motor
324‧‧‧第一帶輪 324‧‧‧First pulley
326‧‧‧齒型帶 326‧‧‧Toothed belt
328‧‧‧第二帶輪 328‧‧‧Second pulley
34‧‧‧空心旋轉軸 34‧‧‧ hollow rotating shaft
342‧‧‧軸承 342‧‧‧ bearing
36‧‧‧支撐結構 36‧‧‧Support structure
38‧‧‧花盤 38‧‧‧Flower plate
40‧‧‧收集單元 40‧‧‧Collection unit
42‧‧‧第二電機 42‧‧‧Second motor
44‧‧‧奈米碳管結構收集器 44‧‧‧Nano Carbon Tube Structure Collector
50‧‧‧定位單元 50‧‧‧ Positioning unit
100‧‧‧製備裝置 100‧‧‧ preparation device
圖1 為本發明實施例奈米碳管複合結構採用的奈米碳管拉膜的SEM照片。 1 is a SEM photograph of a carbon nanotube film taken by a carbon nanotube composite structure according to an embodiment of the present invention.
圖2 為從奈米碳管陣列拉取奈米碳管膜的示意圖。 Figure 2 is a schematic view of the carbon nanotube film taken from the carbon nanotube array.
圖3 為本發明實施例奈米碳管複合結構採用的奈米碳管碾壓膜的SEM照片。 3 is a SEM photograph of a carbon nanotube rolled film used in a carbon nanotube composite structure according to an embodiment of the present invention.
圖4 為本發明實施例奈米碳管複合結構採用的奈米碳管絮化膜的SEM照片。 4 is a SEM photograph of a carbon nanotube flocculation film used in a carbon nanotube composite structure according to an embodiment of the present invention.
圖5 為本發明實施例奈米碳管複合結構製備方法的流程圖。 FIG. 5 is a flow chart of a method for preparing a carbon nanotube composite structure according to an embodiment of the present invention.
圖6 為製備本發明實施例奈米碳管複合結構的製備裝置的俯視局部剖面圖。 Figure 6 is a top plan cross-sectional view showing a preparation apparatus for preparing a carbon nanotube composite structure according to an embodiment of the present invention.
圖7 為製備本發明實施例奈米碳管複合結構的製備裝置的主視局部剖面圖。 Fig. 7 is a front elevation, partial cross-sectional view showing the preparation apparatus for preparing a carbon nanotube composite structure according to an embodiment of the present invention.
下面將結合附圖對本發明實施例作進一步的詳細說明。 The embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.
本發明提供一種奈米碳管複合結構，該奈米碳管複合結構係由複數個奈米碳管及聚合物材料複合而成的一個管狀複合結構。其中 ，該奈米碳管複合結構中的奈米碳管之間通過凡得瓦力緊密相連，相鄰的奈米碳管之間形成複數個間隙，所述聚合物材料填充於所述奈米碳管之間的間隙或包覆於所述奈米碳管表面。 The invention provides a carbon nanotube composite structure, which is a tubular composite structure composed of a plurality of carbon nanotubes and a polymer material. among them The carbon nanotubes in the carbon nanotube composite structure are closely connected by van der Waals force, and a plurality of gaps are formed between adjacent carbon nanotubes, and the polymer material is filled in the nano carbon A gap between the tubes or a surface of the carbon nanotubes is coated.
所述奈米碳管複合結構具有一中空的線狀軸心，該奈米碳管複合結構係由至少一奈米碳管膜或至少一奈米碳管線沿該奈米碳管複合結構的線狀軸心緊密環繞形成一奈米碳管管狀結構，再將該奈米碳管管狀結構與一聚合物材料複合製備而成。該奈米碳管複合結構中的複數個奈米碳管通過凡得瓦力緊密相連。該奈米碳管複合結構中的複數個奈米碳管環繞該線狀軸心並與所述聚合物材料複合形成所述奈米碳管複合結構。 The carbon nanotube composite structure has a hollow linear axis, and the carbon nanotube composite structure is formed by at least one carbon nanotube film or at least one nano carbon line along the line of the carbon nanotube composite structure. The axis of the shaft closely surrounds a tubular structure of a carbon nanotube, and the tubular structure of the carbon nanotube is composited with a polymer material. The plurality of carbon nanotubes in the carbon nanotube composite structure are closely connected by van der Waals force. A plurality of carbon nanotubes in the carbon nanotube composite structure surround the linear axis and are combined with the polymer material to form the carbon nanotube composite structure.
所述奈米碳管複合結構包括一管壁及由管壁圍成的中空的軸心，該奈米碳管複合結構的管壁係由通過凡得瓦力緊密結合的複數個奈米碳管及一聚合物材料組成。通過將至少一奈米碳管膜或至少一奈米碳管線沿該奈米碳管複合結構的線狀軸心緊密環繞，該至少一奈米碳管膜或至少一奈米碳管線會沿該線狀軸心形成一管壁，進而形成所述奈米碳管管狀結構，再將該奈米碳管管狀結構與一聚合物材料複合形成所述奈米碳管複合結構。可以理解，該奈米碳管複合結構的管壁具有一定的厚度，可以通過所環繞的奈米碳管膜或奈米碳管線的層數確定。該奈米碳管複合結構中線狀軸心的截面形狀可以為方形、梯形、圓形或橢圓形等形狀，該線狀軸心的截面大小，可以根據實際要求製備。此外，根據線狀軸心的截面大小及形狀可以製備出不同大小及形狀的奈米碳管複合結構。所述聚合物材料填充於所述奈米碳管管狀結構中奈米碳管之間的間隙或包覆於所述奈米碳管管狀結構的表面。所述聚合物材 料為一有機材料，如環氧樹脂、丙烯酸樹脂、聚醯亞胺、聚乙烯醇、聚酯、丙烯酸樹脂、矽樹脂等樹脂材料或導熱膠材料及其混合物。 The carbon nanotube composite structure comprises a tube wall and a hollow axis surrounded by the tube wall, and the tube wall of the carbon nanotube composite structure is composed of a plurality of carbon nanotubes tightly coupled by van der Waals force And a polymer material composition. By surrounding at least one carbon nanotube film or at least one nano carbon line along the linear axis of the carbon nanotube composite structure, the at least one carbon nanotube film or at least one nano carbon line will follow The linear axis forms a tube wall to form the tubular structure of the carbon nanotube, and the tubular structure of the carbon nanotube is combined with a polymer material to form the carbon nanotube composite structure. It can be understood that the wall of the carbon nanotube composite structure has a certain thickness and can be determined by the number of layers of the surrounding carbon nanotube film or nano carbon line. The cross-sectional shape of the linear axis in the carbon nanotube composite structure may be square, trapezoidal, circular or elliptical, and the cross-sectional size of the linear axis may be prepared according to actual requirements. In addition, a carbon nanotube composite structure of different sizes and shapes can be prepared according to the cross-sectional size and shape of the linear axis. The polymer material is filled in a gap between the carbon nanotubes in the tubular structure of the carbon nanotube or coated on the surface of the tubular structure of the carbon nanotube. Polymer material The material is an organic material, such as an epoxy resin, an acrylic resin, a polyimide, a polyvinyl alcohol, a polyester, an acrylic resin, a resin, or the like, or a thermal conductive adhesive material and a mixture thereof.
所述奈米碳管膜由複數個奈米碳管組成，該複數個奈米碳管具有大致相等的長度，該複數個奈米碳管無序或有序排列。所謂無序排列係指奈米碳管的排列方向無規則。所謂有序排列係指奈米碳管的排列方向有規則。具體地，當奈米碳管膜包括無序排列的奈米碳管時，奈米碳管相互纏繞或者各向同性排列；當奈米碳管膜包括有序排列的奈米碳管時，奈米碳管沿一個方向或者複數個方向擇優取向排列。所謂“擇優取向”係指所述奈米碳管膜中的大多數奈米碳管在一個方向或幾個方向上具有較大的取向幾率；即，該奈米碳管膜中的大多數奈米碳管的軸向基本沿同一方向或幾個方向延伸。 The carbon nanotube membrane is composed of a plurality of carbon nanotubes having substantially the same length, and the plurality of carbon nanotubes are disorderly or orderedly arranged. The so-called disordered arrangement means that the arrangement direction of the carbon nanotubes is irregular. The so-called ordered arrangement means that the arrangement direction of the carbon nanotubes is regular. Specifically, when the carbon nanotube film comprises a disordered arrangement of carbon nanotubes, the carbon nanotubes are entangled or isotropically arranged; when the carbon nanotube film comprises an ordered arrangement of carbon nanotubes, The carbon nanotubes are arranged in a preferred orientation in one direction or in a plurality of directions. By "preferable orientation" is meant that most of the carbon nanotubes in the carbon nanotube membrane have a greater probability of orientation in one direction or in several directions; that is, most of the naphthalene carbon nanotube membranes. The axial direction of the carbon nanotubes extends substantially in the same direction or in several directions.
該奈米碳管膜可為奈米碳管拉膜、奈米碳管絮化膜或奈米碳管碾壓膜等。 The carbon nanotube film can be a carbon nanotube film, a carbon nanotube film or a carbon nanotube film.
