200934725 九、發明說明： 【發明所屬之技術領域】 本發明涉及一種奈米碳管複合材料及其製備方法，尤其 ' 涉及一種奈米碳管高分子複合材料及其製備方法。 【先前技術】 自1991年日本NEC公司的Iijima發現奈米碳管（Carbon Nanotube，CNT )以來（Iijima S.Helical Microtubules of Graphitic Carbon. Nature，1991，354:56-58)，奈米碳管引起了 〇 科學界及產業界的極大重視，成為近年來國際科學研究的熱 點。奈米碳管具有與金剛石相同的熱導和獨特的力學性能， 如抗張強度高達100千兆帕，模量高達1800千兆帕，且耐 強酸、強鹼，600°C以下基本不氧化等。 由於奈米碳管具有如此優異的性能，利用奈米碳管作為 填充物與其他材料複合已成為奈米碳管應用的一個重要方 向。特別地，奈米碳管與其他材料如金屬、半導體或者高分 ©子等的複合可以實現材料的優勢互補或加強。奈米碳管具有 較大的長徑比和中空的結構，具有優異的力學性能，可作為 一種超級纖維，對複合材料起到增強作用。此外，奈米碳管 具有優異的導熱性能，可使該複合材料具有良好的熱傳導 性。 先前技術多以粒子填充高分子的形式來製備奈米碳管 複合材料，由於奈米碳管容易團聚，需先對奈米碳管進行表 面改性和功能化處理，而後採用溶液或溶融的方法與高分子 複合。先前技術中一種製備奈米碳管複合材料的方法包括以 200934725 下步驟將0.3重量份的多壁奈米碳管投入到ι〇重量 •份的濃硝1中’於1G(TC下㈣回流2M、時，賴館水洗去 ，酸液，於赃下真空乾燥1G小時。（二）將上述產物敌酸化 ^米碳管加入到10重量份草酿氣中，於9(rc下擾掉1〇小 柃，条除未反應的草醯氯’從而得到酿氣化的奈米碳管。（三 e醯氣化的奈米碳管放入冰浴中’於慢速攪拌下滴加10-重 置份的乾燥乙二胺，於100t下抽真空乾燥10小時。（ 〇將^述ϋ胺化的奈米碳管加人到2G重量份的乙醇溶劑中， 超聲波處理15分鐘，加人2重量份環氧樹脂，高 =分鐘，蒸除溶劑，加熱至贼，按照環氧樹脂的環氧 基團與固化劑中胺基氫原子物質的摩爾比為ι:ι的比例加 苯：胺，並即將其分散均句。(五）把複 入柄具中，升溫至_固化2小時，然後於携。〇下固化兩 個小時，得到環氧樹脂固化複合材料。 。管隨===:得::奈二管複合材料中，奈米碳 整的外層結構，且奈米上：中:奈米破管具有不完 Ϊ此，^奈米碳管複合㈣衫製財法存在町缺點。 太乎L機械共混的方法混合奈米碳管與高分子，很難將 材料中奈米碳管混合：：:第中:=的奈米破管複合 行表面修飾㈣於奈米碳管/Γ八，=方3對奈米碳管進 構，二;=飾:嚴重的破壞奈米破管的完整結 丁為μ合材料的性能。第三，採用授拌 200934725 的方法分散奈米碳管，奈米碳管的排列雜亂無章，且沒有固 定取向，使得奈米碳管於複合物中不能發揮其軸向優勢，從 而影響了奈米碳管複合材料的性能。第四，該方法需要添加 溶劑，而所添加的溶劑很難除去，從而使得奈米碳管複合材 料成分不純。第五，該方法工藝複雜，成本較高。200934725 IX. Description of the Invention: [Technical Field] The present invention relates to a carbon nanotube composite material and a preparation method thereof, and particularly relates to a nano carbon tube polymer composite material and a preparation method thereof. [Prior Art] Since the discovery of Carbon Nanotube (CNT) by Iijima of NEC Corporation in Japan in 1991 (Iijima S. Helical Microtubules of Graphitic Carbon. Nature, 1991, 354: 56-58), carbon nanotubes have been caused. The great attention of the scientific and industrial circles has become a hot spot in international scientific research in recent years. The carbon nanotubes have the same thermal conductivity and unique mechanical properties as diamond, such as tensile strength up to 100 gigapascals, modulus up to 1800 gigapascals, resistance to strong acids and alkalis, and basic non-oxidation below 600 °C. . Due to the excellent performance of carbon nanotubes, the use of carbon nanotubes as fillers in combination with other materials has become an important direction for carbon nanotube applications. In particular, the combination of carbon nanotubes with other materials such as metals, semiconductors, or high-grade neutrons 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, and can be used as a super fiber to enhance the composite material. In addition, the carbon nanotubes have excellent thermal conductivity, which allows the composite to have good thermal conductivity. In the prior art, the carbon nanotube composite material is prepared in the form of a particle-filled polymer. Since the carbon nanotube is easily agglomerated, the surface modification and functionalization of the carbon nanotube must be performed first, followed by solution or melting. Composite with polymer. A method for preparing a carbon nanotube composite material in the prior art comprises the steps of: 200934725, placing 0.3 parts by weight of a multi-walled carbon nanotube into a concentration of 1 part of concentrated nitric acid 1 at 1G (under TC (four) reflux 2M) At the same time, the Laiguan water is washed away, and the acid solution is dried under vacuum for 1G in the underarms. (2) Add the above-mentioned product to the acidified ^ m carbon tube to 10 parts by weight of the grass brewing gas, and disturb 1 rc under 9 (rc) Small cockroaches, in addition to unreacted grass 醯 chlorine, to obtain a gasified carbon nanotubes. (Three e 醯 gasified carbon nanotubes are placed in an ice bath.) Add 10-weight under slow stirring. The portion of the dried ethylenediamine was dried under vacuum at 100 t for 10 hours. (The hydrazine-treated carbon nanotubes were added to 2 g parts by weight of ethanol solvent, sonicated for 15 minutes, adding 2 weights. Epoxy resin, high = minute, evaporate the solvent, heat to the thief, add benzene:amine according to the molar ratio of the epoxy group of the epoxy resin to the amine hydrogen atom in the curing agent is ι:ι, and It will be dispersed in the sentence. (5) Re-into the handle, heat up to _ curing for 2 hours, then carry it. Obtained epoxy resin cured composite material. Tube with ===: Get:: Naibi tube composite material, the outer structure of nano carbon, and the upper: