TWI415883B - Carbon nanotube composite - Google Patents
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本發明涉及一種複合材料，尤其涉及一種奈米碳管複合材料。 The invention relates to a composite material, in particular to a carbon nanotube composite material.
自九十年代初以來，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，其廣闊的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、化學等性能，大量有關其在場發射電子源、感測器、新型光學材料、軟鐵磁材料等領域的應用研究不斷被報導。 Since the early 1990s, 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 are constantly emerging. For example, due to the unique electromagnetic, optical, mechanical, and chemical properties of carbon nanotubes, a large number of applications in field emission electron sources, sensors, new optical materials, soft ferromagnetic materials, etc. Was reported.
目前一種常見的奈米碳管的應用為將奈米碳管形成於基體的表面上，用作電子器件，比如作為電子發射源或作為導電層和電極，或用作電磁遮罩層等等。將奈米碳管形成於基體表面的方法通常為採用黏結劑將奈米碳管黏合於基體的表面。這種方法所製備的奈米碳管複合材料中，奈米碳管暴露在奈米碳管複合材料的表面上，在使用過程中，容易造成奈米碳管脫落或破壞，從而損害奈米碳管複合材料的表面導電性能以及使用壽命，影響在一些應用領域的應用效果。 A common application of a carbon nanotube is to form a carbon nanotube on the surface of a substrate for use as an electronic device, such as an electron emission source or as a conductive layer and an electrode, or as an electromagnetic mask layer or the like. The method of forming the carbon nanotubes on the surface of the substrate is usually to bond the carbon nanotubes to the surface of the substrate by using a binder. In the carbon nanotube composite material prepared by the method, the carbon nanotubes are exposed on the surface of the carbon nanotube composite material, and during use, the carbon nanotubes are easily detached or destroyed, thereby damaging the nanocarbon. The surface conductivity and service life of the tube composites affect the application in some applications.
有鑒於此，確有必要提供一種奈米碳管複合材料，該複合材料的 表面具有導電性的同時奈米碳管無需暴露於奈米碳管複合材料的表面。 In view of this, it is indeed necessary to provide a carbon nanotube composite material, the composite material The surface is electrically conductive while the carbon nanotubes need not be exposed to the surface of the carbon nanotube composite.
一種奈米碳管複合材料，其包括：一基體，該基體具有一表面；一奈米碳管結構，該奈米碳管結構設置於所述基體內，並靠近所述基體的一表面設置，該奈米碳管結構包括複數個通過凡得瓦力相互連接的奈米碳管，所述表面到奈米碳管結構的距離大於0小於等於10微米。 A carbon nanotube composite material comprising: a substrate having a surface; a carbon nanotube structure, the carbon nanotube structure being disposed in the substrate and disposed adjacent to a surface of the substrate, The carbon nanotube structure comprises a plurality of carbon nanotubes interconnected by van der Waals, the surface being at a distance from the carbon nanotube structure of greater than 0 to less than or equal to 10 microns.
與先前技術相比較，本發明提供的奈米碳管複合材料中，奈米碳管結構直接設置於基體材料內，奈米碳管無需暴露於奈米碳管複合材料的表面，使用過程中不會造成對奈米碳管複合材料的破壞；基體表面到奈米碳管結構的距離小於10微米，奈米碳管複合材料的表面具有導電性能，可應用於各種領域。 Compared with the prior art, in the carbon nanotube composite material provided by the invention, the carbon nanotube structure is directly disposed in the matrix material, and the carbon nanotubes need not be exposed to the surface of the carbon nanotube composite material, and the process is not used during use. It will cause damage to the carbon nanotube composite material; the distance from the surface of the substrate to the structure of the carbon nanotube is less than 10 microns, and the surface of the carbon nanotube composite has electrical conductivity and can be applied to various fields.
10‧‧‧奈米碳管複合材料 10‧‧‧Nano Carbon Tube Composites
12‧‧‧基體 12‧‧‧ base
122‧‧‧表面 122‧‧‧ surface
14‧‧‧奈米碳管結構 14‧‧‧Nano Carbon Tube Structure
圖1為本發明實施例提供的奈米碳管複合材料的結構示意圖。 FIG. 1 is a schematic structural view of a carbon nanotube composite material according to an embodiment of the present invention.
圖2為本發明實施例提供的奈米碳管複合材料的製備方法的流程圖。 2 is a flow chart of a method for preparing a carbon nanotube composite material according to an embodiment of the present invention.
圖3為本發明實施例提供的奈米碳管結構形成於基體表面之後的掃描電鏡照片。 FIG. 3 is a scanning electron micrograph of a carbon nanotube structure formed on a surface of a substrate according to an embodiment of the present invention.
圖4為本發明實施例提供的奈米碳管複合材料表面數碼照片和光學顯微鏡下的照片的組合圖。 4 is a combination diagram of a digital photo of a surface of a carbon nanotube composite material and a photograph under an optical microscope according to an embodiment of the present invention.
圖5為本發明實施例提供的奈米碳管複合材料側面的掃描電鏡照片。 FIG. 5 is a scanning electron micrograph of a side surface of a carbon nanotube composite material according to an embodiment of the present invention.
圖6為本發明實施例提供的將奈米碳管結構鋪設於基體的表面後，未進行微波處理和進行微波處理之後對水滴浸潤性影響的對比照片。 FIG. 6 is a comparative photograph of the effect of the carbon nanotube structure on the surface of the substrate after the microwave treatment and microwave treatment are performed on the wettability of the water droplets according to an embodiment of the present invention.
下面將結合附圖及具體實施例對本發明奈米碳管複合材料及其製備方法作進一步的詳細說明。 The carbon nanotube composite material of the present invention and a preparation method thereof will be further described in detail below with reference to the accompanying drawings and specific embodiments.
本發明提供一種奈米碳管複合材料，包括一基體及一奈米碳管結構。該基體具有一表面，該奈米碳管結構設置於基體內並靠近所述表面設置。所述基體表面到奈米碳管結構的距離大於0小於等於10微米。所述基體材料為高分子材料，所述奈米碳管複合材料表面的方塊電阻小於等於8千歐姆。 The invention provides a carbon nanotube composite material comprising a matrix and a carbon nanotube structure. The substrate has a surface, and the carbon nanotube structure is disposed in the substrate and disposed adjacent to the surface. The distance from the surface of the substrate to the carbon nanotube structure is greater than 0 and less than or equal to 10 microns. The base material is a polymer material, and a sheet resistance of the surface of the carbon nanotube composite material is less than or equal to 8 kilohms.
