TWI468339B - Carbon nanotube structure - Google Patents
Carbon nanotube structureInfo
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- TWI468339B TWI468339B TW99122579A TW99122579A TWI468339B TW I468339 B TWI468339 B TW I468339B TW 99122579 A TW99122579 A TW 99122579A TW 99122579 A TW99122579 A TW 99122579A TW I468339 B TWI468339 B TW I468339B
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Description
本發明涉及一種奈米碳管結構。 The present invention relates to a carbon nanotube structure.
奈米碳管係一種由石墨烯片卷成之中空管狀物。奈米碳管具有優異之力學、熱學及電學性質，其應用領域非常廣闊。例如，奈米碳管可用於製作場效應電晶體、原子力顯微鏡針尖、場發射電子槍、奈米模板等。上述技術中奈米碳管之應用主要係奈米碳管在微觀尺度上之應用，操作較困難。故，使奈米碳管具有宏觀尺度之結構並在宏觀上應用具有重要意義。 The carbon nanotube is a hollow tube rolled from a graphene sheet. Nano carbon tubes have excellent mechanical, thermal and electrical properties and are used in a wide range of applications. For example, carbon nanotubes can be used to make field effect transistors, atomic force microscope tips, field emission electron guns, nano templates, and the like. The application of the carbon nanotubes in the above technology is mainly the application of the carbon nanotubes on the microscopic 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.
為克服上述問題，范守善等人在2008年8月16日公開之第TW200833862號專利申請揭示了一種包括複數奈米碳管且具有宏觀尺度之奈米碳管薄膜之製備方法。所述奈米碳管薄膜包括複數奈米碳管通過凡得瓦力(Van der Waals attractive force)首尾相連，從而形成一由奈米碳管組成之自支撐結構在宏觀上得以應用。 In order to overcome the above problems, the patent application No. TW200833862, which is published on Aug. 16, 2008, discloses a method for preparing a carbon nanotube film having a plurality of carbon nanotubes and having a macroscopic scale. The carbon nanotube film comprises a plurality of carbon nanotubes connected end to end by a Van der Waals attractive force to form a self-supporting structure composed of a carbon nanotube.
然，由所述製備方法所製備之奈米碳管薄膜中之奈米碳管之間之結合力較弱，故，所述奈米碳管薄膜之機械性能還需進一步提高。 However, the bonding force between the carbon nanotubes in the carbon nanotube film prepared by the preparation method is weak, and the mechanical properties of the carbon nanotube film need to be further improved.
有鑒於此，提供一種具有良好機械性能之奈米碳管結構實為必要 。 In view of this, it is necessary to provide a carbon nanotube structure with good mechanical properties. .
一種奈米碳管結構，其包括複數奈米碳管相互連接。彼此相鄰之奈米碳管之間具有碳碳鍵。 A carbon nanotube structure comprising a plurality of carbon nanotubes interconnected. There are carbon-carbon bonds between the carbon nanotubes adjacent to each other.
一種奈米碳管結構，包括複數奈米碳管條緊密結合。所述奈米碳管條包括複數奈米碳管首尾相連，所述首尾相連之奈米碳管之間具有碳碳鍵。 A carbon nanotube structure comprising a plurality of carbon nanotube strips in close combination. The carbon nanotube strip includes a plurality of carbon nanotubes connected end to end, and the carbon nanotube bonds between the end-to-end carbon nanotubes.
相較於先前技術，所述奈米碳管結構中之複數奈米碳管之間具有複數碳碳鍵，從而增加了該複數奈米碳管之間之結合力，使該奈米碳管結構具有優異之機械性能。 Compared with the prior art, the plurality of carbon nanotubes in the carbon nanotube structure have a plurality of carbon-carbon bonds, thereby increasing the bonding force between the plurality of carbon nanotubes, and the carbon nanotube structure is Excellent mechanical properties.
圖1為一奈米碳管絮化膜之掃描電鏡照片。 Figure 1 is a scanning electron micrograph of a carbon nanotube film.
圖2為一奈米碳管碾壓膜之掃描電鏡照片。 Figure 2 is a scanning electron micrograph of a carbon nanotube rolled film.
圖3為一奈米碳管拉膜之掃描電鏡照片。 Figure 3 is a scanning electron micrograph of a carbon nanotube film.
圖4為一奈米碳管交叉膜之掃描電鏡照片。 Figure 4 is a scanning electron micrograph of a carbon nanotube cross film.
圖5為一非扭轉之奈米碳管線之掃描電鏡照片。 Figure 5 is a scanning electron micrograph of a non-twisted nanocarbon pipeline.
圖6為一扭轉之奈米碳管線之掃描電鏡照片。 Figure 6 is a scanning electron micrograph of a twisted nanocarbon line.
圖7為用本發明實施例提供之奈米碳管結構之製備方法及用圖6中之扭轉之奈米碳管線為原料所製備之奈米碳管線之掃描電鏡照片。 7 is a scanning electron micrograph of a method for preparing a carbon nanotube structure provided by an embodiment of the present invention and a nanocarbon line prepared by using the twisted nanocarbon line of FIG.
圖8為圖6中之扭轉之奈米碳管線與圖7中之奈米碳管線之拉曼光譜對比圖。 Figure 8 is a comparison of the Raman spectra of the twisted nanocarbon line of Figure 6 and the nanocarbon line of Figure 7.
圖9為圖6中之扭轉之奈米碳管線與圖7中之奈米碳管線之測力曲線對比圖。 Figure 9 is a comparison of the measured force curves of the twisted nanocarbon line of Figure 6 and the nanocarbon line of Figure 7.
以下將結合附圖對本發明作進一步詳細之說明。 The invention will be further described in detail below with reference to the accompanying drawings.
本發明提供之奈米碳管結構之製備方法，主要係在奈米碳管預製結構中之相連之奈米碳管之間產生碳碳鍵，致力於提高其結合力。當然，並不是奈米碳管預製結構中之所有相連之奈米碳管之間都產生碳碳鍵，而係至少部分相連之奈米碳管之間會產生碳碳鍵。由於碳碳鍵之鍵能大、牢固，故僅至少部分奈米碳管之間產生碳碳鍵也會提高該結構之強度。下面將提供具體實施方式來展開說明本發明如何將奈米碳管預製結構中之相連之奈米碳管之間產生碳碳鍵。 The preparation method of the carbon nanotube structure provided by the invention mainly produces carbon-carbon bonds between the connected carbon nanotubes in the carbon nanotube prefabricated structure, and aims to improve the bonding force. Of course, it is not the carbon-carbon bond between all the connected carbon nanotubes in the carbon nanotube prefabricated structure, but the carbon-carbon bond between the at least partially connected carbon nanotubes. Since the bond of the carbon-carbon bond is large and strong, only the carbon-carbon bond between at least some of the carbon nanotubes increases the strength of the structure. DETAILED DESCRIPTION OF THE INVENTION The following detailed description will be provided to illustrate how the present invention produces carbon-carbon bonds between adjacent carbon nanotubes in a carbon nanotube preform structure.
本發明提供之奈米碳管結構之製備方法，其包括如下步驟：S10，提供一奈米碳管預製結構，所述奈米碳管預製結構包括複數奈米碳管通過凡得瓦力(Van der Waals attractive force)相連；S20，將所述奈米碳管預製結構在低氧環境中進行熱處理，使至少部分相連之奈米碳管之間形成碳碳鍵。 The invention provides a method for preparing a carbon nanotube structure, comprising the steps of: S10, providing a carbon nanotube prefabricated structure, wherein the carbon nanotube prefabricated structure comprises a plurality of carbon nanotubes passing through a van der Waals force (Van) The der Waals attractive force is connected; S20, heat treating the carbon nanotube preform structure in a low oxygen environment to form a carbon-carbon bond between at least partially connected carbon nanotubes.
