TWI501916B - Method for making carbon nanotube composite material - Google Patents
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本發明涉及一種複合材料之製備方法，尤其涉及一種奈米碳管複合材料之製備方法。 The invention relates to a preparation method of a composite material, in particular to a preparation method of a carbon nanotube composite material.
自九十年代初以來，以奈米碳管為代表之奈米材料以其獨特之結構和性質引起了人們極大之關注。近幾年來，隨著奈米碳管及奈米材料研究之不斷深入，其廣闊之應用前景不斷顯現出來。例如，由於奈米碳管所具有之獨特之電磁學、光學、力學、化學等性能，大量有關其於場發射電子源、感測器、新型光學材料、軟鐵磁材料等領域之應用研究不斷被報導。 Since the early 1990s, nanomaterials represented by carbon nanotubes have attracted great attention due to their unique structure and properties. In recent years, with the deepening of research on carbon nanotubes and nanomaterials, its broad application prospects have been continuously revealed. For example, due to the unique electromagnetic, optical, mechanical, and chemical properties of carbon nanotubes, a large number of applications for field emission electron sources, sensors, new optical materials, soft ferromagnetic materials, etc. Was reported.
特別地，奈米碳管與其他材料例如金屬、半導體或者聚合物等之複合可以實現材料之優勢互補或加強。奈米碳管具有較大之長徑比和中空之結構，具有優異之力學性能、電學性能、光學性能等，其於複合材料中，可以對複合材料起到增強作用，使得複合材料具有較好之化學和機械性能。奈米碳管複合材料之研究已經成為一個極為重要之領域。 In particular, the combination of carbon nanotubes with other materials such as metals, semiconductors or polymers can complement or enhance the advantages of the materials. The carbon nanotubes have a large aspect ratio and a hollow structure, and have excellent mechanical properties, electrical properties, optical properties, etc., and in the composite material, the composite material can be enhanced to make the composite material better. Chemical and mechanical properties. Research on carbon nanotube composites has become an extremely important area.
奈米碳管複合材料之製備方法通常有原位聚合法、溶液共混法和熔體共混法。上述三種製備方法係藉由將複數個奈米碳管分散到溶液或熔融物中來製備奈米碳管複合材料的，由於奈米碳管具有 極大之比表面積，導致其於溶液或熔融物中易團聚，使得製備之奈米碳管複合材料中之奈米碳管分散不均勻，影響該奈米碳管複合材料之性能的充分發揮。 The preparation method of the carbon nanotube composite material generally includes an in-situ polymerization method, a solution blending method, and a melt blending method. The above three preparation methods are prepared by dispersing a plurality of carbon nanotubes into a solution or a melt, since the carbon nanotubes have The extremely large specific surface area causes easy agglomeration in the solution or the melt, so that the carbon nanotubes in the prepared carbon nanotube composite material are unevenly dispersed, which affects the full performance of the carbon nanotube composite material.
另外，劉志敏等人發明的、於2007年4月25日公告的、公告號為CN1312032C，標題為“一種製備金屬或金屬氧化物/奈米碳管複合材料之方法”的中國專利中揭示了一種製備金屬或金屬氧化物/奈米碳管複合材料之方法。該方法主要包括以下步驟：“每毫升離子液體中加入1-20毫克之金屬化合物，再按每毫升離子液體加入1-10毫克之比例將奈米碳管分散在離子液體中形成分散體系，80-120W微波加熱1-5分鐘，得到金屬或金屬氧化物/奈米碳管複合材料；其中金屬化合物為易發生熱化學反應之金屬化合物；離子液體為能溶解金屬化合物和穩定分散奈米碳管的、陽離子為四甲基胍之離子液體。”該製備方法雖然於一定程度可以改善奈米碳管分散不均勻之現象，但由於其仍然採用分散之奈米碳管作為原料形成懸浮液，因此在發生熱化學反應之過程中，其中之奈米碳管仍然會存在團聚之現象；另外，由於該製備方法中之離子液體還具有穩定分散奈米碳管之作用，因此所述之離子液體需要特定之介質。 In addition, Liu Zhimin et al., published on April 25, 2007, the publication number CN1312032C, entitled "A Method for Preparing Metal or Metal Oxide/Nano Carbon Tube Composites" discloses a Chinese patent. A method of preparing a metal or metal oxide/nanocarbon nanotube composite. The method mainly comprises the following steps: "add 1-20 mg of metal compound per ml of ionic liquid, and then disperse the carbon nanotubes in the ionic liquid to form a dispersion system by adding 1-10 mg per ml of ionic liquid to form a dispersion system, 80 -120W microwave heating for 1-5 minutes to obtain a metal or metal oxide/nanocarbon tube composite; wherein the metal compound is a metal compound susceptible to thermochemical reaction; the ionic liquid is a soluble metal compound and a stable dispersed carbon nanotube The cation is a tetramethyl hydrazine ionic liquid." Although the preparation method can improve the dispersion of the carbon nanotubes to a certain extent, since it still uses a dispersed carbon nanotube as a raw material to form a suspension, In the process of thermochemical reaction, the carbon nanotubes still have agglomeration; in addition, since the ionic liquid in the preparation method also has the function of stably dispersing the carbon nanotubes, the ionic liquid needs Specific media.
有鑒於此，確有必要提供一種可以避免奈米碳管團聚之奈米碳管複合材料之製備方法。 In view of this, it is indeed necessary to provide a method for preparing a carbon nanotube composite material which can avoid agglomeration of carbon nanotubes.
一種奈米碳管複合材料之製備方法，其包括以下步驟：提供一奈米碳管結構，該奈米碳管結構包括複數個奈米碳管；提供一反應溶液，該反應溶液溶解有至少一種金屬化合物，並採用該反應溶 液浸潤所述奈米碳管結構；以及於真空、氮氣或惰性氣體之氣氛中，熱處理經所述反應溶液浸潤後之奈米碳管結構，使該反應溶液中之金屬化合物發生分解反應，於所述奈米碳管結構中之奈米碳管之表面及相鄰的奈米碳管之間生成奈米金屬氧化物顆粒，所述奈米碳管結構中之奈米碳管藉由該金屬氧化物顆粒緊密作用在一起。 A method for preparing a carbon nanotube composite material, comprising the steps of: providing a carbon nanotube structure, the carbon nanotube structure comprising a plurality of carbon nanotubes; providing a reaction solution, the reaction solution is dissolved in at least one Metal compound and dissolved by the reaction The liquid infiltrates the carbon nanotube structure; and heat-treats the carbon nanotube structure infiltrated by the reaction solution in an atmosphere of vacuum, nitrogen or an inert gas to decompose the metal compound in the reaction solution, a nano metal oxide particle is formed between a surface of the carbon nanotube in the carbon nanotube structure and an adjacent carbon nanotube, and the carbon nanotube in the carbon nanotube structure is made of the metal The oxide particles act closely together.
與先前技術相比較，本發明提供之奈米碳管複合材料之製備方法採用奈米碳管結構而非分散之奈米碳管，該製備方法無需經過奈米碳管之分散，避免了在製備奈米碳管複合材料過程中奈米碳管難以分散之問題，方法簡單。 Compared with the prior art, the preparation method of the carbon nanotube composite material provided by the invention adopts a carbon nanotube structure instead of a dispersed carbon nanotube, and the preparation method does not need to be dispersed by a carbon nanotube, thereby avoiding preparation in the nano carbon tube. The problem that the carbon nanotubes are difficult to disperse during the carbon nanotube composite process is simple.