middle: nano tube is not complete, ^Nano carbon tube composite (four) shirt method of the existence of the shortcomings of the town. Too mechanical blending method of carbon nanotubes and polymer, it is difficult to mix the carbon nanotubes in the material::: the middle: = Nano-tube composite surface modification (four) in the carbon nanotubes / Γ eight, = square 3 pairs of carbon nanotubes, two; = decoration: severe damage to the inner tube of the broken tube is μ composite material Thirdly, the carbon nanotubes were dispersed by the method of mixing 200934725. The arrangement of the carbon nanotubes was disordered and there was no fixed orientation, so that the carbon nanotubes could not exert their axial advantages in the composite, thus affecting the nai. The performance of the carbon nanotube composite. Fourth, the method requires the addition of a solvent, and the added solvent is difficult to remove, so that the composition of the carbon nanotube composite is impure. Fifth, the method is complicated in process and high in cost.
有鑒於此，提供一種具有優良特性的奈米碳管複合材料 及其製備方法實為必要，且該製備方法簡單、易於實現、成 本低廉。 【發明内容】 一種奈米碳管複合材料，包括奈米碳管和高分子基體， 其中該奈米碳管以奈米碳管薄膜結構的形式設置於高分子 基體中。 一種奈米碳管複合材料的製造方法，其包括以下步驟： 製備一高分子基體；製備一奈米碳管薄膜；將至少一個奈米 碳管薄膜設置於高分子基體的至少一個表面形成一奈米碳 〇管薄膜結構，從而形成一奈米碳管複合材料預製體；加熱奈 米碳管複合材料預製體，使奈米碳管薄膜結構與高分子基體 複合，從而得到一奈米碳管複合材料。 與先前技術相比，所述的奈米碳管複合材料及其製備方 法具有以下優點：第一，由於採用奈米碳管薄膜結構自然滲 入高分子材料當中，且奈米碳管薄膜結構中的奈米碳管的間 隙中充滿了高分子。因此，所述的奈米碳管複合材料中，奈 米碳管分佈規則、均勻，使得該複合材料具有優異的性能。 第二，所述的奈米碳管複合材料的製備方法無需對奈米碳管 200934725 進行表面處理，不僅保證了奈米碳管結構上的完整性，簡化 了製備過程，還降低了生產成本，並提高了所述複合材料的 性能。第三，所述的奈米碳管複合材料的製備方法採用將奈 * 米碳管薄膜結構設於高分子材料表面後，對其加壓、加熱、 真空處理，因此具有簡單、容易實現、生產成本低的優點。 【實施方式】 下面將結合附圖對本技術方案作進一步的詳細說明。 _ 請參考圖1，本技術方案實施例提供一種奈米碳管複合 材料10，其包括高分子基體14與分佈於該高分子基體14 中的奈米碳管，該奈米碳管以奈米碳管薄膜結構12的形式 分佈於該高分子基體14中。 所述高分子基體14為一高分子薄膜。高分子基體14材 料可選擇為熱固性高分子材料或熱塑性高分子材料。本實施 例中，熱固性高分子材料包括酚醛樹脂、環氧樹脂、雙馬來 醯亞胺樹脂、聚苯並惡嗪樹脂、氰酸酯樹脂、聚醯亞胺樹脂 〇和不飽和聚醯樹脂中的一種或者幾種的混合物。該熱塑性高 分子材料包括聚乙烯、聚氯乙烯、聚四氟乙烯、聚丙烯，聚 苯乙烯、聚曱基丙烯酸曱酯、聚對苯二曱酸乙二酯、聚碳酸 酯、聚對苯二甲酸丁二酯、聚醯胺、聚醚酮、聚砜、聚醚砜、 熱塑性聚醯亞胺、聚醚醯亞胺、聚苯醚、聚苯硫醚、聚乙酸 乙烯酯、聚對苯撐苯並雙惡唑中的一種或者幾種的混合物。 所述奈米碳管薄膜結構12由一個奈米碳管層或複數個 平行且重疊的奈米碳管層構成，該奈米碳管層由一個奈米碳 管薄膜或複數個平行且無間隙鋪設的奈米碳管薄膜構成。該 200934725 '不米反吕薄膜為擇優取向排列的複數個奈米碳管束首尾相 .=形成的具有一定寬度的薄膜，該奈米碳管薄膜中的奈米碳 .S束具有基本相同的排列方向。奈米碳管束之間通過凡德瓦 爾力緊密連接，該奈米碳管束長度基本相同，且包括複數個 具有基本相同的長度並相互平行的奈米碳管。該奈米碳管薄 膜的厚度為G.G1〜_微米，其中的奈米碳管為單壁奈米碳 ^雙壁不米碳官及多壁奈米碳管中的—種或幾種。當該奈 管薄財的奈米碳管為單壁奈米碳管時，該單壁奈米碳 官的直杈為G.5〜5G奈米。當該奈米碳管薄膜中的奈米碳管 $雙壁奈米礙管時’該魅奈米破管的直徑為奈米。 Ϊ該中的奈米碳管為多壁奈米碳管時，該多壁 不米碳官的直㈣15〜5〇奈米。所述奈米碳管層的面積不 限’可根據實際需求製備。 當所述奈米碳管薄膜結構12由複數個重疊的奈米碳管 s構成時，複數個奈米碳管層之間通過凡德瓦爾力緊密連接 一具有穩定結構的奈米碳管薄膜結構12。由複數個奈米 石反官層組成的奈米碳管薄膜結構12中，相鄰的奈米碳管層 中的奈米碳管的排列方向形成一夾角α，且〇γα $ 90。。如 圖2所不，本實施例中提供的奈米碳管薄膜結構由四個 相互平行疊加的第一奈米碳管層122、第二奈米碳管層124、 f，奈米碳管層126、第四奈米碳管層128組成，該奈米碳 官薄膜結構12的厚度為〇.〇4~400微米，該奈米碳管薄膜結 構12中相鄰奈米碳管層中的奈米碳管的排列方形成的夾角 為 9〇〇 〇 200934725 奈米碳管複合材料10中，奈米碳管薄膜結構12均勻設 置於高分子基體14當中，高分子材料浸潤到奈米碳管薄膜 ' 結構12中相鄰的奈米碳管的間隙當中，高分子材料與奈米 ' 碳管薄膜結構12中的奈米碳管緊密結合在一起。 請參考圖3，本技術方案還提供一種上述奈米碳管複合 材料10的製備方法，其具體包括以下步驟： 步驟一：製備一高分子基體14，其為一高分子薄膜。 該高分子基體14可以採用溶液成膜、熱熔刮塗、流延成膜、 喷塗成膜的方法製備。 本實施例採用熱熔刮塗的方法製備高分子基體14,其具 體包括以下步驟：首先，將液態烯丙基苯酚置於一容器中， 加熱至90〜180°C，使容器維持該溫度並攪拌若干分鐘。其 次，將雙馬來醯亞胺粉末加入液態烯丙基苯酚中，雙馬來醯 亞胺與烯丙基苯酚的品質比於60:5〜60:70範圍内，控制容器 溫度於110〜160°C範圍内，靜置並使容器保持該溫度，抽真 ξ)空若干分鐘充分排空溶液中的氣體，得到一透明紅褐色混合 液體。再次，將上述雙馬來醯亞胺與稀丙基苯酚的混合液倒 入一凹槽中，待混合液降溫後得到一高分子基體14。所述高 分子基體14的厚度及形狀可以通過控制凹槽的深度與形狀 控制。 步驟二：製備一奈米碳管薄膜。 該奈米碳管薄膜的製備方法包括以下步驟： 首先，製備一奈米碳管陣列。 本實施例中，所述奈米碳管陣列為一超順排奈米碳管陣 11 200934725 列，該超順排奈米碳管陣列的製備方法採用化學氣相沈積 ,法’其具體步驟包括：（a)提供一平整基底，該基底可選用 .P型或N型；ε夕基底’或選用形成有氧化層的碎基底，本實施 例優選為採用4英寸的矽基底；（b)於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（c〇)、鎳（Ni) 或其任意組合的合金之一；（c)將上述形成有催化劑層的基 底於700〜900。(：的空氣中退火約3〇分鐘〜9〇分鐘；（d)將處 ❹理過的基底置於反應爐中，於保護氣體環境下加熱到 500〜740°C，然後通入碳源氣體反應約5〜3〇分鐘，生長得到 超順排奈米碳管陣列，其高度為2〇〇〜4〇〇微米。該超順排奈 $碳管陣列為複數個彼此平行且垂直於基底生長的奈米碳 管形成的純奈米碳管陣列。通過上述控制生長條件，該超順 排奈米碳管陣列中基本不含有雜質，如無定型碳或殘留的催 化劑金屬顆粒等。該奈米碳管陣列中的奈米碳管彼此通過凡 德瓦爾力緊密接觸形成陣列。 ❹ 本實施例中碳源氣可選用乙炔、乙烯、甲烷等化學性質 較活潑的碳氫化合物，本實施例優選的碳源氣為乙炔；保護 氣體為氮氣或惰性氣體，本實施例優選的保護氣體為氬氣。 可以理解，本實施例提供的奈米碳管陣列不限於上述製備方 法，還可以採用電弧放電法、雷射蒸發沈積法。本實施例提 供的奈米碳管陣列為單壁奈米碳管陣列、雙壁奈米碳管陣列 及多壁奈米碳管陣列中的一種。 其次，從上述奈米碳管陣列中拉取獲得至少一奈米碳管 薄膜。 μ 、 12 200934725 該奈米碳管薄膜的製備具體包括以下步驟：（a)從上述 奈：碳管陣列中選定一定寬度的複數個奈米碳管束片斷，‘ 實施，優選為採用具有寬度的膠帶接觸奈米碳管陣列 以選定一定寬度的複數個奈米碳管束片斷；（b)以一定速产 =基本垂直于奈米碳管陣列生長方向拉伸該複數個奈米ς 吕束片斷，以形成一連續的奈米碳管薄膜。 下 l上述拉伸過程中，該複數個奈米碳管束片斷於拉力作用 沿拉伸方向逐漸脫離基底的同時，由於凡德瓦爾力作用， 該選定的複數個奈米碳管束片斷分別與其他奈米碳管片斷 I尾相連地連續地被拉出，從而形成—奈米碳管薄膜。該太 米碳管薄膜為擇優取向排列的複數個奈米碳管束首尾相^ I成的具有定覓度的奈来碳管薄膜。該奈米碳管薄膜中的 奈^炭管束之間相互平行’奈米碳管束的排列方向基本平行 于不米碳管薄膜的拉伸方向。 本實施例中，該奈米碳管薄膜的寬度與奈米碳管陣列 底的尺寸有關，該奈米碳管薄膜的長度不限，可根 求制得。該奈米碳管薄膜的厚度為〇〇ι〜ι〇〇微米。 :二=管薄膜中的奈米碳管為單壁奈来碳管時，該單壁 =管，壁奈米碳管時，該雙壁奈米碳管的直】二 ;碳管薄膜中的奈米碳管為多壁奈㈣ u夕不米碳管的直徑為1.5〜50奈米。 