在步驟S10中，所述奈米碳管預製結構為由複數奈米碳管構成之膜狀結構、線狀結構或者其他形狀之結構。所述奈米碳管預製結構可係形成在一個基底上之奈米碳管結構，比如通過沈積、濺射或者過濾等方式形成在基底(耐高溫)上之奈米碳管膜或者奈米碳管線等，僅存在距離達到0.2奈米到9奈米之間之奈米碳管，即 可稱為相連之奈米碳管。所述奈米碳管預製結構也可係一奈米碳管自支撐結構，所謂“自支撐”即該奈米碳管預製結構無需通過設置於一基體表面，即邊緣或者相對端部提供支撐而其未得到支撐之其他部分能保持自身特定之形狀。由於該自支撐之奈米碳管預製結構中大量之奈米碳管通過凡得瓦力相互吸引，從而使該奈米碳管預製結構具有特定之形狀，形成一自支撐結構。通常，所述自支撐之奈米碳管預製結構中距離在0.2奈米到9奈米之間之奈米碳管之數量較多，這部分奈米碳管之間具有較大之凡得瓦力，從而使得所述奈米碳管預製結構僅通過凡得瓦力即可形成自支撐結構。 In step S10, the carbon nanotube preform structure is a film structure, a line structure or other shape structure composed of a plurality of carbon nanotubes. The carbon nanotube preform structure may be a carbon nanotube structure formed on a substrate, such as a carbon nanotube film or a nanocarbon formed on a substrate (high temperature resistance) by deposition, sputtering or filtration. Pipeline, etc., there are only carbon nanotubes with a distance of between 0.2 nm and 9 nm, ie It can be called a connected carbon nanotube. The carbon nanotube preform structure may also be a carbon nanotube self-supporting structure, so-called "self-supporting", that is, the carbon nanotube preform structure does not need to be supported by a surface provided at a substrate, that is, an edge or an opposite end. Other parts that are not supported can maintain their specific shape. Since the large number of carbon nanotubes in the self-supporting carbon nanotube prefabricated structure are attracted to each other by van der Waals force, the carbon nanotube prefabricated structure has a specific shape to form a self-supporting structure. Generally, the number of carbon nanotubes in the prefabricated structure of the self-supporting carbon nanotubes is between 0.2 nm and 9 nm, and the portion of the carbon nanotubes has a larger van der Waals. The force, so that the carbon nanotube preform structure can form a self-supporting structure only by van der Waals force.
所述奈米碳管預製結構可包括至少一奈米碳管預製膜，當所述奈米碳管預製結構包括複數奈米碳管預製膜時，該複數奈米碳管預製膜設置，相鄰之奈米碳管膜之間通過凡得瓦力相結合。 The carbon nanotube preform structure may include at least one carbon nanotube pre-formed film, and when the carbon nanotube prefabricated structure comprises a plurality of carbon nanotube pre-formed films, the plurality of carbon nanotube pre-formed films are disposed adjacent to each other The carbon nanotube membranes are combined by van der Waals force.
請參閱圖1，所述奈米碳管結構預製膜可為一奈米碳管絮化膜，該奈米碳管絮化膜為將一奈米碳管原料，如一超順排陣列，絮化處理獲得之一自支撐之奈米碳管結構預製膜。該奈米碳管絮化膜包括相互纏繞且均勻分佈之奈米碳管。奈米碳管之長度大於10微米，優選為200微米到900微米，從而使奈米碳管相互纏繞在一起。所述奈米碳管之間通過凡得瓦力相互吸引、分佈，形成網路狀結構。由於該自支撐之奈米碳管絮化膜中大量之奈米碳管通過凡得瓦力相互吸引並相互纏繞，從而使該奈米碳管絮化膜具有特定之形狀，形成一自支撐結構。所述奈米碳管絮化膜各向同性。所述奈米碳管絮化膜中之奈米碳管為均勻分佈，無規則排列，形成大量尺寸在1奈米到500奈米之間之間隙或微孔。所述奈米碳管絮 化膜之面積及厚度均不限，厚度大致在0.5奈米到100微米之間。 Referring to FIG. 1 , the carbon nanotube structure pre-formed film may be a carbon nanotube flocculation membrane, and the carbon nanotube flocculation membrane is a flocculation material of a carbon nanotube, such as a super-aligned array. The treatment obtains a self-supporting carbon nanotube structure pre-formed film. The carbon nanotube flocculation membrane comprises carbon nanotubes which are intertwined and uniformly distributed. The length of the carbon nanotubes is greater than 10 microns, preferably from 200 microns to 900 microns, such that the carbon nanotubes are intertwined with one another. The carbon nanotubes are attracted to each other by van der Waals forces to form a network structure. Since the large number of carbon nanotubes in the self-supporting carbon nanotube flocculation membrane are mutually attracted and intertwined by van der Waals force, the carbon nanotube flocculation membrane has a specific shape to form a self-supporting structure. . The carbon nanotube flocculation membrane is isotropic. The carbon nanotubes in the carbon nanotube flocculation membrane are uniformly distributed and randomly arranged to form a plurality of gaps or micropores having a size ranging from 1 nm to 500 nm. The carbon nanotube floc The area and thickness of the film are not limited, and the thickness is approximately between 0.5 nm and 100 μm.
所述奈米碳管結構預製膜可為一奈米碳管碾壓膜，該奈米碳管碾壓膜為通過碾壓一奈米碳管陣列獲得之一種具有自支撐性之奈米碳管結構預製膜。該奈米碳管碾壓膜包括均勻分佈之奈米碳管，奈米碳管沿同一方向或不同方向擇優取向排列。所述奈米碳管碾壓膜中之奈米碳管相互部分交疊，並通過凡得瓦力相互吸引，緊密結合，使得該奈米碳管結構預製膜具有很好之柔韌性，可彎曲折疊成任意形狀而不破裂。且由於奈米碳管碾壓膜中之奈米碳管之間通過凡得瓦力相互吸引，緊密結合，使奈米碳管碾壓膜為一自支撐之結構。所述奈米碳管碾壓膜中之奈米碳管與形成奈米碳管陣列之生長基底之表面形成一夾角β，其中，β大於等於0度且小於等於15度，該夾角β與施加在奈米碳管陣列上之壓力有關，壓力越大，該夾角越小，優選地，該奈米碳管碾壓膜中之奈米碳管平行於該生長基底排列。該奈米碳管碾壓膜為通過碾壓一奈米碳管陣列獲得，依據碾壓之方式不同，該奈米碳管碾壓膜中之奈米碳管具有不同之排列形式。具體地，奈米碳管可無序排列；請參閱圖2，當沿不同方向碾壓時，奈米碳管沿不同方向擇優取向排列；當沿同一方向碾壓時，奈米碳管沿一固定方向擇優取向排列。該奈米碳管碾壓膜中奈米碳管之長度大於50微米。 The carbon nanotube structure prefabricated film may be a carbon nanotube rolled film, and the carbon nanotube rolled film is a self-supporting carbon nanotube obtained by rolling a carbon nanotube array. Structure prefabricated film. The carbon nanotube rolled film comprises uniformly distributed carbon nanotubes, and the carbon nanotubes are arranged in the same direction or in different directions. The carbon nanotubes in the carbon nanotube film are partially overlapped with each other and are attracted to each other by van der Waals force, so that the carbon nanotube structure prefabricated film has good flexibility and can be bent. Fold into any shape without breaking. Moreover, since the carbon nanotubes in the carbon nanotube rolled film are attracted to each other by the van der Waals force, the carbon nanotube film is a self-supporting structure. The carbon nanotubes in the carbon nanotube rolled film form an angle β with the surface of the growth substrate forming the carbon nanotube array, wherein β is greater than or equal to 0 degrees and less than or equal to 15 degrees, and the angle β is applied The pressure on the carbon nanotube array is related. The larger the pressure, the smaller the angle. Preferably, the carbon nanotubes in the carbon nanotube rolled film are aligned parallel to the growth substrate. The carbon nanotube rolled film is obtained by rolling a carbon nanotube array, and the carbon nanotubes in the carbon nanotube rolled film have different arrangement forms according to the manner of rolling. Specifically, the carbon nanotubes can be arranged in disorder; referring to FIG. 2, when rolling in different directions, the carbon nanotubes are arranged in different directions; when crushed in the same direction, the carbon nanotubes are along a The orientation is preferred and the orientation is preferred. The length of the carbon nanotubes in the carbon nanotube rolled film is greater than 50 microns.