100‧‧‧奈米碳管鉑金屬複合膜 100‧‧‧Nano carbon tube platinum metal composite film
110；210；310‧‧‧奈米碳管結構 110;210;310‧‧‧Nano carbon nanotube structure
112；212；312‧‧‧奈米碳管 112;212;312‧‧・nano carbon tube
120‧‧‧鉑奈米顆粒 120‧‧‧Platinum nanoparticles
200‧‧‧奈米碳管四氧化物三鈷複合膜 200‧‧‧Nano Carbon Tube Tetraoxide Cobalt Composite Film
220‧‧‧四氧化三鈷奈米顆粒 220‧‧‧Three Cobalt Oxide Nanoparticles
300‧‧‧奈米碳管二氧化三鐵複合線狀結構 300‧‧‧Nano Carbon Tube Diiron Oxide Composite Wire Structure
320‧‧‧二氧化三鐵奈米顆粒 320‧‧‧ ferrous oxide nanoparticles
圖1為本發明中作為奈米碳管結構之奈米碳管拉膜之掃描電鏡照片。 Fig. 1 is a scanning electron micrograph of a carbon nanotube film as a carbon nanotube structure in the present invention.
圖2為本發明第一實施例提供之奈米碳管鉑金屬複合膜之透射電子顯微鏡照片。 2 is a transmission electron micrograph of a platinum-metal composite film of a carbon nanotube provided by a first embodiment of the present invention.
圖3為本發明第一實施例提供之奈米碳管鉑金屬複合膜之結構示意圖。 3 is a schematic structural view of a platinum metal composite film of a carbon nanotube according to a first embodiment of the present invention.
圖4為本發明第二實施例提供之奈米碳管四氧化三鈷複合膜之透射電子顯微鏡照片。 4 is a transmission electron micrograph of a carbon nanotube galvanic oxide composite film according to a second embodiment of the present invention.
圖5為本發明第二實施例提供之奈米碳管四氧化三鈷複合膜之結構示意圖。 FIG. 5 is a schematic structural view of a carbon nanotube galvanic oxide composite film according to a second embodiment of the present invention.
圖6為本發明第三實施例提供之奈米碳管二氧化三鐵複合線狀結構之低倍掃描電鏡照片。 FIG. 6 is a low-power scanning electron micrograph of a composite structure of a carbon nanotubes of iron oxide according to a third embodiment of the present invention.
圖7為本發明第三實施例提供之奈米碳管二氧化三鐵複合線狀結構之高倍掃描電鏡照片。 FIG. 7 is a high-power scanning electron micrograph of a composite structure of a carbon nanotube-deposited iron oxide according to a third embodiment of the present invention.
圖8為本發明第三實施例提供之奈米碳管二氧化三鐵複合線狀結構之結構示意圖。 FIG. 8 is a schematic structural view of a composite structure of a carbon nanotubes and a ferric oxide composite according to a third embodiment of the present invention.
下面將結合附圖及具體實施例對本發明奈米碳管複合材料之製備方法作進一步之詳細說明。 The preparation method of the carbon nanotube composite material of the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
本發明提供一種奈米碳管複合材料之製備方法。該奈米碳管複合材料之製備方法包括以下步驟：(S11)提供一奈米碳管結構，該奈米碳管結構包括複數個奈米碳管；(S12)提供一反應溶液，該反應溶液溶解有至少一種金屬化合物，並採用該反應溶液浸潤所述奈米碳管結構；(S13)於一無氧氣氛中，熱處理經所述反應溶液浸潤後之奈米碳管結構，使該反應溶液中之金屬化合物發生分解反應。 The invention provides a preparation method of a carbon nanotube composite material. The preparation method of the carbon nanotube composite material comprises the following steps: (S11) providing a carbon nanotube structure, the carbon nanotube structure comprises a plurality of carbon nanotube tubes; (S12) providing a reaction solution, the reaction solution Dissolving at least one metal compound, and infiltrating the carbon nanotube structure with the reaction solution; (S13) heat-treating the carbon nanotube structure infiltrated by the reaction solution in an oxygen-free atmosphere to make the reaction solution The metal compound in the decomposition reaction occurs.
步驟(S11)中，所述奈米碳管結構包括複數個藉由凡德瓦爾力相互連接之奈米碳管，且具有自支撐結構。其中，該複數個奈米碳管均勻分佈於所述奈米碳管結構中。所謂“自支撐結構”即該奈米碳管結構無需藉由一支撐體支撐，也能保持自身特定之形狀。所述奈米碳管結構包括至少一奈米碳管膜，至少一奈米碳管線狀結構或其組合。當所述奈米碳管結構包括複數個奈米碳管膜時，該奈米碳管膜可以共面設置或層疊設置。當所述奈米碳管結構僅包括一奈米碳管線狀結構時，該奈米碳管線狀結構可以折疊或纏繞成一層狀奈米碳管結構。當所述奈米碳管結構包括複數個奈米碳管線狀結構時，該複數個奈米碳管線狀結構可以平行設置、 交叉設置或編織成一層狀奈米碳管結構。當所述奈米碳管結構包括奈米碳管膜及奈米碳管線狀結構時，可以將奈米碳管線狀結構設置於奈米碳管膜之至少一表面。由於該奈米碳管結構中之奈米碳管具有很好之柔韌性，使得該奈米碳管結構具有很好之柔韌性，可以彎曲折疊成任意形狀而不易破裂。 In the step (S11), the carbon nanotube structure comprises a plurality of carbon nanotubes connected to each other by a van der Waals force, and has a self-supporting structure. Wherein, the plurality of carbon nanotubes are evenly distributed in the carbon nanotube structure. The so-called "self-supporting structure" means that the carbon nanotube structure does not need to be supported by a support body, and can maintain its own specific shape. The carbon nanotube structure comprises at least one carbon nanotube membrane, at least one nanocarbon pipeline structure or a combination thereof. When the carbon nanotube structure includes a plurality of carbon nanotube films, the carbon nanotube films may be disposed in a coplanar manner or in a stacked manner. When the carbon nanotube structure includes only one nanocarbon line-like structure, the nanocarbon line structure can be folded or wound into a layered carbon nanotube structure. When the carbon nanotube structure comprises a plurality of nanocarbon pipeline-like structures, the plurality of nanocarbon pipeline structures may be arranged in parallel, Cross-set or weave into a layer of carbon nanotube structure. When the carbon nanotube structure comprises a carbon nanotube film and a nanocarbon line-like structure, a nanocarbon line-like structure may be disposed on at least one surface of the carbon nanotube film. Since the carbon nanotube in the carbon nanotube structure has good flexibility, the carbon nanotube structure has good flexibility and can be bent and folded into any shape without being easily broken.
所述奈米碳管膜包括均勻分佈之複數個奈米碳管，該複數個奈米碳管之間藉由凡德瓦爾力緊密結合。該奈米碳管膜中之奈米碳管為無序或有序排列。所謂無序係指奈米碳管之排列方向無規則。所謂有序係指奈米碳管之排列方向有規則。具體地，當奈米碳管結構包括無序排列之奈米碳管時，奈米碳管相互纏繞或者各向同性排列；當奈米碳管結構包括有序排列之奈米碳管時，奈米碳管沿一個方向或者複數個方向擇優取向排列。所謂“擇優取向”係指奈米碳管結構中的奈米碳管於一個或幾個方向上具有較大的取向幾率；即，該奈米碳管結構中的奈米碳管之軸向基本沿同一方向或幾個方向延伸。所述奈米碳管膜包括奈米碳管拉膜、奈米碳管碾壓膜或奈米碳管絮化膜。 The carbon nanotube film comprises a plurality of carbon nanotubes uniformly distributed, and the plurality of carbon nanotubes are tightly coupled by a van der Waals force. The carbon nanotubes in the carbon nanotube film are disordered or ordered. The so-called disorder means that the arrangement direction of the carbon nanotubes is irregular. The so-called ordering means that the arrangement direction of the carbon nanotubes is regular. Specifically, when the carbon nanotube structure includes a disordered arrangement of carbon nanotubes, the carbon nanotubes are entangled or isotropically aligned; when the carbon nanotube structure includes an ordered arrangement of carbon nanotubes, The carbon nanotubes are arranged in a preferred orientation in one direction or in a plurality of directions. The term "preferable orientation" means that the carbon nanotubes in the carbon nanotube structure have a large orientation probability in one or several directions; that is, the axial direction of the carbon nanotubes in the carbon nanotube structure is basically Extend in the same direction or in several directions. The carbon nanotube film comprises a carbon nanotube film, a carbon nanotube film or a carbon nanotube film.