的至矣將至少一奈米碳管薄膜設置於高分子基體μ 表面形成一奈米碳管薄膜結構12,從而形成—奈 13 200934725 米奴官複合材料預製體2〇。 可以理解，本實施例中，製備一奈米碳管複合材料預製 體20的方去可以為.將至少—層上述奈米碳管薄膜直接鋪 設於該咼分子基體14表面製備奈米碳管複合材料預製體 20。也可錢採用至少—層上述奈米碳管薄膜製備形成一自 支撐的奈米碳管薄膜結構12，再將該奈米碳管薄膜結構12 設置於所述高分子基冑14上形成-奈米碳管複合材料預製 ▲體 20。 所述將至少一層上述奈米碳管薄膜直接鋪設於該高分 子基體14表面製備奈米碳管複合材料預製體2〇的方法具體 包括以下步驟：提供一個高分子基體14;將至少一奈米碳管 薄膜直接鋪设於一高分子基體14表面，形成一奈米碳管薄 膜結構12，去除高分子基體14以外多餘的奈米碳管薄膜， 得到一奈米礙管複合材料預製體2〇。 可以理解’本實施例中，可以將至少兩個奈米碳管薄膜 ©平行且無間隙舖設或/和重疊鋪設於該高分子基體14表面， 形成一奈米碳管薄膜結構12。所述奈米碳管薄膜結構12包 括一奈米碳管層或至少兩個平行且重疊鋪設的奈米碳管 層’相鄰的兩個奈米碳管層中的奈米碳管排列方向形成一夾 角α ’且〇γα $ 9〇。。本實施例中’相鄰的兩個奈米碳管層 中的奈米碳管排列方向的夾角α優選為9〇度。 本實施例中，進一步可以將另一高分子基體14設置於 該奈米碳管薄膜結構12上，形成一三明治結構的奈米碳管 複合材料預製體。可以理解，本實施例中，還可以將複數個 14 200934725 = :結構尸與複數個高分子基體14交互疊加，形 ' 夕θ、不米妷官複合材料預製體。如圖4所示，優選地， .!Π複t材料預製體20為-個奈米碳管薄膜結㈣铺 5又於一個-分子基體14上的結構。 的太=採用至少—層奈米碳管薄‘臈製備形成-自支撐 二方構12，再製備奈采碳管複合材料預製體 乎石…座腔 下步驟:提供一支撐體;將至少-個奈 ❹撐體表面，去除支樓體外多餘的奈米碳 高分子美，二，姜體’形成一奈米碳管薄膜結構12;提供一 =美ί 14 _並將所述奈米碳管薄膜結構12設置於該高 iL二即得到一奈米碳管複合材料預製體20。 ^支#體可以為—基板，也可選用—框架 本實施例提供的超順排奈米碳管陣列中的奈米碳。管非常純 二本身的比表面積非常大，故，該奈米碳管薄 該奈米碳管薄膜可利用其本身的枯性直 上。奈米碳管薄膜黏附於基板或框架 士 士板或框架以外多餘的奈米碳管薄膜部分可以用小刀到 去。去除基㈣框架，即剌—奈米碳管_結構12。 定。該基板或框架的大小可依據實際需求確 :土板或框架的寬度大於上述奈米碳㈣膜的寬度時， 可以將至少兩個奈米碳管薄膜 於基板或框架上，形成-奈米碳管薄膜 結構12包括-奈米碳管層或至少兩個平行且重疊鋪 5 又的不米碳管層’相鄰的兩個奈米碳管層令的奈米碳管排列 15 200934725 方向形成一夹角α，且〜㈣。。 本實施例令，進一步请 管薄膜結構12的步驟嗜^匕括用有機溶劍處理奈米碳 選用乙醇1醇、丙酮、：氯乙=為揮發性有機溶劑，可 有機溶劑採用乙醇。該使用有：：：仿等’本實施例中的 !有機溶劑滴落於奈米碳管薄臈二管 石反官薄膜結構12，或者，也可將上 二0正個不米 ❹ 構12的基板或m定框架整個浸盛^ 嘗缚膜結 ==至基板表面後，將奈米碳管薄膜結構= =小，，從而可以將整個奈米碳管薄膜結構^ 土板或固疋框架表面取下。所述的奈米碳管薄料構 有機溶劑浸潤處理後，於揮發性有機溶劑的表面張力的作二 下，奈米碳管薄膜中平行的奈米碳管片斷會部分聚隼成 碳管束。因此’該奈米碳管薄膜結構12表面體積比小：： 具有良好的機械強度及韌性。 〇 上述方法製備的奈米碳管複合材料預製體20中，相鄰 兩個奈米碳官層中的奈米碳官之間存在複數個微孔結構，誃 微孔結構均勻且規則分佈于奈米碳管薄膜結構12中，其^ 微孔直徑為1奈米〜0.5微米。 ’、 步驟四：加熱奈米；e炭管複合材料預製體2〇，將奈米碳管 薄膜結構12與高分子基體14複合’從而得到一奈米碳管複 合材料10。 如圖5所示，該奈米碳管複合材料10的製備方法具體 包括以下步驟： 16 200934725 首先，將至少一奈米碳管複合材料預製體20放置於一 模具30中，閉合模具的上基板31與下基板33。該模具30 於放置奈米碳管複合材料預製體20之前已經均勻塗抹了脫 模劑，以便獲得奈米碳管複合材料10後可以順利脫模，該 模具30側壁設有流膠槽35，以便多餘的液態高分子流出。 所用脫模劑根據高分子的類別不同而不同，該脫模劑包括高 溫脫模劑、有機矽型脫模劑、蠟類脫模劑或者矽氧烷型脫模In view of the above, it is necessary to provide a carbon nanotube composite material having excellent characteristics and a preparation method thereof, and the preparation method is simple, easy to implement, and low in cost. SUMMARY OF THE INVENTION A carbon nanotube composite material includes a carbon nanotube and a polymer matrix, wherein the carbon nanotube is disposed in a polymer matrix in the form of a carbon nanotube film structure. A method for manufacturing a carbon nanotube composite material, comprising the steps of: preparing a polymer matrix; preparing a carbon nanotube film; and disposing at least one carbon nanotube film on at least one surface of the polymer matrix to form a nanocap. a carbon carbon nanotube film structure, thereby forming a carbon nanotube composite preform; heating the carbon nanotube composite preform to composite the nanocarbon film structure with the polymer matrix, thereby obtaining a carbon nanotube composite material. Compared with the prior art, the carbon nanotube composite material and the preparation method thereof have the following advantages: First, since the nano carbon tube film structure is naturally infiltrated into the polymer material, and the carbon nanotube film structure is The gap between the carbon nanotubes is filled with a polymer. Therefore, in the carbon nanotube composite material, the carbon nanotubes are regularly and uniformly distributed, so that the composite material has excellent properties. Secondly, the preparation method of the carbon nanotube composite material does not require surface treatment of the carbon nanotubes 200934725, which not only ensures the structural integrity of the carbon nanotubes, simplifies the preparation process, but also reduces the production cost. And improve the performance of the composite. Thirdly, the method for preparing the carbon nanotube composite material adopts the method that the carbon nanotube film structure is disposed on the surface of the polymer material, and is pressurized, heated, and vacuum processed, thereby being simple, easy to implement, and produced. The advantage of low cost. [Embodiment] Hereinafter, the technical solution will be further described in detail with reference to the accompanying drawings. Referring to FIG. 1 , an embodiment of the present technical solution provides a carbon nanotube composite material 10 , which comprises a polymer matrix 14 and a carbon nanotube distributed in the polymer matrix 14 , wherein the carbon nanotube is nanometer. The carbon nanotube film structure 12 is distributed in the polymer matrix 14. The