請參見圖1，係本發明一實施例之奈米碳管複合材料10。該奈米碳管複合材料10包括一基體12及一奈米碳管結構14。該基體12具有一表面122，該奈米碳管結構14設置於基體12內並靠近表面122設置。 Referring to FIG. 1, a carbon nanotube composite material 10 according to an embodiment of the present invention. The carbon nanotube composite 10 includes a substrate 12 and a carbon nanotube structure 14. The substrate 12 has a surface 122 that is disposed within the substrate 12 and disposed adjacent the surface 122.
所述基體12的材料可以為高分子材料。所述高分子材料包括環氧樹脂、雙馬來醯亞胺樹脂、氰酸酯樹脂、聚丙烯、聚乙烯、聚苯乙烯、聚乙烯醇、聚苯烯醇、聚碳酸酯或聚甲基丙烯酸甲酯等。優選地，所述基體12的熔點小於600℃。 The material of the substrate 12 may be a polymer material. The polymer material includes epoxy resin, bismaleimide resin, cyanate resin, polypropylene, polyethylene, polystyrene, polyvinyl alcohol, polyphenylene alcohol, polycarbonate or polymethacrylic acid. Methyl ester, etc. Preferably, the base 12 has a melting point of less than 600 °C.
所述奈米碳管結構14包括複數個均勻分佈的奈米碳管，奈米碳管之間通過凡得瓦力緊密結合。奈米碳管結構14還可以為由奈米碳管組成的純結構。奈米碳管結構14中奈米碳管之間存在間隙，從 而使奈米碳管結構14包括複數個微間隙。該奈米碳管結構14中的奈米碳管為無序或有序排列。這裏的無序排列指奈米碳管的排列方向無規律，這裏的有序排列指至少多數奈米碳管的排列方向具有一定規律。具體地，當奈米碳管結構14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；當奈米碳管結構14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。所述奈米碳管結構14的厚度優選為0.5奈米~10微米。所述奈米碳管結構14的單位面積熱容小於2×10-4焦耳每平方厘米開爾文。優選地，所述奈米碳管結構14的單位面積熱容可以小於等於1.7×10-6焦耳每平方厘米開爾文。所述奈米碳管結構14可包括一個奈米碳管膜，或複數個平行且無間隙鋪設或/和層疊鋪設的奈米碳管膜。所述奈米碳管結構14可包括複數個平行設置、交叉設置或按一定方式編織的奈米碳管線狀結構。所述奈米碳管結構14中的奈米碳管包括單壁奈米碳管、雙壁奈米碳管及多壁奈米碳管中的一種或多種。所述單壁奈米碳管的直徑為0.5奈米~50奈米，所述雙壁奈米碳管的直徑為1.0奈米~50奈米，所述多壁奈米碳管的直徑為1.5奈米~50奈米。 The carbon nanotube structure 14 includes a plurality of uniformly distributed carbon nanotubes, and the carbon nanotubes are tightly coupled by van der Waals. The carbon nanotube structure 14 can also be a pure structure composed of carbon nanotubes. There is a gap between the carbon nanotubes in the carbon nanotube structure 14 such that the carbon nanotube structure 14 includes a plurality of micro-gap. The carbon nanotubes in the carbon nanotube structure 14 are disordered or ordered. The disordered arrangement here means that the arrangement direction of the carbon nanotubes is irregular, and the ordered arrangement here means that at least most of the arrangement of the carbon nanotubes has a certain regularity. Specifically, when the carbon nanotube structure 14 includes a disordered arrangement of carbon nanotubes, the carbon nanotubes are intertwined or isotropically aligned; when the carbon nanotube structure 14 includes an ordered arrangement of carbon nanotubes The carbon nanotubes are arranged in a preferred orientation in one direction or in a plurality of directions. The thickness of the carbon nanotube structure 14 is preferably from 0.5 nm to 10 μm. The carbon nanotube structure 14 has a heat capacity per unit area of less than 2 x 10 -4 joules per square centimeter Kelvin. Preferably, the carbon nanotube structure 14 has a heat capacity per unit area of less than or equal to 1.7 x 10 -6 joules per square centimeter Kelvin. The carbon nanotube structure 14 may comprise a carbon nanotube membrane, or a plurality of parallel and gaplessly laid or/and laminated carbon nanotube membranes. The carbon nanotube structure 14 can include a plurality of nanocarbon line-like structures arranged in parallel, intersected, or woven in a manner. The carbon nanotubes in the carbon nanotube structure 14 include one or more of a single-walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube. The single-walled carbon nanotube has a diameter of 0.5 nm to 50 nm, the double-walled carbon nanotube has a diameter of 1.0 nm to 50 nm, and the multi-walled carbon nanotube has a diameter of 1.5. Nano ~ 50 nm.
在奈米碳管複合材料10中，基體12填充於到奈米碳管結構14中微間隙當中，基體12與奈米碳管結構14中的奈米碳管緊密結合。基體12包裹整個奈米碳管結構14。奈米碳管結構14在基體12中保持層狀結構。基體12的表面122到奈米碳管結構14的垂直距離大於0小於等於10微米。優選地，所述基體12表面122到奈米碳管結構14的距離小於100奈米。基體12的表面122到奈米碳管結構14的距 離小於等於10微米時，奈米碳管複合材料的表面122具有導電性，其方塊電阻小於等於8千歐姆。本實施例中，所述基體表面方塊電阻優選5千歐姆以下。每根奈米碳管表面的基體材料的厚度大於0小於等於10微米。優選地，每根奈米碳管表面的基體材料的厚度為20奈米至30奈米。 In the carbon nanotube composite 10, the substrate 12 is filled into the micro-gap in the carbon nanotube structure 14, and the substrate 12 is tightly bonded to the carbon nanotubes in the carbon nanotube structure 14. The substrate 12 encases the entire carbon nanotube structure 14. The carbon nanotube structure 14 maintains a layered structure in the substrate 12. The vertical distance from the surface 122 of the substrate 12 to the carbon nanotube structure 14 is greater than zero and less than or equal to 10 microns. Preferably, the distance from the surface 122 of the substrate 12 to the carbon nanotube structure 14 is less than 100 nanometers. The distance from the surface 122 of the substrate 12 to the carbon nanotube structure 14 When the distance is less than or equal to 10 micrometers, the surface 122 of the carbon nanotube composite has electrical conductivity and a sheet resistance of 8 kilohms or less. In this embodiment, the surface resistance of the substrate is preferably 5 kilohms or less. The thickness of the base material on the surface of each of the carbon nanotubes is greater than 0 and less than or equal to 10 microns. Preferably, the thickness of the base material on the surface of each of the carbon nanotubes is from 20 nm to 30 nm.