該奈米碳管結構中之奈米碳管包括單壁奈米碳管、雙壁奈米碳管及多壁奈米碳管中之一種或多種。所述單壁奈米碳管之直徑為0.5奈米~50奈米，雙壁奈米碳管之直徑為1.0奈米~50奈米，多壁奈米碳管之直徑為1.5奈米~50奈米。所述奈米碳管之長度大於50微米。優選地，該奈米碳管之長度優選為200微米~900微米。 The carbon nanotubes in the carbon nanotube structure include one or more of a single-walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube. The single-walled carbon nanotube has a diameter of 0.5 nm to 50 nm, the double-walled carbon nanotube has a diameter of 1.0 nm to 50 nm, and the multi-walled carbon nanotube has a diameter of 1.5 nm to 50 nm. Nano. The length of the carbon nanotubes is greater than 50 microns. Preferably, the length of the carbon nanotubes is preferably from 200 micrometers to 900 micrometers.
請參閱圖1，所述奈米碳管拉膜包括複數個奈米碳管，該複數個奈米碳管基本沿同一方向擇優取向排列，且基本平行於該奈米碳管拉膜之表面。具體地，所述奈米碳管拉膜包括複數個藉由凡德 瓦爾力首尾相連且基本沿同一方向擇優取向排列之奈米碳管；該複數個奈米碳管之軸向基本沿同一方向延伸。所述奈米碳管拉膜可藉由從奈米碳管陣列直接拉取獲得。可以理解，藉由將複數個奈米碳管拉膜平行且無間隙共面鋪設或/和層疊鋪設，可以製備不同面積與厚度之奈米碳管結構。當奈米碳管結構包括複數個層疊設置之奈米碳管拉膜時，相鄰之奈米碳管拉膜中之奈米碳管之排列方向形成一夾角α，0°≦α≦90°。奈米碳管拉膜中之相鄰的奈米碳管之間具有一定間隙，從而於奈米碳管結構中形成複數個微孔，微孔之孔徑約小於10微米。所述奈米碳管拉膜之結構及其製備方法請參見范守善等人於2008年8月16日公開的第200833862號中華民國公開專利申請公佈本。 Referring to FIG. 1, the carbon nanotube film comprises a plurality of carbon nanotubes, and the plurality of carbon nanotubes are arranged substantially in the same direction and substantially parallel to the surface of the carbon nanotube film. Specifically, the carbon nanotube film comprises a plurality of by virtue The carbon nanotubes are connected end to end and are arranged in a preferred orientation along the same direction; the axial directions of the plurality of carbon nanotubes extend substantially in the same direction. The carbon nanotube film can be obtained by directly drawing from a carbon nanotube array. It can be understood that the carbon nanotube structures of different areas and thicknesses can be prepared by laminating a plurality of carbon nanotube films in parallel and without gaps, or/and laminating. When the carbon nanotube structure comprises a plurality of stacked carbon nanotube film, the arrangement direction of the carbon nanotubes in the adjacent carbon nanotube film forms an angle α, 0°≦α≦90° . There is a certain gap between adjacent carbon nanotubes in the carbon nanotube film, so that a plurality of micropores are formed in the carbon nanotube structure, and the pore diameter of the micropores is less than about 10 micrometers. For the structure of the carbon nanotube film and the preparation method thereof, please refer to the publication of the Chinese Patent Publication No. 200833862, published on August 16, 2008 by Fan Shoushan et al.
所述奈米碳管碾壓膜包括均勻分佈之複數個奈米碳管。所述複數個奈米碳管無序，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，並藉由凡德瓦爾力相互吸引，緊密結合。所述奈米碳管碾壓膜中之相鄰的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個微孔，微孔之孔徑約小於10微米。所述奈米碳管碾壓膜可藉由碾壓一奈米碳管陣列獲得。該奈米碳管陣列形成於一基底表面，所製備之奈米碳管碾壓膜中的奈米碳管與該奈米碳管陣列之基底的表面成一夾角β，其中，β大於等於0度且小於等於15度(0°≦β≦15°)。優選地，所述奈米碳管碾壓膜中之奈米碳管平行於所述奈米碳管碾壓膜之表面。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。由於奈米碳管碾壓膜中之奈米碳管之間藉由凡德瓦爾力相互吸引，緊密結合，使奈米碳管碾壓膜為一自支撐之結構，可無需基底支撐，自支撐存在。所謂自支撐結 構即所述奈米碳管碾壓膜中之複數個奈米碳管間藉由凡德瓦爾力相互吸引，從而使奈米碳管碾壓膜具有特定之形狀。所述奈米碳管碾壓膜及其製備方法請參見范守善等人於2009年1月1日公開的第200900348號中華民國專利申請公佈本。 The carbon nanotube rolled film comprises a plurality of carbon nanotubes uniformly distributed. The plurality of carbon nanotubes are disordered and arranged in the same direction or in different directions. The carbon nanotubes in the carbon nanotube rolled film partially overlap each other and are attracted to each other by the van der Waals force, and are tightly bonded. The carbon nanotubes in the carbon nanotubes have a certain gap between adjacent carbon nanotubes, thereby forming a plurality of micropores in the carbon nanotube rolled film, and the pore diameter of the micropores is less than about 10 micrometers. The carbon nanotube rolled film can be obtained by rolling an array of carbon nanotubes. The carbon nanotube array is formed on a surface of the substrate, and the carbon nanotubes in the prepared carbon nanotube rolled film form an angle β with the surface of the substrate of the carbon nanotube array, wherein β is greater than or equal to 0 degrees. And less than or equal to 15 degrees (0 ° ≦ β ≦ 15 °). Preferably, the carbon nanotubes in the carbon nanotube rolled film are parallel to the surface of the carbon nanotube rolled film. The carbon nanotubes in the carbon nanotube rolled film have different arrangements depending on the manner of rolling. Since the carbon nanotubes in the carbon nanotube film are attracted to each other by the van der Waals force, the carbon nanotube film is a self-supporting structure, which can be self-supported without substrate support. presence. Self-supporting knot The carbon nanotubes in the carbon nanotube film are attracted to each other by van der Waals force, so that the carbon nanotube film has a specific shape. The carbon nanotube rolled film and the preparation method thereof can be found in the publication of the Republic of China patent application No. 200900348 published by Fan Shoushan et al. on January 1, 2009.