該奈米碳管碾壓膜之面積與奈米碳管陣列之尺寸基本相同。該奈米碳管碾壓膜厚度與奈米碳管陣列之高度以及碾壓之壓力有關，可為0.5奈米到100微米之間。可以理解，奈米碳管陣列之高度越大而施加之壓力越小，則製備之奈米碳管碾壓膜之厚度越大；反之，奈米碳管陣列之高度越小而施加之壓力越大，則製備之奈米 碳管碾壓膜之厚度越小。所述奈米碳管碾壓膜之中之相鄰之奈米碳管之間具有一定間隙，從而在奈米碳管碾壓膜中形成複數尺寸在1奈米到500奈米之間之間隙或微孔。 The area of the carbon nanotube rolled film is substantially the same as the size of the carbon nanotube array. The thickness of the carbon nanotube film is related to the height of the carbon nanotube array and the pressure of the rolling, and may be between 0.5 nm and 100 μm. It can be understood that the larger the height of the carbon nanotube array and the lower the pressure applied, the greater the thickness of the prepared carbon nanotube rolled film; on the contrary, the smaller the height of the carbon nanotube array, the more the applied pressure Large, then prepared nano The smaller the thickness of the carbon tube rolled film. a gap between adjacent carbon nanotubes in the carbon nanotube film, thereby forming a plurality of gaps between 1 nm and 500 nm in the carbon nanotube film Or micropores.
所述奈米碳管結構預製膜可為一奈米碳管拉膜。請參見圖3，所述形成之奈米碳管拉膜係由若干奈米碳管組成之自支撐結構。所述若干奈米碳管為沿該奈米碳管拉膜之長度方向擇優取向排列。所述擇優取向係指在奈米碳管拉膜中大多數奈米碳管之整體延伸方向基本朝同一方向。且，所述大多數奈米碳管之整體延伸方向基本平行於奈米碳管拉膜之表面。進一步地，所述奈米碳管拉膜中多數奈米碳管係通過凡得瓦力首尾相連。具體地，所述奈米碳管拉膜中基本朝同一方向延伸之大多數奈米碳管中每一奈米碳管與在延伸方向上相鄰之奈米碳管通過凡得瓦力首尾相連。當然，所述奈米碳管拉膜中存在少數偏離該延伸方向之奈米碳管，這些奈米碳管不會對奈米碳管拉膜中大多數奈米碳管之整體取向排列構成明顯影響。所述自支撐為奈米碳管拉膜不需要大面積之載體支撐，而僅相對兩邊提供支撐力即能整體上懸空而保持自身膜狀狀態，即將該奈米碳管拉膜置於(或固定於)間隔一定距離設置之兩個支撐體上時，位於兩個支撐體之間之奈米碳管拉膜能夠懸空保持自身膜狀狀態。所述自支撐主要通過奈米碳管拉膜中存在連續之通過凡得瓦力首尾相連延伸排列之奈米碳管而實現。具體地，所述奈米碳管拉膜中基本朝同一方向延伸之多數奈米碳管，並非絕對之直線狀，可適當之彎曲；或者並非完全按照延伸方向上排列，可適當之偏離延伸方向。故，不能排除奈米碳管拉膜之基本朝同一方向延伸之多數奈米碳管中並列之奈米碳管之間可能存在部分接觸。 The carbon nanotube structure pre-formed film may be a carbon nanotube film. Referring to FIG. 3, the formed carbon nanotube film is a self-supporting structure composed of a plurality of carbon nanotubes. The plurality of carbon nanotubes are arranged in a preferred orientation along the length of the carbon nanotube film. The preferred orientation means that the overall extension direction of most of the carbon nanotubes in the carbon nanotube film is substantially in the same direction. Moreover, the overall extension direction of the majority of the carbon nanotubes is substantially parallel to the surface of the carbon nanotube film. Further, most of the carbon nanotubes in the carbon nanotube film are connected end to end by van der Waals force. Specifically, each of the carbon nanotubes of the majority of the carbon nanotubes extending substantially in the same direction in the carbon nanotube film is connected end to end with the carbon nanotubes adjacent in the extending direction by van der Waals force . Of course, there are a few carbon nanotubes in the carbon nanotube film that deviate from the extending direction. These carbon nanotubes do not constitute an obvious alignment of the majority of the carbon nanotubes in the carbon nanotube film. influences. The self-supporting carbon nanotube film does not need a large-area carrier support, but only provides support force on both sides, and can be suspended in the whole to maintain its own film state, that is, the carbon nanotube film is placed (or When fixed on two supports arranged at a certain distance, the carbon nanotube film located between the two supports can be suspended to maintain its own film state. The self-supporting is mainly achieved by the presence of a continuous carbon nanotube in the carbon nanotube film which is continuously arranged by van der Waals. Specifically, the majority of the carbon nanotubes extending substantially in the same direction in the carbon nanotube film are not absolutely linear and may be appropriately bent; or are not completely aligned in the extending direction, and may be appropriately deviated from the extending direction. . Therefore, it may not be possible to exclude partial contact between the carbon nanotubes juxtaposed in the majority of the carbon nanotubes extending substantially in the same direction.
具體地，該奈米碳管拉膜包括複數連續且定向排列之奈米碳管片段。該複數奈米碳管片段通過凡得瓦力首尾相連。每一奈米碳管片段由複數相互平行之奈米碳管組成。該奈米碳管片段具有任意之長度、厚度、均勻性及形狀。該奈米碳管拉膜具有較好之透光性，可見光透過率可達到75%以上。 Specifically, the carbon nanotube film comprises a plurality of continuous and aligned carbon nanotube segments. The plurality of carbon nanotube segments are connected end to end by van der Waals force. Each carbon nanotube segment consists of a plurality of carbon nanotubes that are parallel to each other. The carbon nanotube segments have any length, thickness, uniformity, and shape. The carbon nanotube film has good light transmittance and the visible light transmittance can reach more than 75%.
當所述奈米碳管預製結構包括多層奈米碳管拉膜時，相鄰兩層奈米碳管拉膜中之擇優取向排列之奈米碳管之間形成一交叉角度α，α大於等於0度小於等於90度(0°≦α≦90°)。請參閱圖4，優選地，為提高所述奈米碳管預製膜之強度，所述交叉角度α大致為90度，即相鄰兩層奈米碳管拉膜中之奈米碳管之排列方向基本垂直，形成一交叉膜。所述複數奈米碳管拉膜之間或一個奈米碳管拉膜之中之相鄰之奈米碳管之間具有一定間隙，從而在奈米碳管預製結構中形成複數均勻分佈，無規則排列，尺寸在1奈米到500奈米之間之間隙或微孔。 When the carbon nanotube prefabricated structure comprises a multi-layered carbon nanotube film, a preferred angle between the adjacent two layers of carbon nanotube film forming a cross angle α, α is greater than or equal to 0 degrees is less than or equal to 90 degrees (0° ≦ α ≦ 90 °). Referring to FIG. 4, preferably, in order to increase the strength of the carbon nanotube preform film, the intersection angle α is approximately 90 degrees, that is, the arrangement of the carbon nanotubes in the adjacent two layers of carbon nanotube film. The direction is substantially vertical to form a cross film. There is a certain gap between the adjacent carbon nanotube film or between adjacent carbon nanotubes in a nano carbon tube film, thereby forming a plurality of uniform distribution in the carbon nanotube prefabricated structure, Regularly arranged, with a size between 1 nm and 500 nm or micropores.
當所述奈米碳管預製膜為所述奈米碳管拉膜時，為了一體化製備所述奈米碳管預製膜及對奈米碳管預製膜進行熱處理得到奈米碳管膜。所述奈米碳管預製膜之製備方法可包括如下步驟：S110，提供一基底及一形成在該基底上之奈米碳管陣列；S120，將所述奈米碳管陣列連同基底放置於一氣壓小於5*10-2帕之真空環境中；以及S130，從所述奈米碳管陣列拉取所述奈米碳管預製膜。 When the carbon nanotube pre-formed film is the carbon nanotube film, the carbon nanotube film is obtained by integrally preparing the carbon nanotube pre-formed film and heat-treating the carbon nanotube pre-formed film. The method for preparing the carbon nanotube pre-formed film may include the following steps: S110, providing a substrate and an array of carbon nanotubes formed on the substrate; S120, placing the carbon nanotube array together with the substrate The air pressure is less than 5*10 -2 Pa in a vacuum environment; and S130, the carbon nanotube pre-formed film is pulled from the carbon nanotube array.