下面通過介紹上述奈米碳管複合材料的製備方法，對本發明奈米碳管複合材料進一步說明。請參見圖2，本發明進一步提供一種上述實施例的奈米碳管複合材料的製備方法。該奈米碳管複合材料的製備方法包括以下步驟： The carbon nanotube composite of the present invention will be further described below by introducing the preparation method of the above carbon nanotube composite. Referring to FIG. 2, the present invention further provides a method for preparing a carbon nanotube composite material according to the above embodiment. The preparation method of the carbon nanotube composite material comprises the following steps:
步驟一、提供一基體，該基體具有一表面。 Step 1. Providing a substrate having a surface.
所述表面可以為平面，也可以為彎曲表面。本實施例中，所述基體為一長方體結構，厚度為3毫米，邊長為50毫米。所述表面為邊長為50毫米的正方形的平面。所述基體的材料為聚乙烯。 The surface may be a flat surface or a curved surface. In this embodiment, the base body has a rectangular parallelepiped structure with a thickness of 3 mm and a side length of 50 mm. The surface is a square plane with a side length of 50 mm. The material of the substrate is polyethylene.
步驟二、提供一奈米碳管結構，該奈米碳管結構設置於所述基體的表面，所述奈米碳管結構包括複數個奈米碳管，該複數個奈米碳管之間形成有複數個微間隙。 Step 2, providing a carbon nanotube structure, the carbon nanotube structure is disposed on a surface of the substrate, the carbon nanotube structure comprises a plurality of carbon nanotubes, and the plurality of carbon nanotubes are formed There are multiple micro gaps.
奈米碳管結構設置於基體表面的方法可以為通過將一含有奈米碳管的漿料噴塗或塗敷於該片狀結構的表面，然後將溶劑揮發後形成，也可以直接將奈米碳管結構鋪設於表面。本實施例中，優選地，所述奈米碳管結構為一自支撐結構。所述自支撐為奈米碳管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)間隔一固定距離設置的兩個支撐體上時，位於兩個支撐體之間的奈米碳管膜能夠保持自身層狀狀態。所述奈米碳管結構中的微間隙的最大孔徑小於等於10微米。該自支撐的奈米碳管結構可以通過鋪設方式形成於表面。當採用自支撐的奈米碳管結構時，無須將奈米碳管形成漿料，無需解決奈米碳管的分散問題，也不會在奈米碳管結構引入其他雜質。且，採用自支撐的奈米碳管結構可以通過鋪設的方式將奈米碳管結構形成於基體的表面，操作簡單。 The method for disposing the carbon nanotube structure on the surface of the substrate may be formed by spraying or coating a slurry containing a carbon nanotube on the surface of the sheet structure, and then volatilizing the solvent, or directly disposing the carbon The tube structure is laid on the surface. In this embodiment, preferably, the carbon nanotube structure is a self-supporting structure. The self-supporting carbon nanotube film does not require a large-area carrier support, and 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). When the two supports are disposed at a fixed distance, the carbon nanotube film located between the two supports can maintain its own lamellar state. The micro-gap in the carbon nanotube structure has a maximum pore diameter of 10 μm or less. The self-supporting carbon nanotube structure can be formed on the surface by laying. When a self-supporting carbon nanotube structure is used, it is not necessary to form a slurry of the carbon nanotubes, and it is not necessary to solve the problem of dispersion of the carbon nanotubes, and no other impurities are introduced in the carbon nanotube structure. Moreover, the self-supporting carbon nanotube structure can be used to form the carbon nanotube structure on the surface of the substrate by laying, and the operation is simple.
所述奈米碳管結構所述奈米碳管結構可包括一個奈米碳管膜，或複數個平行且無間隙鋪設或/和層疊鋪設的奈米碳管膜。該奈米碳管膜為一奈米碳管拉膜、一奈米碳管絮化膜或一奈米碳管碾壓膜。 The carbon nanotube structure may include a carbon nanotube membrane, or a plurality of carbon nanotube membranes laid in parallel or without gaps. The carbon nanotube film is a carbon nanotube film, a carbon nanotube film or a carbon nanotube film.
(一)奈米碳管拉膜的製備方法包括以下步驟：首先，提供一奈米碳管陣列形成於一生長基底，該陣列為超順排的奈米碳管陣列。 (1) A method for preparing a carbon nanotube film comprises the steps of: firstly, providing a carbon nanotube array formed on a growth substrate, the array being a super-aligned carbon nanotube array.
該奈米碳管陣列的製備方法採用化學氣相沈積法，其具體步驟包括：(a)提供一平整生長基底，該生長基底可選用P型或N型矽生長基底，或選用形成有氧化層的矽生長基底，本發明實施例優選為採用4英寸的矽生長基底；(b)在生長基底表面均勻形成一催化劑層，該催化劑層材料可選用鐵(Fe)、鈷(Co)、鎳(Ni)或其任意組合的合金之一；(c)將上述形成有催化劑層的生長基底在700℃~900℃的空氣中退火約30分鐘~90分鐘；(d)將 處理過的生長基底置於反應爐中，在保護氣體環境下加熱到500℃~740℃，然後通入碳源氣體反應約5分鐘~30分鐘，生長得到奈米碳管陣列。該奈米碳管陣列為複數個彼此平行且垂直於生長基底生長的奈米碳管形成的純奈米碳管陣列。通過上述控制生長條件，該定向排列的奈米碳管陣列中基本不含有雜質，如無定型碳或殘留的催化劑金屬顆粒等。 The method for preparing the carbon nanotube array adopts a chemical vapor deposition method, and the specific steps thereof include: (a) providing a flat growth substrate, the growth substrate may be a P-type or N-type germanium growth substrate, or an oxide layer may be formed. The ruthenium growth substrate, the embodiment of the present invention preferably uses a 4 inch ruthenium growth substrate; (b) uniformly forms a catalyst layer on the surface of the growth substrate, and the catalyst layer material may be selected from iron (Fe), cobalt (Co), nickel ( Ni) or one of any alloy of any combination thereof; (c) annealing the growth substrate on which the catalyst layer is formed in air at 700 ° C to 900 ° C for about 30 minutes to 90 minutes; (d) The treated growth substrate is placed in a reaction furnace, heated to 500 ° C to 740 ° C in a protective gas atmosphere, and then reacted with a carbon source gas for about 5 minutes to 30 minutes to grow to obtain a carbon nanotube array. The carbon nanotube array is a plurality of pure carbon nanotube arrays formed of carbon nanotubes that are parallel to each other and perpendicular to the growth substrate. The aligned carbon nanotube array contains substantially no impurities, such as amorphous carbon or residual catalyst metal particles, etc., by controlling the growth conditions described above.