所述奈米碳管絮化膜包括相互纏繞之奈米碳管，該奈米碳管長度可大於10釐米。所述奈米碳管之間藉由凡德瓦爾力相互吸引、纏繞，形成網路狀結構。所述奈米碳管絮化膜各向同性。所述奈米碳管絮化膜中之奈米碳管為均勻分佈，無規則排列，形成大量之微孔結構，微孔孔徑為1奈米~10微米。可以理解，所述奈米碳管絮化膜之長度、寬度和厚度不限，可根據實際需要選擇。所述奈米碳管絮化膜及其製備方法請參見於2008年11月16日公開的第200844041號中華民國專利申請公佈本。 The carbon nanotube flocculation membrane comprises intertwined carbon nanotubes, the carbon nanotubes having a length greater than 10 cm. The carbon nanotubes are attracted to each other and entangled by van der Waals forces to form a network structure. The carbon nanotube flocculation membrane is isotropic. The carbon nanotubes in the carbon nanotube flocculation membrane are uniformly distributed and randomly arranged to form a large number of microporous structures, and the pore diameter of the micropores is from 1 nm to 10 μm. It can be understood that the length, width and thickness of the carbon nanotube film are not limited and can be selected according to actual needs. The carbon nanotube flocculation membrane and the preparation method thereof are described in the publication of the Chinese Patent Application No. 200844041 published on November 16, 2008.
所述奈米碳管線狀結構包括至少一個奈米碳管線，該奈米碳管線可為一非扭轉之奈米碳管線或扭轉之奈米碳管線。所述奈米碳管線狀結構包括複數個奈米碳管線時，該奈米碳管線狀結構可以為由複數個奈米碳管線平行設置組成之一束狀結構或由複數個奈米碳管線相互扭轉組成之一絞線結構。另外，所述奈米碳管線中相鄰奈米碳管間存在間隙，故該奈米碳管線具有大量微孔，且微孔之孔徑小於10微米。 The nanocarbon line-like structure includes at least one nanocarbon line, which may be a non-twisted nano carbon line or a twisted nano carbon line. When the nanocarbon pipeline-like structure comprises a plurality of nano carbon pipelines, the nanocarbon pipeline-like structure may be a bundle structure formed by a plurality of nano carbon pipelines arranged in parallel or by a plurality of nano carbon pipelines. Twist the composition of one of the stranded structures. In addition, there is a gap between adjacent carbon nanotubes in the nanocarbon pipeline, so the nanocarbon pipeline has a large number of micropores, and the pore diameter of the micropores is less than 10 micrometers.
所述非扭轉之奈米碳管線可包括複數個奈米碳管，該複數個奈米碳管之軸向沿平行於該非扭轉之奈米碳管線軸向的方向延伸。非扭轉之奈米碳管線可藉由將奈米碳管拉膜藉由有機溶劑處理得到。具體地，該奈米碳管拉膜包括複數個奈米碳管片段，該複數個奈米碳管片段藉由凡德瓦爾力首尾相連，每一奈米碳管片段包括 複數個相互平行並藉由凡德瓦爾力緊密結合之奈米碳管。該奈米碳管片段具有任意之長度、厚度、均勻性及形狀。該非扭轉之奈米碳管線長度不限，直徑為0.5奈米-1毫米。具體地，可將有機溶劑浸潤所述奈米碳管拉膜之整個表面，在揮發性有機溶劑揮發時產生之表面張力的作用下，奈米碳管拉膜中之相互平行的複數個奈米碳管藉由凡德瓦爾力緊密結合，從而使奈米碳管拉膜收縮為一非扭轉之奈米碳管線。該有機溶劑為揮發性有機溶劑，如乙醇、甲醇、丙酮、二氯乙烷或氯仿，本實施例中採用乙醇。藉由有機溶劑處理之非扭轉奈米碳管線與未經有機溶劑處理之奈米碳管膜相比，比表面積減小，粘性降低。 The non-twisted nanocarbon pipeline may include a plurality of carbon nanotubes, the axial direction of which extends in a direction parallel to the axial direction of the non-twisted nanocarbon pipeline. The non-twisted nanocarbon line can be obtained by treating the carbon nanotube film with an organic solvent. Specifically, the carbon nanotube film comprises a plurality of carbon nanotube segments, and the plurality of carbon nanotube segments are connected end to end by Van der Waals force, and each carbon nanotube segment comprises A plurality of carbon nanotubes that are parallel to each other and are tightly coupled by Van der Valli. The carbon nanotube segments have any length, thickness, uniformity, and shape. The non-twisted nano carbon line is not limited in length and has a diameter of 0.5 nm to 1 mm. Specifically, the organic solvent may be impregnated into the entire surface of the carbon nanotube film, and the plurality of nanoparticles parallel to each other in the carbon nanotube film may be pulled under the surface tension generated by the volatilization of the volatile organic solvent. The carbon tube is tightly bonded by the van der Waals force, thereby shrinking the carbon nanotube film into a non-twisted nano carbon line. The organic solvent is a volatile organic solvent such as ethanol, methanol, acetone, dichloroethane or chloroform, and ethanol is used in this embodiment. The non-twisted nanocarbon line treated by the organic solvent has a smaller specific surface area and a lower viscosity than the carbon nanotube film which is not treated with the organic solvent.
所述扭轉之奈米碳管線包括複數個奈米碳管，該複數個奈米碳管之軸向繞該扭轉之奈米碳管線軸向螺旋延伸。該奈米碳管線可採用一機械力將所述奈米碳管拉膜兩端沿相反方向扭轉獲得。進一步地，可採用一揮發性有機溶劑處理該扭轉之奈米碳管線。在揮發性有機溶劑揮發時產生之表面張力的作用下，處理後之扭轉之奈米碳管線中相鄰的奈米碳管藉由凡德瓦爾力緊密結合，使扭轉之奈米碳管線的比表面積減小，密度及強度增大。 The twisted nanocarbon pipeline includes a plurality of carbon nanotubes, and an axial direction of the plurality of carbon nanotubes extends axially around the twisted nanocarbon pipeline. The nanocarbon pipeline can be obtained by twisting both ends of the carbon nanotube film in the opposite direction by a mechanical force. Further, the twisted nanocarbon line can be treated with a volatile organic solvent. Under the action of the surface tension generated by the volatilization of the volatile organic solvent, the adjacent carbon nanotubes in the twisted nanocarbon pipeline after treatment are closely combined by the van der Waals force to make the ratio of the twisted nanocarbon pipeline The surface area is reduced, and the density and strength are increased.
所述奈米碳管線及其製備方法請參見2008年11月21日公告的，公告號為I303239的中華民國專利公告本；以及於2009年7月21日公告的，公告號為I312337的中華民國專利公告本。 For the nano carbon pipeline and its preparation method, please refer to the Republic of China Patent Announcement No. I303239 announced on November 21, 2008; and the Republic of China, announced on July 21, 2009, with the announcement number I312337 Patent Announcement.
所述步驟S12具體包括以下步驟：(S121)：提供一反應溶液，該反應溶液溶解有至少一種金屬化合物；以及(S122)採用所述反應溶液浸潤所述奈米碳管結構，使該反應溶液滲透到所述奈米碳管結構中。 The step S12 specifically includes the following steps: (S121): providing a reaction solution in which at least one metal compound is dissolved; and (S122) infiltrating the carbon nanotube structure with the reaction solution to make the reaction solution Infiltrated into the carbon nanotube structure.