polymer matrix 14 is a polymer film. The polymer matrix 14 material may be selected from a thermosetting polymer material or a thermoplastic polymer material. In this embodiment, the thermosetting polymer material includes a phenol resin, an epoxy resin, a bismaleimide resin, a polybenzoxazine resin, a cyanate resin, a polyimide resin, and an unsaturated polyfluorene resin. One or a mixture of several. The thermoplastic polymer material comprises polyethylene, polyvinyl chloride, polytetrafluoroethylene, polypropylene, polystyrene, polydecyl methacrylate, polyethylene terephthalate, polycarbonate, poly(p-phenylene terephthalate). Butylene formate, polydecylamine, polyether ketone, polysulfone, polyether sulfone, thermoplastic polyimide, polyether phthalimide, polyphenylene ether, polyphenylene sulfide, polyvinyl acetate, polyparaphenylene a mixture of one or more of benzobisoxazoles. The carbon nanotube film structure 12 is composed of a carbon nanotube layer or a plurality of parallel and overlapping carbon nanotube layers consisting of a carbon nanotube film or a plurality of parallel and no gaps. The carbon nanotube film is laid. The 200934725 'Nomi-Anti-Lu film is a plurality of carbon nanotube bundles arranged in a preferential orientation. The film has a certain width, and the carbon nanotubes in the carbon nanotube film have substantially the same arrangement. direction. The carbon nanotube bundles are closely connected by van der Waals force, and the nanotube bundles are substantially the same length and include a plurality of carbon nanotubes having substantially the same length and parallel to each other. The thickness of the carbon nanotube film is G.G1~_micron, and the carbon nanotubes are one or several of single-walled nanocarbons, double-walled carbon-free and multi-walled carbon nanotubes. When the carbon nanotube of the tube is a single-walled carbon nanotube, the straight wall of the single-walled nanocarbon is G.5~5G nanometer. When the carbon nanotube in the carbon nanotube film is obstructed by the double-walled nano tube, the diameter of the charm tube is nanometer. When the carbon nanotubes are multi-walled carbon nanotubes, the multi-walled carbon-free officer has a straight (four) 15 to 5 〇 nanometer. The area of the carbon nanotube layer is not limited to 'can be prepared according to actual needs. When the carbon nanotube film structure 12 is composed of a plurality of overlapping carbon nanotubes s, a plurality of carbon nanotube layers are closely connected by a van der Waals force to form a stable structure of the carbon nanotube film structure. 12. In the carbon nanotube film structure 12 composed of a plurality of nanometer stone reverse layer, the arrangement direction of the carbon nanotubes in the adjacent carbon nanotube layers forms an angle α, and 〇γα $90. . As shown in FIG. 2, the carbon nanotube film structure provided in this embodiment consists of four first carbon nanotube layers 122, a second carbon nanotube layer 124, and a carbon nanotube layer stacked in parallel with each other. 126, a fourth carbon nanotube layer 128, the thickness of the nano carbon film structure 12 is 〇. 〇 4 ~ 400 microns, the carbon nanotube film structure 12 in the adjacent carbon nanotube layer The arrangement angle of the carbon nanotubes is 9〇〇〇200934725. In the carbon nanotube composite material 10, the carbon nanotube film structure 12 is uniformly disposed in the polymer matrix 14, and the polymer material is infiltrated into the carbon nanotube film. In the gap between adjacent carbon nanotubes in structure 12, the polymer material is tightly bonded to the carbon nanotubes in the nano-carbon nanotube film structure 12. Referring to FIG. 3, the technical solution further provides a method for preparing the above-mentioned carbon nanotube composite material 10, which specifically includes the following steps: Step 1: Prepare a polymer matrix 14, which is a polymer film. The polymer matrix 14 can be prepared by a solution film formation, hot melt coating, casting film formation, or spray coating. In this embodiment, the polymer matrix 14 is prepared by a hot melt knife coating method, which specifically includes the following steps: First, the liquid allyl phenol is placed in a container and heated to 90 to 180 ° C to maintain the temperature of the container. Stir for a few minutes. Secondly, the bismaleimide powder is added to the liquid allyl phenol. The quality ratio of bismaleimide to allyl phenol is in the range of 