TWI478865B - Carbon nanotube film - Google Patents
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本發明涉及一種奈米材料膜，尤其涉及一種奈米碳管膜。 The invention relates to a nano material film, in particular to a carbon nanotube film.
奈米碳管(Carbon Nanotube,CNT)係一種新型碳材料，1991年由日本研究人員Iijima在實驗室製備獲得(請參見，Helical Microtubules of Graphitic Carbon,Nature,V354,P56~58(1991))。奈米碳管的特殊結構决定了其具有特殊的性質，如高抗張强度和高熱穩定性；隨著奈米碳管螺旋方式的變化，奈米碳管可呈現出金屬性或半導體性等。由於奈米碳管具有理想的一維結構以及在力學、電學、熱學等領域優良的性質，其在材料科學、化學、物理學等交叉學科領域已展現出廣闊的應用前景，包括場發射平板顯示，電子器件，原子力顯微鏡(Atomic Force Microscope,AFM)針尖，熱傳感器，光學傳感器，過濾器等。 Carbon Nanotube (CNT) is a new type of carbon material that was prepared in the laboratory by Japanese researcher Iijima in 1991 (see, Helical Microtubules of Graphitic Carbon, Nature, V354, P56-58 (1991)). The special structure of the carbon nanotubes determines its special properties, such as high tensile strength and high thermal stability. With the change of the helical mode of the carbon nanotubes, the carbon nanotubes can exhibit metallic or semiconducting properties. Because the carbon nanotubes have an ideal one-dimensional structure and excellent properties in the fields of mechanics, electricity, heat, etc., they have shown broad application prospects in the fields of materials science, chemistry, physics, etc., including field emission flat panel display. , electronic devices, Atomic Force Microscope (AFM) tips, thermal sensors, optical sensors, filters, etc.
雖然奈米碳管性能優異，具有廣泛的應用前景，然，由於奈米碳管為奈米級，大量奈米碳管易團聚，不易分散形成均勻的宏觀的奈米碳管結構，從而限制了奈米碳管在宏觀領域的應用。有鑒於此，如何獲得宏觀的奈米碳管結構係奈米領域研究的關鍵問題。 Although the performance of the carbon nanotubes is excellent, it has a wide application prospect. However, since the carbon nanotubes are nanometer-scale, a large number of carbon nanotubes are easily agglomerated and are not easily dispersed to form a uniform macroscopic carbon nanotube structure, thereby limiting the The application of carbon nanotubes in macroscopic fields. In view of this, how to obtain macroscopic carbon nanotube structure is a key issue in the field of nanotechnology research.
為了製成宏觀的奈米碳管結構，先前的方法主要包括：直接生長法、噴塗法或朗繆爾．布洛節塔(Langmuir．Blodgett,LB)法。其中，直接生長法一般通過控制反 應條件，如以硫磺作為添加劑或設置多層催化劑等，通過化學氣相沈積法直接生長得到奈米碳管薄膜結構。噴塗法一般通過將奈米碳管粉末形成水性溶液並塗覆於一基材表面，經乾燥後形成奈米碳管薄膜結構。LB法一般通過將一奈米碳管溶液混入另一具有不同密度之溶液(如有機溶劑)中，利用分子自組裝運動，奈米碳管浮出溶液表面形成奈米碳管薄膜結構。 In order to make a macroscopic carbon nanotube structure, the previous methods mainly include: direct growth method, spray method or Langmuir. Langmuir.Blodgett (LB) method. Among them, the direct growth method is generally controlled by The carbon nanotube film structure is directly grown by chemical vapor deposition, for example, using sulfur as an additive or a multilayer catalyst or the like. The spraying method generally forms a carbon nanotube film structure by drying a carbon nanotube solution into an aqueous solution and coating it on a surface of a substrate. The LB method generally uses a nanocarbon tube solution to be mixed into another solution having a different density (such as an organic solvent), and utilizes molecular self-assembly motion, and the carbon nanotubes float out of the surface of the solution to form a carbon nanotube film structure.
然而，上述製備奈米碳管結構的方法通常步驟較為繁雜，且通過直接生長法或噴塗法獲得的奈米碳管薄膜結構中，奈米碳管往往容易聚集成團，導致薄膜厚度不均。奈米碳管在奈米碳管結構中為無序排列，不利於充分發揮奈米碳管的性能。 However, the above method for preparing the carbon nanotube structure is generally complicated, and in the carbon nanotube film structure obtained by the direct growth method or the spray method, the carbon nanotubes tend to aggregate easily, resulting in uneven thickness of the film. The carbon nanotubes are disorderly arranged in the carbon nanotube structure, which is not conducive to giving full play to the performance of the carbon nanotubes.
為克服上述問題，申請人於2002年9月16日申請的2008年8月20日公告的專利號為ZL02134760.3中國專利中揭示了一種簡單的獲得有序的奈米碳管結構的方法。該奈米碳管結構為一連續的奈米碳管繩，其為直接從一超順排奈米碳管陣列中拉取獲得。所製備的奈米碳管繩中的奈米碳管首尾相連且通過凡德瓦爾力緊密結合。該奈米碳管繩的長度不限。其寬度與奈米碳管陣列所生長的基底尺寸有關。進一步地，所述奈米碳管繩包括多個首尾相連的奈米碳管片段，每個奈米碳管片段具有大致相等的長度且每個奈米碳管片段由多個相互平行的奈米碳管構成，奈米碳管片段兩端通過凡德瓦爾力相互連接。 In order to overcome the above problems, a simple method for obtaining an ordered carbon nanotube structure is disclosed in the Chinese patent No. ZL02134760.3, which was filed on Sep. 20, 2008, which is hereby incorporated by reference. The carbon nanotube structure is a continuous carbon nanotube rope obtained by directly pulling from an array of super-sequential carbon nanotubes. The carbon nanotubes in the prepared carbon nanotube rope are connected end to end and tightly bonded by van der Waals force. The length of the carbon nanotube string is not limited. Its width is related to the size of the substrate on which the carbon nanotube array is grown. Further, the carbon nanotube string comprises a plurality of end-to-end carbon nanotube segments, each of the carbon nanotube segments having substantially equal lengths and each of the carbon nanotube segments being composed of a plurality of mutually parallel nanometers. The carbon tube is formed, and the carbon nanotube segments are connected to each other by Van der Waals force.