所述步驟(S121)中之反應溶液係藉由將所述至少一金屬化合物溶解到一介質溶劑中而形成的。所述金屬化合物包括有機金屬鹽、無機金屬鹽或金屬配合物。所述有機金屬鹽含有一有機物基團，該有機物基團與奈米碳管有較好之親和力，可以使得該有機金屬鹽較好地與奈米碳管結合。所述無機金屬鹽包括硝酸錳、硝酸鐵、硝酸鈷、硝酸鎳、硝酸銅、硝酸鋅、醋酸銅、醋酸鎳、醋酸鈷、醋酸鋅、硝酸銀、氯化鉑、氯化銠、二氯化錫、四氯化錫、水溶性三氯化釕或氯化鈀。所述金屬配合物主要包括鉑、金、銠、釕或鈀等金屬之配合物，如氯鉑酸(H2PtCl6‧H2O)、氯金酸(AuCl3‧HCl‧4H2O)等。 The reaction solution in the step (S121) is formed by dissolving the at least one metal compound into a medium solvent. The metal compound includes an organic metal salt, an inorganic metal salt or a metal complex. The organometallic salt contains an organic group which has a good affinity with the carbon nanotubes, so that the organometallic salt can be better combined with the carbon nanotubes. The inorganic metal salt includes manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, copper acetate, nickel acetate, cobalt acetate, zinc acetate, silver nitrate, platinum chloride, barium chloride, tin dichloride. , tin tetrachloride, water-soluble antimony trichloride or palladium chloride. The metal complex mainly comprises a complex of a metal such as platinum, gold, rhodium, ruthenium or palladium, such as chloroplatinic acid (H 2 PtCl 6 ‧H 2 O), chloroauric acid (AuCl 3 ‧HCl‧4H 2 O) Wait.
所述介質溶劑為水及有機溶劑中之一種或幾種。其中，由於有機溶劑與奈米碳管之親和力較大，其可以促使所述反應溶液滲透到所述奈米碳管結構中。此外，所述有機溶劑還可以減少奈米碳管結構之比表面積，使得奈米碳管結構中之奈米碳管排列更緊密。另外，由於本發明提供之奈米碳管結構中之奈米碳管藉由凡德瓦爾力緊密作用在一起形成一特定形狀，而不係分散之奈米碳管，所以該製備方法不需要特定之有機溶劑，只要該有機溶劑能夠較好地促使所述金屬化合物與奈米碳管結合即可。所述有機溶劑包括甲醇、乙醇、丙醇、乙二醇、丙三醇、丙酮及四氫呋喃中之一種或其任意組合。 The medium solvent is one or more of water and an organic solvent. Among them, since the organic solvent has a large affinity with the carbon nanotube, it can promote the penetration of the reaction solution into the carbon nanotube structure. In addition, the organic solvent can also reduce the specific surface area of the carbon nanotube structure, so that the carbon nanotubes in the carbon nanotube structure are arranged more closely. In addition, since the carbon nanotubes in the carbon nanotube structure provided by the present invention form a specific shape by the van der Waals force, and do not form a dispersed carbon nanotube, the preparation method does not need to be specific. The organic solvent is as long as the organic solvent can better promote the bonding of the metal compound to the carbon nanotube. The organic solvent includes one of methanol, ethanol, propanol, ethylene glycol, glycerin, acetone, and tetrahydrofuran, or any combination thereof.
步驟(S122)之實現方法包括將所述奈米碳管結構置於所述反應溶液中浸泡一段時間，或將所述反應溶液滴於所述奈米碳管結構之表面。 The method of implementing the step (S122) comprises: immersing the carbon nanotube structure in the reaction solution for a period of time, or dropping the reaction solution onto the surface of the carbon nanotube structure.
由於所述奈米碳管結構中具有微孔，該微孔具有毛細作用；於毛 細作用下，所述反應溶液藉由所述微孔滲透到該奈米碳管結構中，使得該奈米碳管結構中之相鄰的奈米碳管之間也滲透有所述反應溶液。由於所述反應溶液具有流動性，即使奈米碳管結構中之微孔比較小，也可以滲透到奈米碳管結構中；而採用蒸鍍、濺鍍等方法則較難使所述待製備之物質滲透到奈米碳管結構中較小的微孔中。故，在該步驟中，所述反應溶液會滲透到所述奈米碳管結構中之微孔中。 Due to the micropores in the carbon nanotube structure, the micropores have capillary action; Under the fine action, the reaction solution penetrates into the carbon nanotube structure by the micropores, so that the reaction solution is also infiltrated between adjacent carbon nanotubes in the carbon nanotube structure. Since the reaction solution has fluidity, even if the micropores in the carbon nanotube structure are relatively small, it can penetrate into the carbon nanotube structure; and it is difficult to prepare the sample to be prepared by evaporation, sputtering or the like. The substance penetrates into the smaller pores of the carbon nanotube structure. Therefore, in this step, the reaction solution permeates into the micropores in the carbon nanotube structure.
將所述奈米碳管結構浸泡於所述反應溶液中一段時間後，再從所述反應溶液中取出；或將所述反應溶液滴於所述奈米碳管結構之表面，可以使得滲透於該奈米碳管結構中之反應溶液充分暴露於周圍氣氛中，促進反應溶液中之介質溶液的揮發，所述介質溶液之揮發有利於縮短該滲透有反應溶液之奈米碳管結構的後續處理時間。另外，取出奈米碳管結構後，剩餘之反應溶液可以重複利用，可以多次浸泡所述奈米碳管結構；從而可以提高所述反應溶液之利用率，進而降低製備所述奈米碳管複合材料之成本。 Soaking the carbon nanotube structure in the reaction solution for a period of time, and then taking it out from the reaction solution; or dripping the reaction solution on the surface of the carbon nanotube structure to make it penetrate The reaction solution in the carbon nanotube structure is sufficiently exposed to the surrounding atmosphere to promote the volatilization of the medium solution in the reaction solution, and the volatilization of the medium solution is beneficial to shorten the subsequent treatment of the carbon nanotube structure infiltrated with the reaction solution. time. In addition, after the carbon nanotube structure is taken out, the remaining reaction solution can be reused, and the carbon nanotube structure can be immersed multiple times; thereby, the utilization rate of the reaction solution can be improved, thereby reducing the preparation of the carbon nanotube. The cost of composite materials.
另外，由於所述奈米碳管結構具有自支撐之特性，而非分散之奈米碳管，所以，所述奈米碳管結構於所述反應溶液之加入量可以不受奈米碳管分散問題之限制；進而可以提高所述奈米碳管複合材料之產率。 In addition, since the carbon nanotube structure has a self-supporting property instead of a dispersed carbon nanotube, the amount of the carbon nanotube structure added to the reaction solution may not be dispersed by the carbon nanotube. The problem is limited; in turn, the yield of the carbon nanotube composite can be increased.
所述步驟(S13)於無氧氣氛下，熱處理經所述反應溶液浸潤後之奈米碳管結構，使該反應溶液中之金屬化合物發生分解反應。由於所述奈米碳管結構具有自支撐結構，其於該熱處理過程中可以維持其自身之特定形狀。 The step (S13) heat-treats the carbon nanotube structure infiltrated by the reaction solution in an oxygen-free atmosphere to cause a decomposition reaction of the metal compound in the reaction solution. Since the carbon nanotube structure has a self-supporting structure, it can maintain its own specific shape during the heat treatment.
所述無氧氣氛可以減少或防止奈米碳管結構中之奈米碳管的氧化 ，該無氧氣氛包括真空、氮氣、惰性氣體或還原性氣體之氣氛。所述還原性氣體為氫氣、一氧化碳或硫化氫氣體。熱處理之溫度根據金屬鹽之不同而不同。熱處理之溫度一般係所述反應溶液中之金屬化合物發生分解的溫度。該熱處理之溫度一般小於或等於450℃。所述熱處理之方法包括高溫爐直接加熱、電流加熱或雷射照射加熱等方法。 The oxygen-free atmosphere can reduce or prevent oxidation of the carbon nanotubes in the carbon nanotube structure The oxygen-free atmosphere includes an atmosphere of vacuum, nitrogen, an inert gas or a reducing gas. The reducing gas is hydrogen, carbon monoxide or hydrogen sulfide gas. The temperature of the heat treatment varies depending on the metal salt. The temperature of the heat treatment is generally the temperature at which the metal compound in the reaction solution is decomposed. The temperature of the heat treatment is generally less than or equal to 450 °C. The heat treatment method includes direct heating of a high temperature furnace, current heating, or laser irradiation heating.
