TWI402210B - Carbon nanotube wire structure and method for making the same - Google Patents
Carbon nanotube wire structure and method for making the same Download PDFInfo
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本發明涉及一種奈米碳管結構及其製備方法，尤其涉及一種奈米碳管線狀結構及其製備方法。 The invention relates to a carbon nanotube structure and a preparation method thereof, in particular to a nano carbon pipeline structure and a preparation method thereof.
奈米碳管係一種由石墨烯片卷成之中空管狀物，其具有優異之力學、熱學及電學性質。奈米碳管應用領域非常廣闊，例如，它可用於製作場效應電晶體、原子力顯微鏡針尖、場發射電子槍、奈米模板等等。惟，先前技術中奈米碳管之應用主要係奈米碳管於微觀尺度之應用，而且操作較困難。所以，使奈米碳管具有宏觀尺度之結構並於宏觀上應用具有重要意義。 The carbon nanotube is a hollow tube rolled from a graphene sheet, which has excellent mechanical, thermal and electrical properties. Nano carbon nanotubes are used in a wide range of applications, for example, in the production of field effect transistors, atomic force microscope tips, field emission electron guns, nano templates, and the like. However, the application of the carbon nanotubes in the prior art is mainly the application of the carbon nanotubes on the micro scale, and the operation is difficult. Therefore, it is of great significance to make the carbon nanotubes have a macroscopic structure and to be applied at a macroscopic level.
奈米碳管線狀結構係奈米碳管宏觀結構中之一種。奈米碳管線狀結構由複數個奈米碳管組成，被認為係一種具有取代碳纖維、石墨纖維及玻璃纖維潛力之新型材料，可以廣泛之應用於電磁遮罩電纜、印刷電路板及特種防護服裝之紡織等領域。 The nanocarbon line structure is one of the macrostructures of the carbon nanotubes. The nano carbon line structure consists of a plurality of carbon nanotubes and is considered to be a new material with the potential to replace carbon fiber, graphite fiber and glass fiber. It can be widely used in electromagnetic shielding cables, printed circuit boards and special protective clothing. In the field of textiles and so on.
Baughman等人於2005年11月9日公開之，公開號為WO 2007/015710 A2，標題為“THE FABRICATION AND APPLICATION OF NANOFIBER RIBBONS AND SHEETS AND TWISTED AND NONTWISTED NANOFIBER YARNS”之PCT國際專利申請中揭示了一種奈米碳管線狀結構之製備方法，其包括以下步驟：提供一奈米纖維陣列，該奈米纖維陣列中之奈米纖維基本平行；從所述奈米纖維陣列中抽出所述奈米纖維，獲得一奈米纖維膜；扭轉該奈 米纖維膜得到一奈米纖維紗。然，上述方法中奈米纖維紗之直徑受到奈米纖維陣列尺寸之限制。由於生長奈米纖維陣列之基底為矽片，且由於矽片製備工藝之限制，較大尺寸之矽片較難取得，而奈米纖維陣列之生長面積與生長該奈米纖維陣列之矽片尺寸有關；也就是說較難獲得較大生長面積之奈米纖維陣列。因此，上述方法獲得之奈米纖維紗之直徑較小，機械強度及韌性不夠好，限制了該奈米纖維紗之實際應用。 A PCT International Patent Application No. WO 2007/015710 A2, entitled "THE FABRICATION AND APPLICATION OF NANOFIBER RIBBONS AND SHEETS AND TWISTED AND NONTWISTED NANOFIBER YARNS", is disclosed in U.S. Patent Application Serial No. A method for preparing a nanocarbon line-like structure, comprising the steps of: providing a nanofiber array, wherein the nanofibers in the nanofiber array are substantially parallel; and extracting the nanofibers from the nanofiber array, Obtaining a nanofiber membrane; twisting the naphthalene The rice fiber membrane obtained a nanofiber yarn. However, the diameter of the nanofiber yarn in the above method is limited by the size of the nanofiber array. Since the substrate of the grown nanofiber array is a cymbal, and the slab of larger size is difficult to obtain due to the limitation of the preparation process of the cymbal, the growth area of the nanofiber array and the size of the cymbal of the nanofiber array are grown. Related; that is, it is difficult to obtain a nanofiber array with a large growth area. Therefore, the diameter of the nanofiber yarn obtained by the above method is small, and the mechanical strength and toughness are not good enough, which limits the practical application of the nanofiber yarn.
有鑒於此，確有必要提供一種直徑較大，具有較好之機械強度及韌性之奈米碳管線狀結構及其製備方法。 In view of this, it is indeed necessary to provide a nanocarbon line-like structure having a large diameter, good mechanical strength and toughness, and a preparation method thereof.
一種奈米碳管線狀結構，其包括複數個藉由凡德瓦爾力首尾相連之奈米碳管，且該複數個奈米碳管沿該奈米碳管線狀結構之軸向擇優取向排列或沿該奈米碳管線狀結構之軸向螺旋排列。 A nanocarbon pipeline-like structure comprising a plurality of carbon nanotubes connected end to end by a van der Waals force, and the plurality of carbon nanotubes are arranged along the axial preferred orientation of the nanocarbon pipeline structure or along The nano-carbon line-like structure is arranged in an axial spiral.