Baughma,Ray,H.等人2005於文獻“Strong,Transparent,Multifunctional,Carbon Nanotube Sheets”Mei Zhang,Shaoli Fang,Anvar A.Zakhidov,Ray H.Baughman,etc..Science,Vol.309,P1215-1219(2005)中揭示了一種奈米碳管膜的製備方法。所述奈米碳管膜同樣可從一奈米碳管陣列中拉取製備。該奈米碳管陣列為一生長在一基底上的奈米碳管陣列。所述奈米碳管膜的長度不限。然而，上述兩種方式製備的奈米碳管膜或繩的寬度均受所述奈米碳管陣列生長基底的尺寸的限制(先前的用於生長奈米碳管陣列的基底一般為4英寸)，無法製備大面積奈米碳管膜。另外，所製備的奈米碳管膜的透光度不够好。 Baughma, Ray, H. et al. 2005 in the literature "Strong, Transparent, Multifunctional, Carbon A method for preparing a carbon nanotube film is disclosed in Nanotube Sheets "Mei Zhang, Shaoli Fang, Anvar A. Zakhidov, Ray H. Baughman, etc.. Science, Vol. 309, P1215-1219 (2005). The carbon nanotube film can also be prepared by drawing from a carbon nanotube array. The carbon nanotube array is an array of carbon nanotubes grown on a substrate. The length of the carbon nanotube film is not limited. However, the width of the carbon nanotube film or rope prepared by the above two methods is limited by the size of the carbon nanotube array growth substrate (the previous substrate for growing the carbon nanotube array is generally 4 inches). It is impossible to prepare a large-area carbon nanotube film. In addition, the prepared carbon nanotube film has insufficient transmittance.
有鑒於此，提供一種尺寸不受製備基底限制的奈米碳管膜實為必要。 In view of this, it is necessary to provide a carbon nanotube film of a size that is not limited by the preparation substrate.
一種奈米碳管膜，其包括：多個第一奈米碳管；以及多個第二奈米碳管，其中，所述多個第一奈米碳管沿同一方向定向排列，至少部分第二奈米碳管與至少兩個第一奈米碳管接觸。 A carbon nanotube film comprising: a plurality of first carbon nanotubes; and a plurality of second carbon nanotubes, wherein the plurality of first carbon nanotubes are oriented in the same direction, at least partially The two carbon nanotubes are in contact with at least two first carbon nanotubes.
相較於先前技術，本技術方案提供的奈米碳管膜具有以下優點：其一，本技術方案提供的奈米碳管膜可通過對奈米碳管膜進行拉伸來提高其透光度，無需採用繁雜的工序或昂貴的設備對奈米碳管膜進行後續處理來提高奈米碳管膜透光度，方法簡單易控，且不會破壞奈米碳管膜的結構，其可廣泛應用於對透光度具有較高要求的裝置中，如觸摸屏等。其二，所述奈米碳管膜具有較好的 拉伸性能，故所述奈米碳管膜可用於彈性可拉伸元件及設備中。其三，本技術方案奈米碳管膜具有較大尺寸，不受製備基底的限制，進而有利於擴大奈米碳管膜在大尺寸裝置中的應用。 Compared with the prior art, the carbon nanotube film provided by the technical solution has the following advantages: First, the carbon nanotube film provided by the technical solution can improve the transmittance of the carbon nanotube film by stretching the film. There is no need to use complicated processes or expensive equipment to carry out subsequent treatment on the carbon nanotube film to improve the transparency of the carbon nanotube film. The method is simple and easy to control, and does not damage the structure of the carbon nanotube film. It is applied to devices with high requirements for transmittance, such as touch screens. Second, the carbon nanotube film has better The tensile properties, so the carbon nanotube film can be used in elastic stretchable components and equipment. Thirdly, the nano carbon tube membrane of the technical solution has a large size and is not restricted by the preparation substrate, thereby facilitating the application of the carbon nanotube film in a large-sized device.
以下將結合附圖詳細說明本技術方案實施例提供的奈米碳管膜及其拉伸方法。 The carbon nanotube film provided by the embodiment of the present technical solution and the stretching method thereof will be described in detail below with reference to the accompanying drawings.