60:5~60:70, and the temperature of the container is controlled at 110~160. In the range of °C, the sample was allowed to stand and the temperature was maintained at this temperature, and the gas in the solution was sufficiently evacuated for several minutes to obtain a transparent reddish brown mixed liquid. Further, a mixture of the above bismaleimide and dilute propylphenol is poured into a recess, and after the mixture is cooled, a polymer matrix 14 is obtained. The thickness and shape of the high molecular matrix 14 can be controlled by controlling the depth and shape of the grooves. Step 2: Prepare a carbon nanotube film. The preparation method of the carbon nanotube film comprises the following steps: First, preparing a carbon nanotube array. In this embodiment, the carbon nanotube array is a super-sequential carbon nanotube array 11 200934725 column, and the method for preparing the super-sequential carbon nanotube array is chemical vapor deposition, and the specific steps thereof include (a) providing a flat substrate, the substrate may be selected from a .P type or an N type; an ε substrate may be selected from a broken substrate formed with an oxide layer, and this embodiment preferably employs a 4 inch ruthenium substrate; (b) A catalyst layer is uniformly formed on the surface of the substrate, and the catalyst layer material may be one selected from the group consisting of iron (Fe), cobalt (c), nickel (Ni) or any combination thereof; (c) the substrate on which the catalyst layer is formed is 700~900. (: Annealing in air for about 3 minutes to 9 minutes; (d) placing the treated substrate in a reaction furnace, heating to 500 to 740 ° C in a protective gas atmosphere, and then introducing a carbon source gas. The reaction is carried out for about 5 to 3 minutes, and a super-sequential carbon nanotube array is grown to have a height of 2 〇〇 4 4 μm. The super-aligned carbon nanotube array is a plurality of parallel and perpendicular to the substrate. The array of pure carbon nanotubes formed by the carbon nanotubes. The super-sequential carbon nanotube array contains substantially no impurities, such as amorphous carbon or residual catalyst metal particles, etc., by controlling the growth conditions described above. The carbon nanotubes in the carbon tube array are in close contact with each other by van der Waals force to form an array. ❹ The carbon source gas in this embodiment may be a chemically active hydrocarbon such as acetylene, ethylene or methane, which is preferred in this embodiment. The carbon source gas is acetylene; the shielding gas is nitrogen or an inert gas, and the preferred shielding gas in this embodiment is argon. It is understood that the carbon nanotube array provided in the embodiment is not limited to the above preparation method, and the arc discharge method may also be employed. Laser evaporation deposition method. The carbon nanotube array provided in this embodiment is one of a single-walled carbon nanotube array, a double-walled carbon nanotube array, and a multi-walled carbon nanotube array. At least one carbon nanotube film is obtained by drawing in the carbon tube array. μ, 12 200934725 The preparation of the carbon nanotube film specifically includes the following steps: (a) selecting a plurality of nanometers of a certain width from the above-mentioned carbon nanotube array a carbon nanotube bundle segment, 'implemented, preferably using a tape having a width to contact the array of carbon nanotubes to select a plurality of carbon nanotube bundle segments of a certain width; (b) producing at a certain speed = substantially perpendicular to the array of carbon nanotubes The plurality of nano-tube segments are stretched in the growth direction to form a continuous carbon nanotube film. In the above stretching process, the plurality of carbon nanotube bundle segments are gradually separated from the tensile direction by the tensile force. At the same time as the substrate, due to the van der Waals force, the selected plurality of carbon nanotube bundle segments are continuously pulled out together with the other carbon nanotube segments, respectively, to form a carbon nanotube film. The carbon nanotube film is a carbon nanotube film having a certain degree of twist and is formed by a plurality of carbon nanotube bundles arranged in a preferred orientation. The carbon nanotube bundles in the carbon nanotube film are parallel to each other. The arrangement direction of the carbon nanotube bundle is substantially