請參見圖1，所述奈米碳管拉膜係由複數個奈米碳管組成的自支撐結構。所述複數個奈米碳管沿同一方向擇優取向排列。該奈米碳管拉膜中大多數奈米碳管的整體延伸方向基本朝同一方向。而且，所述大多數奈米碳管的整體延伸方向基本平行於奈米碳管拉膜的表面。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的大多數奈米碳管中每一奈米碳管與在延伸方向上相鄰的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隨機排列的奈米碳管，這些奈米碳管不會對奈米碳管拉膜 中大多數奈米碳管的整體取向排列構成明顯影響。所述奈米碳管拉膜不需要大面積的載體支撐，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)間隔設置的兩個線狀支撐體上時，位於兩個線狀支撐體之間的奈米碳管膜能夠懸空保持自身膜狀狀態。 Referring to FIG. 1, the carbon nanotube film is a self-supporting structure composed of a plurality of carbon nanotubes. The plurality of carbon nanotubes are arranged in a preferred orientation along the same direction. Most of the carbon nanotubes in the carbon nanotube film are oriented 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 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 pull the film on the carbon nanotubes. The overall orientation of most of the carbon nanotubes constitutes a significant impact. The carbon nanotube film does not need a large area of support, but as long as the supporting force is provided on both sides, the whole film can be suspended and maintained in a self-membranous state, that is, the carbon nanotube film is placed (or fixed) at intervals. When the two linear supports are disposed, the carbon nanotube film located between the two linear supports can be suspended to maintain the self-film state.
所述奈米碳管拉膜中基本朝同一方向延伸的多數奈米碳管，並非絕對的直線狀，可以適當的彎曲；或者並非完全按照延伸方向排列，可以適當的偏離延伸方向。因此，不能排除奈米碳管拉膜的基本朝同一方向延伸的多數奈米碳管中並列的奈米碳管之間可能存在部分接觸。 Most of the carbon nanotubes extending in the same direction in the carbon nanotube film are not absolutely linear, and may be appropriately bent; or may not be 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 extending substantially in the same direction of the carbon nanotube film.
具體地，所述奈米碳管拉膜包括複數個連續且定向排列的奈米碳管片段。該複數個奈米碳管片段通過凡得瓦力首尾相連。每一奈米碳管片段包括複數個相互平行的奈米碳管，該複數個相互平行的奈米碳管通過凡得瓦力緊密結合。複數個相互平行的奈米碳管中相鄰的奈米碳管之間形成複數個間隙。該奈米碳管片段具有任意的長度、厚度、均勻性及形狀。該奈米碳管拉膜中的奈米碳管沿同一方向擇優取向排列。 Specifically, the carbon nanotube film comprises a plurality of continuous and aligned carbon nanotube segments. The plurality of carbon nanotube segments are connected end to end by van der Waals force. Each of the carbon nanotube segments includes a plurality of mutually parallel carbon nanotubes, and the plurality of mutually parallel carbon nanotubes are tightly coupled by van der Waals force. A plurality of gaps are formed between adjacent carbon nanotubes in a plurality of mutually parallel carbon nanotubes. The carbon nanotube segments have any length, thickness, uniformity, and shape. The carbon nanotubes in the carbon nanotube film are arranged in a preferred orientation in the same direction.
請參見圖2，所述奈米碳管拉膜可通過從奈米碳管陣列直接拉取獲得。從奈米碳管陣列中拉取獲得所述奈米碳管拉膜的具體方法包括：(a)利用一拉伸工具從所述奈米碳管陣列中選定一奈米碳管片段，本實施例優選為採用具有一定寬度的膠帶或黏性基條接觸該奈米碳管陣列以選定具有一定寬度的一奈米碳管片段；(b)通過移動該拉伸工具，以一定速度拉取該選定的奈米碳管片段，從而首尾相連的拉出複數個奈米碳管片段，進而形成一連續 的奈米碳管拉膜。該複數個奈米碳管相互並排使該奈米碳管片段具有一定寬度。當該被選定的奈米碳管片段在拉力作用下沿拉取方向逐漸脫離奈米碳管陣列的生長基底的同時，由於凡得瓦力作用，與該選定的奈米碳管片段相鄰的其他奈米碳管片段首尾相連地相繼地被拉出，從而形成一連續、均勻且具有一定寬度和擇優取向的奈米碳管拉膜。所述奈米碳管拉膜及其製備方法請參見2007年2月12日申請的，2010年7月11日公告的，公告號為TW I327177的台灣發明專利申請公開說明書。 Referring to FIG. 2, the carbon nanotube film can be obtained by directly pulling from a carbon nanotube array. The specific method for extracting the carbon nanotube film from the carbon nanotube array comprises: (a) selecting a carbon nanotube segment from the carbon nanotube array by using a stretching tool, the implementation Preferably, the carbon nanotube array is contacted with a tape or a viscous strip having a certain width to select a carbon nanotube segment having a certain width; (b) the workpiece is pulled at a certain speed by moving the stretching tool. Selected carbon nanotube fragments, thereby pulling out a plurality of carbon nanotube segments end to end, thereby forming a continuous The carbon nanotube film is pulled. The plurality of carbon nanotubes are arranged side by side such that the carbon nanotube segments have a certain width. When the selected carbon nanotube segment is gradually separated from the growth substrate of the carbon nanotube array in the pulling direction under the pulling force, adjacent to the selected carbon nanotube segment due to the effect of van der Waals force The other carbon nanotube segments are successively pulled out end to end to form a continuous, uniform carbon nanotube film having a certain width and a preferred orientation. For the carbon nanotube film and the preparation method thereof, please refer to the Taiwan invention patent application publication specification of the TW I327177 filed on July 12, 2010, filed on July 11, 2010.
可以理解，通過將至少一奈米碳管拉膜沿該奈米碳管複合結構的線狀軸心緊密環繞形成一奈米碳管管狀結構，再將該奈米碳管管狀結構與一聚合物材料複合形成所述具有空心管狀結構的奈米碳管複合結構時，該奈米碳管複合結構中大多數奈米碳管通過凡得瓦力首尾相連並在該奈米碳管複合結構線狀軸心的延伸方向環繞該線狀軸心螺旋狀緊密排列，相鄰的奈米碳管之間通過凡得瓦力緊密相連並形成複數個間隙。該奈米碳管複合結構中大多數奈米碳管基本沿線狀軸心的延伸方向延伸。具體地，該奈米碳管複合結構中大多數奈米碳管均首尾相連地沿著線狀軸心的長度方向螺旋狀延伸。該奈米碳管複合結構中的大多數奈米碳管中每一奈米碳管與在延伸方向上相鄰的奈米碳管通過凡得瓦力首尾相連。該大多數奈米碳管中每一奈米碳管基本沿所述奈米碳管複合結構的線狀軸心的延伸方向螺旋狀緊密排列。該大多數奈米碳管中每一奈米碳管的延伸方向與所述奈米碳管複合結構的線狀軸心的延伸方向形成一定的交叉角α，0°<α≦90°。所述聚合物材料填充於奈米碳管之間的間隙或包覆於奈米碳管的表面。 It can be understood that by forming at least one carbon nanotube film along the linear axis of the carbon nanotube composite structure, a tubular structure of a carbon nanotube is formed, and the tubular structure of the carbon nanotube is combined with a polymer. When the material is composited to form the carbon nanotube composite structure having a hollow tubular structure, most of the carbon nanotubes in the carbon nanotube composite structure are connected end to end by van der Waals force and are linear in the carbon nanotube composite structure The extending direction of the axis is spirally arranged tightly around the linear axis, and the adjacent carbon nanotubes are closely connected by van der Waals and form a plurality of gaps. Most of the carbon nanotubes in the carbon nanotube composite structure extend substantially along the extending direction of the linear axis. Specifically, most of the carbon nanotubes in the carbon nanotube composite structure extend spirally end to end along the length of the linear axis. Each of the carbon nanotubes in the majority of the carbon nanotube composite structures is connected end to end with a vanadium tube in the extending direction. Each of the carbon nanotubes in the majority of the carbon nanotubes is arranged in a spiral shape closely along the extending direction of the linear axis of the carbon nanotube composite structure. The extending direction of each of the carbon nanotubes in the majority of the carbon nanotubes forms a certain intersection angle α with the extending direction of the linear axis of the carbon nanotube composite structure, 0° < α ≦ 90°. The polymer material is filled in a gap between the carbon nanotubes or coated on the surface of the carbon nanotube.
所述奈米碳管碾壓膜包括均勻分佈的奈米碳管，奈米碳管無序，沿同一方向或不同方向擇優取向排列。請參見圖3，優選地，所述奈米碳管碾壓膜中的奈米碳管平行於該奈米碳管碾壓膜的表面。所述奈米碳管碾壓膜中的奈米碳管相互交疊並形成複數個間隙。所述奈米碳管碾壓膜中奈米碳管之間通過凡得瓦力相互吸引，緊密結合，使得該奈米碳管碾壓膜具有很好的柔韌性，可以彎曲折疊成任意形狀而不破裂。且由於奈米碳管碾壓膜中的奈米碳管之間通過凡得瓦力相互吸引，緊密結合，使奈米碳管碾壓膜為一自支撐的結構，可無需基底支撐，自支撐存在。該奈米碳管碾壓膜可通過碾壓一奈米碳管陣列獲得。該奈米碳管陣列形成在一基體表面，所製備的奈米碳管碾壓膜中的奈米碳管與該奈米碳管陣列的基體的表面成一夾角β，其中，β大於等於0度且小於等於15度(0°≦β≦15°)。優選地，所述奈米碳管碾壓膜中的奈米碳管的軸向基本沿同一方向延伸並且平行於該奈米碳管碾壓膜的表面。依據碾壓的方式不同，該奈米碳管碾壓膜中的奈米碳管具有不同的排列形式。該奈米碳管碾壓膜的面積和厚度不限，可根據實際需要選擇。該奈米碳管碾壓膜的面積與奈米碳管陣列的尺寸基本相同。該奈米碳管碾壓膜厚度與奈米碳管陣列的高度以及碾壓的壓力有關，可為1微米~100微米。所述奈米碳管碾壓膜及其製備方法請參見2009年1月1日公開的，公開號為TW200900348的台灣發明專利申請公開說明書。 The carbon nanotube rolled film comprises uniformly distributed carbon nanotubes, and the carbon nanotubes are disordered and arranged in the same direction or in different directions. Referring to FIG. 3, preferably, the carbon nanotubes in the carbon nanotube rolled film are parallel to the surface of the carbon nanotube rolled film. The carbon nanotubes in the carbon nanotube rolled film overlap each other and form a plurality of gaps. The carbon nanotubes in the carbon nanotube rolled film are mutually attracted by van der Waals force and tightly combined, so that the carbon nanotube rolled film has good flexibility and can be bent and folded into an arbitrary shape. Does not break. And because the carbon nanotubes in the carbon nanotube film are mutually attracted by the van der Waals force, the carbon nanotube film is a self-supporting structure, which can be self-supported without substrate support. presence. The carbon nanotube rolled film can be obtained by rolling an array of carbon nanotubes. The carbon nanotube array is formed on a surface of the substrate, and the carbon nanotubes in the prepared carbon nanotube rolled film form an angle β with the surface of the substrate of the carbon nanotube array, wherein β is greater than or equal to 0 degrees. And less than or equal to 15 degrees (0 ° ≦ β ≦ 15 °). Preferably, the axial direction of the carbon nanotubes in the carbon nanotube rolled film extends substantially in the same direction and is parallel to the surface of the carbon nanotube rolled film. The carbon nanotubes in the carbon nanotube rolled film have different arrangements depending on the manner of rolling. The area and thickness of the carbon nanotube rolled film are not limited and can be selected according to actual needs. 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 from 1 micrometer to 100 micrometers. The carbon nanotube rolled film and the preparation method thereof are described in the Taiwan Patent Application Publication No. TW200900348, which is published on Jan. 1, 2009.