請參閱圖1至圖4，本技術方案實施例提供一種奈米碳管膜10。該奈米碳管膜10包括多個奈米碳管100。該奈米碳管100包括多個第一奈米碳管102以及多個第二奈米碳管104。其中，所述多個第一奈米碳管102均勻分布在所述奈米碳管膜10中且沿第一方向定向排列。所述第一方向為D1方向。具體地，在第一方向上第一奈米碳管102首尾相連。所述多個首尾相連的第一奈米碳管102之間通過凡德瓦爾力緊密連接。在第二方向上，所述第一奈米碳管102相互平行。該第二方向為D2方向，所述D2方向垂直於所述D1方向。所述第二奈米碳管104均勻分布在所述奈米碳管膜10中且與所述第一奈米碳管102形成網絡結構。至少部分第二奈米碳管104與至少兩個第一奈米碳管102通過凡德瓦爾力接觸。優選地，至少部分第二奈米碳管104與至少兩個並排設置的第一奈米碳管102接觸。所述第二奈米碳管104的排列方向不限，所述第二奈米碳管104的排列方向可不同。所述多個第一奈米碳管102和多個第二奈米碳管104形成一具有自支撑結構的奈米碳管膜10。所謂自支撑結構的奈米碳管膜10即所述奈米碳管膜10無需 通過一支撑體支撑，也能保持自身特定的形狀或只需部分設置在一支撑體上即可維持其膜狀結構，且奈米碳管膜10本身的結構不會發生變化。如將所述奈米碳管膜10設置在一框架或兩個間隔設置的支撑結構上，位於中間未與框架或支撑結構接觸的奈米碳管膜10可懸空設置。所述奈米碳管膜10中，多個第一奈米碳管102和多個第二奈米碳管104形成多個間隙106。所述碳納管膜10可沿第二方向，即D2方向拉伸。由於多個第二奈米碳管104的存在，所述奈米碳管膜10在維持膜的結構的前提下可在D2方向上拉伸。在拉伸過程中，平行的第一奈米碳管102之間的距離可變化，所述間隙106也可變化，即其隨著奈米碳管膜10在D2方向上形變率的增加而變大。所述平行的第一奈米碳管102之間的距離(即沿D2方向的距離)大於0微米且小於等於50微米。所述第一奈米碳管102和第二奈米碳管104在奈米碳管膜10中的數量比大於等於2：1且小於等於6：1。本技術方案實施例中，所述第一奈米碳管102和第二奈米碳管104在奈米碳管膜10中的數量比為4：1。 Referring to FIG. 1 to FIG. 4 , an embodiment of the present technical solution provides a carbon nanotube film 10 . The carbon nanotube film 10 includes a plurality of carbon nanotubes 100. The carbon nanotube 100 includes a plurality of first carbon nanotubes 102 and a plurality of second carbon nanotubes 104. Wherein, the plurality of first carbon nanotubes 102 are uniformly distributed in the carbon nanotube film 10 and aligned in the first direction. The first direction is the D1 direction. Specifically, the first carbon nanotubes 102 are connected end to end in the first direction. The plurality of first and second carbon nanotubes 102 connected end to end are closely connected by a van der Waals force. In the second direction, the first carbon nanotubes 102 are parallel to each other. The second direction is the D2 direction, and the D2 direction is perpendicular to the D1 direction. The second carbon nanotubes 104 are uniformly distributed in the carbon nanotube film 10 and form a network structure with the first carbon nanotubes 102. At least a portion of the second carbon nanotubes 104 are in contact with the at least two first carbon nanotubes 102 by van der Waals forces. Preferably, at least a portion of the second carbon nanotubes 104 are in contact with at least two first carbon nanotubes 102 disposed side by side. The arrangement direction of the second carbon nanotubes 104 is not limited, and the arrangement direction of the second carbon nanotubes 104 may be different. The plurality of first carbon nanotubes 102 and the plurality of second carbon nanotubes 104 form a carbon nanotube film 10 having a self-supporting structure. The so-called self-supporting structure of the carbon nanotube film 10, that is, the carbon nanotube film 10 does not need By supporting a support body, it is also possible to maintain its specific shape or to be partially disposed on a support to maintain its film-like structure, and the structure of the carbon nanotube film 10 itself does not change. If the carbon nanotube film 10 is placed on a frame or two spaced apart support structures, the carbon nanotube film 10, which is not in contact with the frame or the support structure, can be suspended. In the carbon nanotube film 10, the plurality of first carbon nanotubes 102 and the plurality of second carbon nanotubes 104 form a plurality of gaps 106. The carbon nanotube film 10 can be stretched in the second direction, that is, in the D2 direction. Due to the presence of the plurality of second carbon nanotubes 104, the carbon nanotube film 10 can be stretched in the D2 direction while maintaining the structure of the film. During the stretching process, the distance between the parallel first carbon nanotubes 102 may vary, and the gap 106 may also vary, that is, as the deformation rate of the carbon nanotube film 10 in the D2 direction increases. Big. The distance between the parallel first carbon nanotubes 102 (i.e., the distance along the D2 direction) is greater than 0 micrometers and less than or equal to 50 micrometers. The number ratio of the first carbon nanotube 102 and the second carbon nanotube 104 in the carbon nanotube film 10 is 2:1 or more and 6:1 or less. In the embodiment of the technical solution, the ratio of the first carbon nanotube 102 and the second carbon nanotube 104 in the carbon nanotube film 10 is 4:1.
所述奈米碳管膜10的長度、寬度及厚度不限，可根據實際需求製備。所述奈米碳管膜10的厚度優選為大於等於0.5奈米且小於等於1毫米。所述奈米碳管膜10中的奈米碳管100的直徑大於等於0.5奈米且小於等於50奈米。所述奈米碳管100的長度為大於等於50微米且小於等於5毫米。 The length, width and thickness of the carbon nanotube film 10 are not limited and can be prepared according to actual needs. The thickness of the carbon nanotube film 10 is preferably 0.5 nm or more and 1 mm or less. The diameter of the carbon nanotubes 100 in the carbon nanotube film 10 is 0.5 nm or more and 50 nm or less. The length of the carbon nanotube 100 is 50 μm or more and 5 mm or less.