parallel to the stretching direction of the carbon nanotube film. In this embodiment, the width of the carbon nanotube film is related to the size of the bottom of the carbon nanotube array, and the carbon nanotube film is The length of the carbon nanotube film is 〇〇ι~ι〇〇μm. When the carbon nanotube in the tube film is a single-walled carbon nanotube, the When the single wall = tube, the wall of the carbon nanotube, the double-walled carbon nanotube is straight; the carbon nanotube in the carbon nanotube film is multi-walled (four), the diameter of the carbon nanotube is 1.5~50 The nanometer is formed by disposing at least one carbon nanotube film on the surface of the polymer matrix μ to form a carbon nanotube film structure 12, thereby forming a Nylon 13 200934725 m slave composite prefabricated body 2〇. It can be understood that, in this embodiment, the preparation of a carbon nanotube composite preform 20 can be performed by directly laying at least the above-mentioned carbon nanotube film on the surface of the ruthenium molecular substrate 14 to prepare a carbon nanotube composite. Material preform 20. Alternatively, at least one layer of the above carbon nanotube film can be used to form a self-supporting carbon nanotube film structure 12, and the carbon nanotube film structure 12 is disposed on the polymer substrate 14 to form The carbon nanotube composite is prefabricated by the ▲ body 20. The method for preparing at least one layer of the carbon nanotube film directly on the surface of the polymer substrate 14 to prepare the carbon nanotube composite preform 2 includes the following steps: providing a polymer matrix 14; at least one nanometer The carbon tube film is directly laid on the surface of a polymer matrix 14 to form a carbon nanotube film structure 12, and the excess carbon nanotube film other than the polymer matrix 14 is removed to obtain a nanometer-insensitive composite preform. . It can be understood that in the present embodiment, at least two carbon nanotube films can be laid and/or overlapped on the surface of the polymer substrate 14 in parallel and without gaps to form a carbon nanotube film structure 12. The carbon nanotube film structure 12 comprises a carbon nanotube layer or at least two parallel and overlapping carbon nanotube layers. The arrangement of the carbon nanotubes in the adjacent two carbon nanotube layers is formed. An angle α 'and 〇γα $ 9〇. . In the present embodiment, the angle α of the arrangement of the carbon nanotubes in the adjacent two carbon nanotube layers is preferably 9 〇. In this embodiment, another polymer matrix 14 may be further disposed on the carbon nanotube film structure 12 to form a sandwich structure of a carbon nanotube composite preform. It can be understood that, in this embodiment, a plurality of 14 200934725 = : structural corpses and a plurality of polymer substrates 14 may be alternately superposed, and the shape of the singular θ, 不 妷 复合 composite composite preform. As shown in Fig. 4, preferably, the ?? complex t material preform 20 is a structure in which a carbon nanotube film junction (4) is laminated on a molecular matrix 14. Too = use at least - layer of carbon nanotubes thin '臈 to form a self-supporting two-sided structure 12, and then prepare a carbon nanotube composite material prefabricated body stone ... cavity step: provide a support; will at least - The surface of the nano-supporting body removes the excess nano-carbon polymer in the outer wall of the branch, and the second, the ginger body forms a carbon nanotube film structure 12; provides a = ί 14 _ and the carbon nanotube The thin film structure 12 is disposed at the high iL to obtain a carbon nanotube composite preform 20. The body can be a substrate, and can also be used as a frame. The carbon in the super-sequential carbon nanotube array provided in this embodiment. The tube is very pure. The specific surface area of the tube itself is very large. Therefore, the carbon nanotube film can be used for its own dryness. The carbon nanotube film adheres to the substrate or frame. The excess carbon nanotube film portion outside the frame or frame can be accessed with a knife. The base (four) frame is removed, ie the 剌-nanocarbon tube _ structure 12. set. The size of the substrate or the frame can be determined according to actual needs: when the width of the soil plate or the frame is larger than the width of the above-mentioned nano carbon (four) film, at least two carbon nanotube films can be formed on the substrate