可以理解，通過將至少一奈米碳管碾壓膜沿該奈米碳管複合結構的線狀軸心緊密環繞形成一奈米碳管管狀結構，再將該奈米碳管管狀結構與一聚合物材料複合形成所述具有空心管狀結構的奈米碳管複合結構時，該奈米碳管複合結構中複數個奈米碳管在該奈 米碳管複合結構的線狀軸心緊密排列，且相鄰的奈米碳管之間通過凡得瓦力緊密排列並形成複數個間隙。可以理解，該奈米碳管複合結構中複數個奈米碳管的排列方向取決於所述奈米碳管碾壓膜中奈米碳管的排列方向。優選地，當所述奈米碳管碾壓膜中的大多數奈米碳管基本沿同一方向延伸並且平行於該奈米碳管碾壓膜的表面時，將至少一奈米碳管碾壓膜沿該奈米碳管複合結構的線狀軸心緊密環繞形成一奈米碳管管狀結構，再將該奈米碳管管狀結構與一聚合物材料複合形成所述奈米碳管複合結構，該奈米碳管複合結構中大多數奈米碳管在該奈米碳管複合結構表面緊密排列。該奈米碳管複合結構中大多數奈米碳管基本沿線狀軸心的延伸方向延伸。具體地，該奈米碳管複合結構中大多數奈米碳管均首尾相連地沿著線狀軸心的長度方向螺旋狀延伸，該大多數奈米碳管中每一奈米碳管的延伸方向與所述奈米碳管複合結構的線狀軸心的延伸方向形成一定的交叉角α，該交叉角α可以為任意角度，優選0°<α≦90°。該奈米碳管複合結構中相鄰的奈米碳管之間通過凡得瓦力緊密相連。所述聚合物材料填充於奈米碳管之間的間隙或包覆於奈米碳管的表面。 It can be understood that by forming at least one carbon nanotube rolled film tightly around the linear axis of the carbon nanotube composite structure to form a tubular structure of a carbon nanotube, and then polymerizing the tubular structure of the carbon nanotube When the material material is composited to form the carbon nanotube composite structure having a hollow tubular structure, the plurality of carbon nanotubes in the carbon nanotube composite structure are in the nai The linear axes of the carbon nanotube composite structure are closely arranged, and the adjacent carbon nanotubes are closely arranged by van der Waals and form a plurality of gaps. It can be understood that the arrangement direction of the plurality of carbon nanotubes in the carbon nanotube composite structure depends on the arrangement direction of the carbon nanotubes in the carbon nanotube rolled film. Preferably, when most of the carbon nanotubes in the carbon nanotube rolled film extend substantially in the same direction and are parallel to the surface of the carbon nanotube film, at least one carbon nanotube is laminated The film is closely surrounded by a linear axis of the carbon nanotube composite structure to form a tubular structure of a carbon nanotube, and the tubular structure of the carbon nanotube is combined with a polymer material to form the composite structure of the carbon nanotube. Most of the carbon nanotubes in the carbon nanotube composite structure are closely arranged on the surface of the carbon nanotube composite structure. Most of the carbon nanotubes in the carbon nanotube composite structure extend substantially along the extending direction of the linear axis. Specifically, most of the carbon nanotubes in the carbon nanotube composite structure are spirally extended end to end along the length of the linear axis, and the extension of each carbon nanotube in the majority of the carbon nanotubes The direction forms a certain crossing angle α with the extending direction of the linear axis of the carbon nanotube composite structure, and the crossing angle α may be any angle, preferably 0° < α ≦ 90°. The adjacent carbon nanotubes in the carbon nanotube composite structure are closely connected by van der Waals force. The polymer material is filled in a gap between the carbon nanotubes or coated on the surface of the carbon nanotube.
請參見圖4，所述奈米碳管絮化膜包括相互纏繞的奈米碳管，該奈米碳管長度可大於10釐米。所述奈米碳管之間通過凡得瓦力相互吸引、纏繞，形成網路狀結構。所述奈米碳管絮化膜各向同性。所述奈米碳管絮化膜中的奈米碳管為均勻分佈，無規則排列，形成大量的微孔結構。可以理解，所述奈米碳管絮化膜的長度、寬度和厚度不限，可根據實際需要選擇，厚度可為1微米~100微米。所述奈米碳管絮化膜及其製備方法請參見2008年11月16日公開的，公開號為TW200844041的台灣發明專利申請公開說明書。 Referring to FIG. 4, the carbon nanotube flocculation membrane comprises intertwined carbon nanotubes, and the carbon nanotubes may be longer than 10 cm. The carbon nanotubes are attracted and entangled with each other by van der Waals force to form a network structure. The carbon nanotube flocculation membrane is isotropic. The carbon nanotubes in the carbon nanotube flocculation membrane are uniformly distributed and randomly arranged to form a large number of microporous structures. It can be understood that the length, width and thickness of the carbon nanotube film are not limited, and may be selected according to actual needs, and the thickness may be from 1 micrometer to 100 micrometers. The carbon nanotube flocculation film and the preparation method thereof are described in the Taiwan invention patent application publication No. TW200844041, which is published on Nov. 16, 2008.
可以理解，通過將至少一奈米碳管絮化膜沿該奈米碳管複合結構的線狀軸心緊密環繞形成一奈米碳管管狀結構，再將奈米碳管管狀結構與一聚合物材料複合形成所述具有空心管狀結構的奈米碳管複合結構，該奈米碳管複合結構中複數個奈米碳管相互吸引、纏繞形成網格狀結構，並在該奈米碳管複合結構的線狀軸心緊密排列。該奈米碳管複合結構中複數個奈米碳管通過凡得瓦力首尾相連。該奈米碳管複合結構中相鄰的奈米碳管之間通過凡得瓦力緊密相連。所述聚合物材料填充於奈米碳管之間的微孔結構或包覆於奈米碳管的表面。 It can be understood that the carbon nanotube tubular structure and the polymer are formed by closely surrounding at least one carbon nanotube flocculation membrane along the linear axis of the carbon nanotube composite structure to form a tubular structure of a carbon nanotube. The composite material forms a carbon nanotube composite structure having a hollow tubular structure, wherein the plurality of carbon nanotubes are attracted to each other and entangled to form a grid-like structure, and the carbon nanotube composite structure is The linear axes are closely arranged. In the carbon nanotube composite structure, a plurality of carbon nanotubes are connected end to end by van der Waals force. The adjacent carbon nanotubes in the carbon nanotube composite structure are closely connected by van der Waals force. The polymeric material is filled in a microporous structure between the carbon nanotubes or coated on the surface of the carbon nanotube.
所述奈米碳管線可為一非扭轉的奈米碳管線或扭轉的奈米碳管線。 The nanocarbon line can be a non-twisted nano carbon line or a twisted nano carbon line.
所述非扭轉的奈米碳管線包括大多數沿該非扭轉的奈米碳管線軸向方向排列的奈米碳管。非扭轉的奈米碳管線可通過將一奈米碳管拉膜經過有機溶劑處理得到。該非扭轉的奈米碳管線長度不限，直徑為0.5奈米-1毫米。具體地，可將揮發性有機溶劑浸潤所述奈米碳管拉膜的整個表面，在揮發性有機溶劑揮發時產生的表面張力的作用下，奈米碳管拉膜中的相互平行的複數個奈米碳管通過凡得瓦力緊密結合，從而使奈米碳管拉膜收縮為一非扭轉的奈米碳管線。該奈米碳管線中相鄰的奈米碳管之間形成複數個間隙。該揮發性有機溶劑為乙醇、甲醇、丙酮、二氯乙烷或氯仿。通過揮發性有機溶劑處理的非扭轉奈米碳管線與未經揮發性有機溶劑處理的奈米碳管拉膜相比，比表面積減小，黏性降低。 The non-twisted nanocarbon pipeline includes a majority of carbon nanotubes aligned along the axial direction of the non-twisted nanocarbon pipeline. The non-twisted nano carbon line can be obtained by subjecting a carbon nanotube film to an organic solvent treatment. The non-twisted nanocarbon line is not limited in length and has a diameter of 0.5 nm to 1 mm. Specifically, the volatile organic solvent may be immersed in the entire surface of the carbon nanotube film, and the surface tension generated by the volatilization of the volatile organic solvent is a plurality of mutually parallel in the carbon nanotube film. The carbon nanotubes are tightly coupled by van der Waals to shrink the carbon nanotube film into a non-twisted nanocarbon line. A plurality of gaps are formed between adjacent carbon nanotubes in the nanocarbon pipeline. The volatile organic solvent is ethanol, methanol, acetone, dichloroethane or chloroform. The non-twisted nanocarbon line treated by the volatile organic solvent has a smaller specific surface area and a lower viscosity than a carbon nanotube film that has not been treated with a volatile organic solvent.