所述奈米碳管膜10在D2方向上的形變率與奈米碳管膜10 的厚度及密度有關。所述奈米碳管膜10的厚度及密度愈大，其在D2方向上的形變率愈大。進一步地，所述奈米碳管膜10的透光度與第二奈米碳管104的含量有關。在一定含量範圍內，所述第二奈米碳管104的含量越多，所述奈米碳管膜10在D2方向上的形變率越大。所述奈米碳管膜10在D2方向上的形變率可達300%。拉伸前後的奈米碳管膜10的電阻不發生變化。本技術方案實施例中，所述奈米碳管膜10的厚度為50奈米，其在D2方向上的形變率可達到150%。 The deformation rate of the carbon nanotube film 10 in the D2 direction and the carbon nanotube film 10 The thickness and density are related. The larger the thickness and density of the carbon nanotube film 10, the greater the deformation rate in the D2 direction. Further, the transmittance of the carbon nanotube film 10 is related to the content of the second carbon nanotube 104. The greater the content of the second carbon nanotubes 104, the greater the deformation rate of the carbon nanotube film 10 in the D2 direction. The carbon nanotube film 10 has a deformation rate of 300% in the D2 direction. The electric resistance of the carbon nanotube film 10 before and after stretching does not change. In the embodiment of the technical solution, the carbon nanotube film 10 has a thickness of 50 nm, and the deformation rate in the D2 direction can reach 150%.
所述奈米碳管膜10的透光度(光透過比率)與奈米碳管膜10的厚度及密度有關。所述奈米碳管膜10的厚度及密度越大，所述奈米碳管膜10的透光度越小。進一步地，所述奈米碳管膜10的透光度與間隙106及第二奈米碳管104的含量有關。所述間隙106越大，第二奈米碳管104的含量越少，則所述奈米碳管膜10的透光度越大。所述奈米碳管膜10的透光度大於等於60%且小於等於95%。請參閱圖7，本技術方案實施例中，當奈米碳管膜10的厚度為50奈米時，拉伸前該奈米碳管膜10的透光度為大於等於67%且小於等於82%。當其形變率為120%時，所述奈米碳管膜10的透光度為大於等於84%且小於等於92%。以波長為550奈米的綠光為例，拉伸前所述奈米碳管膜10的透光度為78%，當形變率為120%時，該奈米碳管膜10的透光度可達89%。 The transmittance (light transmission ratio) of the carbon nanotube film 10 is related to the thickness and density of the carbon nanotube film 10. The greater the thickness and density of the carbon nanotube film 10, the smaller the transmittance of the carbon nanotube film 10. Further, the transmittance of the carbon nanotube film 10 is related to the content of the gap 106 and the second carbon nanotube 104. The larger the gap 106 is, the smaller the content of the second carbon nanotube 104 is, and the greater the transmittance of the carbon nanotube film 10. The carbon nanotube film 10 has a transmittance of 60% or more and 95% or less. Referring to FIG. 7, in the embodiment of the present invention, when the thickness of the carbon nanotube film 10 is 50 nm, the transmittance of the carbon nanotube film 10 before stretching is 67% or more and less than or equal to 82. %. When the deformation rate is 120%, the transmittance of the carbon nanotube film 10 is 84% or more and 92% or less. Taking the green light having a wavelength of 550 nm as an example, the transmittance of the carbon nanotube film 10 before stretching is 78%, and the transmittance of the carbon nanotube film 10 when the deformation rate is 120%. Up to 89%.
由於所述奈米碳管膜10可在D2方向上被拉伸，故所述奈米碳管膜10可廣泛應用於彈性可拉伸元件和設備中。另 外，本技術方案提供的奈米碳管膜10的拉伸方法避免了採用繁雜的設備對奈米碳管膜10進行後續處理來提高奈米碳管膜10透光度的步驟，其可廣泛應用於對透光度具有較高要求的裝置中，如觸摸屏等。另外，所述奈米碳管膜10可用於發聲裝置中，且奈米碳管10在拉伸過程中不影響發聲效果。 Since the carbon nanotube film 10 can be stretched in the D2 direction, the carbon nanotube film 10 can be widely used in elastic stretchable members and equipment. another In addition, the stretching method of the carbon nanotube film 10 provided by the technical solution avoids the step of improving the transmittance of the carbon nanotube film 10 by using a complicated device for subsequent treatment of the carbon nanotube film 10, which can be widely used. It is applied to devices with high requirements for transmittance, such as touch screens. In addition, the carbon nanotube film 10 can be used in a sounding device, and the carbon nanotube 10 does not affect the sounding effect during stretching.
請同時參閱圖5及圖6，本技術方案實施例進一步提供一種拉伸奈米碳管膜的方法，具體包括以下步驟： Please refer to FIG. 5 and FIG. 6 simultaneously. The embodiment of the present technical solution further provides a method for stretching a carbon nanotube film, which specifically includes the following steps:
步驟一：提供至少一奈米碳管膜10及至少一彈性支撑體20。 Step 1: providing at least one carbon nanotube film 10 and at least one elastic support body 20.