根據所採用之金屬化合物、無氧氣體及所發生之反應之不同，所得到之奈米碳管複合材料也不同。具體地，當所述金屬化合物為硝酸錳、硝酸鐵、硝酸鈷、硝酸鎳、硝酸銅、硝酸鋅時，於真空、氮氣或惰性氣體之氣氛下，加熱處理經過含有上述金屬化合物之反應溶液處理後之奈米碳管結構，上述金屬化合物發生分解反應，其沿著所述奈米碳管結構中之奈米碳管之表面被分解成奈米金屬氧化物，故得到奈米碳管金屬氧化物複合材料。當上述金屬鹽於還原性氣體之作用下，先發生分解反應得到金屬氧化物，然後金屬氧化物再被還原性氣體還原成金屬單質，該金屬單質形成於所述奈米碳管結構中之奈米碳管之表面，得到奈米碳管金屬複合材料。當所述金屬化合物為醋酸銅、醋酸鎳、醋酸鈷、醋酸鋅、硝酸銀、氯化鉑、氯化銠、二氯化錫、四氯化錫、水溶性三氯化釕、氯化鈀、氯鉑酸或氯金酸時，於真空、氮氣、惰性氣體或還原性氣體中，加熱處理經過含有上述金屬化合物之反應溶液浸潤過之奈米碳管結構，上述金屬化合物發生分解反應直接沿所述奈米碳管結構中之奈米碳管之表面生成奈米金屬單質，從而得到奈米碳管金屬複合材料。 The resulting carbon nanotube composites vary depending on the metal compound employed, the oxygen-free gas, and the reaction that occurs. Specifically, when the metal compound is manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, the heat treatment is carried out in a vacuum, nitrogen or an inert gas atmosphere through a reaction solution containing the above metal compound. In the latter carbon nanotube structure, the above metal compound undergoes a decomposition reaction, which is decomposed into nano metal oxide along the surface of the carbon nanotube in the carbon nanotube structure, thereby obtaining metal oxidation of the carbon nanotube Composite material. When the metal salt is decomposed by a reducing gas, a metal oxide is first obtained, and then the metal oxide is reduced by a reducing gas to a metal element, and the metal element is formed in the nano carbon tube structure. On the surface of the carbon tube, a carbon nanotube metal composite is obtained. When the metal compound is copper acetate, nickel acetate, cobalt acetate, zinc acetate, silver nitrate, platinum chloride, barium chloride, tin dichloride, tin tetrachloride, water-soluble antimony trichloride, palladium chloride, chlorine In the case of platinum or chloroauric acid, the carbon nanotube structure infiltrated by the reaction solution containing the above metal compound is heated in a vacuum, nitrogen, inert gas or reducing gas, and the metal compound is decomposed directly along the The surface of the carbon nanotubes in the carbon nanotube structure forms a nano-metal element, thereby obtaining a carbon nanotube metal composite.
當奈米碳管結構為奈米碳管膜時，採用上述方法可以直接製備得 到奈米碳管複合膜。對該奈米碳管複合膜進行扭轉或雷射切割處理可以得到奈米碳管複合線狀結構。 When the carbon nanotube structure is a carbon nanotube film, it can be directly prepared by the above method. To the carbon nanotube composite membrane. The carbon nanotube composite wire structure can be obtained by twisting or laser cutting the carbon nanotube composite film.
本發明製備之奈米碳管複合材料包括至少一奈米碳管結構，該至少一奈米碳管結構包括複數個奈米碳管，每個奈米碳管之表面分佈有金屬奈米顆粒或金屬氧化物顆粒，相鄰的奈米碳管之間也分佈有所述金屬奈米顆粒或金屬氧化物顆粒，並藉由該金屬奈米顆粒或金屬氧化物顆粒緊密作用在一起。當所使用之金屬化合物之濃度較高時，由上述方法製備之奈米碳管複合材料中之金屬奈米顆粒或金屬氧化物顆粒形成一金屬層，包覆於每一個奈米碳管之表面。當所使用之金屬化合物之濃度較低時，由上述方法製備之奈米碳管複合材料中的金屬奈米顆粒或金屬氧化物顆粒間隔分佈於每一個奈米碳管之表面。由於金屬、金屬氧化物及奈米碳管均具有較大之楊氏模量及拉伸強度，故，所述奈米碳管複合材料具有良好之拉伸強度及楊氏模量，其相較於所述自支撐之奈米碳管結構也具有較好之拉伸強度及楊氏模量。另外，由於金屬還具有良好之導電性，因此奈米碳管金屬複合材料還具有較好之導電性。 The carbon nanotube composite material prepared by the invention comprises at least one carbon nanotube structure, the at least one carbon nanotube structure comprises a plurality of carbon nanotubes, and the surface of each carbon nanotube is distributed with metal nanoparticles or The metal oxide particles are also distributed between the adjacent carbon nanotubes, and the metal nanoparticles or metal oxide particles are closely acted upon by the metal nanoparticles or metal oxide particles. When the concentration of the metal compound used is high, the metal nanoparticles or metal oxide particles in the carbon nanotube composite prepared by the above method form a metal layer coated on the surface of each of the carbon nanotubes. . When the concentration of the metal compound used is low, the metal nanoparticles or metal oxide particles in the carbon nanotube composite prepared by the above method are distributed on the surface of each of the carbon nanotubes. Since the metal, the metal oxide and the carbon nanotube have a large Young's modulus and tensile strength, the carbon nanotube composite has good tensile strength and Young's modulus, which is compared with The self-supporting carbon nanotube structure also has good tensile strength and Young's modulus. In addition, since the metal also has good electrical conductivity, the carbon nanotube metal composite material also has good electrical conductivity.
可以理解，在製備所述奈米碳管複合材料之過程中，當所述反應溶液中包括兩種或兩種以上之金屬鹽或配合物時，由本發明提供之製備方法製備之奈米碳管複材料中包括兩種或兩種以上之奈米顆粒，該奈米顆粒在奈米碳管複合材料中之分佈形式與上述奈米碳管金屬複合材料中之金屬奈米顆粒的分佈形式相同；該奈米顆粒包括金屬奈米顆粒、金屬氧化物顆粒或兩者之組合。 It can be understood that in the process of preparing the carbon nanotube composite material, when two or more metal salts or complexes are included in the reaction solution, the carbon nanotubes prepared by the preparation method provided by the invention are understood. The composite material comprises two or more kinds of nano particles, and the distribution form of the nano particles in the carbon nanotube composite material is the same as that of the metal nano particles in the above-mentioned carbon nanotube metal composite material; The nanoparticles include metal nanoparticles, metal oxide particles, or a combination of the two.