所述非扭轉的奈米碳管線及其製備方法請參見范守善等人於2002年11月5日申請的，2008年11月21日公告的，公告號為TW I303239的台灣專利。 The non-twisted nano carbon pipeline and its preparation method are referred to by Fan Shoushan et al., which was filed on November 5, 2002, and announced on November 21, 2008, the announcement number is TW. Taiwan patent of I303239.
可以理解，通過將至少一非扭轉的奈米碳管線沿該奈米碳管複合結構的線狀軸心緊密環繞形成一奈米碳管管狀結構，再將該奈米碳管管狀結構與一聚合物材料複合形成所述具有空心管狀結構的奈米碳管複合結構時，該奈米碳管複合結構中大多數奈米碳管通過凡得瓦力首尾相連並在該奈米碳管複合結構線狀軸心的延伸方向環繞該線狀軸心螺旋狀緊密排列，相鄰的奈米碳管之間通過凡得瓦力緊密相連並形成複數個間隙。該奈米碳管複合結構中大多數奈米碳管基本沿線狀軸心的延伸方向延伸。具體地，該奈米碳管複合結構中大多數奈米碳管均首尾相連地沿著線狀軸心的長度方向螺旋狀延伸。該奈米碳管複合結構中的大多數奈米碳管中每一奈米碳管與在延伸方向上相鄰的奈米碳管通過凡得瓦力首尾相連。該大多數奈米碳管中每一奈米碳管基本沿所述奈米碳管複合結構的線狀軸心螺旋狀緊密排列。該大多數奈米碳管中每一奈米碳管的延伸方向與所述奈米碳管複合結構線狀軸心的延伸方向形成一定的交叉角α，0°<α≦90°。所述聚合物材料填充於奈米碳管之間的間隙或包覆於奈米碳管的表面。 It can be understood that by forming at least one non-twisted nano carbon pipeline along the linear axis of the carbon nanotube composite structure to form a tubular structure of a carbon nanotube, and then polymerizing the tubular structure of the carbon nanotube When the material material is composited to form the carbon nanotube composite structure having a hollow tubular structure, most of the carbon nanotubes in the carbon nanotube composite structure are connected end to end by van der Waals force and are in the carbon nanotube composite structure line The extending direction of the axis is spirally arranged tightly around the linear axis, and the adjacent carbon nanotubes are closely connected by van der Waals and form a plurality of gaps. Most of the carbon nanotubes in the carbon nanotube composite structure extend substantially along the extending direction of the linear axis. Specifically, most of the carbon nanotubes in the carbon nanotube composite structure extend spirally end to end along the length of the linear axis. Each of the carbon nanotubes in the majority of the carbon nanotube composite structures is connected end to end with a vanadium tube in the extending direction. Each of the carbon nanotubes in the majority of the carbon nanotubes is closely arranged in a spiral shape substantially along the linear axis of the carbon nanotube composite structure. The extending direction of each of the carbon nanotubes in the majority of the carbon nanotubes forms a certain intersection angle α with the extending direction of the linear axis of the carbon nanotube composite structure, 0° < α ≦ 90°. The polymer material is filled in a gap between the carbon nanotubes or coated on the surface of the carbon nanotube.
所述扭轉的奈米碳管線包括大多數繞該扭轉的奈米碳管線軸向螺旋排列的奈米碳管。該奈米碳管線可採用一機械力將所述奈米碳管拉膜兩端沿相反方向扭轉獲得。進一步地，可採用一揮發性有機溶劑處理該扭轉的奈米碳管線。在揮發性有機溶劑揮發時產生的表面張力的作用下，處理後的扭轉的奈米碳管線中相鄰的奈米碳管通過凡得瓦力緊密結合，使扭轉的奈米碳管線的比表面積減小，密度及強度增大。該扭轉的奈米碳管線中相鄰的奈米碳管之 間形成複數個間隙。 The twisted nanocarbon line includes a majority of carbon nanotubes axially helically arranged around the twisted nanocarbon line. The nanocarbon pipeline can be obtained by twisting both ends of the carbon nanotube film in the opposite direction by a mechanical force. Further, the twisted nanocarbon line can be treated with a volatile organic solvent. Under the action of the surface tension generated by the volatilization of the volatile organic solvent, the adjacent carbon nanotubes in the treated twisted nanocarbon pipeline are tightly bonded by van der Waals to make the specific surface area of the twisted nanocarbon pipeline Decrease, increase in density and strength. Adjacent carbon nanotubes in the twisted nanocarbon pipeline A plurality of gaps are formed therebetween.
所述扭轉的奈米碳管線及其製備方法請參見范守善等人於2005年12月16日申請的，2009年7月21日公告的，公告號為TW I312337的台灣專利。 The twisted nano carbon pipeline and its preparation method can be found in the Taiwan patent filed on December 16, 2005 by Fan Shoushan et al., published on July 21, 2009, with the announcement number TW I312337.
可以理解，通過將至少一扭轉的奈米碳管線沿該奈米碳管複合結構的線狀軸心緊密環繞形成一奈米碳管管狀結構，再將該奈米碳管管狀結構與一聚合物材料複合形成所述具有空心管狀結構的奈米碳管複合結構時，該奈米碳管複合結構中大多數奈米碳管通過凡得瓦力首尾相連並在該奈米碳管複合結構的線狀軸心的延伸方向環繞該線狀軸心螺旋狀緊密排列，相鄰的奈米碳管之間通過凡得瓦力緊密結合並形成複數個間隙。所述聚合物材料填充於奈米碳管之間的間隙或包覆於奈米碳管的表面。 It can be understood that the carbon nanotube tubular structure and the polymer are formed by closely surrounding at least one twisted nanocarbon pipeline along the linear axis of the carbon nanotube composite structure to form a tubular structure of the carbon nanotube. When the material is composited to form the carbon nanotube composite structure having a hollow tubular structure, most of the carbon nanotubes in the carbon nanotube composite structure are connected end to end by van der Waals force and in the line of the carbon nanotube composite structure The extending direction of the axis is spirally arranged tightly around the linear axis, and the adjacent carbon nanotubes are tightly coupled by van der Waals and form a plurality of gaps. The polymer material is filled in a gap between the carbon nanotubes or coated on the surface of the carbon nanotube.
本發明實施例提供一種奈米碳管複合結構。該奈米碳管複合結構係由複數個奈米碳管及聚合物材料複合而成的一個管狀複合結構。該奈米碳管複合結構具有一中空的線狀軸心。該線狀軸心整體係空的，係虛擬的。該奈米碳管複合結構中大多數奈米碳管通過凡得瓦力首尾相連並在該奈米碳管複合結構線狀軸心的延伸方向環繞該線狀軸心螺旋狀緊密排列，奈米碳管之間通過凡得瓦力緊密相連。該奈米碳管複合結構中大多數奈米碳管基本沿線狀軸心的延伸方向延伸。具體地，該奈米碳管複合結構中大多數奈米碳管均首尾相連地沿著線狀軸心的長度方向螺旋狀延伸。該奈米碳管複合結構中的大多數奈米碳管中每一奈米碳管與在延伸方向上相鄰的奈米碳管通過凡得瓦力首尾相連。該大多數奈米碳管中每一奈米碳管的延伸方向與所述奈米碳管複合結構線狀軸心的延伸 方向形成一定的交叉角α，0°<α≦90°。 Embodiments of the present invention provide a carbon nanotube composite structure. The carbon nanotube composite structure is a tubular composite structure composed of a plurality of carbon nanotubes and a polymer material. The carbon nanotube composite structure has a hollow linear axis. The linear axis is entirely empty and is virtual. Most of the carbon nanotubes in the carbon nanotube composite structure are connected end to end by a van der Waals force and are closely arranged in a spiral shape around the linear axis in the extending direction of the linear axis of the carbon nanotube composite structure, and the nanometer The carbon tubes are closely connected by van der Waals. Most of the carbon nanotubes in the carbon nanotube composite structure extend substantially along the extending direction of the linear axis. Specifically, most of the carbon nanotubes in the carbon nanotube composite structure extend spirally end to end along the length of the linear axis. Each of the carbon nanotubes in the majority of the carbon nanotube composite structures is connected end to end with a vanadium tube in the extending direction. The extension direction of each of the carbon nanotubes in the majority of the carbon nanotubes and the extension of the linear axis of the composite structure of the carbon nanotubes The direction forms a certain angle of intersection α, 0° < α ≦ 90 °.
所述奈米碳管複合結構係由奈米碳管膜沿該奈米碳管複合結構的線狀軸心環繞形成一奈米碳管管狀結構，再將所述奈米碳管管狀結構與一聚合物複合製備而成的一個管狀複合結構。可以理解，該奈米碳管複合結構內徑和外徑的大小可以根據實際需求製備，本實施例中，該奈米碳管複合結構的內徑為25微米，外徑為50微米。 The carbon nanotube composite structure is formed by a carbon nanotube film surrounding a linear axis of the carbon nanotube composite structure to form a tubular structure of a carbon nanotube, and then polymerizing the tubular structure of the carbon nanotube A tubular composite structure prepared by compounding. It can be understood that the inner diameter and the outer diameter of the carbon nanotube composite structure can be prepared according to actual needs. In this embodiment, the inner diameter of the carbon nanotube composite structure is 25 micrometers and the outer diameter is 50 micrometers.