一種奈米碳管線狀結構之製備方法，包括以下步驟：提供複數個共面設置之奈米碳管陣列；分別從所述複數個奈米碳管陣列中拉取複數個奈米碳管，以獲得複數個奈米碳管膜；將所述複數個奈米碳管膜於一基準處匯合；以及合併處理所述匯合之複數個奈米碳管膜，獲得一個奈米碳管線狀結構。 A method for preparing a nanocarbon pipeline-like structure, comprising the steps of: providing a plurality of coplanar carbon nanotube arrays; respectively, drawing a plurality of carbon nanotubes from the plurality of carbon nanotube arrays, respectively Obtaining a plurality of carbon nanotube membranes; merging the plurality of carbon nanotube membranes at a reference; and combining the processing of the plurality of carbon nanotube membranes to obtain a nanocarbon line-like structure.
與先前技術相比較，本發明提供之奈米碳管線狀結構之製備方法，分別從複數個奈米碳管陣列獲得複數個奈米碳管膜，再將該複數個奈米碳管膜同時處理為一個奈米碳管線狀結構之方法，該奈米碳管線狀結構之直徑不受 單個奈米碳管陣列大小之限制，且具有較好之機械強度及韌性。 Compared with the prior art, the present invention provides a method for preparing a nanocarbon line-like structure, which obtains a plurality of carbon nanotube films from a plurality of carbon nanotube arrays, and simultaneously processes the plurality of carbon nanotube membranes simultaneously. For a nanocarbon line-like structure, the diameter of the nanocarbon line-like structure is not The size of a single carbon nanotube array is limited and has good mechanical strength and toughness.
下面將結合附圖以及具體實施例對本發明提供之奈米碳管線狀結構及其製備方法作進一步之詳細說明。 The nanocarbon line-like structure and the preparation method thereof provided by the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
請一併參閱圖1、圖2及圖3，本發明第一實施例提供一種奈米碳管線狀結構之製備方法，該製備方法主要包括以下步驟：步驟S101：提供複數個共面設置之奈米碳管陣列10。 Referring to FIG. 1 , FIG. 2 and FIG. 3 , a first embodiment of the present invention provides a method for preparing a nano carbon line structure. The preparation method mainly includes the following steps: Step S101 : providing a plurality of coplanar settings Carbon tube array 10.
具體地，所述複數個奈米碳管陣列10分別形成於複數個基底12上。所述複數個基底12分別具有一第一表面122及與該第一表面122相對之第二表面124。每個基底12之第一表面122上生長有奈米碳管陣列10。每個基底12之第二表面124均固定設置於同一平面上。該複數個形成有奈米碳管陣列10之基底12可以於一個平面內排列成直線形、弧形、鋸齒形或其他形狀。該形成有奈米碳管陣列10之基底12之數量不限。本實施例中，包括三個形成有奈米碳管陣列10之基底12，且該三個基底12排列成直線形。 Specifically, the plurality of carbon nanotube arrays 10 are formed on a plurality of substrates 12, respectively. The plurality of substrates 12 respectively have a first surface 122 and a second surface 124 opposite the first surface 122. A carbon nanotube array 10 is grown on the first surface 122 of each substrate 12. The second surface 124 of each substrate 12 is fixedly disposed on the same plane. The plurality of substrates 12 formed with the carbon nanotube array 10 may be arranged in a line in a straight line, an arc shape, a zigzag shape or the like. The number of the substrates 12 on which the carbon nanotube array 10 is formed is not limited. In this embodiment, three substrates 12 are formed which are formed with a carbon nanotube array 10, and the three substrates 12 are arranged in a straight line.
所述奈米碳管陣列10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之一種或多種。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，不含雜質，如無定型碳或殘留之催化劑金屬顆粒等。所述奈米碳管陣列10之製備方法不限，可採用化學氣相沈積法或 其他方法制得。優選地，該奈米碳管陣列10為超順排奈米碳管陣列。 The carbon nanotube array 10 is composed of a plurality of carbon nanotubes, which are one or more of a single-walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube. In this embodiment, the plurality of carbon nanotubes are multi-walled carbon nanotubes, and the plurality of carbon nanotubes are substantially parallel to each other and contain no impurities, such as amorphous carbon or residual catalyst metal particles. The preparation method of the carbon nanotube array 10 is not limited, and chemical vapor deposition may be used or Other methods are made. Preferably, the carbon nanotube array 10 is a super-sequential carbon nanotube array.
步驟S102：分別從所述複數個奈米碳管陣列10中拉取複數個奈米碳管，以獲得複數個奈米碳管膜20。 Step S102: Pulling a plurality of carbon nanotubes from the plurality of carbon nanotube arrays 10 to obtain a plurality of carbon nanotube films 20.