其次，採用一拉伸工具從奈米碳管陣列中拉取奈米碳管獲得至少一奈米碳管拉膜，其具體包括以下步驟：(a)從所述超順排奈米碳管陣列中選定一個或具有一定寬度的複數個奈米碳管，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以選定一個或具有一定寬度的複數個奈米碳管；(b)以一定速度拉伸該選定的奈米碳管，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。該拉取方向沿基本垂直於奈米碳管陣列的生長方向。 Secondly, a drawing tool is used to pull the carbon nanotubes from the carbon nanotube array to obtain at least one carbon nanotube film, which specifically comprises the following steps: (a) from the super-sequential carbon nanotube array Selecting one or a plurality of carbon nanotubes having a certain width, preferably adopting a tape, a braid or a clip having a certain width to contact the array of carbon nanotubes to select one or a plurality of carbon nanotubes having a certain width; (b The selected carbon nanotubes are drawn at a certain speed to form a plurality of carbon nanotube fragments connected end to end, thereby forming a continuous carbon nanotube film. The pull direction is substantially perpendicular to the growth direction of the nanotube array.
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生長基底的同時，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。 In the above stretching process, the plurality of carbon nanotube segments are gradually separated from the growth substrate in the stretching direction under the tensile force, and the selected plurality of carbon nanotube segments are respectively combined with the other 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, uniform, and wide-width carbon nanotube film.
該奈米碳管拉膜的寬度與奈米碳管陣列的尺寸有關，該奈米碳管拉膜的長度不限，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，該奈米碳管拉膜的寬度為0.5奈米~10厘米，該奈米碳管拉膜的厚度為0.5奈米~10微米。 The width of the carbon nanotube film is related to the size of the carbon nanotube array. The length of the carbon nanotube film 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 is 0.5 nm to 10 cm, and the thickness of the carbon nanotube film is 0.5 nm to 10 μm.
該奈米碳管拉膜可作為一奈米碳管結構使用，也可以將至少兩層奈米碳管拉膜層疊設置或並排設置形成一奈米碳管結構。 The carbon nanotube film can be used as a carbon nanotube structure, or at least two layers of carbon nanotube film can be stacked or arranged side by side to form a carbon nanotube structure.
(二)奈米碳管絮化膜的製備方法包括以下步驟：首先，提供一奈米碳管原料。 (2) The preparation method of the carbon nanotube flocculation membrane comprises the following steps: First, a carbon nanotube raw material is provided.
所述奈米碳管原料可以為通過化學氣相沈積法、石墨電極恒流電弧放電沈積法或鐳射蒸發沈積法等各種方法製備的奈米碳管。 The carbon nanotube raw material may be a carbon nanotube prepared by various methods such as chemical vapor deposition, graphite electrode constant current arc discharge deposition or laser evaporation deposition.
採用刀片或其他工具將上述定向排列的奈米碳管陣列從基底刮落，獲得一奈米碳管原料。優選地，所述之奈米碳管原料中，奈米碳管的長度大於100微米。 The aligned carbon nanotube arrays are scraped off the substrate using a blade or other tool to obtain a carbon nanotube material. Preferably, in the carbon nanotube raw material, the length of the carbon nanotube is greater than 100 micrometers.
其次，將上述奈米碳管原料添加到一溶劑中並進行絮化處理獲得一奈米碳管絮狀結構，將上述奈米碳管絮狀結構從溶劑中分離，並對該奈米碳管絮狀結構定型處理以獲得一奈米碳管絮化膜。 Next, the above carbon nanotube raw material is added to a solvent and subjected to flocculation treatment to obtain a nano carbon tube floc structure, and the above carbon nanotube floc structure is separated from the solvent, and the carbon nanotube is separated. The flocculated structure is shaped to obtain a carbon nanotube flocculation film.
溶劑可選用水、易揮發的有機溶劑等。絮化處理可通過採用超聲波分散處理或高強度攪拌等方法。優選地，本發明實施例採用超聲波分散10分鐘~30分鐘。由於奈米碳管具有極大的比表面積，相互纏繞的奈米碳管之間具有較大的凡得瓦力。上述絮化處理並不會將該奈米碳管原料中的奈米碳管完全分散在溶劑中，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。 The solvent can be selected from water, a volatile organic solvent, and the like. The flocculation treatment can be carried out by a method such as ultrasonic dispersion treatment or high-intensity stirring. Preferably, the embodiment of the invention uses ultrasonic dispersion for 10 minutes to 30 minutes. Due to the extremely large specific surface area of the carbon nanotubes, there is a large van der Waals force between the intertwined carbon nanotubes. The above flocculation treatment does not completely disperse the carbon nanotubes in the carbon nanotube raw material in the solvent, and the carbon nanotubes are mutually attracted and entangled by the van der Waals force to form a network structure.
所述之分離奈米碳管絮狀結構的方法具體包括以下步驟：將上述含有奈米碳管絮狀結構的溶劑倒入一放有濾紙的漏斗中；靜置乾燥一段時間從而獲得一分離的奈米碳管絮狀結構。 The method for separating the carbon nanotube floc structure specifically comprises the steps of: pouring the solvent containing the carbon nanotube floc structure into a funnel with a filter paper; and drying for a period of time to obtain a separation. Nano carbon tube floc structure.
所述之奈米碳管絮狀結構的定型處理過程具體包括以下步驟：將上述奈米碳管絮狀結構置於一容器中；將該奈米碳管絮狀結構按照預定形狀攤開；施加一定壓力於攤開的奈米碳管絮狀結構；以及，將該奈米碳管絮狀結構中殘留的溶劑烘乾或等溶劑自然揮發後獲得一奈米碳管絮化膜。 The shaping treatment process of the nano carbon tube floc structure specifically comprises the steps of: placing the above carbon nanotube floc structure in a container; spreading the nano carbon tube floc structure according to a predetermined shape; applying A certain pressure is applied to the expanded carbon nanotube floc structure; and the residual solvent in the nano carbon tube floc structure is dried or the solvent is naturally volatilized to obtain a carbon nanotube flocculation film.
可以理解，本發明可通過控制該奈米碳管絮狀結構攤開的面積來控制該奈米碳管絮化膜的厚度和面密度。奈米碳管絮狀結構攤開的面積越大，則該奈米碳管絮化膜的厚度和麵密度就越小。 It will be appreciated that the present invention controls the thickness and areal density of the carbon nanotube flocculation membrane by controlling the area over which the carbon nanotube floc is spread. The larger the area spread by the carbon nanotube floc structure, the smaller the thickness and areal density of the carbon nanotube flocculation film.