本實施例中的奈米碳管膜為一奈米碳管拉膜，該奈米碳管拉膜為從一奈米碳管陣列中直接拉取獲得。通過從六個生長於基底的奈米碳管陣列中拉取獲得六個奈米碳管拉膜，並直接將該六個奈米碳管拉膜沿所述奈米碳管複合結構的線狀軸心螺旋環繞形成一奈米碳管管狀結構，再將該奈米碳管管狀結構與一聚合物材料複合，形成所述具有管狀結構的奈米碳管複合結構。可以理解，由於奈米碳管拉膜係從一奈米碳管陣列中直接拉取獲得，其本身具有一定的黏性，當所述的奈米碳管拉膜沿該奈米碳管複合結構的線狀軸心螺旋環繞在一起時，相互層疊的奈米碳管拉膜會通過凡得瓦力的吸引而緊密地結合在一起。 The carbon nanotube film in this embodiment is a carbon nanotube film, and the carbon nanotube film is directly drawn from a carbon nanotube array. Six nanocarbon tube films were obtained by pulling from six carbon nanotube arrays grown on the substrate, and the six carbon nanotube tubes were directly drawn along the line of the carbon nanotube composite structure. The axial spiral surrounds a tubular structure of a carbon nanotube, and the tubular structure of the carbon nanotube is combined with a polymer material to form the composite structure of the carbon nanotube having a tubular structure. It can be understood that since the carbon nanotube film is directly drawn from a carbon nanotube array, it has a certain viscosity, and the nano carbon tube is pulled along the carbon nanotube composite structure. When the linear axes are spirally wound together, the stacked carbon nanotube films are tightly bonded by the attraction of van der Waals.
本實施例中選用矽橡膠與沿所述奈米碳管複合結構線狀軸心螺旋環繞的奈米碳管拉膜複合。該矽橡膠填充於奈米碳管之間的間隙或包覆於所述奈米碳管的表面。 In this embodiment, the ruthenium rubber is compounded with a nano carbon tube film which is spirally surrounded by a linear axis of the nano carbon tube composite structure. The tantalum rubber is filled in a gap between the carbon nanotubes or coated on the surface of the carbon nanotube.
請參閱圖5，本發明實施例還提供一種所述奈米碳管複合結構的製備方法。該奈米碳管複合結構的製備方法主要包括以下幾個步驟：(S101)提供一線狀支撐體，和至少一奈米碳管膜或至少一奈米碳管線；(S102)將所述至少一奈米碳管膜或至少一奈米碳 管線纏繞在所述線狀支撐體表面；(S103)將一聚合物材料與所述纏繞於該線狀支撐體表面的奈米碳管膜或奈米碳管線複合；(S104)移除所述線狀支撐體，形成一奈米碳管複合結構。 Referring to FIG. 5, an embodiment of the present invention further provides a method for preparing the carbon nanotube composite structure. The preparation method of the carbon nanotube composite structure mainly comprises the following steps: (S101) providing a linear support body, and at least one carbon nanotube film or at least one nano carbon line; (S102) the at least one Nano carbon tube membrane or at least one nanometer carbon a line wound around the surface of the linear support; (S103) compounding a polymer material with the carbon nanotube film or the nanocarbon line wound on the surface of the linear support; (S104) removing the The linear support forms a carbon nanotube composite structure.
步驟S101，提供一線狀支撐體，和至少一奈米碳管膜或至少一奈米碳管線。 In step S101, a linear support body and at least one carbon nanotube film or at least one nano carbon line are provided.
請參閱圖6及圖7，首先，提供一奈米碳管複合結構的製備裝置100，該製備裝置100包括一供給單元20，一包覆單元30以及一收集單元40。 Referring to FIG. 6 and FIG. 7 , firstly, a preparation device 100 for a carbon nanotube composite structure is provided. The preparation device 100 includes a supply unit 20 , a cladding unit 30 and a collection unit 40 .
所述供給單元20用於向包覆單元30供給一線狀支撐體。該供給單元20包括一線軸24、一支撐座22以及一導向軸28。所述導向軸28一端固定於所述支撐座22，另一端懸空設置。所述線軸24套設於所述導向軸28，並可以圍繞該導向軸28自由旋轉。提供一線狀支撐體，該線狀支撐體纏繞於所述線軸24。 The supply unit 20 is for supplying a linear support to the cladding unit 30. The supply unit 20 includes a bobbin 24, a support base 22 and a guide shaft 28. One end of the guide shaft 28 is fixed to the support base 22, and the other end is suspended. The bobbin 24 is sleeved on the guide shaft 28 and is free to rotate about the guide shaft 28. A linear support body is provided which is wound around the bobbin 24.
所述包覆單元30用於提供所述奈米碳管膜或奈米碳管線，並將該奈米碳管膜或奈米碳管線纏繞於所述線狀支撐體。該包覆單元30包括：一驅動機構32，一通過該驅動機構32驅動的空心旋轉軸34以及一固定於該空心旋轉軸34一端的花盤38。所述驅動機構32包括一第一電機322，一設置於該第一電機322旋轉軸的第一帶輪324，一第二帶輪328以及一設置於所述第一帶輪324以及所述第二帶輪328間的齒型帶326。所述空心旋轉軸34通過一軸承342設置於一支撐結構36，其中，所述空心旋轉軸34的一端套設於第二帶輪328，另一端固定有所述花盤38。所述空心旋轉軸34為一空心的管狀結構，可以使所述線狀支撐體從其空心的管狀結構穿過並纏繞於所述收集單元40。所述花盤38可以採用三棱臺、四棱臺 、五棱臺等棱臺。可以理解，根據所採用棱臺的幾何形狀的不同，所述花盤38具有複數個支撐面，該支撐面即為所述棱臺的側面，該複數個支撐面朝向所述收集單元40。各個支撐面用於承載超順排奈米碳管陣列。在本實施例中，所述花盤38採用具有六個支撐面的六棱臺。 The coating unit 30 is configured to provide the carbon nanotube film or a nano carbon line, and wind the carbon nanotube film or a nano carbon line on the linear support. The covering unit 30 includes a driving mechanism 32, a hollow rotating shaft 34 driven by the driving mechanism 32, and a disk 38 fixed to one end of the hollow rotating shaft 34. The driving mechanism 32 includes a first motor 322, a first pulley 324 disposed on the rotating shaft of the first motor 322, a second pulley 328, and a first pulley 324 and the first A toothed belt 326 between the two pulleys 328. The hollow rotating shaft 34 is disposed on a supporting structure 36 through a bearing 342. One end of the hollow rotating shaft 34 is sleeved on the second pulley 328, and the other end is fixed with the disk 38. The hollow rotating shaft 34 is a hollow tubular structure through which the linear support body can pass and be wound around the hollow tubular structure. The face plate 38 can adopt a triangular prism and a quadrangular prism , five-sided platform and other prisms. It will be understood that the face 38 has a plurality of support faces which are the sides of the ridges, the plurality of support faces facing the collection unit 40, depending on the geometry of the ridges employed. Each support surface is used to carry an array of super-sequential carbon nanotubes. In the present embodiment, the face plate 38 is a hexagonal table having six support faces.
所述收集單元40用於收集具有線狀支撐體的奈米碳管結構。該收集單元40包括一第二電機42，以及一設置於該第二電機42旋轉軸的奈米碳管結構收集器44。該奈米碳管結構收集器44在所述第二電機42的帶動下可以旋轉運動。 The collecting unit 40 is for collecting a carbon nanotube structure having a linear support. The collecting unit 40 includes a second motor 42 and a carbon nanotube structure collector 44 disposed on the rotating shaft of the second motor 42. The carbon nanotube structure collector 44 is rotatably movable by the second motor 42.
所述供給單元20設置於第二帶輪328一側，所述收集單元40設置於所述花盤38一側。 The supply unit 20 is disposed on a side of the second pulley 328, and the collection unit 40 is disposed on a side of the faceplate 38.
可以理解，通過控制所述第一電機322運轉可以帶動所述第一帶輪324旋轉，該第一帶輪324的旋轉可以通過所述齒型帶326帶動所述第二帶輪328旋轉。由於所述空心旋轉軸34套設於所述第二帶輪328，所以，所述空心旋轉軸34在所述驅動機構32的驅動下可以繞其中心軸旋轉。此外，由於所述花盤38固定於所述空心旋轉軸34，所以，該花盤38亦可以繞所述空心旋轉軸34的中心軸旋轉。該花盤38的旋轉速度由第一電機322的運轉速度來控制。 It can be understood that the first pulley 324 can be rotated by controlling the operation of the first motor 322, and the rotation of the first pulley 324 can drive the second pulley 328 to rotate through the toothed belt 326. Since the hollow rotating shaft 34 is sleeved on the second pulley 328, the hollow rotating shaft 34 can be rotated about its central axis by the driving mechanism 32. Further, since the face plate 38 is fixed to the hollow rotating shaft 34, the face plate 38 can also rotate about the central axis of the hollow rotating shaft 34. The rotational speed of the faceplate 38 is controlled by the operating speed of the first motor 322.
其次，從所述供給單元20中的線軸24拉取一線狀支撐體。所述線狀支撐體主要起支撐奈米碳管膜或奈米碳管線的作用，其本身具有一定的穩定性及機械強度，但可以通過化學方法、物理方法或機械方法移除。該線狀支撐體的材料可以選用金屬材料、合金材料及塑膠等材料，其中，所述金屬材料由單一的金屬元素組成。可以理解，該線狀支撐體可以選用不同的直徑。本實施例中選用 直徑為25微米的鋁線作為該線狀支撐體。 Next, a linear support body is pulled from the bobbin 24 in the supply unit 20. The linear support mainly functions to support a carbon nanotube film or a nano carbon pipeline, and has a certain stability and mechanical strength, but can be removed by chemical, physical or mechanical methods. The material of the linear support body may be selected from a metal material, an alloy material, and a plastic material, wherein the metal material is composed of a single metal element. It can be understood that the linear support body can be selected from different diameters. Selected in this embodiment An aluminum wire having a diameter of 25 μm was used as the linear support.