從所述奈米碳管陣列10中拉取獲得奈米碳管膜20之方法具體包括以下步驟：首先，採用一拉伸工具與一個奈米碳管陣列10中之複數個奈米碳管相粘結；其次，以一定速度沿與該奈米碳管陣列10之基底12之第一表面122成預定角度，並沿遠離奈米碳管陣列10之方向拉伸該複數個奈米碳管，該複數個奈米碳管於拉力作用下沿該拉伸方向逐漸脫離基底12之第一表面122之同時，由於凡德瓦爾力作用，該複數個奈米碳管分別與其他奈米碳管首尾相連地連續地被拉出，以形成一連續之奈米碳管膜20。該奈米碳管膜20中之奈米碳管之軸向基本平行於該奈米碳管膜20之拉伸方向。其中，所述拉伸過程中之預定角度之範圍為大於0°，小於等於30°，優選為大於0°，小於等於5°。本實施例中，所述拉伸工具優選為一具有一定寬度之膠帶，該膠帶之寬度略大於該膠帶與奈米碳管陣列10粘結處之寬度，所述預定角度為5°左右。 The method for obtaining the carbon nanotube film 20 from the carbon nanotube array 10 specifically includes the following steps: First, using a stretching tool and a plurality of carbon nanotubes in a carbon nanotube array 10 Bonding; secondly, at a predetermined angle along the first surface 122 of the substrate 12 of the carbon nanotube array 10, and stretching the plurality of carbon nanotubes in a direction away from the array of carbon nanotubes 10, The plurality of carbon nanotubes gradually disengage from the first surface 122 of the substrate 12 along the tensile direction under the tensile force, and the plurality of carbon nanotubes and the other carbon nanotubes are respectively end-to-end due to the van der Waals force. The film is continuously drawn continuously to form a continuous carbon nanotube film 20. The axial direction of the carbon nanotubes in the carbon nanotube film 20 is substantially parallel to the stretching direction of the carbon nanotube film 20. Wherein, the predetermined angle in the stretching process is greater than 0°, less than or equal to 30°, preferably greater than 0°, and less than or equal to 5°. In this embodiment, the stretching tool is preferably a tape having a width, the width of the tape being slightly larger than the width of the bond between the tape and the carbon nanotube array 10, and the predetermined angle is about 5°.
步驟S103：將所述複數個奈米碳管膜20於一基準處22匯合。 Step S103: The plurality of carbon nanotube films 20 are joined at a reference point 22.
由於所述複數個奈米碳管陣列10共面設置，從所述複數個奈米碳管陣列10中拉膜時，應確保拉伸之方向均從各個奈米碳管陣列10朝向基準處22。於拉伸複數個奈米碳 管之過程中，所述複數個奈米碳管膜20逐漸向基準處22靠近並最終於基準處22匯合。由於每個奈米碳管膜20都有較強之粘性，所以，所述複數個奈米碳管膜20於基準處22會相互粘結在一起。 Since the plurality of carbon nanotube arrays 10 are coplanarly disposed, when the film is drawn from the plurality of carbon nanotube arrays 10, it is ensured that the direction of stretching is from the respective carbon nanotube arrays 10 toward the reference portion 22 . Stretching a plurality of nanocarbons During the tube process, the plurality of carbon nanotube membranes 20 gradually approach the reference point 22 and eventually merge at the reference point 22. Since each of the carbon nanotube films 20 has a strong viscosity, the plurality of carbon nanotube films 20 are bonded to each other at the reference portion 22.
其中，在所述複數個奈米碳管膜20向所述基準處22匯合之過程中，所述複數個奈米碳管膜20中最外端之兩個奈米碳管膜20於所述基準處22之最大夾角α大於0°，且小於180°；優選地，該最大夾角α大於0°，且小於等於60°。本實施例中，所述複數個奈米碳管膜20中最外端之兩個奈米碳管膜20於所述基準處22之最大夾角α為60°。 Wherein, in the process of the plurality of carbon nanotube films 20 meeting the reference point 22, the outermost two carbon nanotube films 20 of the plurality of carbon nanotube films 20 are as described The maximum angle α of the reference 22 is greater than 0° and less than 180°; preferably, the maximum angle α is greater than 0° and less than or equal to 60°. In this embodiment, the maximum angle α between the outermost two carbon nanotube films 20 of the plurality of carbon nanotube films 20 at the reference portion 22 is 60°.
步驟S104：合併處理所述匯合之複數個奈米碳管膜20，獲得一個奈米碳管線狀結構24。 Step S104: Combining the confluent plurality of carbon nanotube membranes 20 to obtain a nanocarbon line-like structure 24.
所述合併處理所述複數個奈米碳管膜20，獲得一個奈米碳管線狀結構24之方法包括機械力處理法或有機溶劑處理法。 The method of combining the plurality of carbon nanotube films 20 to obtain a nanocarbon line-like structure 24 includes a mechanical force treatment or an organic solvent treatment.