請參閱圖3，該奈米碳管膜10包括多個第一奈米碳管102以及多個第二奈米碳管104。其中，所述多個第一奈米碳管102均勻分布在所述奈米碳管膜10中且沿第一方向定向排列。所述多個第一奈米碳管102在第二方向上相互平行。所述第一方向為D1方向，所述第二方向為D2方向，所述D2方向垂直於所述D1方向。具體地，在第一方向上第一奈米碳管102首尾相連。所述多個首尾相連的第一奈米碳管102之間通過凡德瓦爾力緊密連接。所述第二奈米碳管104均勻分布在所述奈米碳管膜10中且與所述第一奈米碳管102形成網絡結構。至少部分第二奈米碳管104與至少兩個第一奈米碳管102通過凡德瓦爾力接觸。優選地，至少部分第二奈米碳管104與至少兩個相互平行的第一奈米碳管102接觸。所述第二奈米碳管104的排列方向不限，所述第二奈米碳管104的排列方向可不同。所述多個第一奈米碳管102和多個第二奈米碳管104形成一具有自支 撑結構的奈米碳管膜10。所述奈米碳管膜10中，多個第一奈米碳管102和多個第二奈米碳管104形成多個間隙106。所述平行的第一奈米碳管102之間的距離(即沿D2方向的距離)大於0微米小於等於50微米。所述第一奈米碳管102和第二奈米碳管104在奈米碳管膜10中的數量比大於等於2：1且小於等於6：1。本技術方案實施例中，所述第一奈米碳管102和第二奈米碳管104在奈米碳管膜10中的數量比為4：1。 Referring to FIG. 3, the carbon nanotube film 10 includes a plurality of first carbon nanotubes 102 and a plurality of second carbon nanotubes 104. Wherein, the plurality of first carbon nanotubes 102 are uniformly distributed in the carbon nanotube film 10 and aligned in the first direction. The plurality of first carbon nanotubes 102 are parallel to each other in the second direction. The first direction is a D1 direction, the second direction is a D2 direction, and the D2 direction is perpendicular to the D1 direction. Specifically, the first carbon nanotubes 102 are connected end to end in the first direction. The plurality of first and second carbon nanotubes 102 connected end to end are closely connected by a van der Waals force. The second carbon nanotubes 104 are uniformly distributed in the carbon nanotube film 10 and form a network structure with the first carbon nanotubes 102. At least a portion of the second carbon nanotubes 104 are in contact with the at least two first carbon nanotubes 102 by van der Waals forces. Preferably, at least a portion of the second carbon nanotubes 104 are in contact with at least two first carbon nanotubes 102 that are parallel to each other. The arrangement direction of the second carbon nanotubes 104 is not limited, and the arrangement direction of the second carbon nanotubes 104 may be different. The plurality of first carbon nanotubes 102 and the plurality of second carbon nanotubes 104 form a self-supporting The carbon nanotube film 10 of the support structure. In the carbon nanotube film 10, the plurality of first carbon nanotubes 102 and the plurality of second carbon nanotubes 104 form a plurality of gaps 106. The distance between the parallel first carbon nanotubes 102 (i.e., the distance along the D2 direction) is greater than 0 micrometers and less than or equal to 50 micrometers. The number ratio of the first carbon nanotube 102 and the second carbon nanotube 104 in the carbon nanotube film 10 is 2:1 or more and 6:1 or less. In the embodiment of the technical solution, the ratio of the first carbon nanotube 102 and the second carbon nanotube 104 in the carbon nanotube film 10 is 4:1.
所述奈米碳管膜10的透光度(光透過比率)與奈米碳管膜10的厚度及密度有關。所述奈米碳管膜10的厚度及密度越大，所述奈米碳管膜10的透光度越小。進一步地，所述奈米碳管膜10的透光度與間隙及第二奈米碳管的含量有關。所述間隙106越大，第二奈米碳管的含量越少，則所述奈米碳管膜10的透光度越大。請參閱圖6，本技術方案實施例中，該直接製備的奈米碳管膜10的厚度為50奈米，其透光度大於等於67%且小於等於82%。 The transmittance (light transmission ratio) of the carbon nanotube film 10 is related to the thickness and density of the carbon nanotube film 10. The greater the thickness and density of the carbon nanotube film 10, the smaller the transmittance of the carbon nanotube film 10. Further, the transmittance of the carbon nanotube film 10 is related to the gap and the content of the second carbon nanotube. The larger the gap 106 is, the smaller the content of the second carbon nanotubes is, and the greater the transmittance of the carbon nanotube film 10. Referring to FIG. 6, in the embodiment of the present technical solution, the directly prepared carbon nanotube film 10 has a thickness of 50 nm, and the transmittance is 67% or more and 82% or less.
所述彈性支撑體20具有較好的彈性。所述彈性支撑體20的形狀和結構不限，其可為一平面結構或一曲面結構。所述彈性支撑體20包括一彈性橡膠、彈簧及橡皮筋中的一種或幾種。該彈性支撑體20可用於支撑並拉伸所述奈米碳管膜10。 The elastic support body 20 has better elasticity. The shape and structure of the elastic support body 20 are not limited, and may be a planar structure or a curved structure. The elastic support body 20 includes one or more of an elastic rubber, a spring, and a rubber band. The elastic support 20 can be used to support and stretch the carbon nanotube film 10.
步驟二：將所述至少一奈米碳管膜10至少部分固定設置在所述至少一彈性支撑體20。 Step 2: The at least one carbon nanotube film 10 is at least partially fixedly disposed on the at least one elastic support body 20.