另外，上述分離與定型處理奈米碳管絮狀結構的步驟也可直接通過抽濾的方式實現，具體包括以下步驟：提供一孔隙濾膜及一抽氣漏斗；將上述含有奈米碳管絮狀結構的溶劑經過該孔隙濾膜倒入該抽氣漏斗中；抽濾並乾燥後獲得一奈米碳管絮化膜。該孔隙濾膜為一表面光滑、尺寸為0.22微米的濾膜。由於抽濾方式本身將提供一較大的氣壓作用於該奈米碳管絮狀結構，該奈米碳管絮狀結構經過抽濾會直接形成一均勻的奈米碳管絮化膜。且，由於孔隙濾膜表面光滑，該奈米碳管絮化膜容易剝離，得到一自支撐的奈米碳管絮化膜。 In addition, the step of separating and shaping the carbon nanotube floc structure can also be directly carried out by suction filtration, and specifically includes the following steps: providing a pore filter membrane and an air suction funnel; and the above-mentioned carbon nanotube containing The solvent of the structure is poured into the suction funnel through the pore filter membrane; after suction filtration and drying, a carbon nanotube flocculation membrane is obtained. The pore filter membrane is a filter membrane having a smooth surface and a size of 0.22 μm. Since the suction filtration method itself will provide a large gas pressure on the carbon nanotube floc structure, the carbon nanotube floc structure directly forms a uniform carbon nanotube flocculation membrane by suction filtration. Moreover, since the pore filter membrane surface is smooth, the carbon nanotube flocculation membrane is easily peeled off, and a self-supporting carbon nanotube flocculation membrane is obtained.
可以理解，該奈米碳管絮化膜具有一定的厚度，且通過控制該奈米碳管絮狀結構攤開的面積以及壓力大小可以控制奈米碳管絮化膜的厚度。該奈米碳管絮化膜可作為一奈米碳管結構使用，也可以將至少兩層奈米碳管絮化膜層疊設置或並排設置形成一奈米碳管結構。 It can be understood that the carbon nanotube flocculation membrane has a certain thickness, and the thickness of the carbon nanotube flocculation membrane can be controlled by controlling the area spread by the carbon nanotube floc structure and the pressure. The carbon nanotube flocculation membrane can be used as a carbon nanotube structure, or at least two layers of carbon nanotube flocculation membranes can be stacked or arranged side by side to form a carbon nanotube structure.
(三)奈米碳管碾壓膜的製備方法包括以下步驟：首先，提供一奈米碳管陣列形成於一生長基底，該陣列為定向排列的奈米碳管陣列。 (C) The preparation method of the carbon nanotube rolled film comprises the following steps: First, an array of carbon nanotubes is provided on a growth substrate, and the array is an array of aligned carbon nanotubes.
所述奈米碳管陣列優選為一超順排的奈米碳管陣列。所述奈米碳管陣列與上述奈米碳管陣列的製備方法相同。 The carbon nanotube array is preferably a super-aligned array of carbon nanotubes. The carbon nanotube array is prepared in the same manner as the above-described carbon nanotube array.
其次，採用一施壓裝置，擠壓上述奈米碳管陣列獲得一奈米碳管碾壓膜，其具體過程為：該施壓裝置施加一定的壓力於上述奈米碳管陣列上。在施壓的過程中，奈米碳管陣列在壓力的作用下會與生長基底分離，從而形成由複數個奈米碳管組成的具有自支撐結構的奈米碳管碾壓膜，且所述之複數個奈米碳管基本上與奈米碳管碾壓膜的表面平行。 Next, a carbon nanotube array is extruded by using a pressing device to obtain a carbon nanotube rolled film, wherein the pressing device applies a certain pressure to the carbon nanotube array. During the pressing process, the carbon nanotube array is separated from the growth substrate by pressure to form a carbon nanotube rolled film having a self-supporting structure composed of a plurality of carbon nanotubes, and The plurality of carbon nanotubes are substantially parallel to the surface of the carbon nanotube rolled film.
施壓裝置為一壓頭，壓頭表面光滑，壓頭的形狀及擠壓方向決定製備的奈米碳管碾壓膜中奈米碳管的排列方式。優選地，當採用平面壓頭沿垂直於上述奈米碳管陣列生長基底的方向擠壓時，可獲得奈米碳管為各向同性排列的奈米碳管碾壓膜；當採用滾軸狀壓頭沿某一固定方向碾壓時，可獲得奈米碳管沿該固定方向取向排列的奈米碳管碾壓膜；當採用滾軸狀壓頭沿不同方向碾壓時，可獲得奈米碳管沿不同方向取向排列的奈米碳管碾壓膜。 The pressing device is an indenter, the surface of the indenter is smooth, and the shape and extrusion direction of the indenter determine the arrangement of the carbon nanotubes in the prepared carbon nanotube rolled film. Preferably, when the planar indenter is pressed in a direction perpendicular to the growth substrate of the carbon nanotube array, the carbon nanotubes are obtained as isotropically arranged carbon nanotubes; when the roller is used When the indenter is rolled in a certain fixed direction, a carbon nanotube film which is aligned along the fixed direction of the carbon nanotubes can be obtained; when the roller-shaped indenter is rolled in different directions, the nanometer can be obtained. A carbon nanotube rolled film in which carbon tubes are aligned in different directions.
可以理解，當採用上述不同方式擠壓上述的奈米碳管陣列時，奈米碳管會在壓力的作用下傾倒，並與相鄰的奈米碳管通過凡得瓦力相互吸引、連接形成由複數個奈米碳管組成的具有自支撐結構的奈米碳管碾壓膜。 It can be understood that when the above-mentioned carbon nanotube array is extruded by the above different methods, the carbon nanotubes are poured under the action of pressure, and are attracted and connected with the adjacent carbon nanotubes through the van der Waals force. A carbon nanotube laminated film having a self-supporting structure composed of a plurality of carbon nanotubes.
可以理解，該奈米碳管碾壓膜具有一定的厚度，且通過奈米碳管陣列的高度以及壓力大小可以控制其厚度。所以該奈米碳管碾壓膜可以直接作為一奈米碳管結構使用。另外，可以將至少兩層奈米碳管碾壓膜層疊設置或並排設置形成一奈米碳管結構。 It can be understood that the carbon nanotube rolled film has a certain thickness, and the thickness can be controlled by the height of the carbon nanotube array and the pressure. Therefore, the carbon nanotube rolled film can be directly used as a carbon nanotube structure. In addition, at least two layers of carbon nanotube rolled films may be stacked or arranged side by side to form a carbon nanotube structure.