在步驟S110中，所述奈米碳管陣列為一超順排奈米碳管陣列，該超順排奈米碳管陣列之製備方法採用化學氣相沈積法、鐳射誘導 氣相沈積法或者其他方法。在本實施例中，該超順排奈米碳管陣列之製備方法採用化學氣相沈積法，其具體步驟包括：提供一平整基底，該基底可選用P型或N型矽基底，或選用形成有氧化層之矽基底，本實施例優選為採用4英寸之矽基底；在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)或其任意組合之合金之一；將上述形成有催化劑層之基底在300攝氏度~900攝氏度(如700攝氏度)之空氣中退火約30分鐘~90分鐘；將處理過之基底置於反應爐中，在保護氣體環境下加熱到500攝氏度~900攝氏度(如740攝氏度)，然後通入碳源氣體反應約5~30分鐘，生長得到超順排奈米碳管陣列。該超順排奈米碳管陣列為複數彼此平行且垂直於基底生長之奈米碳管形成之純奈米碳管陣列，其高度為2微米~10毫米，優選為100微米~900微米。通過上述控制生長條件，該超順排奈米碳管陣列中基本不含有雜質，如無定型碳或殘留之催化劑金屬顆粒等。該奈米碳管陣列中之奈米碳管彼此通過凡得瓦力緊密接觸形成陣列。本實施例中碳源氣可選用乙炔等化學性質較活潑之碳氫化合物，保護氣體可選用氮氣、氨氣或惰性氣體。可以理解，所述奈米碳管陣列之生長方法不限於上述具體方法，通過調整化學氣相沈積方法之具體條件得到之其他方法，僅能夠生長出適於從中拉取奈米碳管預製膜之奈米碳管陣列即可。 In step S110, the carbon nanotube array is a super-sequential carbon nanotube array, and the super-sequential carbon nanotube array is prepared by chemical vapor deposition and laser induction. Vapor deposition or other methods. In this embodiment, the method for preparing the super-sequential carbon nanotube array adopts a chemical vapor deposition method, and the specific steps thereof include: providing a flat substrate, the substrate may be selected from a P-type or N-type germanium substrate, or selected to form The substrate having an oxide layer is preferably a 4-inch germanium substrate; a catalyst layer is uniformly formed on the surface of the substrate, and the catalyst layer material may be iron (Fe), cobalt (Co), nickel (Ni) or One of the alloys of any combination; the substrate on which the catalyst layer is formed is annealed in air at 300 degrees Celsius to 900 degrees Celsius (e.g., 700 degrees Celsius) for about 30 minutes to 90 minutes; the treated substrate is placed in a reaction furnace for protection It is heated to 500 degrees Celsius to 900 degrees Celsius (such as 740 degrees Celsius) in a gaseous environment, and then reacted with a carbon source gas for about 5 to 30 minutes to grow a super-aligned carbon nanotube array. The super-sequential carbon nanotube array is a pure carbon nanotube array formed by a plurality of carbon nanotubes parallel to each other and perpendicular to the substrate, and has a height of 2 micrometers to 10 millimeters, preferably 100 micrometers to 900 micrometers. The super-sequential carbon nanotube array is substantially free of impurities, such as amorphous carbon or residual catalyst metal particles, by controlling the growth conditions as described above. The carbon nanotubes in the array of carbon nanotubes are in close contact with each other to form an array by van der Waals force. In the present embodiment, the carbon source gas may be a chemically active hydrocarbon such as acetylene, and the protective gas may be nitrogen, ammonia or an inert gas. It can be understood that the growth method of the carbon nanotube array is not limited to the specific method described above, and other methods obtained by adjusting the specific conditions of the chemical vapor deposition method can only grow a suitable film for drawing a carbon nanotube from the film. The carbon nanotube array can be used.
步驟S130中，所述從奈米碳管陣列拉取一奈米碳管預製膜之步驟進一步包括：S131，提供一黏性基條，使該黏性基條接觸所述奈米碳管陣列；以及 S132，沿遠離所述奈米碳管陣列之方向移動所述黏性基條，使奈米碳管首尾相連地從奈米碳管陣列中連續地被拉出，從而獲得所述奈米碳管預製膜。 In step S130, the step of drawing a carbon nanotube pre-formed film from the carbon nanotube array further comprises: S131, providing a viscous base strip, contacting the viscous base strip with the carbon nanotube array; as well as S132, moving the viscous strip in a direction away from the array of carbon nanotubes, so that the carbon nanotubes are continuously pulled out from the array of carbon nanotubes end to end, thereby obtaining the carbon nanotubes. Prefabricated film.
在步驟S131中，該黏性基條通過卡扣、吸附等方式安裝在一拉膜裝置上。該拉膜裝置由電腦實現自動控制，使黏性基條移動。該黏性基條至少一表面具有黏膠，該黏性基條具黏膠之表面接觸所述奈米碳管陣列時能夠黏結部分奈米碳管，從而選定了由該複數奈米碳管組成之一奈米碳管片段。該黏性基條具有一長度，優選地，該黏性基條之長度與使用該黏性基條拉取得到之奈米碳管預製膜之寬度基本相等。 In step S131, the adhesive strip is mounted on a film pulling device by snapping, suctioning or the like. The film pulling device is automatically controlled by a computer to move the adhesive base strip. At least one surface of the viscous strip has a glue, and the surface of the viscous strip with the adhesive contacts the carbon nanotube array to bond a portion of the carbon nanotube, thereby selecting a composition consisting of the plurality of carbon nanotubes One of the carbon nanotube fragments. The viscous strip has a length. Preferably, the length of the viscous strip is substantially equal to the width of the carbon nanotube pre-formed film obtained by drawing the viscous strip.
在步驟S132中，所述奈米碳管預製膜為所述奈米碳管拉膜。當沿遠離所述奈米碳管陣列之方向移動所述黏性基條時，從而以一定速度拉取該選定之奈米碳管片段，從而首尾相連之拉出連續之複數奈米碳管片段，進而形成一連續之奈米碳管預製膜。通過所述拉膜裝置，以一定之速度和拉伸角度移動所述黏性基條，在黏性基條沿遠離所述奈米碳管陣列之方向移動之過程中，所述選定之奈米碳管片段從奈米碳管陣列中被拉出。當該選定之奈米碳管片段在拉力作用下沿拉伸方向逐漸脫離基底之同時，由於凡得瓦力作用，在奈米碳管陣列中與該選定之奈米碳管片段相鄰之其他奈米碳管片段首尾相連地相繼地被拉出，從而形成一連續、均勻之奈米碳管預製膜。 In step S132, the carbon nanotube pre-formed film is the carbon nanotube film. When the viscous base strip is moved in a direction away from the array of carbon nanotubes, the selected carbon nanotube segments are pulled at a certain speed, thereby pulling the continuous plurality of carbon nanotube segments end to end. And forming a continuous carbon nanotube pre-formed film. Moving the viscous strip at a certain speed and a stretching angle by the film pulling device, the selected nanometer in the process of moving the viscous strip away from the array of carbon nanotubes The carbon tube segments are pulled from the array of carbon nanotubes. When the selected carbon nanotube segment is gradually separated from the substrate in the stretching direction by the tensile force, the other adjacent to the selected carbon nanotube segment in the carbon nanotube array due to the effect of van der Waals The carbon nanotube segments are successively pulled out end to end to form a continuous, uniform carbon nanotube pre-formed film.
當所述奈米碳管預製膜自所述奈米碳管陣列拉取出來時，該奈米碳管預製膜之拉伸方向與所述奈米碳管陣列之生長方向之間之夾角為30度~90度，該生長方向為奈米碳管陣列中之大多數奈米碳 管之軸向延伸方向，即垂直於所述基底表面之方法。即，該拉伸方向與所述基底表面之夾角應該控制在0度~60度之間，以進一步提高所述奈米碳管預製膜之均勻性。在本實施例，所述拉伸方向與所述奈米碳管陣列之生長方向之間之夾角為85度。 When the carbon nanotube preform film is pulled out from the carbon nanotube array, the angle between the stretching direction of the carbon nanotube preform film and the growth direction of the carbon nanotube array is 30 Degree ~90 degrees, the growth direction is the majority of nanocarbon in the carbon nanotube array The direction in which the tube extends axially, i.e., perpendicular to the surface of the substrate. That is, the angle between the stretching direction and the surface of the substrate should be controlled between 0 and 60 degrees to further improve the uniformity of the carbon nanotube pre-formed film. In this embodiment, the angle between the stretching direction and the growth direction of the carbon nanotube array is 85 degrees.