該彈性支撑體20可用於支撑並拉伸所述奈米碳管膜10。 所述奈米碳管膜10可直接設置並貼合在彈性支撑體20的表面，此時，所述彈性支撑體20為具有一表面的基體，如一彈性橡膠。另外，所述奈米碳管膜10也可部分設置在所述彈性支撑體20的表面。如鋪設在兩個彈性支撑體20如彈簧或橡皮筋之間。由於奈米碳管具有極大的比表面積，在凡德瓦爾力的作用下，該奈米碳管膜10本身有很好的黏附性，可直接設置在彈性支撑體20上。可以理解，為提高奈米碳管膜10與彈性支撑體20之間的結合力，所述奈米碳管膜10也可通過黏結劑固定於所述彈性支撑體20上。另外，可將所述多個奈米碳管膜10沿同一方向重叠鋪設，形成一多層奈米碳管膜。相鄰兩層奈米碳管膜10中的第一奈米碳管的排列方向相同。多個奈米碳管膜重叠設置可增加奈米碳管膜的厚度，提高奈米碳管膜的形變率。 The elastic support 20 can be used to support and stretch the carbon nanotube film 10. The carbon nanotube film 10 can be directly disposed and attached to the surface of the elastic support body 20. At this time, the elastic support body 20 is a substrate having a surface such as an elastic rubber. In addition, the carbon nanotube film 10 may also be partially disposed on the surface of the elastic support body 20. For example, it is laid between two elastic support bodies 20 such as springs or rubber bands. Since the carbon nanotube has a large specific surface area, the carbon nanotube film 10 itself has good adhesion under the action of the van der Waals force, and can be directly disposed on the elastic support body 20. It can be understood that in order to improve the bonding force between the carbon nanotube film 10 and the elastic support 20, the carbon nanotube film 10 can also be fixed to the elastic support 20 by an adhesive. In addition, the plurality of carbon nanotube films 10 may be stacked in the same direction to form a multilayered carbon nanotube film. The first carbon nanotubes in the adjacent two layers of carbon nanotube film 10 are arranged in the same direction. The overlapping of a plurality of carbon nanotube films can increase the thickness of the carbon nanotube film and increase the deformation rate of the carbon nanotube film.
本技術方案實施例中，將直接拉取的一層奈米碳管膜10設置於兩個彈性支撑體20上。請參閱圖6，所述兩個彈性支撑體20平行且間隔設置。所述兩個彈性支撑體20均沿D2方向設置。所述奈米碳管膜10通過黏結劑設置在所述彈性支撑體20表面。所述奈米碳管膜10沿D1方向的兩端分別固定於該兩個彈性支撑體20上。該黏結劑為一層銀膠。所述奈米碳管膜10在設置時，奈米碳管膜10中的第一奈米碳管沿一個彈性支撑體20至另一個彈性支撑體20的方向延伸。 In the embodiment of the technical solution, a layer of the carbon nanotube film 10 directly pulled is disposed on the two elastic support bodies 20. Referring to FIG. 6, the two elastic support bodies 20 are arranged in parallel and at intervals. The two elastic support bodies 20 are all disposed along the D2 direction. The carbon nanotube film 10 is disposed on the surface of the elastic support 20 by a binder. Both ends of the carbon nanotube film 10 in the D1 direction are respectively fixed to the two elastic support bodies 20. The binder is a layer of silver glue. When the carbon nanotube film 10 is disposed, the first carbon nanotubes in the carbon nanotube film 10 extend in the direction of one elastic support 20 to the other elastic support 20.
步驟三：拉伸該彈性支撑體20。 Step 3: The elastic support 20 is stretched.
具體地，可通過將上述彈性支撑體20固定於一拉伸裝置 (圖未示)中，通過該拉伸裝置拉伸該彈性支撑體20。本技術方案實施例中，可分別將兩個彈性支撑體20的兩端分別固定於拉伸裝置上。 Specifically, the elastic support body 20 can be fixed to a stretching device. In the drawing (not shown), the elastic support 20 is stretched by the stretching device. In the embodiment of the technical solution, the two ends of the two elastic support bodies 20 can be respectively fixed on the stretching device.
所述拉伸速度不限，可根據所要拉伸的奈米碳管膜10具體進行選擇。拉伸速度太大，則奈米碳管膜10容易發生破裂。優選地，所述彈性支撑體20的拉伸速度小於10厘米每秒。本技術方案實施例中，所述彈性支撑體20的拉伸速度為2厘米每秒。 The stretching speed is not limited and may be specifically selected depending on the carbon nanotube film 10 to be stretched. When the stretching speed is too large, the carbon nanotube film 10 is liable to be broken. Preferably, the elastic support 20 has a stretching speed of less than 10 cm per second. In the embodiment of the technical solution, the elastic support body 20 has a stretching speed of 2 cm per second.
所述拉伸方向與至少一層奈米碳管膜10中的第一奈米碳管102的排列方向有關。所述拉伸方向為沿垂直於第一奈米碳管的排列方向，即D2方向。 The stretching direction is related to the arrangement direction of the first carbon nanotubes 102 in at least one of the carbon nanotube films 10. The stretching direction is along an alignment direction perpendicular to the first carbon nanotubes, that is, a direction D2.