or the frame to form a nano carbon. The tube film structure 12 comprises a layer of carbon nanotubes or at least two parallel and overlapping layers of carbon nanotubes. The two carbon nanotube layers adjacent to each other are arranged in a direction of a carbon nanotube arrangement 15 200934725. Angle α, and ~ (four). . In this embodiment, the step of further processing the film structure 12 includes treating the nanocarbon with an organic spirulina. The alcohol 1 alcohol, acetone, and chlorine B = a volatile organic solvent, and the organic solvent is ethanol. The use is::: imitation, etc. in the present embodiment! The organic solvent is dropped on the carbon nanotube thin tube two-tube stone anti-official film structure 12, or, the upper two zero-n-square structure 12 can also be The substrate or the m-frame is completely immersed in the ^ 缚 结 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = Remove the surface. After the organic carbon solvent is infiltrated by the thin carbon nanotube material, the parallel carbon nanotube fragments in the carbon nanotube film are partially aggregated into a carbon tube bundle under the surface tension of the volatile organic solvent. Therefore, the surface area ratio of the carbon nanotube film structure 12 is small:: has good mechanical strength and toughness. In the carbon nanotube composite preform 20 prepared by the above method, a plurality of microporous structures exist between the carbon directors in two adjacent carbon carbon layers, and the pore structure of the crucible is uniform and regularly distributed in the naphthalene In the carbon nanotube film structure 12, the diameter of the micropores is from 1 nm to 0.5 μm. Step 4: heating the nanometer; e carbon tube composite material preform 2, and combining the carbon nanotube film structure 12 with the polymer matrix 14 to obtain a carbon nanotube composite material 10. As shown in FIG. 5, the method for preparing the carbon nanotube composite material 10 specifically includes the following steps: 16 200934725 First, at least one carbon nanotube composite preform 20 is placed in a mold 30 to close the upper substrate of the mold. 31 and the lower substrate 33. The mold 30 has been evenly coated with a release agent before the carbon nanotube composite preform 20 is placed, so that the carbon nanotube composite 10 can be smoothly demolded, and the side wall of the mold 30 is provided with a flow tank 35. Excess liquid polymer flows out. The release agent used varies depending on the type of the polymer, and the release agent includes a high temperature release agent, an organic oxime release agent, a wax release agent, or a siloxane type release agent.
可以理解，本實施例中，也可以將複數個奈米碳管複合 材料預製體20疊加或平行放置於該模具30中。 其次，加熱該模具30，使高分子基體14變為液態浸潤 到奈米碳管薄膜結構12中的奈米碳管間隙當中。先將該模 具30放入加熱裝置40中，將低於lOOMpa的壓力作用於模 具30的上基板31，對模具30中的複合材料預製體20加壓。 然後，使加熱裝置40升溫至100〜150°C，再對模具30抽真 〇空，使其絕對真空度低於-O.OIMpa，並維持該狀態1-5小時。 完成液態高分子基體14與奈米碳管薄膜結構12的複合後， 停止抽真空。所述加熱裝置40可為加熱板、熱壓機、平板 硫化機、熱壓罐或者烘箱。高分子基體14於100〜150°C時為 液態，於該溫度下液態高分子基體14的粘度很低。對模具 30加壓，液態高分子基體14於壓力的作用下能夠很好的浸 潤到奈米碳管薄膜結構12中的奈米碳管間隙當中，多餘的 液態高分子會從流膠槽35中流出。對加熱裝置40抽真空， 使其絕對真空度低於-O.OIMpa，奈米碳管薄膜結構12中的 17 200934725 奈米碳管間隙中的空氣被抽出，使得到的奈米碳管複合材料 10中不存在空氣，並且該奈米碳管複合材料10不存在結構 缺陷。 '最後，使高分子基體14固化成型，待加熱裝置40降溫 後，將模具30從加熱裝置40中取出，.脫模可得奈米碳管複 合材料10。 本實施例中，使得高分子基體14固化成型的方法依據 &高分子基體14材料的不同而不同。 〇 當高分子基體14材料為熱固性高分子時，高分子基體 14的固化又進一步包括一升溫的過程。升溫過快會導致熱固 性高分子爆聚，從而影響材料性能，故，熱固性液態高分子 的固化需要逐步升溫的步驟。首先，使加熱裝置40繼續升 溫至150〜180°C，於該溫度下高分子基體14為凝膠狀，維持 該溫度2〜4小時，使得高分子基體14繼續吸熱以增加其固 化度。其次，繼續升溫至180〜200°C，於該溫度下高分子基 〇體14為固態，維持該溫度1~5小時，使得高分子基體14繼 續吸熱以增加其固化度。再次，繼續升溫至200~230°C，維 持該溫度2〜20小時，使得高分子基體14繼續吸熱以增加其 固化度。最後，將加熱裝置40降溫後，將模具30從加熱裝 置40中取出，脫模可得奈米碳管複合材料10。 當高分子基體14材料為熱塑性高分子時，高分子基體 14的固化無需進一步升溫，只需將加熱裝置40降溫後，將 模具30從加熱裝置40中取出，脫模可得奈米碳管複合材料 10 ° 18 200934725 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内。 【圖式簡單說明】 圖1為本技術方案實施例的奈米碳管複合材料的剖面 圖。 圖2為圖1中的奈米碳管薄膜結構的結構分解示意圖。 圖3為本技術方案實施例的奈米碳管複合材料 法的流程圖。 拘乃 預製體的 圖4為本技術方案實施例的奈米碳管複合材料 剖面圖。 圖5為本技術方案 的結構示意圖。 