所述機械力處理法包括：於所述基準處22，將匯合之複數個奈米碳管膜20直接採用施加機械力之方式扭轉為一個奈米碳管線狀結構24。具體地，首先，將於基準處22匯合之複數個奈米碳管膜20固定於一個可旋轉之輥子上；其次，使所述輥子一邊旋轉一邊基本沿遠離奈米碳管陣列10之方向運動，其中該輥子以拉伸方向為軸心進行逆時針或順時針旋轉。優選地，該輥子以拉伸方向為軸心進行逆時針旋轉。在所述輥子之運動過程中，複數個奈米碳管膜20分別從複數個奈米碳管陣列10中被拉出後 ，又於該輥子產生之機械力之作用下逆時針或順時針扭轉成一個奈米碳管線狀結構24，從而可以實現奈米碳管線狀結構24之連續製備。由於每個奈米碳管膜20都有較強之粘性，所以所述複數個奈米碳管膜20扭轉之後將會緊密之相互粘結在一起，各個奈米碳管膜20之間沒有明顯之介面，所以，從該奈米碳管線狀結構24之橫截面分不出該奈米碳管線狀結構24係由幾個奈米碳管膜20組成的，各個奈米碳管膜20均勻分散於該奈米碳管線狀結構24中。採用機械力處理法獲得之奈米碳管線狀結構24包括複數個藉由凡德瓦爾力首尾相連之奈米碳管，且該複數個奈米碳管繞該奈米碳管線狀結構24之軸向螺旋排列。該奈米碳管線狀結構24之長度不限。 The mechanical force treatment method comprises: at the reference point 22, twisting a plurality of confluent carbon nanotube films 20 into a nano carbon line-like structure 24 by applying mechanical force. Specifically, first, a plurality of carbon nanotube films 20 that are joined at the reference point 22 are fixed to a rotatable roller; secondly, the rollers are moved along the direction away from the carbon nanotube array 10 while rotating. Wherein the roller is rotated counterclockwise or clockwise with the stretching direction as the axis. Preferably, the roller is rotated counterclockwise with the stretching direction as the axis. During the movement of the roller, a plurality of carbon nanotube films 20 are respectively pulled out from the plurality of carbon nanotube arrays 10 Further, the nano carbon line-like structure 24 is twisted counterclockwise or clockwise under the action of the mechanical force generated by the roller, so that the continuous preparation of the nanocarbon line structure 24 can be realized. Since each of the carbon nanotube films 20 has a strong viscosity, the plurality of carbon nanotube films 20 will be closely bonded to each other after being twisted, and there is no obvious difference between the respective carbon nanotube films 20. The interface is so that the nanocarbon line-like structure 24 is composed of a plurality of carbon nanotube membranes 20, and the individual carbon nanotube membranes 20 are uniformly dispersed from the cross section of the nanocarbon line-like structure 24. In the nanocarbon line structure 24 . The nanocarbon carbon line structure 24 obtained by the mechanical force treatment method comprises a plurality of carbon nanotubes connected end to end by a van der Waals force, and the plurality of carbon nanotubes surround the axis of the nano carbon line structure 24 Arranged in a spiral. The length of the nanocarbon line-like structure 24 is not limited.
另外，由上述方法獲得之奈米碳管線狀結構24可進一步採用有機溶劑處理。具體地，可以藉由試管或滴瓶將有機溶劑32滴落於所述奈米碳管線狀結構24之表面，浸潤整個奈米碳管線狀結構24。本實施例中，將一滴瓶30放置於奈米碳管線狀結構24上方，滴瓶30底部具有一滴口34，有機溶劑32從滴口34滴落於奈米碳管線狀結構24之表面。該有機溶劑32為易揮發性之有機溶劑，如，乙醇、甲醇、丙酮、二氯乙烷或氯仿，本實施例中優選採用乙醇。該奈米碳管線狀結構24經有機溶劑32浸潤處理後，在揮發性有機溶劑32之表面張力之作用下，該奈米碳管線狀結構24中之奈米碳管收縮更為緊密。有機溶劑處理後之該奈米碳管線狀結構24包括複數個藉由凡德瓦爾力首尾相連之奈米碳管，且該複數個奈米碳管繞該扭轉 之奈米碳管線狀結構24之軸向螺旋排列。從有機溶劑處理後之該奈米碳管線狀結構24之橫截面分不出有機溶劑處理後之該奈米碳管線狀結構24係由幾個奈米碳管膜20組成的，各個奈米碳管膜20均勻分散於該有機溶劑處理後之奈米碳管線狀結構24中，且各個奈米碳管膜20之間沒有明顯之介面。 Further, the nanocarbon line-like structure 24 obtained by the above method may be further treated with an organic solvent. Specifically, the organic solvent 32 may be dropped on the surface of the nanocarbon line-like structure 24 by a test tube or a drop bottle to infiltrate the entire nanocarbon line-like structure 24. In the present embodiment, a drop bottle 30 is placed above the nanocarbon line-like structure 24, and a drop port 34 is formed at the bottom of the drop bottle 30, and the organic solvent 32 is dropped from the drip port 34 on the surface of the nanocarbon line-like structure 24. The organic solvent 32 is a volatile organic solvent such as ethanol, methanol, acetone, dichloroethane or chloroform, and ethanol is preferably used in this embodiment. After the nanocarbon line-like structure 24 is wetted by the organic solvent 32, the carbon nanotubes in the nanocarbon line-like structure 24 shrink more tightly under the surface tension of the volatile organic solvent 32. The nanocarbon carbon line structure 24 after the organic solvent treatment comprises a plurality of carbon nanotubes connected end to end by a van der Waals force, and the plurality of carbon nanotubes are wound around the twisted carbon nanotubes The axial alignment of the nanocarbon line-like structure 24 is helical. The nanocarbon carbon line structure 24 after the organic solvent treatment is not separated from the organic solvent, and the nano carbon line structure 24 is composed of several carbon nanotube films 20, each of which is composed of nano carbon. The tube film 20 is uniformly dispersed in the organic solvent-treated nanocarbon line-like structure 24, and there is no obvious interface between the respective carbon nanotube films 20.