由於所述至少一奈米碳管膜10固定在所述彈性支撑體20上，故在拉力的作用下，隨著所述彈性支撑體20被拉伸，該奈米碳管膜10也隨之被拉伸。由於所述第一奈米碳管102為首尾相連，且至少部分第二奈米碳管104與至少兩個第一奈米碳管102通過凡德瓦爾力接觸，所述多個第一奈米碳管102和多個第二奈米碳管104之間形成多個間隙106，在奈米碳管膜10被拉伸過程中，所述第一奈米碳管102和第二奈米碳管104之間可維持凡德瓦爾力連接，平行的第一奈米碳管102之間的距離增大。其中，拉伸前所述平行的第一奈米碳管102之間的距離大於0微米小於10微米，拉伸後平行的第一奈米碳管102之間的距離最大可達50微米。所述奈米碳管膜10仍維持膜狀結構。當所述多個奈米碳管膜10重叠設置形成一多層奈米碳管膜時，由於該多層奈米碳管膜中的奈米碳管100分布更均勻、 密度更大，故當對該多層奈米碳管膜進行拉伸時，可獲得更高的形變率。所述奈米碳管膜10的形變率小於等於300%，且可基本維持奈米碳管膜10的形態。即所述奈米碳管膜10可在原有尺寸的基礎上增加300%。本實施例中，所述奈米碳管膜為單層奈米碳管膜，拉伸方向為沿與第一奈米碳管102排列方向垂直的方向。所述奈米碳管膜10在垂直於所述第一奈米碳管102的排列方向上可拉伸25%至150%。圖4為奈米碳管膜10拉伸120%時放大500倍的掃描電鏡照片，從圖中可以看出拉伸後的奈米碳管膜10相對拉伸前的奈米碳管膜10，平行的第一奈米碳管102之間的距離變大。從圖7中可以看出，當形變率為120%時，所述奈米碳管膜10對波長大於190奈米小於900奈米的光的透光度可達84%至92%。在拉伸過程中，所述奈米碳管膜10在拉伸方向上的電阻不發生變化。 Since the at least one carbon nanotube film 10 is fixed on the elastic support body 20, the carbon nanotube film 10 is also followed by the tensile force as the elastic support body 20 is stretched. Stretched. Since the first carbon nanotubes 102 are connected end to end, and at least a portion of the second carbon nanotubes 104 are in contact with at least two first carbon nanotubes 102 by van der Waals force, the plurality of first nanoparticles A plurality of gaps 106 are formed between the carbon tube 102 and the plurality of second carbon nanotube tubes 104. During the stretching of the carbon nanotube film 10, the first carbon nanotube 102 and the second carbon nanotube The Van der Waals force connection is maintained between 104 and the distance between the parallel first carbon nanotubes 102 is increased. Wherein, the distance between the parallel first carbon nanotubes 102 before stretching is greater than 0 micrometers and less than 10 micrometers, and the distance between the parallel first carbon nanotubes 102 after stretching is up to 50 micrometers. The carbon nanotube film 10 still maintains a film-like structure. When the plurality of carbon nanotube films 10 are overlapped to form a multilayer carbon nanotube film, since the carbon nanotubes 100 in the multilayer carbon nanotube film are more uniformly distributed, The density is greater, so that when the multilayered carbon nanotube film is stretched, a higher deformation rate can be obtained. The deformation rate of the carbon nanotube film 10 is 300% or less, and the morphology of the carbon nanotube film 10 can be substantially maintained. That is, the carbon nanotube film 10 can be increased by 300% based on the original size. In this embodiment, the carbon nanotube film is a single-layer carbon nanotube film, and the stretching direction is a direction perpendicular to the direction in which the first carbon nanotubes 102 are arranged. The carbon nanotube film 10 is stretchable by 25% to 150% in a direction perpendicular to the arrangement of the first carbon nanotubes 102. Fig. 4 is a scanning electron micrograph at a magnification of 500 times when the carbon nanotube film 10 is stretched by 120%. From the figure, it can be seen that the carbon nanotube film 10 after stretching is relatively thinner than the carbon nanotube film 10 before stretching. The distance between the parallel first carbon nanotubes 102 becomes large. As can be seen from FIG. 7, when the deformation rate is 120%, the carbon nanotube film 10 has a transmittance of light of 84% to 92% for light having a wavelength of more than 190 nm and less than 900 nm. The resistance of the carbon nanotube film 10 in the stretching direction does not change during stretching.
進一步地，當形變率小於60%時，所述平行的第一奈米碳管102之間的距離最大可達20微米。該拉伸後的奈米碳管膜10可在反向拉力的作用下逐漸回復為拉伸前的奈米碳管膜10。在回復的過程中，所述平行的第一奈米碳管102之間的距離逐漸减小。故所述奈米碳管膜10可在拉力的作用下實現伸縮。所述奈米碳管膜10可廣泛應用於可伸縮的裝置中。 Further, when the deformation rate is less than 60%, the distance between the parallel first carbon nanotubes 102 can be up to 20 microns. The stretched carbon nanotube film 10 can be gradually returned to the carbon nanotube film 10 before stretching by the reverse pulling force. During the recovery, the distance between the parallel first carbon nanotubes 102 gradually decreases. Therefore, the carbon nanotube film 10 can be expanded and contracted under the action of tensile force. The carbon nanotube film 10 can be widely used in a retractable device.