可選擇地，所述奈米碳管結構可進一步採用有機溶劑浸潤處理之後，再晾乾。所述有機溶劑可以為乙醇、甲醇、氯仿或丙醇等。優選地，所述有機溶劑為揮發性的有機溶劑。奈米碳管結構可以直接放入盛有有機溶劑的容器中浸泡。奈米碳管結構也可以鋪設於一基底上之後，將有機溶劑滴到奈米碳管結構的表面浸潤奈米碳管結構。可以理解，奈米碳管結構可以在形成於基體的表面上之後，將有機溶劑滴在奈米碳管結構的表面，至奈米碳管結構完全被有機溶劑浸潤後，晾乾。本實施例中，在奈米碳管結構形成於基體上之後，採用乙醇浸潤奈米碳管結構。 Alternatively, the carbon nanotube structure may be further dried with an organic solvent and then dried. The organic solvent may be ethanol, methanol, chloroform or propanol or the like. Preferably, the organic solvent is a volatile organic solvent. The carbon nanotube structure can be directly immersed in a container containing an organic solvent. After the carbon nanotube structure can also be laid on a substrate, the organic solvent is dropped onto the surface of the carbon nanotube structure to infiltrate the carbon nanotube structure. It can be understood that the carbon nanotube structure can be formed on the surface of the substrate, and the organic solvent is dropped on the surface of the carbon nanotube structure until the carbon nanotube structure is completely wetted by the organic solvent, and then dried. In this embodiment, after the carbon nanotube structure is formed on the substrate, the carbon nanotube structure is infiltrated with ethanol.
本實施例中，所述奈米碳管結構包括一層奈米碳管拉膜，該奈米碳管結構的厚度為奈米。圖3為本實施例中，奈米碳管結構形成於基體的表面上之後的掃描電鏡照片。從圖3可以看出，奈米碳管結構位於表面的上方。 In this embodiment, the carbon nanotube structure comprises a layer of carbon nanotube film, and the carbon nanotube structure has a thickness of nanometer. Figure 3 is a scanning electron micrograph of the carbon nanotube structure formed on the surface of the substrate in the present embodiment. As can be seen from Figure 3, the carbon nanotube structure is located above the surface.
步驟三、將所述奈米碳管結構與基體放置於一電磁波環境中，使基體表面熔化後滲透至所述奈米碳管結構的複數個微間隙中。 Step 3: placing the carbon nanotube structure and the substrate in an electromagnetic wave environment, so that the surface of the substrate melts and penetrates into a plurality of micro gaps of the carbon nanotube structure.
所述電磁波的功率為300瓦至2000瓦，頻率為1GHz至10GHz。所述電磁波可以為無線電波、微波、紅外線或遠紅外線。本實施例中，所述電磁波為微波，所述微波的功率為300瓦至1500瓦，頻率 為1GHz至5GHz，奈米碳管結構和基體在微波環境中放置的時間為1秒至300秒，優選地，為3秒至90秒。所述基體材料相同時，微波的功率越大，奈米碳管結構和基體在微波環境中的放置時間越短。基體材料為高分子材料，高分子材料一般與奈米碳管的浸潤性都較好，在基體的表面熔化後可以容易地滲透於奈米碳管結構的空隙中。由於基體為高分子材料，其對微波能量的吸收遠小於奈米碳管結構，且基體熱容大於奈米碳管層狀結構，因此，基體本身靠其自身吸收的微波能量所產生的溫度升高可以忽略，即，不會使整個基體熔化。由於奈米碳管結構的熱容較小，且與微波之間的相互作用較強，吸收微波能量之後的奈米碳管結構快速升高溫度，從而使與奈米碳管結構接觸的基體的表面溫度升高。當基體的表面達到一定溫度之後，開始熔化。當表面熔化時，奈米碳管結構中的奈米碳管外壁與基體之間的接觸更加充分，從而使奈米碳管結構與基體表面的介面熱阻顯著降低，有利於更大的熱流進入基體。在奈米碳管結構與微波相互作用並快速升溫的同時，高比表面積的奈米碳管可有效地將熱量傳遞給具有更大熱容的基體。故，微波加熱過程中，奈米碳管結構的上升溫度能被有效地控制在700℃以下，避免奈米碳管結構在空氣中氧化燃燒。在基體熔化的過程中，基體會膨脹和吸熱，在基體吸熱和膨脹的過程中，熔化的基體將滲透到奈米碳管結構的微間隙中。可以理解的，通過控制微波強度以及加熱溫度和時間來達成奈米碳管結構在基體中的適當範圍內的沉入深度，比如奈米碳管結構沉入基體表面至完全被埋沒或者奈米碳管結構沉入基體表面至剛好與基體表面平齊為止，即，奈米碳管結構表面的奈米碳管剛好從基體的 表面露出為止。在此過程中，由於奈米碳管結構中存在微間隙，熔化的基體材料將會填充於該微間隙中，並包覆在奈米碳管的表面，當微間隙被填滿後，奈米碳管結構在基體材料中的下沉動力減緩，進而可將包覆奈米碳管結構上表面的基體材料的厚度控制在100奈米以內。當基體滲透至奈米碳管結構的微間隙之後，基體可以將奈米碳管結構中的奈米碳管完全包覆。即，奈米碳管結構被埋在表面下。 The electromagnetic wave has a power of 300 watts to 2000 watts and a frequency of 1 GHz to 10 GHz. The electromagnetic wave may be radio waves, microwaves, infrared rays or far infrared rays. In this embodiment, the electromagnetic wave is a microwave, and the power of the microwave is 300 watts to 1500 watts, and the frequency is From 1 GHz to 5 GHz, the carbon nanotube structure and the substrate are placed in a microwave environment for a period of from 1 second to 300 seconds, preferably from 3 seconds to 90 seconds. When the matrix material is the same, the greater the power of the microwave, the shorter the placement time of the carbon nanotube structure and the matrix in the microwave environment. The base material is a polymer material, and the polymer material generally has good wettability with the carbon nanotubes, and can easily penetrate into the voids of the carbon nanotube structure after being melted on the surface of the substrate. Since the matrix is a polymer material, the absorption of microwave energy is much smaller than that of the carbon nanotube structure, and the heat capacity of the matrix is larger than that of the nanocarbon tube layer. Therefore, the temperature rise of the matrix itself by the microwave energy absorbed by itself The height is negligible, that is, it does not melt the entire substrate. Since the heat capacity of the carbon nanotube structure is small and the interaction with the microwave is strong, the structure of the carbon nanotubes after absorbing the microwave energy rapidly raises the temperature, thereby making the matrix in contact with the carbon nanotube structure. The surface temperature rises. When the surface of the substrate reaches a certain temperature, melting begins. When the surface is melted, the contact between the outer wall of the carbon nanotube and the substrate in the carbon nanotube structure is more sufficient, so that the thermal resistance of the interface between the carbon nanotube structure and the surface of the substrate is significantly