201014788 九、發明說明： 【發明所屬之技術領域】 本發明是有關於一種製備奈米碳材的方法，特別是指 一種利用通電加熱來製備奈米碳材的方法，以及製備含有 該奈米碳材的基板與高分子膜的方法及其應用。 【先前技術】 近年來，奈米碳管及奈米碳纖維等的奈米碳材由於質 量輕、表面積大、具有導電性等物化性質，使其可以被應 用於很多領域，例如：M電池兩極材料、生物材料、燃料 電池、生物感測器、場發射元件及儲氫材料等領域。 •目前，製備奈米碳材的方法主要有電弧放電（arc_ discharge)、雷射蒸發法〇aser vap〇dzati〇n邮化⑷及化 學氣相沉積法（chemical vap〇r dep〇siti〇n )等三種方式其 中，雖然電弧放電法製得的奈米碳材品質佳且碳管筆直， 但是產量小且需要在兩三千唐的高π 卞度的间，皿下進仃，而雷射蒸發 主單壁奈米碳管，但是其所使用的設備昂 貝，導致裝程成本過高，至於化學氣相沉積法雖缺可以藉 ===量的奈米碳材，但是合成出來的產物多 疋 #壁的奈米碳材，且其製備過程繁瑣，需要 藉由多個流量控制閥來控制氣體的流量，此外，上述製備 方法都需要在抽真空的環境下進行，因此仍有需要發j 一種製程簡易且成本低的製備奈米碳材的方法有需要發展出 【發明内容】 因此， 本發明之第一目 的，即在提供一種製程簡易且 5 201014788 成本低的製備奈米碳材的方法。 於是，本發明製備奈米碳材的方法係包含以下步驟： ⑴提供一基材，該基材包括一碳源層及一形成於該碳源層 之部份表面上的導電層，且該碳源層的材質是選自於酚甲 酸·樹脂（phenol-formaldehyde resin)、聚對苯二曱酸丁二醋 (polybutylene terephthalate;簡稱 PBT)、聚乙烯吡咯烷酮 (polyvinyl pyrrolidone ;簡稱 PVP )、聚四氟乙烯（ polytetrafluoroethylene ;簡稱 PTFE )、偏氟乙烯/三氟乙烯 共聚物（vinylidene fluoride-trifluoroethylene copolymer ); ❹ 間稱 P(VDF-TrFE))、聚乙稀醇（p〇iyVinyi aic〇h〇l )，或此 等之一組合，該導電層的材質是選自於銅、鐵、鈷、鎳， 或此等之一組合；（ii)對該導電層通以一電流，使該碳源層 表面進行熱裂解，以製得一含有一底層及一形成該底層上 的奈米碳材的基板；以及（in)將該奈米碳材自該步驟（丨〇的 底層上移除，進而得到一奈米碳材。 因此’本發明之第二目的，即在提供一種製程簡易且 成本低的製備含有奈米碳材的基板的方法。 © 於是’本發明製備含有奈米碳材的基板的方法係包含 以下步驟：（1)提供一基材’該基材包括一碳源層及一形成 於該兔源層之部份表面上的導電層，且該碳源層的材質是 選自於紛甲酸樹脂、聚對苯二甲酸丁二酯、聚乙烯吡咯烷 嗣、聚四氟乙烯、偏氟乙烯/三氟乙烯共聚物、聚乙烯醇， 或此等之一組合，該導電層的材質是選自於銅、鐵、鈷、 鎳，或此等之一組合；以及（π)對該導電層通以一電流，使 6 201014788 該碳源層表面進行熱裂解，進而製得一含有一底層及一形 成於該底層上的奈米碳材的基板。 本發明之第三目的，即在提供一種製程簡易且成本低 的含有奈米碳材的基板，其係藉由如上所述之方法所製得 的。 本發明之第四目的，即在提供一種製程簡易且成本低 的製備含有奈米碳材的高分子膜的方法。 