本技術方案實施例提供的奈米碳管膜10及其拉伸方法具有以下優點：其一，所述拉伸奈米碳管膜10的方法為通過將所述奈米碳管膜10設置在一彈性支撑體20上，拉伸該彈性支撑體20，該拉伸方法簡單、成本較低。其二， 本技術方案提供的奈米碳管膜10的拉伸方法避免了採用繁雜的工序和昂貴的設備(如雷射器)對奈米碳管膜10進行後續處理來提高奈米碳管膜10透光度的步驟，其可廣泛應用於對透光度具有較高要求的裝置中，如觸摸屏等。其三，由於所述奈米碳管膜10具有較好的拉伸性能，其可在一定方向上被拉伸，故所述奈米碳管膜10可用於彈性可拉伸元件及設備中。其四，本技術方案拉伸奈米碳管膜10的方法有利於製備大尺寸奈米碳管膜，進而有利於擴大奈米碳管膜在大尺寸裝置中的應用。 The carbon nanotube film 10 and the stretching method thereof provided by the embodiments of the present technical solution have the following advantages: First, the method of stretching the carbon nanotube film 10 is by disposing the carbon nanotube film 10 in The elastic support body 20 is stretched on an elastic support body 20, and the stretching method is simple and low in cost. Second, The stretching method of the carbon nanotube film 10 provided by the technical solution avoids the subsequent treatment of the carbon nanotube film 10 by a complicated process and expensive equipment (such as a laser) to improve the permeability of the carbon nanotube film 10. The step of luminosity, which can be widely applied to devices having high requirements for transmittance, such as a touch screen. Third, since the carbon nanotube film 10 has good tensile properties, it can be stretched in a certain direction, so the carbon nanotube film 10 can be used in an elastic stretchable member and equipment. Fourth, the method of the present invention for stretching the carbon nanotube film 10 is advantageous for preparing a large-sized carbon nanotube film, thereby facilitating the expansion of the application of the carbon nanotube film in a large-sized device.
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.
10‧‧‧奈米碳管膜 10‧‧‧Nano carbon nanotube film
100‧‧‧奈米碳管 100‧‧‧Nano Carbon Tube
102‧‧‧第一奈米碳管 102‧‧‧First carbon nanotube
104‧‧‧第二奈米碳管 104‧‧‧Second carbon nanotube
106‧‧‧間隙 106‧‧‧ gap
20‧‧‧彈性支撑體 20‧‧‧elastic support
圖1係本技術方案實施例奈米碳管膜的結構示意圖。 FIG. 1 is a schematic structural view of a carbon nanotube film according to an embodiment of the present technical solution.
圖2係圖1中的局部放大結構示意圖。 2 is a partial enlarged structural view of FIG. 1.
圖3係本技術方案實施例拉伸前奈米碳管膜的掃描電鏡照片。 3 is a scanning electron micrograph of a carbon nanotube film before stretching in the embodiment of the present technical solution.
圖4係本技術方案實施例拉伸後奈米碳管膜的掃描電鏡照片。 4 is a scanning electron micrograph of a carbon nanotube film after stretching in the embodiment of the present technical solution.
圖5係本技術方案實施例奈米碳管膜的拉伸方法流程圖。 FIG. 5 is a flow chart of a method for stretching a carbon nanotube film according to an embodiment of the present technical solution.
圖6係本技術方案實施例奈米碳管膜的拉伸示意圖。 FIG. 6 is a schematic view showing the stretching of a carbon nanotube film according to an embodiment of the present technical solution.
圖7係本技術方案實施例奈米碳管膜拉伸前後透光度對比示意圖。 Fig. 7 is a schematic view showing the comparison of the transmittance of the carbon nanotube film before and after stretching in the embodiment of the present technical solution.
10‧‧‧奈米碳管膜 10‧‧‧Nano carbon nanotube film
100‧‧‧奈米碳管 100‧‧‧Nano Carbon Tube
102‧‧‧第一奈米碳管 102‧‧‧First carbon nanotube
104‧‧‧第二奈米碳管 104‧‧‧Second carbon nanotube
106‧‧‧間隙 106‧‧‧ gap
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| CN103373719B (en) | 2012-04-25 | 2015-11-25 | 北京富纳特创新科技有限公司 | The preparation method of carbon nano-tube film |
| CN103377774B (en) * | 2012-04-25 | 2015-11-25 | 北京富纳特创新科技有限公司 | The preparation facilities of conducting element and preparation method |
| CN103377749B (en) | 2012-04-25 | 2016-08-10 | 北京富纳特创新科技有限公司 | Electronic component |
| CN103377755B (en) | 2012-04-25 | 2015-12-09 | 北京富纳特创新科技有限公司 | Conducting element |
| CN103728744B (en) | 2012-10-15 | 2016-12-21 | 北京富纳特创新科技有限公司 | Thermotropic display element and thermotropic display device |
| CN103728741B (en) * | 2012-10-15 | 2016-08-10 | 北京富纳特创新科技有限公司 | Thermochromatic element and thermochromatic display device |
| CN103728742B (en) * | 2012-10-15 | 2017-01-18 | 北京富纳特创新科技有限公司 | Thermochromism display element and thermochromism display device |
| CN103728743B (en) | 2012-10-15 | 2017-02-01 | 北京富纳特创新科技有限公司 | Thermochromism display element and thermochromism display device |
| CN103813554B (en) * | 2012-11-06 | 2016-01-13 | 北京富纳特创新科技有限公司 | Defrosting glass and apply the automobile of this defrosting glass |
| EP3671342B1 (en) * | 2018-12-20 | 2021-03-17 | IMEC vzw | Induced stress for euv pellicle tensioning |
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| US20080170982A1 (en) * | 2004-11-09 | 2008-07-17 | Board Of Regents, The University Of Texas System | Fabrication and Application of Nanofiber Ribbons and Sheets and Twisted and Non-Twisted Nanofiber Yarns |
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| US20080170982A1 (en) * | 2004-11-09 | 2008-07-17 | Board Of Regents, The University Of Texas System | Fabrication and Application of Nanofiber Ribbons and Sheets and Twisted and Non-Twisted Nanofiber Yarns |
| TW200724486A (en) * | 2005-12-16 | 2007-07-01 | Hon Hai Prec Ind Co Ltd | Carbon nanotubes silk and method for making the same |
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| TW201020208A (en) | 2010-06-01 |
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