實施例製備奈米碳管複合材料的裝 置 〇【主要元件符號說明】 奈米碳管符合材料 10 奈米碳管符合材料預製體 20 奈米碳管薄膜結構 12 高分子基體 14 第一奈米碳管層 122 第二奈米碳管層 124 第三奈米碳管層 126 第四奈米碳管層 128 19 200934725 模具 30 加熱裝置 40 上基板 31 下基板 33 流膠槽 35It can be understood that, in this embodiment, a plurality of carbon nanotube composite preforms 20 may be stacked or placed in the mold 30 in parallel. Next, the mold 30 is heated to cause the polymer matrix 14 to be infiltrated into the carbon nanotube gap in the carbon nanotube film structure 12. The mold 30 is first placed in the heating device 40, and a pressure lower than 100 MPa is applied to the upper substrate 31 of the mold 30 to pressurize the composite preform 20 in the mold 30. Then, the heating device 40 is heated to 100 to 150 ° C, and the mold 30 is evacuated to have an absolute vacuum of less than -O.OIMpa, and this state is maintained for 1-5 hours. After the liquid polymer matrix 14 is combined with the carbon nanotube film structure 12, the vacuum is stopped. The heating device 40 can be a heating plate, a hot press, a flat vulcanizer, an autoclave or an oven. The polymer matrix 14 is in a liquid state at 100 to 150 ° C, and the viscosity of the liquid polymer matrix 14 is low at this temperature. When the mold 30 is pressurized, the liquid polymer matrix 14 can be infiltrated into the carbon nanotube gap in the carbon nanotube film structure 12 under the action of pressure, and the excess liquid polymer will flow from the glue tank 35. Flow out. The heating device 40 is evacuated so that the absolute vacuum is lower than -O.OIMpa, and the air in the 17200934725 carbon nanotube gap in the carbon nanotube film structure 12 is extracted, so that the obtained carbon nanotube composite material There is no air in 10, and the carbon nanotube composite 10 has no structural defects. 'Finally, the polymer matrix 14 is solidified and formed. After the heating device 40 is cooled, the mold 30 is taken out from the heating device 40. The demolding can obtain the carbon nanotube composite material 10. In the present embodiment, the method of solidifying the polymer matrix 14 is different depending on the material of the polymer matrix 14. 〇 When the polymer matrix 14 material is a thermosetting polymer, the curing of the polymer matrix 14 further includes a temperature rising process. If the temperature rises too fast, the thermosetting polymer will be polymerized, which will affect the material properties. Therefore, the curing of the thermosetting liquid polymer requires a step of gradually increasing the temperature. First, the heating device 40 is further heated to 150 to 180 ° C. At this temperature, the polymer matrix 14 is gelatinous, and the temperature is maintained for 2 to 4 hours, so that the polymer matrix 14 continues to absorb heat to increase the degree of curing. Next, the temperature is further raised to 180 to 200 ° C. At this temperature, the polymer matrix 14 is solid, and the temperature is maintained for 1 to 5 hours, so that the polymer matrix 14 continues to absorb heat to increase the degree of solidification. Again, the temperature is raised to 200 to 230 ° C, and the temperature is maintained for 2 to 20 hours, so that the polymer matrix 14 continues to absorb heat to increase its degree of solidification. Finally, after the heating device 40 is cooled, the mold 30 is taken out from the heating device 40, and the carbon nanotube composite material 10 is obtained by demolding. When the polymer matrix 14 material is a thermoplastic polymer, the curing of the polymer matrix 14 does not require further temperature increase, and after the heating device 40 is cooled, the mold 30 is taken out from the heating device 40, and the mold release can be obtained by using a carbon nanotube composite. Material 10 ° 18 200934725 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 in this case. Equivalent modifications or variations made by persons skilled in the art in light of the spirit of the present invention are intended to be included in the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a carbon nanotube composite material according to an embodiment of the present technical solution. 2 is a schematic exploded view showing the structure of the carbon nanotube film of FIG. 1. Fig. 3 is a flow chart of a carbon nanotube composite material method according to an embodiment of the present technical solution. Figure 4 is a cross-sectional view of a carbon nanotube composite material according to an embodiment of the present technical solution. Fig. 5 is a schematic structural view of the technical solution of the present invention. EXAMPLES Apparatus for preparing carbon nanotube composite material 〇 [Main component symbol description] Carbon nanotube conforming material 10 Carbon nanotube conforming material preform 20 Carbon nanotube film structure 12 Polymer matrix 14 First nano carbon Tube layer 122 second carbon nanotube layer 124 third carbon nanotube layer 126 fourth carbon nanotube layer 128 19 200934725 mold 30 heating device 40 upper substrate 31 lower substrate 33 flow tank 35
2020