所述奈米碳管預製膜從所述奈米碳管陣列拉出時，該拉膜裝置及奈米碳管預製膜與所述真空環境內之氣體相對運動，產生氣流擾動，當該氣流擾動之強度大於所述奈米碳管預製膜之承受強度時，所述奈米碳管預製膜產生黑線甚至破損。所述氣流擾動之強度與所述真空環境內之氣體密度及奈米碳管預製膜之拉伸速度相關。具體地，隨著該真空環境內之氣體密度之下降(即氣壓之降低)，該奈米碳管預製膜以一定速度移動時，該氣流擾動對該奈米碳管預製膜之作用力將隨之減少，該奈米碳管預製膜所受到之氣流擾動之強度越小，所述奈米碳管預製膜受氣流擾動而破損之幾率就越大。在該真空環境氣壓固定之情況下，所述奈米碳管預製膜被拉出之速度越快，受到之氣流擾動越大，該奈米碳管預製膜受氣流擾動而破損之幾率就越小。故，在所述真空環境內之氣壓較大時，用較快之拉伸速度，如0.1米每秒之拉伸速度，拉伸所述奈米碳管預製膜時，所述奈米碳管預製膜容易受到破壞。而，在本實施例中，由於所述真空環境中之氣壓小於5*10-2帕，將所述奈米碳管陣列該真空環境中製備奈米碳管預製膜，能夠用較快之拉伸速度，如0.1米每秒之拉伸速度，拉伸出品質較好之奈米碳管預製膜，即在所述真空環境下製備奈米碳管預製膜能夠提高所述奈米碳管預製膜之品質。進一步地，當所述真空環境內之氣壓小於5*10-5帕時，所述拉伸速度可大於等於10米每秒，即降低所述真空環境之氣壓能夠提高所述奈米碳管預製膜之拉伸速度， 使所述奈米碳管預製膜更快地被拉伸出來，且不會因氣流擾動而破壞。 When the carbon nanotube pre-formed film is pulled out from the carbon nanotube array, the film pulling device and the carbon nanotube pre-formed film move relative to the gas in the vacuum environment to generate airflow disturbance, when the airflow is disturbed When the strength is greater than the tensile strength of the carbon nanotube pre-formed film, the carbon nanotube pre-formed film produces black lines or even breakage. The intensity of the gas flow disturbance is related to the gas density in the vacuum environment and the tensile speed of the carbon nanotube pre-formed film. Specifically, as the density of the gas in the vacuum environment decreases (ie, the pressure is lowered), when the carbon nanotube pre-formed film moves at a certain speed, the force of the gas flow disturbing the pre-formed film of the carbon nanotube will follow The smaller the intensity of the gas flow disturbance received by the carbon nanotube pre-formed film, the greater the probability that the carbon nanotube pre-formed film is damaged by the air flow. In the case where the vacuum atmosphere is fixed, the faster the carbon nanotube pre-film is pulled out, the greater the disturbance of the gas flow, and the smaller the probability that the carbon nanotube pre-film is damaged by the air flow. . Therefore, when the gas pressure in the vacuum environment is large, the carbon nanotubes are pre-formed by stretching the film at a faster drawing speed, such as a tensile speed of 0.1 m per second. The pre-formed film is easily damaged. However, in the embodiment, since the air pressure in the vacuum environment is less than 5*10 −2 Pa, the carbon nanotubes are prepared in the vacuum environment to prepare a carbon nanotube pre-formed film, which can be pulled faster. Stretching speed, such as a tensile speed of 0.1 m per second, stretching a better quality carbon nanotube pre-formed film, that is, preparing a carbon nanotube pre-formed film under the vacuum environment can improve the carbon nanotube prefabrication The quality of the film. Further, when the air pressure in the vacuum environment is less than 5*10 -5 Pa, the stretching speed may be greater than or equal to 10 meters per second, that is, reducing the air pressure in the vacuum environment can improve the carbon nanotube prefabrication. The stretching speed of the film allows the carbon nanotube pre-formed film to be stretched out more quickly without being disturbed by air flow disturbance.
由於所述奈米碳管預製膜之拉取過程在氣壓小於5*10-2帕之真空環境進行，該真空環境內之氣體密度較小，在保證所述奈米碳管預製膜之品質之同時，該奈米碳管預製膜能夠以較快之速度移動，從而使得所述奈米碳管預製膜能夠以較快之速度被拉出，提高了該奈米碳管預製膜之製備速度與效率。進一步地，由於該真空環境之氣體密度較小，其浮力較小，灰塵等雜質容易沉澱，即該真空環境容易保持較高之潔淨度。 Since the drawing process of the carbon nanotube pre-formed film is carried out in a vacuum environment with a gas pressure of less than 5*10 -2 Pa, the gas density in the vacuum environment is small, and the quality of the pre-formed film of the carbon nanotube is ensured. At the same time, the carbon nanotube pre-film can be moved at a faster speed, so that the carbon nanotube pre-film can be pulled out at a faster speed, which improves the preparation speed of the carbon nanotube pre-film. effectiveness. Further, since the gas density of the vacuum environment is small, the buoyancy is small, and impurities such as dust are easily precipitated, that is, the vacuum environment is easy to maintain high cleanliness.
所述奈米碳管預製結構可包括至少一奈米碳管預製線。當所述奈米碳管預製結構包括複數奈米碳管預製線時，所述複數奈米碳管預製線可相互平行、纏繞或編織設置。 The carbon nanotube preform structure may include at least one carbon nanotube preform line. When the carbon nanotube preform structure includes a plurality of carbon nanotube preforms, the plurality of carbon nanotube preforms may be disposed in parallel, wound or braided with each other.
所述奈米碳管預製線可為將一奈米碳管拉膜經過處理形成之線狀結構，所述奈米碳管拉膜之處理方法包括用揮發性有機溶劑浸潤處理或機械扭轉處理。所述揮發性有機溶劑浸潤處理可通過試管將有機溶劑滴落在奈米碳管拉膜表面浸潤整個奈米碳管拉膜，或者，也可將上述形成有奈米碳管拉膜之固定框架整個浸入盛有有機溶劑之容器中浸潤。該揮發性有機溶劑為乙醇、甲醇、丙酮、二氯乙烷或氯仿，本實施例中採用乙醇。所述有機溶劑在揮發時產生之張力使所述奈米碳管拉膜收縮形成所述奈米碳管預製線。請參閱圖5，通過揮發性有機溶劑浸潤處理所得到之奈米碳管預製線為一非扭轉之奈米碳管線，該非扭轉之奈米碳管線包括複數沿奈米碳管線長度方向排列之奈米碳管。具體地，該非扭轉之奈米碳管線包括複數奈米碳管通過凡得瓦力首尾相連且沿奈米碳管 線軸向擇優取向排列。所述機械扭轉處理可通過採用一機械力將所述奈米碳管拉膜兩端沿相反方向扭轉。請參閱圖6，通過機械扭轉處理而得到之奈米碳管預製線為一扭轉之奈米碳管線，該扭轉之奈米碳管線包括複數繞奈米碳管線軸向螺旋排列之奈米碳管。具體地，該扭轉之奈米碳管線包括複數奈米碳管通過凡得瓦力首尾相連且沿奈米碳管線軸向呈螺旋狀延伸。可以理解，也可對獲得之奈米碳管拉膜同時或者依次進行有機溶劑揮發性有機溶劑浸潤處理或機械扭轉處理來獲得扭轉之奈米碳管線。 The carbon nanotube preform line may be a linear structure formed by processing a carbon nanotube film, and the method for treating the carbon nanotube film includes a volatile organic solvent infiltration treatment or a mechanical torsion treatment. The volatile organic solvent infiltration treatment may immerse the organic solvent on the surface of the carbon nanotube film by a test tube to infiltrate the entire carbon nanotube film, or the above-mentioned fixed frame formed with the carbon nanotube film may be formed. The whole is immersed in a container containing an organic solvent to infiltrate. The volatile organic solvent is ethanol, methanol, acetone, dichloroethane or chloroform, and ethanol is used in this embodiment. The tension generated by the organic solvent upon volatilization causes the carbon nanotube film to shrink to form the carbon nanotube preform. Referring to FIG. 5, the carbon nanotube preform obtained by the volatile organic solvent infiltration treatment is a non-twisted nano carbon pipeline, and the non-twisted nano carbon pipeline includes a plurality of nanometers arranged along the length of the nanocarbon pipeline. Carbon tube. Specifically, the non-twisted nanocarbon pipeline includes a plurality of carbon nanotubes connected end to end by van der Waals and along the carbon nanotubes The lines are arranged in an axially preferred orientation. The mechanical torsion treatment may be performed by twisting both ends of the carbon nanotube film in the opposite direction by using a mechanical force. Referring to FIG. 6 , the nano carbon tube preform line obtained by the mechanical torsion treatment is a twisted nano carbon line, and the twisted nano carbon line includes a plurality of carbon nanotubes arranged in an axial spiral arrangement around the carbon carbon line. . Specifically, the twisted nanocarbon pipeline includes a plurality of carbon nanotubes connected end to end by van der Waals force and extending helically along the axial direction of the carbon nanotubes. It can be understood that the obtained nanocarbon tube can be obtained by simultaneously or sequentially performing an organic solvent volatile organic solvent infiltration treatment or a mechanical torsion treatment to obtain a twisted nanocarbon line.