所述有機溶劑處理法合併處理所述複數個奈米碳管膜20，獲得一個奈米碳管線狀結構24之方法具體包括以下步驟：首先，於基準處22，藉由合股將所述複數個奈米碳管膜20合併為一個預處理奈米碳管結構。所述預處理奈米碳管結構係指該複數個奈米碳管膜20之簡單交疊。由於每個奈米碳管膜20都有較大之比表面積，所以所述複數個奈米碳管膜20合股之後將會相互粘結在一起，各個奈米碳管膜之間沒有明顯之介面。其次，用有機溶劑處理所述預處理奈米碳管結構，得到一個奈米碳管線狀結構24。從該奈米碳管線狀結構24之橫截面分不出該奈米碳管線狀結構24係由幾個奈米碳管膜20組成的，各個奈米碳管膜20均勻分散於該奈米碳管線狀結構24中，且各個奈米碳管膜20之間沒有明顯之介面。所述用有機溶劑處理所述預處理奈米碳管結構之方法與上述用有機溶劑處理扭轉後之奈米碳管線狀結構24之方法相同。可採用試管或滴瓶將有機溶劑32滴落於所述預處理奈米碳管結構之表面，浸潤整個預處理奈米碳管結構。不同之處在於，於有機溶劑之作用下，預處理奈米碳管結構之表面張力減小，自動收縮成一個奈米碳管線狀結構24；於該 有機溶劑處理法中，所述奈米碳管線狀結構24在形成過程中不需要扭轉所述預處理奈米碳管結構。其中，所述奈米碳管線狀結構24包括複數個藉由凡德瓦爾力首尾相連之奈米碳管，且該複數個奈米碳管基本沿奈米碳管線狀結構24之軸向擇優取向排列。 The method of combining the plurality of carbon nanotube membranes 20 by the organic solvent treatment method to obtain a nanocarbon line-like structure 24 specifically includes the following steps: First, at the reference point 22, the plurality of The carbon nanotube film 20 is combined into a pretreated carbon nanotube structure. The pretreated carbon nanotube structure refers to a simple overlap of the plurality of carbon nanotube films 20. Since each of the carbon nanotube films 20 has a large specific surface area, the plurality of carbon nanotube films 20 will be bonded to each other after plying, and there is no obvious interface between the respective carbon nanotube films. . Next, the pretreated carbon nanotube structure is treated with an organic solvent to obtain a nanocarbon line-like structure 24. From the cross section of the nanocarbon line-like structure 24, the nanocarbon line-like structure 24 is composed of several carbon nanotube films 20, and the respective carbon nanotube film 20 is uniformly dispersed in the nanocarbon. In the line-like structure 24, there is no distinct interface between the individual carbon nanotube films 20. The method of treating the pretreated carbon nanotube structure with an organic solvent is the same as the method of treating the twisted nanocarbon line-like structure 24 with an organic solvent. The organic solvent 32 may be dropped onto the surface of the pretreated carbon nanotube structure by using a test tube or a drop bottle to infiltrate the entire pretreated carbon nanotube structure. The difference is that under the action of the organic solvent, the surface tension of the pretreated carbon nanotube structure is reduced and automatically shrinks into a nano carbon line structure 24; In the organic solvent treatment, the nanocarbon line-like structure 24 does not need to twist the pretreated carbon nanotube structure during formation. Wherein, the nanocarbon line-like structure 24 comprises a plurality of carbon nanotubes connected end to end by a van der Waals force, and the plurality of carbon nanotubes are substantially oriented along the axial direction of the nanocarbon line structure 24 arrangement.
本實施例中，採用機械力處理法得到一個奈米碳管線狀結構24，並對該奈米碳管線狀結構24進行有機溶劑處理。 In this embodiment, a nanocarbon line-like structure 24 is obtained by mechanical force treatment, and the nanocarbon line-like structure 24 is subjected to an organic solvent treatment.
進一步地，烘乾上述採用有機溶劑處理後之奈米碳管線狀結構24。具體地，可以使所述經有機溶劑處理後之奈米碳管線狀結構24藉由一個烘乾箱36烘乾，該烘乾箱36之溫度為80℃~100℃，可以加快有機溶劑處理後之奈米碳管線狀結構24中的有機溶劑的揮發，使得奈米碳管線狀結構24中之奈米碳管排列更緊密。另外，也可以採用一吹風機將該經過有機溶劑處理之奈米碳管線狀結構24中之有機溶劑吹乾。 Further, the above-described nanocarbon line-like structure 24 treated with an organic solvent is dried. Specifically, the organic solvent-treated nanocarbon line-like structure 24 can be dried by a drying box 36. The temperature of the drying box 36 is 80° C. to 100° C., which can speed up the organic solvent treatment. The volatilization of the organic solvent in the nanocarbon line-like structure 24 causes the carbon nanotubes in the nanocarbon line-like structure 24 to be arranged more closely. Alternatively, the organic solvent in the organic solvent-treated nanocarbon line-like structure 24 may be blown dry using a blower.