reduced, which facilitates greater heat flow. Matrix. While the carbon nanotube structure interacts with the microwave and rapidly heats up, the high specific surface area carbon nanotubes can effectively transfer heat to the matrix with greater heat capacity. Therefore, during the microwave heating process, the rising temperature of the carbon nanotube structure can be effectively controlled below 700 ° C to avoid oxidation combustion of the carbon nanotube structure in the air. During the melting of the matrix, the matrix expands and absorbs heat. During the heat absorption and expansion of the matrix, the molten matrix will penetrate into the micro-gap of the carbon nanotube structure. It can be understood that the sinking depth of the carbon nanotube structure in a suitable range in the matrix is achieved by controlling the microwave intensity as well as the heating temperature and time, such as the sinking of the carbon nanotube structure into the surface of the substrate to be completely buried or nanocarbon. The tube structure sinks into the surface of the substrate until it is flush with the surface of the substrate, that is, the carbon nanotubes on the surface of the carbon nanotube structure are just from the substrate. The surface is exposed. During this process, due to the presence of micro-gap in the carbon nanotube structure, the molten matrix material will be filled in the micro-gap and coated on the surface of the carbon nanotube. When the micro-gap is filled, the nano-particles are filled. The sinking power of the carbon tube structure in the base material is slowed down, and the thickness of the base material covering the upper surface of the carbon nanotube structure can be controlled within 100 nm. After the matrix penetrates into the micro-gap of the carbon nanotube structure, the matrix can completely encapsulate the carbon nanotubes in the carbon nanotube structure. That is, the carbon nanotube structure is buried under the surface.
本實施例中，基體的材料為聚乙烯，聚乙烯的熔點為137℃左右，因此當奈米碳管結構的溫度達到137℃或略高於聚乙烯的熔點時，基體的表面122開始熔化，在微波環境中放置10秒後，基體將奈米碳管結構完全包覆。 In this embodiment, the material of the substrate is polyethylene, and the melting point of the polyethylene is about 137 ° C. Therefore, when the temperature of the carbon nanotube structure reaches 137 ° C or slightly higher than the melting point of the polyethylene, the surface 122 of the substrate begins to melt. After standing for 10 seconds in a microwave environment, the substrate completely encapsulates the carbon nanotube structure.
可以理解，上述步驟也可在真空環境下或有保護氣體存在的環境下進行。所述真空環境的真空度可以為10-2~10-6帕。所述保護氣體包括氮氣和惰性氣體。在真空環境或保護氣體存在的情況下，可以保護奈米碳管結構在高溫時不被破壞，奈米碳管結構的溫度可以達到2000℃左右。 It will be understood that the above steps can also be carried out in a vacuum environment or in the presence of a protective gas. The vacuum environment may have a vacuum of 10 -2 to 10 -6 Pa. The shielding gas includes nitrogen and an inert gas. In the presence of a vacuum environment or a protective gas, the carbon nanotube structure can be protected from being destroyed at a high temperature, and the temperature of the carbon nanotube structure can reach about 2000 °C.
請一併參見圖1及圖4，本實施例中，奈米碳管結構14與基體12在微波環境中放置10秒之後，取出冷卻後的所得到的奈米碳管複合材料10的表面掃描電鏡照片。對比於圖3，奈米碳管結構14與基體12在微波環境中放置10秒之後，奈米碳管結構14被基體12埋在表面122下方，奈米碳管複合材料10的表面係相對光滑而且平整的。從圖5奈米碳管複合材料10的側視的掃描電鏡照片可以看出，奈米碳管結構14中的奈米碳管都被基體材料覆蓋。比較圖5中 奈米碳管複合材料10中的單根奈米碳管被基體材料包覆後的直徑與原奈米碳管結構14中奈米碳管的直徑發現，奈米碳管的直徑原來為10-30nm，被基體材料包覆後形成的結構的直徑增大到70-90nm。從而可以知道，所述基體表面到奈米碳管結構的距離可認為原奈米碳管半徑與被包覆後的半徑之差，即30nm左右。 Referring to FIG. 1 and FIG. 4 together, in this embodiment, after the carbon nanotube structure 14 and the substrate 12 are placed in a microwave environment for 10 seconds, the surface scan of the obtained obtained carbon nanotube composite material 10 is taken out. Electron micrograph. Referring to FIG. 3, after the carbon nanotube structure 14 and the substrate 12 are placed in a microwave environment for 10 seconds, the carbon nanotube structure 14 is buried under the surface 122 by the substrate 12, and the surface of the carbon nanotube composite 10 is relatively smooth. And flat. It can be seen from the side view of the scanning electron micrograph of the carbon nanotube composite material 10 of Fig. 5 that the carbon nanotubes in the carbon nanotube structure 14 are covered by the matrix material. Compare Figure 5 The diameter of the single carbon nanotube in the carbon nanotube composite material 10 is covered by the matrix material and the diameter of the carbon nanotube in the original carbon nanotube structure 14 is found to be 10 - the diameter of the carbon nanotube is originally 10- At 30 nm, the diameter of the structure formed by coating with the base material is increased to 70-90 nm. Therefore, it can be known that the distance from the surface of the substrate to the structure of the carbon nanotube can be considered as the difference between the radius of the original carbon nanotube and the radius after being coated, that is, about 30 nm.