在步驟S20中，所述低氧環境中之氧氣分壓小於1*10-2帕，從而使得所述奈米碳管在高溫環境中儘量少地被氧化。優選地，所述低氧環境之氧氣分壓小於1*10-5帕，此時，所述奈米碳管在高溫環境中基本不被氧化。為使所述低氧環境中之氧氣之分壓小於1*10-2帕，該低氧環境中可充滿惰性氣體或直接抽真空降低該低氧環境中之氣壓。在本實施例中，為節約成本及操作便利，採取直接抽真空之方法，使該低氧環境中之大氣氣壓小於5*10-2帕，優選地，所述低氧環境中之大氣氣壓小於5*10-5帕。 In step S20, the partial pressure of oxygen in the low oxygen environment is less than 1*10 -2 Pa, so that the carbon nanotubes are oxidized as little as possible in a high temperature environment. Preferably, the oxygen partial pressure of the low oxygen environment is less than 1*10 -5 Pa, and at this time, the carbon nanotube is not substantially oxidized in a high temperature environment. In order to make the partial pressure of oxygen in the low oxygen environment less than 1*10 -2 Pa, the low oxygen environment may be filled with an inert gas or directly evacuated to lower the gas pressure in the low oxygen environment. In this embodiment, in order to save cost and facilitate operation, a direct vacuuming method is adopted to make the atmospheric pressure in the low oxygen environment less than 5*10 -2 Pa, preferably, the atmospheric pressure in the low oxygen environment is less than 5*10 -5 Pa.
所述熱處理之溫度大於1500攝氏度，優選地，所述熱處理之溫度大於2000攝氏度以形成更多之碳碳鍵。所述熱處理之方式不限，可通過放置於一真空加熱爐中直接進行加熱，也可通過鐳射照射之方式進行加熱。在本實施例中，所述熱處理為通過用鐳射照射所述奈米碳管結構而完成。具體地，所述鐳射之照射功率在10兆瓦到30兆瓦之間，掃描頻率在5毫米每秒到300毫米每秒之間。通過鐳射照射之方式進行熱處理，可在奈米碳管預製結構之選定區域或者部分區域進行加熱並形成碳碳鍵。 The heat treatment temperature is greater than 1500 degrees Celsius, and preferably, the heat treatment temperature is greater than 2000 degrees Celsius to form more carbon-carbon bonds. The manner of the heat treatment is not limited, and it may be directly heated by being placed in a vacuum heating furnace, or may be heated by laser irradiation. In the present embodiment, the heat treatment is performed by irradiating the carbon nanotube structure with laser light. Specifically, the laser irradiation power is between 10 megawatts and 30 megawatts, and the scanning frequency is between 5 millimeters per second and 300 millimeters per second. Heat treatment by means of laser irradiation heats and forms carbon-carbon bonds in selected regions or portions of the carbon nanotube preform structure.
可以理解，當所述低氧環境通過降低氣壓(趨於真空)之方式而得到時，且所述奈米碳管預製結構為奈米碳管拉膜或線時，在本實施方式中之奈米碳管結構之製備方法中，所述奈米碳管預製膜或線之製備及熱處理可在同一真空工作環境中進行，從而實現連續作業。此時，所述熱處理之之方式優選為鐳射照射，且用鐳射照射之方式進行熱處理操作起來較為方便，成本低。 It can be understood that when the low-oxygen environment is obtained by lowering the air pressure (which tends to be vacuum), and the carbon nanotube preform structure is a carbon nanotube film or wire, in the present embodiment, In the preparation method of the carbon nanotube structure, the preparation and heat treatment of the carbon nanotube pre-formed film or wire can be carried out in the same vacuum working environment, thereby realizing continuous operation. At this time, the manner of the heat treatment is preferably laser irradiation, and the heat treatment by laser irradiation is convenient and the cost is low.
在熱處理過程中，所述奈米碳管中之碳原子將進行晶格重排，尤其係奈米碳管中由碳原子形成之五圓環、七圓環等不穩定結構容易在高溫環境下進行晶格重排過程中形成穩定之六圓環。該奈米碳管中由碳原子形成之五圓環、七圓環等不穩定結構係奈米碳管在生長時所產生之缺陷，如通過MOCVD法生長奈米碳管時，必然會具有上述缺陷，這些缺陷將降低奈米碳管之機械性能。而經過熱處理後，所述奈米碳管中之缺陷將變少，石墨化程度較好，提高所述奈米碳管結構之機械性能。進一步地，在熱處理時，相鄰之奈米碳管之間容易在晶格重組時形成碳碳鍵，尤其係相鄰之奈米碳管之間之距離小於1奈米時產生碳碳鍵之概率更大。可以理解，由於相鄰之奈米碳管之間通過碳碳鍵結合形成之結合力將大於相鄰之奈米碳管之間通過凡得瓦力結合形成之結合力，故，所述奈米碳管結構之機械性能優於所述奈米碳管預製結構之機械性能。 During the heat treatment, the carbon atoms in the carbon nanotubes will undergo lattice rearrangement, especially the unstable structures such as five rings and seven rings formed by carbon atoms in the carbon nanotubes are easy to be in a high temperature environment. A stable six-ring is formed during the lattice rearrangement process. The unstable structure of the five-ring, seven-ring, etc. formed by carbon atoms in the carbon nanotubes is a defect generated during growth, such as when the carbon nanotubes are grown by MOCVD. Defects that will reduce the mechanical properties of the carbon nanotubes. After the heat treatment, the defects in the carbon nanotubes will be less, the degree of graphitization is better, and the mechanical properties of the carbon nanotube structure are improved. Further, in the heat treatment, carbon nanotube bonds are easily formed between adjacent carbon nanotubes during lattice recombination, especially when the distance between adjacent carbon nanotubes is less than 1 nm, and carbon-carbon bonds are generated. The probability is greater. It can be understood that since the bonding force formed by the carbon-carbon bond between adjacent carbon nanotubes will be greater than the bonding force formed by the combination of van der Waals force between the adjacent carbon nanotubes, the nanometer is The mechanical properties of the carbon tube structure are superior to the mechanical properties of the carbon nanotube preform structure.
本發明提供之奈米碳管結構可包括由上述奈米碳管結構之製備方法對一奈米碳管預製結構在低氧環境下進行熱處理而得到之產品。 The carbon nanotube structure provided by the present invention may include a product obtained by heat-treating a carbon nanotube preform structure in a low-oxygen environment by the above-described method for preparing a carbon nanotube structure.