上述藉由有機溶劑處理後之奈米碳管線狀結構24粘性降低，可以很容易收集起來。具體地，本實施例採用電機38將有機溶劑處理後之該奈米碳管線狀結構24纏繞到該電機38之線軸28上。另外，也可採用手工之方法將有機溶劑處理後之該奈米碳管線狀結構24卷到線軸28上。 The nanocarbon line-like structure 24 treated by the organic solvent described above has a reduced viscosity and can be easily collected. Specifically, the present embodiment employs a motor 38 to wind the nanocarbon line-like structure 24 after the organic solvent treatment onto the bobbin 28 of the motor 38. Alternatively, the nanocarbon line-like structure 24 after the organic solvent treatment may be wound onto the bobbin 28 by hand.
所述奈米碳管線狀結構24之直徑與奈米碳管陣列10之大小及奈米碳管陣列10之數量有關。奈米碳管線狀結構24之直徑大於1微米，可以達到50微米以上。本實施例中， 所述奈米碳管線狀結構24之直徑為130微米。 The diameter of the nanocarbon line-like structure 24 is related to the size of the carbon nanotube array 10 and the number of carbon nanotube arrays 10. The nanocarbon line-like structure 24 has a diameter greater than 1 micron and can reach more than 50 microns. In this embodiment, The nanocarbon line-like structure 24 has a diameter of 130 microns.
可以理解，上述製備奈米碳管線狀結構24之過程係連續進行的；即步驟S101至步驟S104可以同時連續進行，在收集奈米碳管線狀結構24的同時，分別從所述複數個奈米碳管陣列10中拉取複數個奈米碳管，獲得複數個奈米碳管膜20；並對該複數個奈米碳管膜20進形匯合、合併處理。 It can be understood that the above process of preparing the nanocarbon line-like structure 24 is continuously performed; that is, the steps S101 to S104 can be continuously performed simultaneously, and the plurality of nanometers are separately collected from the nano carbon line-like structure 24, respectively. A plurality of carbon nanotube tubes are drawn from the carbon tube array 10 to obtain a plurality of carbon nanotube films 20; and the plurality of carbon nanotube films 20 are merged and combined.
請參閱圖4，本發明第二實施例提供一種奈米碳管線狀結構之製備方法，主要包括以下步驟：步驟S201：提供複數個共面設置之奈米碳管陣列40。 Referring to FIG. 4, a second embodiment of the present invention provides a method for preparing a nanocarbon line-like structure, which mainly includes the following steps: Step S201: providing a plurality of coplanar carbon nanotube arrays 40.
步驟S202：分別從所述複數個奈米碳管陣列40中拉取複數個奈米碳管，以獲得複數個奈米碳管膜50。 Step S202: Pulling a plurality of carbon nanotubes from the plurality of carbon nanotube arrays 40 to obtain a plurality of carbon nanotube films 50.
步驟S203：於所述複數個奈米碳管膜50表面形成至少一金屬層，從而形成複數個奈米碳管複合膜52。 Step S203: forming at least one metal layer on the surface of the plurality of carbon nanotube films 50, thereby forming a plurality of carbon nanotube composite membranes 52.
所述金屬層之材料優選為金、銀、鉑、銅或其合金，該金屬層之厚度優選為1奈米~20奈米。所述在所述複數個奈米碳管膜50表面形成至少一金屬層之方法可採用物理方法，如物理氣相沈積法(PVD)，PVD法包括真空蒸鍍或離子濺射等；也可採用化學方法，如電鍍或化學鍍等。所述奈米碳管複合膜52中金屬層形成於該奈米碳管膜50中之奈米碳管表面。優選地，本實施例中，可直接將拉出之奈米碳管膜50藉由一個真空腔體60，採用PVD法中之真空蒸鍍法分別在所述複數個奈米碳管膜50表面形成先形成一銅金屬層，再形成一鉑金屬層於所述銅金屬層 上，以形成所述複數個奈米碳管複合膜52。 The material of the metal layer is preferably gold, silver, platinum, copper or an alloy thereof, and the thickness of the metal layer is preferably from 1 nm to 20 nm. The method for forming at least one metal layer on the surface of the plurality of carbon nanotube films 50 may adopt a physical method such as physical vapor deposition (PVD), the PVD method includes vacuum evaporation or ion sputtering, or the like; Use chemical methods such as electroplating or electroless plating. A metal layer in the carbon nanotube composite film 52 is formed on the surface of the carbon nanotube in the carbon nanotube film 50. Preferably, in this embodiment, the drawn carbon nanotube film 50 can be directly applied to the surface of the plurality of carbon nanotube films 50 by vacuum evaporation in a PVD method by a vacuum chamber 60. Forming a copper metal layer first, and then forming a platinum metal layer on the copper metal layer Upper to form the plurality of carbon nanotube composite membranes 52.