請參見圖6，本實施例中，將奈米碳管結構14鋪設於基體12的表面122之後，未進行微波處理和進行微波處理之後的微觀結構的不同造成對水滴浸潤角的不同。圖6A中，單層奈米碳管拉膜設置於基體12表面，且未進行微波處理。採用一滴5μL水滴滴在奈米碳管拉膜的表面，水滴順著奈米碳管拉膜中奈米碳管延伸的方向延展，形成截面積為5.69mm2的橢圓形態。請參見圖6B，進行微波處理形成奈米碳管複合材料之後，等量的水滴滴在本發明奈米碳管複合材料的表面後能保持圓形態，截面積為5.14mm2，在襯底上的接觸角各向同性。這種現象表明了奈米碳管拉膜已被一層奈米級厚度的光滑基體材料所覆蓋，奈米碳管拉膜中的間隙被基體材料所填充，奈米碳管拉膜中的奈米碳管被基體材料所包覆，由此確保了奈米碳管複合材料表面的導電性不受潮濕環境的影響，起到了保護奈米碳管導電層的作用。 Referring to FIG. 6, in the present embodiment, after the carbon nanotube structure 14 is laid on the surface 122 of the substrate 12, the difference in microstructure after the microwave treatment and the microwave treatment causes a difference in the water droplet wetting angle. In Fig. 6A, a single-layered carbon nanotube film is provided on the surface of the substrate 12 without microwave treatment. A drop of 5 μL of water was dropped on the surface of the carbon nanotube film, and the water droplets were extended in the direction in which the carbon nanotubes were stretched in the carbon nanotube film to form an elliptical shape having a cross-sectional area of 5.69 mm 2 . Referring to FIG. 6B, after the microwave treatment is performed to form the carbon nanotube composite material, an equal amount of water droplets can be kept in a circular shape after the surface of the carbon nanotube composite material of the present invention, and the cross-sectional area is 5.14 mm 2 on the substrate. The contact angle is isotropic. This phenomenon indicates that the carbon nanotube film has been covered by a layer of nanometer-thick smooth matrix material, the gap in the carbon nanotube film is filled by the matrix material, and the nanometer in the carbon nanotube film is pulled. The carbon tube is covered by the base material, thereby ensuring that the conductivity of the surface of the carbon nanotube composite material is not affected by the humid environment, and functions to protect the conductive layer of the carbon nanotube.
奈米碳管複合材料10的表面具有導電性能，本實施例中，將單層的奈米碳管拉膜形成該奈米碳管複合材料之後，奈米碳管複合材料表面的導電性能具有各向同性，對奈米碳管複合材料10表面的各個方向進行方塊電阻的測試，其方塊電阻為5千歐姆左右。而且，奈米碳管複合材料10的基體12表面122具有較好的耐刮擦性 能。將本實施例中所得到的奈米碳管複合材料10製備成體積為8×8mm2正方形，將一組銅電極用導電膠黏附在其邊緣兩端，以測量奈米碳管複合材料10表面電阻。一枚頂端面積約為0.25mm2針尖被施以恒定速度垂直於表面122摩擦奈米碳管複合材料10的表面122，該針尖被由酒精浸潤的棉絮包裹，並對針尖施加0.7牛頓的力按壓表面122。沿同一直線刮擦50次之後，奈米碳管複合材料10表面122的方塊電阻的變化幅度很小，不到10%。此類充分發揮CNT導電性的耐磨表面能滿足各種抗靜電器件的需求。如果將奈米碳管結構14直接鋪設於基體表面，在未經過微波處理的情況下，在一次針尖刮擦後，摩擦處的奈米碳管結構14便被全部剝離，奈米碳管複合材料的表面失去整體導電性。 The surface of the carbon nanotube composite material 10 has electrical conductivity. In this embodiment, after the single-layer carbon nanotube film is formed into the carbon nanotube composite material, the conductive properties of the surface of the carbon nanotube composite material have respective To the same sex, the sheet resistance was tested in all directions on the surface of the carbon nanotube composite material 10, and the sheet resistance was about 5 kΩ. Moreover, the surface 122 of the substrate 12 of the carbon nanotube composite 10 has better scratch resistance. The carbon nanotube composite material 10 obtained in the present embodiment was prepared into a volume of 8×8 mm 2 square, and a set of copper electrodes were adhered to the ends of the edges with a conductive adhesive to measure the surface of the carbon nanotube composite material 10. resistance. A tip area of about 0.25 mm 2 is applied to the surface 122 of the carbon nanotube composite 10 at a constant velocity perpendicular to the surface 122. The tip is wrapped by an alcohol-impregnated batt and applies a force of 0.7 Newtons to the tip. Surface 122. After scraping 50 times along the same line, the sheet resistance of the surface 122 of the carbon nanotube composite 10 varies little, less than 10%. Such a wear-resistant surface that fully utilizes CNT conductivity can meet the needs of various antistatic devices. If the carbon nanotube structure 14 is directly laid on the surface of the substrate, the carbon nanotube structure 14 at the friction portion is completely peeled off after the tip of the needle is not subjected to microwave treatment, and the carbon nanotube composite material is completely removed. The surface loses overall conductivity.
本發明所提供的奈米碳管複合材料及其製備方法具有以下優點：其一，本發明通過奈米碳管結構與電磁波加熱基體與該奈米碳管結構接觸的表面，從而形成表面導電的奈米碳管複合材料，無需將基體整體加熱，不會對基體本身造成傷害，且有利於節約能源。其二，本發明所提供的方法，簡單可控，適用於工業化應用。其三，本發明所提供的奈米碳管複合材料的表面具有良好的導電性能，具有較好的使用性能。其四，奈米碳管複合材料的表面具有較強的耐刮擦性能，使奈米碳管複合材料壽命較長，應用範圍廣泛。其五、本發明所提供的奈米碳管複合材料可以用作觸摸屏的透明導電基板，由於不需要黏結劑，該奈米碳管複合材料的介面少，可具有良好的透光性。 The carbon nanotube composite material provided by the invention and the preparation method thereof have the following advantages: First, the surface of the invention is formed by the surface of the carbon nanotube structure and the electromagnetic wave heating substrate contacting the carbon nanotube structure, thereby forming a surface conductive The carbon nanotube composite material does not need to heat the entire substrate, does not cause damage to the substrate itself, and is beneficial to save energy. Second, the method provided by the invention is simple and controllable and is suitable for industrial applications. Third, the surface of the carbon nanotube composite material provided by the invention has good electrical conductivity and good performance. Fourth, the surface of the carbon nanotube composite material has strong scratch resistance, so that the carbon nanotube composite material has a long service life and a wide application range. Fifthly, the carbon nanotube composite material provided by the invention can be used as a transparent conductive substrate of a touch screen, and since the binder is not required, the carbon nanotube composite material has a small interface and can have good light transmittance.
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。舉凡熟悉本案技藝之人士援依本發明之精神所作之等效修飾或變化，皆應涵蓋於以下申請專利範圍內。 In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. please. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by persons skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims.
10‧‧‧奈米碳管複合材料 10‧‧‧Nano Carbon Tube Composites
12‧‧‧基體 12‧‧‧ base
122‧‧‧表面 122‧‧‧ surface
14‧‧‧奈米碳管結構 14‧‧‧Nano Carbon Tube Structure
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