所述奈米碳管結構包括複數奈米碳管相互連接，所述複數奈米碳 管之間具有碳碳鍵。即，所述複數奈米碳管中，至少有部分奈米碳管通過碳碳鍵連接，而未通過碳碳鍵結合之奈米碳管之間可通過凡得瓦力相連。優選地，所述複數奈米碳管均可通過碳碳鍵連接。所述碳碳鍵之碳原子分別來自相鄰之兩個奈米碳管，即相當於所述複數奈米碳管具有複數“焊點”使相鄰之奈米碳管結合成一整體之物質結構，所述焊點即為所述碳碳鍵。所述碳碳鍵在所述奈米碳管之位置不限，可在所述奈米碳管之管壁，也可在所述奈米碳管之端部。所述碳碳鍵為共價鍵，包括Sp2及Sp3鍵。由於碳碳鍵之鍵長限制，具有碳碳鍵之相鄰之奈米碳管之間之距離小於1奈米，而此時，具有碳碳鍵之相鄰之奈米碳管之間同時還具有較強之凡得瓦力，故，相鄰之奈米碳管之間具有碳碳鍵時之結合力較大。 The carbon nanotube structure includes a plurality of carbon nanotubes interconnected with carbon carbon bonds between the plurality of carbon nanotubes. That is, in the plurality of carbon nanotubes, at least some of the carbon nanotubes are connected by carbon-carbon bonds, and the carbon nanotubes not bonded by carbon-carbon bonds may be connected by van der Waals. Preferably, the plurality of carbon nanotubes may be connected by a carbon-carbon bond. The carbon atoms of the carbon-carbon bond are respectively derived from two adjacent carbon nanotubes, that is, the material structure of the plurality of carbon nanotubes having a plurality of "solder joints" to combine adjacent carbon nanotubes into a whole. The solder joint is the carbon-carbon bond. The carbon-carbon bond is not limited at the position of the carbon nanotube, and may be at the wall of the carbon nanotube or at the end of the carbon nanotube. The carbon-carbon bond is a covalent bond, including Sp 2 and Sp 3 bonds. Due to the bond length limitation of the carbon-carbon bond, the distance between adjacent carbon nanotubes having carbon-carbon bonds is less than 1 nm, and at this time, adjacent carbon nanotubes having carbon-carbon bonds are simultaneously It has a strong van der Waals force, so the bonding force between the adjacent carbon nanotubes has a carbon-carbon bond.
所述奈米碳管結構可包括至少一奈米碳管膜，所述奈米碳管膜可通過上述熱處理一奈米碳管預製膜而得到。當所述奈米碳管結構包括複數奈米碳管膜時，所述複數奈米碳管膜相互層疊設置，相鄰之奈米碳管膜之間具有複數碳碳鍵，從而使得所述相鄰之奈米碳管膜通過之間即可通過凡得瓦力及碳碳鍵結合。 The carbon nanotube structure may include at least one carbon nanotube film, and the carbon nanotube film may be obtained by preheating a carbon nanotube pre-formed film. When the carbon nanotube structure comprises a plurality of carbon nanotube membranes, the plurality of carbon nanotube membranes are stacked one on another, and the adjacent carbon nanotube membranes have a plurality of carbon-carbon bonds therebetween, thereby causing the phases to The adjacent nanotube film can be bonded through van der Waals and carbon-carbon bonds.
所述奈米碳管膜可包括相互纏繞且均勻分佈之複數奈米碳管，相互纏繞之複數奈米碳管之間具有碳碳鍵，從而使得所述奈米碳管膜中之奈米碳管之間通過凡得瓦力及碳碳鍵相互結合、分佈，形成網路狀結構。所述奈米碳管膜可各向同性，即所述奈米碳管絮化膜中之奈米碳管為均勻分佈，無規則排列。所述奈米碳管膜可通過上述製備方法熱處理所述奈米碳管絮化膜而得到。 The carbon nanotube film may include a plurality of carbon nanotubes intertwined and uniformly distributed, and carbon nanotube bonds between the plurality of carbon nanotubes intertwined to each other, thereby causing nanocarbon in the carbon nanotube film The tubes are connected and distributed by van der Waals and carbon-carbon bonds to form a network structure. The carbon nanotube film can be isotropic, that is, the carbon nanotubes in the carbon nanotube flocculation film are uniformly distributed and randomly arranged. The carbon nanotube film can be obtained by heat-treating the carbon nanotube flocculation film by the above preparation method.
所述奈米碳管膜可包括複數均勻分佈且沿同一方向或複數不同方 向擇優取向排列之奈米碳管。所述奈米碳管之複數奈米碳管可基本平行於該奈米碳管膜之一表面。所述奈米碳管膜中之奈米碳管相互部分交疊，所述相互部分交疊之奈米碳管之間具有碳碳鍵，而未具有碳碳鍵之相互部分交疊之奈米碳管則通過凡得瓦力相互吸引，從而使得所述奈米碳管膜中之奈米碳管之間通過凡得瓦力及碳碳鍵相互結合。所述奈米碳管膜可通過上述製備方法熱處理所述奈米碳管碾壓膜而得到。 The carbon nanotube film may comprise a plurality of evenly distributed and different directions in the same direction or in plural A carbon nanotube arranged in a preferred orientation. The plurality of carbon nanotubes of the carbon nanotubes may be substantially parallel to a surface of the carbon nanotube film. The carbon nanotubes in the carbon nanotube film partially overlap each other, and the mutually overlapping carbon nanotubes have a carbon-carbon bond, and the carbon carbon-carbon bonds do not overlap each other. The carbon tubes are attracted to each other by van der Waals force, so that the carbon nanotubes in the carbon nanotube film are bonded to each other by van der Waals and carbon-carbon bonds. The carbon nanotube film can be obtained by heat-treating the carbon nanotube rolled film by the above preparation method.
所述奈米碳管膜可包括複數均勻分佈且沿同一方向擇優取向排列之奈米碳管，所述擇優取向係指在奈米碳管膜中大多數奈米碳管之整體延伸方向基本朝同一方向。且，所述大多數奈米碳管之整體延伸方向基本平行於奈米碳管膜之表面。進一步地，所述奈米碳管膜中多數奈米碳管係通過碳碳鍵首尾相連。具體地，所述奈米碳管膜中基本朝同一方向延伸之大多數奈米碳管中每一奈米碳管與在延伸方向上相鄰之奈米碳管通過碳碳鍵首尾相連。由於通過碳碳鍵首尾相連之奈米碳管能夠形成一個整體之物質結構，故，所述奈米碳管膜也可描述為包括複數彼此平行之奈米碳管條，每一奈米碳管條均包括複數奈米碳管通過碳碳鍵首尾相連，而相鄰之奈米碳管條基本通過凡得瓦力連接。當然，也不排除少量奈米碳管條之間具有碳碳鍵，也不排除奈米碳管條中少量之奈米碳管之間依然通過凡得瓦力首尾相連，但這並不影響本發明之效果及性能。所述奈米碳管膜可通過上述製備方法熱處理所述奈米碳管拉膜而得到。 The carbon nanotube film may comprise a plurality of carbon nanotubes uniformly distributed and arranged in a preferred orientation in the same direction, wherein the preferred orientation means that the overall extension direction of the majority of the carbon nanotubes in the carbon nanotube film is substantially In the same direction. Moreover, the overall extension direction of the majority of the carbon nanotubes is substantially parallel to the surface of the carbon nanotube film. Further, most of the carbon nanotubes in the carbon nanotube membrane are connected end to end by carbon-carbon bonds. Specifically, each of the carbon nanotubes in the majority of the carbon nanotube membranes extending in the same direction and the carbon nanotubes adjacent in the extending direction are connected end to end by a carbon-carbon bond. Since the carbon nanotubes connected end to end through the carbon-carbon bond can form a unitary material structure, the carbon nanotube film can also be described as including a plurality of carbon nanotube strips parallel to each other, each carbon nanotube The strips each include a plurality of carbon nanotubes connected end to end by carbon-carbon bonds, and adjacent carbon nanotube strips are substantially connected by van der Waals. Of course, it is not excluded that there are carbon-carbon bonds between a small number of carbon nanotubes, and it is not excluded that a small amount of carbon nanotubes in the carbon nanotubes are still connected end to end by van der Waals force, but this does not affect this. The effect and performance of the invention. The carbon nanotube film can be obtained by heat-treating the carbon nanotube film by the above preparation method.
所述奈米碳管結構可包括至少一奈米碳管線，當所述奈米碳管結構包括複數奈米碳管線時，所述複數奈米碳管線相互平行、纏繞 或編織設置，複數奈米碳管線之間具有碳碳鍵，從而使得所述複數奈米碳管線能夠通過凡得瓦力及碳碳鍵結合。 The carbon nanotube structure may include at least one nano carbon line, and when the carbon nanotube structure includes a plurality of nano carbon lines, the plurality of carbon carbon lines are parallel and entangled with each other Or a braided arrangement having carbon-carbon bonds between the plurality of nanocarbon lines such that the plurality of carbon nanotubes can be bonded by van der Waals and carbon-carbon bonds.