以下為本發明採用上述方法製備奈米碳管複合材料之具體實施例 ： The following is a specific embodiment of the invention for preparing a carbon nanotube composite material by the above method. :
實施例1 Example 1
請參閱圖2至圖3，本發明第一實施例提供一種奈米碳管鉑金屬複合膜100之製備方法，具體包括以下步驟： Referring to FIG. 2 to FIG. 3, a first embodiment of the present invention provides a method for preparing a carbon nanotube platinum metal composite film 100, which specifically includes the following steps:
(S101)提供一奈米碳管結構110，該奈米碳管結構110包括6層層疊設置之奈米碳管拉膜，其中，相鄰兩層奈米碳管拉膜中之擇優取向排列的奈米碳管之間形成的交叉角度為90°。所述奈米碳管結構110設置於一金屬環上。 (S101) providing a carbon nanotube structure 110, the carbon nanotube structure 110 comprising 6 layers of laminated carbon nanotube film, wherein the adjacent two layers of carbon nanotube film are arranged in a preferred orientation The angle of intersection formed between the carbon nanotubes is 90°. The carbon nanotube structure 110 is disposed on a metal ring.
(S102)採用一氯鉑酸溶液浸潤所述奈米碳管結構110，使該氯鉑酸溶液分散到所述奈米碳管結構110中。具體地，將一定氯鉑酸(H2PtCl6‧H2O)溶於甲醇中，得到質量百分數為2%的氯鉑酸溶液；然後將該質量百分數為2%的氯鉑酸溶液滴到所述奈米碳管結構110之表面。 (S102) The carbon nanotube structure 110 is impregnated with a solution of chloroplatinic acid, and the chloroplatinic acid solution is dispersed in the carbon nanotube structure 110. Specifically, a certain amount of chloroplatinic acid (H 2 PtCl 6 ‧H 2 O) is dissolved in methanol to obtain a chloroplatinic acid solution having a mass percentage of 2%; and then the chloroplatinic acid solution having a mass percentage of 2% is dropped The surface of the carbon nanotube structure 110.
(S103)於氮氣之作用下，將所述經過氯鉑酸溶液處理後之奈米碳管結構110置於加熱爐中，高溫加熱至300℃，使該氯鉑酸發生氧化還原反應，生成鉑奈米顆粒120，即制得奈米碳管鉑金屬複合膜100。所述鉑奈米顆粒120連成一片分佈於所述奈米碳管結構110中之每個奈米碳管112之表面，相鄰之奈米碳管112之間分佈有所述鉑金屬奈米顆粒120，並藉由該鉑金屬奈米顆粒120緊密作用在一起。由於鉑金屬具有良好之導電性能，故該奈米碳管鉑金屬複合膜100具有良好之導電性能。 (S103) The carbon nanotube structure 110 treated with the chloroplatinic acid solution is placed in a heating furnace under the action of nitrogen gas, and heated to 300 ° C at a high temperature to cause oxidation-reduction reaction of the chloroplatinic acid to form platinum. The nanoparticle 120, that is, the nanocarbon tube platinum metal composite film 100 is produced. The platinum nanoparticles 120 are connected to each other on the surface of each of the carbon nanotubes 112 in the carbon nanotube structure 110, and the platinum metal nanoparticles are distributed between the adjacent carbon nanotubes 112. The particles 120 are tightly bound together by the platinum metal nanoparticles 120. Since the platinum metal has good electrical conductivity, the carbon nanotube platinum metal composite film 100 has good electrical conductivity.
可以理解，本實施例中之奈米碳管鉑金屬複合膜100經過雷射切割或扭轉處理之後，形成奈米碳管鉑金屬複合線狀結構。 It can be understood that the carbon nanotube platinum metal composite film 100 in this embodiment is subjected to laser cutting or torsion treatment to form a platinum carbon metal composite linear structure.
實施例2 Example 2
請參閱圖4至圖5，本發明第二實施例提供一種奈米碳管四氧化物三鈷複合膜200之製備方法。所述奈米碳管四氧化物三鈷複合膜200之製備方法與本發明第一實施例中奈米碳管鉑複合膜100之製備方法基本相同，其區別在於，本實施例中，採用之金屬化合物為硝酸鈷。 Referring to FIG. 4 to FIG. 5, a second embodiment of the present invention provides a method for preparing a carbon nanotube tetraoxide tri-cobalt composite film 200. The preparation method of the carbon nanotube tetraoxide tri-cobalt composite film 200 is basically the same as the preparation method of the carbon nanotube platinum composite film 100 in the first embodiment of the present invention, and the difference is that, in the embodiment, the method is adopted. The metal compound is cobalt nitrate.
本實施例具體包括以下步驟： This embodiment specifically includes the following steps:
(S201)提供一奈米碳管結構210，該奈米碳管結構210包括20層層疊設置之奈米碳管拉膜，其中，相鄰兩層奈米碳管拉膜中之擇優取向排列的奈米碳管之間形成的交叉角度為90°。所述奈米碳管結構210設置於一金屬環上。 (S201) providing a carbon nanotube structure 210, the carbon nanotube structure 210 comprising 20 layers of laminated carbon nanotubes, wherein the adjacent two layers of carbon nanotubes are arranged in a preferred orientation The angle of intersection formed between the carbon nanotubes is 90°. The carbon nanotube structure 210 is disposed on a metal ring.
(S202)採用一硝酸鈷溶液浸潤所述奈米碳管結構210，使該硝酸鈷溶液分散到所述奈米碳管結構210中。具體地，將一定之六水合硝酸鈷(Co(NO3)2‧6H2O)溶於甲醇溶劑中，得到質量百分數為20%的硝酸鈷溶液；然後將該質量百分數為20%的硝酸鈷溶液滴到所述奈米碳管結構210之表面。 (S202) The carbon nanotube structure 210 is impregnated with a cobalt nitrate solution to disperse the cobalt nitrate solution into the carbon nanotube structure 210. Specifically, a certain amount of cobalt nitrate hexahydrate (Co(NO 3 ) 2 ‧6H 2 O) is dissolved in a methanol solvent to obtain a cobalt nitrate solution having a mass percentage of 20%; and then the mass percentage is 20% of cobalt nitrate. The solution is dropped onto the surface of the carbon nanotube structure 210.
(S203)於氫氣之作用下，將所述經過硝酸鈷溶液浸潤後之奈米碳管結構210置於加熱爐中，高溫加熱至300℃，使硝酸鈷發生分解反應，生成四氧化三鈷奈米顆粒220，即制得奈米碳管四氧化三鈷複合膜200。所述奈米碳管結構210中的每個奈米碳管212之表面分佈有所述四氧化三鈷奈米顆粒220，相鄰之奈米碳管212之間也分佈有所述四氧化三鈷奈米顆粒220，並藉由該四氧化三鈷奈米顆粒220緊密作用在一起。 (S203) under the action of hydrogen, the carbon nanotube structure 210 after being infiltrated by the cobalt nitrate solution is placed in a heating furnace, and heated at a high temperature to 300 ° C to cause decomposition reaction of cobalt nitrate to form a cobalt tetraoxide nanoparticle 220. That is, a carbon nanotube galvanic oxide composite film 200 is obtained. The surface of each of the carbon nanotubes 212 in the carbon nanotube structure 210 is distributed with the cobalt tetraoxide nanoparticles 220, and the cobalt tetraoxide nanoparticles 220 are also distributed between the adjacent carbon nanotubes 212. And the three cobalt oxide nano particles 220 act closely together.
可以理解，本實施例中之奈米碳管四氧化三鈷複合膜200經過雷射切割或扭轉處理之後，形成奈米碳管四氧化三鈷複合線狀結構。 It can be understood that the carbon nanotube galvanic oxide composite film 200 in the present embodiment is subjected to laser cutting or torsion treatment to form a nano-carbon nanotube tricobalt oxide composite linear structure.