步驟S204：將所述複數個奈米碳管複合膜52於一基準處54匯合。 Step S204: The plurality of carbon nanotube composite membranes 52 are joined at a reference point 54.
該步驟之形成方法與第一實施例中之步驟S103之形成方法相同。在所述複數個奈米碳管複合膜52向所述基準處54匯合的過程中，所述複數個奈米碳管複合膜54中最外端之兩個奈米碳管複合膜52於所述基準處54之最大夾角α大於0°，且小於180°，優選大於0°，且小於等於60°。本實施例中，所述複數個奈米碳管複合膜52中最外端之兩個奈米碳管複合膜52於所述基準處54之最大夾角α為60°。 This step is formed in the same manner as the method of forming step S103 in the first embodiment. During the process in which the plurality of carbon nanotube composite membranes 52 are merged toward the reference portion 54, the outermost two carbon nanotube composite membranes 52 of the plurality of carbon nanotube composite membranes 54 are disposed at The maximum angle α of the reference 54 is greater than 0° and less than 180°, preferably greater than 0° and less than or equal to 60°. In this embodiment, the maximum angle α between the outermost two carbon nanotube composite membranes 52 of the plurality of carbon nanotube composite membranes 52 at the reference 54 is 60°.
步驟S205：合併處理所述匯合之複數個奈米碳管複合膜52，以獲得一個奈米碳管線狀結構56。 Step S205: Combining the confluent plurality of carbon nanotube composite membranes 52 to obtain a nanocarbon line-like structure 56.
所述步驟S205與第一實施例之步驟S104相似。本實施例中，採用有機溶劑處理法合併處理所述複數個奈米碳管複合膜52。所述匯合之複數個奈米碳管複合膜52為一預處理奈米碳管複合結構，該預處理奈米碳管複合結構為該複數個奈米碳管複合膜52之簡單交疊。用有機溶劑32處理所述預處理奈米碳管複合結構，得到一個奈米碳管線狀結構56，該奈米碳管線狀結構56經過烘乾箱36烘乾後纏繞到電機38之線軸28上。所述有機溶劑32處理預處理奈米碳管複合結構之方法為：將滴瓶30放置於該預處理奈米碳管複合結構上方，有機溶劑32從滴瓶30之滴口34滴落於該預處理奈米碳管複合結構之表面。 The step S205 is similar to the step S104 of the first embodiment. In this embodiment, the plurality of carbon nanotube composite membranes 52 are combined and treated by an organic solvent treatment. The confluent plurality of carbon nanotube composite membranes 52 is a pretreated nanocarbon tube composite structure, and the pretreated carbon nanotube composite structure is a simple overlap of the plurality of carbon nanotube composite membranes 52. The pretreated nanocarbon tube composite structure is treated with an organic solvent 32 to obtain a nanocarbon line-like structure 56 which is dried by a drying oven 36 and wound onto a bobbin 28 of the motor 38. . The method for treating the pretreated nano carbon tube composite structure by the organic solvent 32 is: placing the dropping bottle 30 above the pretreated carbon nanotube composite structure, and the organic solvent 32 is dropped from the dropping port 34 of the dropping bottle 30. The surface of the nanocarbon tube composite structure is pretreated.
本實施例提供之奈米碳管線狀結構56之結構與第一實施例提供之奈米碳管線狀結構24之結構基本相同：從該奈米碳管線狀結構56之橫截面分不出該奈米碳管線狀結構56係由幾個奈米碳管複合膜52組成的，各個奈米碳管複合膜52均勻分散於該奈米碳管線狀結構56中，且各個奈米碳管複合膜52之間沒有明顯之介面；不同之處在於：該奈米碳管線狀結構56為奈米碳管複合線狀結構。該奈米碳管線狀結構56包括複數個藉由凡德瓦爾力首尾相連之奈米碳管，且該複數個奈米碳管沿同一方向擇優取向排列；且該複數個奈米碳管之表面設置有至少一金屬層。具體地，本實施例中，該奈米碳管線狀結構56中之所述複數個奈米碳管之表面設置有銅金屬層及鉑金屬層，且該銅金屬層設置於該複數個奈米碳管與鉑金屬層之間。所述奈米碳管線狀結構56之直徑大於1微米，可以達到50微米以上。本實施例中，奈米碳管線狀結構56之直徑為200微米。 The structure of the nanocarbon line-like structure 56 provided in this embodiment is substantially the same as the structure of the nanocarbon line-like structure 24 provided in the first embodiment: the naphthalene is not separated from the cross section of the nanocarbon line-like structure 56. The carbon carbon line-like structure 56 is composed of a plurality of carbon nanotube composite membranes 52, and each of the carbon nanotube composite membranes 52 is uniformly dispersed in the nanocarbon line-like structure 56, and each of the carbon nanotube composite membranes 52 is 52. There is no obvious interface between them; the difference is that the nanocarbon line-like structure 56 is a carbon nanotube composite linear structure. The nanocarbon line-like structure 56 includes a plurality of carbon nanotubes connected end to end by a van der Waals force, and the plurality of carbon nanotubes are arranged in a preferred orientation in the same direction; and the surface of the plurality of carbon nanotubes At least one metal layer is provided. Specifically, in this embodiment, the surface of the plurality of carbon nanotubes in the nanocarbon line-like structure 56 is provided with a copper metal layer and a platinum metal layer, and the copper metal layer is disposed on the plurality of nanometers. Between the carbon tube and the platinum metal layer. The nanocarbon line-like structure 56 has a diameter greater than 1 micron and can be above 50 microns. In this embodiment, the nanocarbon line-like structure 56 has a diameter of 200 microns.