從所述供給單元20中拉取一線狀支撐體後，將所述線狀支撐體穿過所述空心旋轉軸34的中心軸並纏繞到奈米碳管結構收集器44。可以理解，將所述線狀支撐體穿過所述空心旋轉軸34的中心軸並纏繞到奈米碳管結構收集器44後，可以通過所述第二電機42帶動所述奈米碳管結構收集器44旋轉，使所述線狀支撐體沿所述空心旋轉軸34的中心軸延伸方向延伸並纏繞於所述奈米碳管結構收集器44。 After pulling a linear support from the supply unit 20, the linear support is passed through the central axis of the hollow rotating shaft 34 and wound around the carbon nanotube structure collector 44. It can be understood that after the linear support body passes through the central axis of the hollow rotating shaft 34 and is wound around the carbon nanotube structure collector 44, the carbon nanotube structure can be driven by the second motor 42. The collector 44 is rotated such that the linear support extends in the direction in which the central axis of the hollow rotating shaft 34 extends and is wound around the carbon nanotube structure collector 44.
進一步地，可以通過一定位單元50來調整線狀支撐體與其他單元的位置關係，使所述線狀支撐體始終位於所述空心旋轉軸34的中心軸及其延長線上做直線運動。具體地，可以在所述線軸24與所述第二帶輪328之間以及在所述花盤38與所述奈米碳管結構收集器44之間分別設置一定位單元50，該定位單元50包括一定位孔，可以使線狀支撐體從所述定位單元50的定位孔穿過，並使所述線狀支撐體始終保持在所述空心旋轉軸34的中心軸及其延長線上。該步驟為可選步驟。 Further, the positional relationship between the linear support body and the other units can be adjusted by a positioning unit 50 such that the linear support body is always in a linear motion on the central axis of the hollow rotary shaft 34 and its extension line. Specifically, a positioning unit 50 may be disposed between the bobbin 24 and the second pulley 328 and between the face plate 38 and the carbon nanotube structure collector 44. The positioning unit 50 may be respectively disposed. A positioning hole is included to allow the linear support body to pass through the positioning hole of the positioning unit 50, and the linear support body is always maintained on the central axis of the hollow rotating shaft 34 and its extension line. This step is an optional step.
最後，提供至少一奈米碳管陣列，從所述至少一奈米碳管陣列中製備出至少一奈米碳管膜或至少一奈米碳管線，本實施例為從奈米碳管陣列中拉出一奈米碳管拉膜，具體包括以下步驟： Finally, at least one carbon nanotube array is provided, and at least one carbon nanotube film or at least one nano carbon line is prepared from the at least one carbon nanotube array, and the embodiment is from a carbon nanotube array. Pull out a carbon nanotube film, including the following steps:
請參見圖2，提供至少一奈米碳管陣列12。所述奈米碳管陣列12形成於一基底10。本實施例中，提供六個形成於基底10的奈米碳管陣列12。所述奈米碳管陣列12由複數個奈米碳管組成，該奈米碳管為單壁奈米碳管、雙壁奈米碳管及多壁奈米碳管中的一種或複數種。本實施例中，該複數個奈米碳管為多壁奈米碳管，且該 複數個奈米碳管基本上相互平行且垂直於所述基底10，該奈米碳管陣列不含雜質，如無定型碳或殘留的催化劑金屬顆粒等。所述奈米碳管陣列12的製備方法不限，可參見台灣專利公告第I303239號。優選地，該奈米碳管陣列12為超順排奈米碳管陣列。 Referring to Figure 2, at least one carbon nanotube array 12 is provided. The carbon nanotube array 12 is formed on a substrate 10. In this embodiment, six carbon nanotube arrays 12 formed on the substrate 10 are provided. The carbon nanotube array 12 is composed of a plurality of carbon nanotubes, which are one or a plurality of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes. In this embodiment, the plurality of carbon nanotubes are multi-walled carbon nanotubes, and the The plurality of carbon nanotubes are substantially parallel to each other and perpendicular to the substrate 10, and the array of carbon nanotubes is free of impurities such as amorphous carbon or residual catalyst metal particles. The preparation method of the carbon nanotube array 12 is not limited, and can be referred to Taiwan Patent Publication No. I303239. Preferably, the carbon nanotube array 12 is a super-sequential carbon nanotube array.
將所述的至少一奈米碳管陣列12設置於所述花盤38的支撐面上。該至少一奈米碳管陣列12就可以隨所述花盤38繞空心旋轉軸34的中心軸旋轉。具體地，可以通過一黏合劑或一固定裝置將所述形成有奈米碳管陣列12的基底10固定於所述花盤38的一個支撐面上。本實施例中，將六個形成有奈米碳管陣列12的基底10通過固定裝置分別固定於所述花盤38的六個支撐面。 The at least one carbon nanotube array 12 is disposed on a support surface of the faceplate 38. The at least one carbon nanotube array 12 is rotatable about the central axis of the hollow rotating shaft 34 with the disk 38. Specifically, the substrate 10 on which the carbon nanotube array 12 is formed may be fixed to a support surface of the disk 38 by an adhesive or a fixing device. In the present embodiment, six substrates 10 on which the carbon nanotube array 12 is formed are respectively fixed to the six support faces of the face plate 38 by fixing means.
將所述的至少一奈米碳管陣列12設置於所述花盤38的支撐面後，進一步包括：從所述的至少一奈米碳管陣列20中拉取複數個奈米碳管，獲得一個奈米碳管拉膜14，並將該奈米碳管拉膜14的一端固定於所述線狀支撐體表面。本實施例優選為採用具有一定寬度的膠帶、鑷子或夾子接觸奈米碳管陣列12以選定一具有一定寬度的複數個奈米碳管；以一定速度拉伸該選定的奈米碳管，該拉取方向沿基本垂直於奈米碳管陣列的生長方向。從而形成首尾相連的複數個奈米碳管片段，進而形成一連續的奈米碳管拉膜14；並將該至少一奈米碳管拉膜14的一端固定於所述花盤38與所述奈米碳管結構收集器44之間的線狀支撐體表面。在上述拉伸過程中，該複數個奈米碳管片段在拉力作用下沿拉伸方向逐漸脫離基底的同時，由於凡得瓦力作用，該選定的複數個奈米碳管片段分別與其他奈米碳管片段首尾相連地連續地被拉出，從而形成一連續、 均勻且具有一定寬度的奈米碳管拉膜14。該奈米碳管拉膜14的寬度與奈米碳管陣列所生長的基底的尺寸有關，該奈米碳管拉膜14的長度不限，可根據實際需求制得。當該奈米碳管陣列的面積為4英寸時，該奈米碳管拉膜14的寬度為0.5奈米~10釐米，該奈米碳管拉膜14的厚度為0.5奈米~100微米。可以理解，當該奈米碳管拉膜14的寬度很窄的情況下，可以形成所述奈米碳管線。 After the at least one carbon nanotube array 12 is disposed on the support surface of the disk 38, the method further includes: pulling a plurality of carbon nanotubes from the at least one carbon nanotube array 20 to obtain A carbon nanotube film 14 is pulled, and one end of the carbon nanotube film 14 is fixed to the surface of the linear support. In this embodiment, it is preferred to contact the carbon nanotube array 12 with a tape, a tweezers or a clip having a certain width to select a plurality of carbon nanotubes having a certain width; and to stretch the selected carbon nanotubes at a certain speed, The pull direction is substantially perpendicular to the growth direction of the nanotube array. Thereby forming a plurality of carbon nanotube segments connected end to end, thereby forming a continuous carbon nanotube film 14; and fixing one end of the at least one carbon nanotube film 14 to the disk 38 and the The surface of the linear support between the carbon nanotube structure collectors 44. In the above stretching process, the plurality of carbon nanotube segments are gradually separated from the substrate in the stretching direction under the action of the tensile force, and the selected plurality of carbon nanotube segments are respectively associated with the other naphthalenes due to the effect of the van der Waals force. The carbon nanotube segments are continuously pulled out end to end to form a continuous, A carbon nanotube film 14 having a uniform width and a certain width. The width of the carbon nanotube film 14 is related to the size of the substrate on which the carbon nanotube array is grown. The length of the carbon nanotube film 14 is not limited and can be obtained according to actual needs. When the area of the carbon nanotube array is 4 inches, the width of the carbon nanotube film 14 is 0.5 nm to 10 cm, and the thickness of the carbon nanotube film 14 is 0.5 nm to 100 μm. It can be understood that the nanocarbon line can be formed when the width of the carbon nanotube film 14 is narrow.
步驟S102，將所述至少一奈米碳管膜或至少一奈米碳管線纏繞在所述線狀支撐體表面。 Step S102, winding the at least one carbon nanotube film or at least one nano carbon line on the surface of the linear support.
通過控制所述第一電機322運轉帶動所述空心旋轉軸34、花盤38以及奈米碳管陣列12沿所述空心旋轉軸34的中心軸以一定的轉速旋轉，並同時通過控制所述第二電機42運轉帶動所述奈米碳管結構收集器44旋轉，使所述線狀支撐體沿所述空心旋轉軸34的中心軸的延伸方向做直線運動並纏繞於所述奈米碳管結構收集器44。所述奈米碳管拉膜14就可以從所述奈米碳管陣列12中連續地拉出，並均勻地纏繞於所述線狀支撐體的表面。 Controlling the operation of the first motor 322 to drive the hollow rotating shaft 34, the disk 38 and the carbon nanotube array 12 to rotate at a certain rotational speed along a central axis of the hollow rotating shaft 34, and simultaneously control the first The operation of the second motor 42 drives the rotation of the carbon nanotube structure collector 44 to linearly move the linear support body along the extending direction of the central axis of the hollow rotating shaft 34 and wrap around the carbon nanotube structure. Collector 44. The carbon nanotube film 14 can be continuously drawn from the carbon nanotube array 12 and uniformly wound around the surface of the linear support.