實施例3 Example 3
請參閱圖6至圖8，本發明第三實施例提供一種奈米碳管二氧化三鐵複合線狀結構300。該奈米碳管二氧化三鐵複合線狀結構300具體包括以下步驟： Referring to FIG. 6 to FIG. 8 , a third embodiment of the present invention provides a carbon nanotube triiron oxide composite linear structure 300 . The carbon nanotube diiron oxide composite linear structure 300 specifically includes the following steps:
(S301)提供一奈米碳管結構310，該奈米碳管結構310為一奈米碳管線狀結構。該奈米碳管線狀結構為一扭轉之奈米碳管線。 (S301) A carbon nanotube structure 310 is provided, the carbon nanotube structure 310 being a nanocarbon line structure. The nanocarbon line-like structure is a twisted nanocarbon line.
(S302)採用一硝酸鐵溶液處理所述奈米碳管結構310，使該硝酸鐵溶液分散到所述奈米碳管結構310中。具體地，將一定之硝酸鐵溶於甲醇溶劑中，得到質量百分數為20%之硝酸鐵溶液；其次將所述奈米碳管結構310置於所述質量百分數為20%之硝酸鐵溶液中浸泡大約20分鐘，使得硝酸鐵溶液儘量均勻之分散到所述奈米碳管結構310中；然後從所述硝酸鐵溶液中取出經過該硝酸鐵溶液浸泡過之奈米碳管結構。 (S302) treating the carbon nanotube structure 310 with a ferric nitrate solution to disperse the ferric nitrate solution into the carbon nanotube structure 310. Specifically, a certain amount of ferric nitrate is dissolved in a methanol solvent to obtain a ferric nitrate solution having a mass percentage of 20%; secondly, the carbon nanotube structure 310 is placed in the ferric nitrate solution having a mass percentage of 20%. The ferric nitrate solution was dispersed as uniformly as possible into the carbon nanotube structure 310 for about 20 minutes; then the carbon nanotube structure soaked through the ferric nitrate solution was taken out from the ferric nitrate solution.
(S303)於氬氣之作用下，將所述經過硝酸鐵溶液浸潤後之奈米碳管結構310置於加熱爐中，高溫加熱至300℃，使硝酸鐵發生分解反應，生成二氧化三鐵奈米顆粒320，即制得奈米碳管二氧化三鐵複合線狀結構300。所述二氧化三鐵奈米顆粒320形成一層狀，包覆於所述奈米碳管結構310中之每個奈米碳管312之表面，相鄰之奈米碳管312之間也分佈有所述二氧化三鐵奈米顆粒320，並藉由該二氧化三鐵奈米顆粒320緊密作用在一起。 (S303) The carbon nanotube structure 310 infiltrated by the ferric nitrate solution is placed in a heating furnace under the action of argon gas, and heated at a high temperature to 300 ° C to decompose the ferric nitrate to form triiron tetroxide. The nanoparticle 320, that is, the carbon nanotube diiron oxide composite linear structure 300 is obtained. The galvanic dioxide particles 320 are formed in a layer and coated on the surface of each of the carbon nanotubes 312 in the carbon nanotube structure 310, and are also distributed between the adjacent carbon nanotubes 312. There are said triiron tetroxide particles 320 and are closely acted upon by the ferric oxide particles 320.
本發明實施例提供的奈米碳管複合材料之製備方法具有以下優點：其一，該製備方法所採用之奈米碳管結構具有自支撐之特點，其中的奈米碳管緊密作用在一起形成一特定形狀，無需將奈米碳管分散到基體溶液中，避免了於製備奈米碳管複合材料中之奈米碳管的團聚，方法簡單。其二，該製備方法採用之奈米碳管結構具有自支撐的特點，其不需要特殊的介質溶解所述金屬化合物，採用常見的介質即可，因此，該方法成本較低。其三，由於該奈米碳管複合材料之製備方法採用具有自支撐特性的奈米碳管結構，其於製備該奈米碳管複合材料的過程中，可以維持其自身之特定形狀，所以該方法製備之奈米碳管複合材料也具有自支撐的特點，可以廣泛應用於各種領域。其四，由於所述奈米碳管結構具有自支撐之特性，而非分散之奈米碳管，所以，所述奈米碳管結構於所述反應溶液之加入量可以不受奈米碳管分散問題之限制；進而可以提高所述所述奈米碳管複合材料之產率。其五，由該方法製備之奈米碳管複合材料包括奈米碳管結構及奈米顆粒，由於奈米碳管及奈米顆粒具有良好之拉伸強度及楊氏模量，故該奈米碳管複合材料具有良好之拉伸強度及楊氏模量，其相較於所述自支撐之奈米碳管結構也具有較好之拉伸強度及楊氏模量。其六，當所述奈米顆粒為金屬奈米顆粒時，由於金屬具有良好之導電性，因此包括奈米碳管結構及金屬奈米顆粒之奈米碳管複合材料比純之奈米碳管結構具有更好之導電性能。 The preparation method of the carbon nanotube composite material provided by the embodiment of the invention has the following advantages: First, the carbon nanotube structure used in the preparation method has the characteristics of self-supporting, wherein the carbon nanotubes are closely combined to form In a specific shape, it is not necessary to disperse the carbon nanotubes into the matrix solution, and the agglomeration of the carbon nanotubes in the preparation of the carbon nanotube composite material is avoided, and the method is simple. Secondly, the carbon nanotube structure adopting the preparation method has the characteristics of self-supporting, and does not require a special medium to dissolve the metal compound, and a common medium can be used. Therefore, the method has low cost. Thirdly, since the preparation method of the carbon nanotube composite material adopts a carbon nanotube structure with self-supporting property, it can maintain its own specific shape in the process of preparing the carbon nanotube composite material, so The carbon nanotube composite prepared by the method is also self-supporting and can be widely used in various fields. Fourth, since the carbon nanotube structure has self-supporting properties instead of dispersed carbon nanotubes, the carbon nanotube structure can be added to the reaction solution without being affected by the carbon nanotubes. The limitation of the dispersion problem; in turn, the yield of the carbon nanotube composite material can be increased. Fifth, the carbon nanotube composite material prepared by the method comprises a carbon nanotube structure and a nano particle, and the nano carbon tube and the nano particle have a good tensile strength and a Young's modulus, so the nanometer The carbon tube composite has good tensile strength and Young's modulus, and has better tensile strength and Young's modulus than the self-supporting carbon nanotube structure. Sixth, when the nanoparticle is a metal nanoparticle, since the metal has good electrical conductivity, the carbon nanotube composite material including the carbon nanotube structure and the metal nanoparticle is more pure than the pure carbon nanotube The structure has better electrical conductivity.
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.
300‧‧‧奈米碳管二氧化三鐵複合線狀結構 300‧‧‧Nano Carbon Tube Diiron Oxide Composite Wire Structure
310‧‧‧奈米碳管結構 310‧‧‧Nano Carbon Tube Structure
312‧‧‧奈米碳管 312‧‧‧Nano Carbon Tube
320‧‧‧二氧化三鐵奈米顆粒 320‧‧‧ ferrous oxide nanoparticles
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| WO2009031349A1 (en) * | 2007-09-07 | 2009-03-12 | Nec Corporation | Semiconductor device using carbon nanotube film and process for producing the semiconductor device |
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| CN101499328A (en) * | 2008-02-01 | 2009-08-05 | 清华大学 | Stranded wire |
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| WO2009031349A1 (en) * | 2007-09-07 | 2009-03-12 | Nec Corporation | Semiconductor device using carbon nanotube film and process for producing the semiconductor device |
| CN101456277A (en) * | 2007-12-14 | 2009-06-17 | 清华大学 | Method for preparing carbon nanotube composite material |
| CN101499328A (en) * | 2008-02-01 | 2009-08-05 | 清华大学 | Stranded wire |
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