本發明實施例提供之奈米碳管線狀結構及其製備方法具有以下優點：第一，藉由從複數個奈米碳管陣列獲得複數個奈米碳管膜，再將該複數個奈米碳管膜合併處理為一奈米碳管線狀結構，該奈米碳管線狀結構之直徑不受單個奈米碳管陣列大小之限制，從而可以簡單、方便的得到所需直徑之奈米碳管線狀結構。第二，本發明實施例還可以提供直徑不受限制之奈米碳管複合線狀結構。第三，藉由本發明實施例提供之奈米碳管線狀結構之製備方法得到之奈米碳管線狀結構具有良好之導電性能、 導熱性能、機械強度及韌性，可以廣泛的應用於電磁遮罩電纜、印刷電路板、燈絲以及各種防護服裝之紡織等宏觀領域。 The nanocarbon line-like structure and the preparation method thereof provided by the embodiments of the present invention have the following advantages: First, a plurality of carbon nanotube films are obtained from a plurality of carbon nanotube arrays, and the plurality of nanocarbons are further obtained The tube membrane is combined into a nano carbon line structure, and the diameter of the nano carbon line structure is not limited by the size of a single carbon nanotube array, so that the nanometer carbon line shape of the desired diameter can be obtained simply and conveniently. structure. Second, the embodiment of the present invention can also provide a carbon nanotube composite wire structure having an unrestricted diameter. Thirdly, the nanocarbon line-like structure obtained by the preparation method of the nanocarbon line-like structure provided by the embodiment of the invention has good electrical conductivity, Thermal conductivity, mechanical strength and toughness can be widely used in macroscopic fields such as electromagnetic mask cables, printed circuit boards, filaments, and textiles for various protective garments.
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. 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；40‧‧‧奈米碳管陣列 10;40‧‧‧Nano Carbon Tube Array
12‧‧‧基底 12‧‧‧Base
122‧‧‧基底之第一表面 122‧‧‧The first surface of the substrate
124‧‧‧基底之第二表面 124‧‧‧Second surface of the substrate
20；50‧‧‧奈米碳管膜 20; 50‧‧‧Nano carbon nanotube film
22；54‧‧‧基準處 22; 54‧‧‧ benchmark
24；56‧‧‧奈米碳管線狀結構 24; 56‧‧‧Nano carbon pipeline structure
28‧‧‧線軸 28‧‧‧ spool
30‧‧‧滴瓶 30‧‧‧Dripper
32‧‧‧有機溶劑 32‧‧‧Organic solvents
34‧‧‧滴口 34‧‧‧ drip
36‧‧‧烘乾箱 36‧‧‧drying box
38‧‧‧電機 38‧‧‧Motor
52‧‧‧奈米碳管複合膜 52‧‧‧Nano Carbon Tube Composite Film
60‧‧‧真空腔體 60‧‧‧vacuum chamber
圖1係本發明第一實施例提供之奈米碳管線狀結構之製備方法的流程圖。 1 is a flow chart showing a method of preparing a nanocarbon line-like structure provided by a first embodiment of the present invention.
圖2係本發明第一實施例提供之生長有奈米碳管陣列之基底的示意圖。 2 is a schematic view showing a substrate on which a carbon nanotube array is grown according to a first embodiment of the present invention.
圖3係本發明第一實施例提供之奈米碳管線狀結構之製備過程的示意圖。 3 is a schematic view showing a preparation process of a nanocarbon line-like structure provided by a first embodiment of the present invention.
圖4係本發明第二實施例提供之奈米碳管線狀結構之製備方法的流程圖。 4 is a flow chart showing a method of preparing a nanocarbon line-like structure provided by a second embodiment of the present invention.
圖5係本發明第二實施例提供之奈米碳管線狀結構之製備過程的示意圖。 Fig. 5 is a schematic view showing the preparation process of the nanocarbon line-like structure provided by the second embodiment of the present invention.
10‧‧‧奈米碳管陣列 10‧‧‧Nano Carbon Tube Array
20‧‧‧奈米碳管膜 20‧‧‧Nano carbon nanotube film
22‧‧‧基準處 22‧‧‧ benchmark
24‧‧‧奈米碳管線狀結構 24‧‧‧Nano carbon pipeline structure
28‧‧‧線軸 28‧‧‧ spool
30‧‧‧滴瓶 30‧‧‧Dripper
32‧‧‧有機溶劑 32‧‧‧Organic solvents
34‧‧‧滴口 34‧‧‧ drip
36‧‧‧烘乾箱 36‧‧‧drying box
38‧‧‧電機 38‧‧‧Motor
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