所述奈米碳管線可包括複數奈米碳管通過所述碳碳鍵首尾相連且沿奈米碳管線軸向呈螺旋狀延伸。由於通過碳碳鍵首尾相連之奈米碳管能夠形成一個整體之物質結構，故，所述奈米碳管線也可描述為包括複數沿奈米碳管線軸向呈螺旋狀延伸之奈米碳管條，每一奈米碳管條均包括複數奈米碳管通過碳碳鍵首尾相連，而並列之相鄰之奈米碳管條基本通過凡得瓦力連接。所述奈米碳管線可通過上述製備方法熱處理一扭轉之奈米碳管線而得到。 The nanocarbon pipeline may include a plurality of carbon nanotubes connected end to end through the carbon-carbon bond and extending helically along the axial direction of the nanocarbon pipeline. Since the carbon nanotubes connected end to end through the carbon-carbon bond can form a monolithic material structure, the nanocarbon pipeline can also be described as including a plurality of carbon nanotubes extending helically along the carbon nanotube line in the axial direction. Each of the carbon nanotube strips includes a plurality of carbon nanotubes connected end to end by a carbon-carbon bond, and the adjacent adjacent carbon nanotube strips are substantially connected by van der Waals. The nanocarbon line can be obtained by heat-treating a twisted nanocarbon line by the above preparation method.
所述奈米碳管線可包括複數奈米碳管通過所述碳碳鍵首尾相連且沿奈米碳管線軸向擇優取向排列。由於通過碳碳鍵首尾相連之奈米碳管能夠形成一個整體之物質結構，故，所述奈米碳管線也可描述為包括複數沿奈米碳管線軸向擇優取向排列之奈米碳管條，每一奈米碳管條均包括複數奈米碳管通過碳碳鍵首尾相連，而並列之相鄰之奈米碳管條基本通過凡得瓦力連接。所述奈米碳管線可通過上述製備方法熱處理一非扭轉之奈米碳管線而得到。 The nanocarbon pipeline may include a plurality of carbon nanotubes connected end to end by the carbon-carbon bonds and arranged in an axially preferred orientation along the nanocarbon pipeline. Since the carbon nanotubes connected end to end through the carbon-carbon bond can form a monolithic material structure, the nanocarbon pipeline can also be described as including a plurality of carbon nanotube strips arranged in an axially preferred orientation along the nanocarbon pipeline. Each nano carbon tube strip includes a plurality of carbon nanotubes connected end to end by a carbon-carbon bond, and the adjacent adjacent carbon nanotube strips are substantially connected by van der Waals force. The nanocarbon line can be obtained by heat-treating a non-twisted nanocarbon line by the above preparation method.
為了更清楚地說明本發明之奈米碳管結構之製備方法及由該製備方法製備之奈米碳管結構，下面以具體實施例予以說明。對於奈米碳管預製膜、線或者其他形狀之結構而言，其處理之方法較為相近，故本具體實施例以奈米碳管預製線中之扭轉之奈米碳管線為例進行說明。 In order to more clearly illustrate the preparation method of the carbon nanotube structure of the present invention and the structure of the carbon nanotube prepared by the preparation method, the following description will be given by way of specific examples. For the structure of the carbon nanotube pre-formed film, wire or other shape, the treatment method is relatively similar, so the specific embodiment is described by taking the twisted nanocarbon pipeline in the carbon nanotube preform line as an example.
選擇圖6所示之扭轉之奈米碳管線放置於一真空環境中，所述真空環境中之氣壓小於等於5*10-5帕。通過一鐳射對所述扭轉之奈米碳管線進行鐳射掃描處理，所述鐳射之掃描功率大致為30瓦， 所述鐳射之掃描頻率大致為50毫米每秒。 The twisted nanocarbon line shown in Fig. 6 is selected to be placed in a vacuum environment having a gas pressure of 5*10 - 5 Pa or less. The twisted nanocarbon pipeline is subjected to a laser scanning process by a laser having a scanning power of approximately 30 watts and a scanning frequency of the laser of approximately 50 millimeters per second.
請參閱圖7，為熱處理後得到之奈米碳管線，對比圖6與圖7，發現奈米碳管結構與奈米碳管預製結構通過掃描電鏡照片看，在外觀上之區別並不大。請參閱圖8，分別獲取圖6中之扭轉之奈米碳管線及圖7中之奈米碳管線之拉曼光譜並進行對比形成一拉曼光譜對比圖。從圖中可看出，經過熱處理後，所述奈米碳管線之G峰相較扭轉之奈米碳管線明顯變強，D峰相較非扭轉奈米碳管線明顯減弱。證明經過熱處理後，奈米碳管線中之奈米碳管之缺陷相較於扭轉之奈米碳管線變少，石墨化程度較好。進一步地，請參見圖9，為所述奈米碳管線與扭轉之奈米碳管線沿延伸方向所得到之測力曲線對比圖。從圖中可看出，經過熱處理後，所述奈米碳管線之拉伸強度較所述扭轉之奈米碳管線提高約20%，楊氏模量提高約50%。這係由於所述扭轉之奈米碳管線中相鄰之奈米碳管之間之距離大多在0.2奈米在9奈米之間，而碳碳鍵如Sp2，Sp3鍵之鍵長大致在1.4埃左右。故，在熱處理時，相鄰之奈米碳管之間容易在晶格重組時形成碳碳鍵，尤其係相鄰之奈米碳管之間之距離小於1奈米時產生碳碳鍵之概率更大。可以理解，由於相鄰之奈米碳管之間通過碳碳鍵結合形成之結合力將大於相鄰之奈米碳管之間通過凡得瓦力結合形成之結合力，故，所述奈米碳管線之機械性能優於所述扭轉之奈米碳管線之機械性能。 Please refer to FIG. 7 , which is a nano carbon pipeline obtained after heat treatment. Comparing FIG. 6 and FIG. 7 , it is found that the carbon nanotube structure and the carbon nanotube prefabricated structure are not closely different in appearance by scanning electron micrograph. Referring to FIG. 8, the Raman spectra of the twisted nanocarbon pipeline of FIG. 6 and the nanocarbon pipeline of FIG. 7 are respectively obtained and compared to form a Raman spectrum comparison diagram. It can be seen from the figure that after the heat treatment, the G peak phase of the nano carbon pipeline is significantly stronger than the twisted nanocarbon pipeline, and the D peak phase is significantly weaker than the non-twisted nanocarbon pipeline. It is proved that after heat treatment, the defects of the carbon nanotubes in the nanocarbon pipeline are less than that of the twisted nanocarbon pipeline, and the degree of graphitization is better. Further, please refer to FIG. 9 , which is a comparison diagram of the force curve obtained by extending the nano carbon pipeline and the twisted nano carbon pipeline along the extending direction. As can be seen from the figure, after the heat treatment, the tensile strength of the nanocarbon pipeline is increased by about 20% compared with the twisted nanocarbon pipeline, and the Young's modulus is increased by about 50%. This is because the distance between adjacent carbon nanotubes in the twisted nanocarbon pipeline is mostly between 0.2 nm and 9 nm, and the bond length of carbon-carbon bonds such as Sp 2 and Sp 3 is approximately At around 1.4 angstroms. Therefore, during heat treatment, carbon nanotube bonds are easily formed between adjacent carbon nanotubes during lattice recombination, especially the probability of carbon-carbon bonds occurring when the distance between adjacent carbon nanotubes is less than 1 nm. Bigger. It can be understood that since the bonding force formed by the carbon-carbon bond between adjacent carbon nanotubes will be greater than the bonding force formed by the combination of van der Waals force between the adjacent carbon nanotubes, the nanometer is The mechanical properties of the carbon line are superior to the mechanical properties of the twisted nanocarbon line.
綜上所述，本發明確已符合發明專利之要件，遂依法提出專利申請。惟，以上所述者僅為本發明之較佳實施例，自不能以此限制本案之申請專利範圍。舉凡習知本案技藝之人士援依本發明之精神所作之等效修飾或變化，皆應涵蓋於以下申請專利範圍內。 In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims.
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