具體地，當控制所述第一電機322運轉帶動所述第一帶輪324及第二帶輪328旋轉，可以進一步帶動所述空心旋轉軸34、花盤38以及奈米碳管陣列12沿所述空心旋轉軸34的中心軸以一定的轉速旋轉。由於從所述奈米碳管陣列12拉出的所述奈米碳管拉膜14的一端被固定於所述支撐體表面，因此，所述支撐體對所述奈米碳管拉膜14會產生一個沿該奈米碳管拉膜14延伸方向的拉力，從而使得奈米碳管拉膜14連續地被拉出。另外，由於所述花盤38帶動所述奈米碳管陣列旋轉，使得該奈米碳管拉膜14在連續被拉出的同時旋轉纏繞於所述支撐體表面。當以一定轉速旋轉所述奈米碳管 陣列12並以一定速率牽引所述支撐體使其做勻速直線運動時，可以使所述奈米碳管拉膜14從所述奈米碳管陣列12中拉出並均勻地纏繞於所述支撐體表面。進一步地，當所述奈米碳管拉膜14從所述奈米碳管陣列12中拉出並均勻地纏繞於所述支撐體表面後，由於所述第二電機42運轉帶動所述奈米碳管結構收集器44旋轉，可以使所述纏繞有奈米碳管拉膜14的支撐體纏繞於所述奈米碳管結構收集器44，並通過所述奈米碳管結構收集器44收集。 Specifically, when the first motor 322 is controlled to drive the first pulley 324 and the second pulley 328 to rotate, the hollow rotating shaft 34, the disk 38, and the carbon nanotube array 12 can be further driven. The central axis of the hollow rotating shaft 34 is rotated at a constant rotational speed. Since one end of the carbon nanotube film 14 pulled out from the carbon nanotube array 12 is fixed to the surface of the support body, the support body will be applied to the carbon nanotube film 14 A pulling force is generated along the extending direction of the carbon nanotube film 14, so that the carbon nanotube film 14 is continuously pulled out. In addition, since the face plate 38 drives the carbon nanotube array to rotate, the carbon nanotube film 14 is rotatably wound around the surface of the support while being continuously pulled out. Rotating the carbon nanotube at a certain speed The array of carbon nanotubes 14 can be pulled from the array of carbon nanotubes 12 and evenly wound around the support 12 when the array 12 is pulled at a constant rate for linear motion. Body surface. Further, after the carbon nanotube film 14 is pulled out from the carbon nanotube array 12 and evenly wound around the surface of the support body, the nano motor 42 is operated to drive the nanometer. The carbon tube structure collector 44 is rotated, and the support body around which the carbon nanotube film 14 is wound is wound around the carbon nanotube structure collector 44 and collected by the carbon nanotube structure collector 44. .
可以理解，可以通過所述第一電機322控制所述空心旋轉軸34及所述奈米碳管陣列12的轉速，並同時通過所述第二電機42控制所述線狀支撐體的做勻速直線運動的速率來控制纏繞於該線狀支撐體表面的奈米碳管複合結構的厚度。此外，由於奈米碳管拉膜14本身具有一定的黏性，當奈米碳管拉膜14纏繞於所述線狀支撐體表面時，相互層疊的奈米碳管拉膜14會通過凡得瓦力的吸引而緊密地結合在一起。 It can be understood that the rotational speed of the hollow rotating shaft 34 and the carbon nanotube array 12 can be controlled by the first motor 322, and at the same time, the linear support body can be controlled by the second motor 42 to make a uniform straight line. The rate of motion controls the thickness of the carbon nanotube composite structure wound around the surface of the linear support. In addition, since the carbon nanotube film 14 itself has a certain viscosity, when the carbon nanotube film 14 is wound around the surface of the linear support, the carbon nanotube film 14 laminated on each other will pass through. The attraction of the tile is tightly combined.
可以理解，將所述纏繞有奈米碳管拉膜14的線狀支撐體通過所述奈米碳管結構收集器44收集後，可以進一步包括：將所述纏繞有奈米碳管拉膜14的線狀支撐體纏繞於所述線軸24表面，重複上述步驟並通過控制所述第一電機322的轉動方向使所述空心旋轉軸34以及花盤38沿另一方向旋轉，使另一奈米碳管拉膜14沿反方向旋轉纏繞於所述線狀支撐體的奈米碳管拉膜14的表面。可以理解，通過將奈米碳管拉膜14沿不同方向旋轉層疊纏繞於所述線狀支撐體表面，可以獲得交叉的奈米碳管拉膜14纏繞於所述線狀支撐體的表面。可以理解，該步驟為可選步驟。 It can be understood that after the linear support body wrapped with the carbon nanotube film 14 is collected by the carbon nanotube structure collector 44, the method further includes: winding the carbon nanotube film 14 with the carbon nanotubes. The linear support is wound around the surface of the bobbin 24, and the above steps are repeated and the hollow rotary shaft 34 and the disk 38 are rotated in the other direction by controlling the rotational direction of the first motor 322 to make another nanometer. The carbon tube drawn film 14 is wound and wound in the opposite direction to the surface of the carbon nanotube film 14 of the linear support. It can be understood that by rotating and winding the carbon nanotube film 14 in different directions and winding on the surface of the linear support, it is possible to obtain a cross-shaped carbon nanotube film 14 wound around the surface of the linear support. It can be understood that this step is an optional step.
將所述纏繞有奈米碳管拉膜14的線狀支撐體通過所述奈米碳管結 構收集器44收集後，可進一步包括：使用一有機溶劑處理該纏繞於所述線狀支撐體的奈米碳管拉膜14，從而使奈米碳管拉膜14之間緊密結合並降低奈米碳管拉膜14表面的黏性。該有機溶劑與該奈米碳管具有較好的濕潤性。該有機溶劑為常溫下易揮發的有機溶劑，可選用乙醇、甲醇、丙酮、二氯乙烷和氯仿中一種或者幾種的混合。本實施例中的有機溶劑採用乙醇。該使用有機溶劑處理的步驟具體為：將有機溶劑均勻滴灑在奈米碳管拉膜14的表面上並浸潤整個奈米碳管拉膜14，或者，亦可將上述纏繞有奈米碳管拉膜14的線狀支撐體浸入盛有有機溶劑的容器中浸潤。 Passing the linear support wrapped with the carbon nanotube film 14 through the carbon nanotube junction After collecting the collector 44, the method further includes: treating the carbon nanotube film 14 wound around the linear support with an organic solvent, so that the carbon nanotube film 14 is tightly bonded and reduced. The viscosity of the surface of the carbon nanotube film 14 is removed. The organic solvent has good wettability with the carbon nanotubes. The organic solvent is an organic solvent which is volatile at normal temperature, and may be a mixture of one or more of ethanol, methanol, acetone, dichloroethane and chloroform. The organic solvent in this embodiment employs ethanol. The step of treating with an organic solvent is specifically: uniformly depositing an organic solvent on the surface of the carbon nanotube film 14 and infiltrating the entire carbon nanotube film 14 or, alternatively, winding the carbon nanotube The linear support of the drawn film 14 is immersed in a container containing an organic solvent to be infiltrated.
步驟S103，將一聚合物材料與所述纏繞於該線狀支撐體表面的奈米碳管膜或奈米碳管線複合。 In step S103, a polymer material is compounded with the carbon nanotube film or the nano carbon line wound around the surface of the linear support.
將所述表面纏繞有奈米碳管拉膜14的線狀支撐體浸入一聚合物材料的溶液或熔融液中，或將聚合物材料的溶液或熔融液噴灑或塗抹於所述含有線狀支撐體的奈米碳管拉膜14，使所述奈米碳管拉膜14中的奈米碳管與所述聚合物材料複合。所述聚合物材料為一有機材料，如環氧樹脂、丙烯酸樹脂、聚醯亞胺、聚乙烯醇、聚酯、丙烯酸樹脂、矽樹脂等樹脂材料或導熱膠材料及其混合物，本實施例以矽橡膠為例。具體方法包括：在矽橡膠中加入適量***稀釋，形成一矽橡膠溶液，並在矽橡膠溶液中加入少量固化劑，控制矽橡膠溶液的固化時間多於兩個小時。固化劑包括環氧樹脂固化劑、鹼性類固化劑及酸性類固化劑等。最後，將所述表面纏繞有奈米碳管拉膜14的線狀支撐體浸入矽橡膠溶液，使奈米碳管與矽橡膠複合。 The linear support having the surface wrapped with the carbon nanotube film 14 is immersed in a solution or melt of a polymer material, or a solution or melt of the polymer material is sprayed or applied to the wire-containing support. The body of the carbon nanotube film 14 is such that the carbon nanotubes in the carbon nanotube film 14 are combined with the polymer material. The polymer material is an organic material, such as an epoxy resin, an acrylic resin, a polyimide, a polyvinyl alcohol, a polyester, an acrylic resin, a resin, or the like, or a thermal conductive adhesive material and a mixture thereof. For example, 矽 rubber. The specific method comprises: adding an appropriate amount of diethyl ether to the ruthenium rubber to form a ruthenium rubber solution, and adding a small amount of a curing agent to the ruthenium rubber solution to control the curing time of the ruthenium rubber solution for more than two hours. The curing agent includes an epoxy resin curing agent, a basic curing agent, and an acidic curing agent. Finally, the linear support having the surface around which the carbon nanotube film 14 is wound is immersed in a ruthenium rubber solution to composite the carbon nanotubes with the ruthenium rubber.
步驟S104，移除所述線狀支撐體，形成一奈米碳管複合結構。 Step S104, removing the linear support to form a carbon nanotube composite structure.
使用化學方法或機械方法將所述的線狀支撐體移除。當採用活潑的金屬材料及其合金作該線狀支撐體時，如鐵或鋁及其合金，可以使用一酸性溶液與該活潑的金屬材料反應，並將該線狀支撐體移除；當採用高分子材料作線狀支撐體時，可以使用一拉伸裝置沿所述線狀支撐體的中心軸方向拉出所述線狀支撐體。本實施例採用濃度為0.5mol/L的鹽酸溶液腐蝕纏繞有奈米碳管拉膜14的鋁線，將該鋁線移除。可以理解，根據線狀支撐體直徑的不同可以得到不同內徑的奈米碳管複合結構。 The linear support is removed using chemical or mechanical means. When a living metal material and an alloy thereof are used as the linear support, such as iron or aluminum and alloys thereof, an acidic solution may be used to react with the active metal material, and the linear support may be removed; When the polymer material is used as the linear support, the linear support can be pulled out along the central axis direction of the linear support by using a stretching device. In this embodiment, an aluminum wire wound with a carbon nanotube film 14 is etched using a hydrochloric acid solution having a concentration of 0.5 mol/L, and the aluminum wire is removed. It can be understood that the carbon nanotube composite structures with different inner diameters can be obtained according to the diameter of the linear support.
另外，本發明實施例的奈米碳管複合結構亦不限於使用上述裝置來製備，亦可以通過將複數個奈米碳管膜或奈米碳管線分別依次纏繞於一線狀支撐體表面；或者通過將複數個奈米碳管膜層疊，然後直接纏繞於一線狀支撐體，然後將所述纏繞於線狀支撐體表面的奈米碳管膜或奈米碳管線與一聚合物複合，最後將該線狀支撐體移除製備得到。此外，所述奈米碳管複合結構的製備方法亦可以通過：提供一線狀支撐體，該線狀支撐體在一控制裝置的控制下既能夠繞其中心軸旋轉又能夠沿其中心軸延伸方向做直線運動；提供至少一奈米碳管陣列，將所述奈米碳管陣列固定並從所述奈米碳管陣列中拉取獲得至少一奈米碳管膜或至少一奈米碳管線，並將所述奈米碳管膜或奈米碳管線的一端固定於所述線狀支撐體；使該線狀支撐體繞其中心軸旋轉的同時沿其中心軸延伸方向做直線運動，即可得到一表面纏繞有奈米碳管膜或奈米碳管線的線狀支撐體；然後將表面纏繞有奈米碳管膜或奈米碳管線的線狀支撐體浸入一聚合物材料的溶液或熔融液中，或將聚合物材料的溶液或熔融液噴灑或塗抹於所述含有線狀支撐體的奈米碳管膜或奈米碳管線，最後，使用化學方法機械方法將所述的線狀支撐 體移除，得到一具有管狀結構的奈米碳管複合結構。該奈米碳管膜可以係奈米碳管拉膜、奈米碳管碾壓膜或奈米碳管絮化膜，該奈米碳管線可以係非扭轉或扭轉的奈米碳管線。可以理解，根據膜和線的種類的不同，可以獲得不同排列結構的奈米碳管複合結構；此外，該奈米碳管複合結構的厚度亦可以通過控制奈米碳管膜或奈米碳管線的層數以及聚合物材料的厚度來控制。 In addition, the carbon nanotube composite structure of the embodiment of the present invention is not limited to being prepared by using the above device, and may also be obtained by sequentially winding a plurality of carbon nanotube films or nano carbon pipelines on the surface of a linear support body respectively; Laminating a plurality of carbon nanotube films, and then directly winding them on a linear support, and then compounding the carbon nanotube film or the nano carbon line wound on the surface of the linear support with a polymer, and finally Linear support removal was prepared. In addition, the method for preparing the carbon nanotube composite structure can also be provided by: providing a linear support body which can rotate around its central axis and extend along its central axis under the control of a control device. Performing a linear motion; providing at least one carbon nanotube array, fixing the carbon nanotube array and pulling at least one carbon nanotube film or at least one nano carbon pipeline from the carbon nanotube array, And fixing one end of the carbon nanotube film or the nano carbon line to the linear support body; and linearly moving the linear support body along the central axis while rotating around the central axis thereof Obtaining a linear support having a surface surrounded by a carbon nanotube film or a carbon carbon line; and then immersing a linear support having a surface of a carbon nanotube film or a nanocarbon line in a solution or melting of a polymer material Spraying or applying a solution or melt of a polymer material to the carbon nanotube film or nanocarbon line containing the linear support in the liquid, and finally, using the chemical mechanical method to form the linear support The body is removed to obtain a carbon nanotube composite structure having a tubular structure. The carbon nanotube membrane may be a carbon nanotube membrane, a carbon nanotube membrane or a carbon nanotube membrane, and the nanocarbon pipeline may be a non-twisted or twisted nanocarbon pipeline. It can be understood that the carbon nanotube composite structure with different arrangement structures can be obtained according to the type of the film and the wire; in addition, the thickness of the carbon nanotube composite structure can also be controlled by the carbon nanotube film or the nano carbon pipeline. The number of layers and the thickness of the polymer material are controlled.
本發明實施例所提供的奈米碳管複合結構及其製備方法具有以下優點。 The carbon nanotube composite structure and the preparation method thereof provided by the embodiments of the present invention have the following advantages.
本發明奈米碳管複合結構係一個空心的管狀複合結構，該奈米碳管複合結構具有質量輕、熱容小，強度高以及耐彎折等特性，能方便地應用於複數個宏觀領域。該奈米碳管複合結構中相鄰的奈米碳管之間通過聚合物材料的相互作用而緊密結合在一起，因此該奈米碳管複合結構具有良好的拉伸強度及抗張模量。此外，本發明實施例奈米碳管複合結構係由至少一奈米碳管拉膜沿該奈米碳管複合結構的線狀軸心環繞形成一奈米碳管管狀結構，再將所述奈米碳管管狀結構與一聚合物複合製備而成。由於該奈米碳管拉膜係從一奈米碳管陣列中直接拉取獲得，其本身具有一定的黏性，經過螺旋狀纏繞排列，相互層疊的奈米碳管拉膜之間會通過凡得瓦力相互吸引，從而形成一個穩定結構。最後，該奈米碳管複合結構中的奈米碳管拉膜通過固化的聚合物材料固定形成一穩定的複合結構，使奈米碳管不易脫落，最後形成一穩定的、密封性良好的奈米碳管複合結構。 The nano carbon tube composite structure of the invention is a hollow tubular composite structure, and the carbon nanotube composite structure has the characteristics of light weight, small heat capacity, high strength and bending resistance, and can be conveniently applied to a plurality of macroscopic fields. The adjacent carbon nanotubes in the carbon nanotube composite structure are tightly bonded by the interaction of the polymer materials, so the carbon nanotube composite structure has good tensile strength and tensile modulus. In addition, in the embodiment of the present invention, the carbon nanotube composite structure is formed by forming at least one carbon nanotube film along a linear axis of the carbon nanotube composite structure to form a tubular structure of a carbon nanotube, and then The carbon nanotube tubular structure is prepared by compounding a polymer. Since the carbon nanotube film is directly drawn from a carbon nanotube array, it has a certain viscosity, and after being spirally wound, the mutually stacked nano carbon film is passed between The Walsh forces attract each other to form a stable structure. Finally, the carbon nanotube film in the carbon nanotube composite structure is fixed by a solidified polymer material to form a stable composite structure, so that the carbon nanotubes are not easily peeled off, and finally a stable, well-sealed naphthalene is formed. Carbon tube composite structure.
本發明奈米碳管複合結構的製備方法係通過將至少一奈米碳管膜或至少一奈米碳管線直接纏繞於一線狀支撐體結構表面，然後將 一聚合物材料與所述纏繞於該線狀線狀支撐體表面的奈米碳管膜或奈米碳管線複合，最後移除該線狀支撐體，得到一奈米碳管複合結構。該方法可用於簡單、快速地製備宏觀的具有管狀結構的奈米碳管複合結構。 The method for preparing a carbon nanotube composite structure of the present invention is characterized in that at least one carbon nanotube film or at least one nano carbon line is directly wound on a surface of a linear support structure, and then A polymer material is compounded with the carbon nanotube film or the nano carbon line wound on the surface of the linear linear support, and finally the linear support is removed to obtain a carbon nanotube composite structure. The method can be used to prepare a macroscopic carbon nanotube composite structure having a tubular structure simply and quickly.
本發明奈米碳管複合結構的製備方法係通過將至少一奈米碳管膜或至少一奈米碳管線直接纏繞於一線狀支撐體結構表面，然後將一聚合物材料與所述纏繞於該線狀線狀支撐體表面的奈米碳管膜或奈米碳管線複合，最後移除該線狀支撐體，得到一奈米碳管複合結構。該方法可用於簡單、快速地製備宏觀的具有管狀結構的奈米碳管複合結構。 The method for preparing a carbon nanotube composite structure of the present invention is characterized in that at least one carbon nanotube film or at least one nano carbon line is directly wound on a surface of a linear support structure, and then a polymer material is entangled with the The carbon nanotube film or the nano carbon line on the surface of the linear linear support is composited, and finally the linear support is removed to obtain a carbon nanotube composite structure. The method can be used to prepare a macroscopic carbon nanotube composite structure having a tubular structure simply and quickly.
綜上所述，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例，自不能以此限制本案之申請專利範圍。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內。 In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application 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 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.
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