本發明製備含有奈米碳材的高分子膜的方法係包含以 下步驟：（a)提供一基材，該基材包括一碳源層、一形成於 該碳源層之部份表面上的導電層，及一可撕離地附著於該 碳源層之鄰近該導電層的部分表面上的高分子層，且該碳 源層的材質是選自於酚甲醛樹脂、聚對苯二甲酸丁二酯、 聚四氟乙烯、偏氟乙烯、聚乙烯醇、聚丙稀、聚乙烯吡咯 烷酮，或此等之一組合，該導電層的材質是選自於銅、鐵 、鈷、鎳，或此等之一組合，及該高分子層包含一玻璃轉 換溫度（glass transition temperature)高於 200。(：的高分子 ，（b)對該導電層通以一電流，使該碳源層表面進行熱裂解 並使該奈米被材形成於該高分子層之表面上；以及（c)使該 南分子層脫離該碳源層之表面，進而製得一含有一高分子 層及一形成於該高分子層上的奈米碳材的高分子膜。 本發明之第五目的，即在提供一種製程簡易且成本低 的含有奈米礙材的高分子膜，其係藉由如上所述之方法所 製得的。 本發明製備方法是利用對一含有一碳源層及一導電層 7 201014788 .一=施予電机的方式使一奈米碳材形成於該碳源層或 該同为子層上，更進_步地說，該等方法係利用對導電層 通電並將電月b轉換成熱能，使該碳源層有足夠的熱量發 生熱裂解，進而提供形成該奈米碳材所需的碳，因此，比 現有的製備方法的製程都來得簡易且成本低，故能達到本 發明之功效。 【實施方式】 審於以往裝備奈米碳材的方式不是需要添加觸媒，如 化學亂相 >儿積法，就是必須要在兩三千度的高溫環境下， 如電弧放電法才能製備出有結晶性的奈米碳材，且現有製 備奈米碳材的技術幾乎都是在已知製備方式上做改良，於 是、，本案發明人跳脫既有的思想，以現有製備奈米碳材之 方法的原理為出發點做思考，進而發展出一種有別於習知 技術的製備方法。 目則已知的製備奈米碳材之方法的原理主要有二：一 、要有碳源（earbon SQUlxe);二、要有加熱源提供足夠的 熱量使碳源熱裂解（py吻sis)產生碳，故本發明利用對一 含有一碳源層及一導電層的基材施予一電流的方式來製備 一奈米碳材，藉此使該碳源層有足夠的熱量發生熱裂解， 其中的碳源層即是碳源’導電層即是加熱源，進而在該基 材的表面上形成該奈米碳材。 有關本發明之前述及其他技術内容、特點與功效，在 以下配合參考圓式之二個較佳具體例的詳細說明中，將可 清楚的呈現。 201014788 在本發明被詳細描述之前，要注意的是，在以下的說 明内容中，類似的元件是以相同的編號來表示。 如圖1所示’本發明含有奈米碳材的基板1的一具體 例係包含一底層11，及一形成於該底層11上的奈米碳材10 ’且該基板1是藉由如下所述之方法所製得的。 本發明製備含有奈米碳材的基板1的方法係包含以下 步驟：⑴提供一基材9,如圖2所示，該基材9包括一碳源 層91及一形成於該碳源層91之部份表面上的導電層92, 且該碳源層91的材質是選自於酚甲醛樹脂、聚對苯二甲酸 丁二酯、聚四氟乙烯、偏氟乙烯、聚乙烯醇、聚丙烯、聚 乙烯吡咯烷酮，或此等之一組合，該導電層92的材質是選 自於銅、鐵、鈷、鎳，或此等之一組合；以及（ϋ)對該導電 層92通以一電流，使該碳源層91表面進行熱裂解，進而 製得一含有一底層11及一形成於該底層u上的奈米碳材 10的基板1。 較佳地’該步驟（π)還進一步地藉由裁切方式將含有導 電層92的部分基材9裁除，進而製得本發明基板。 附註說明的是，本發明含有奈米碳材的基板丨中的底 層Π是源自於該步驟⑴中的基材9的碳源層91，也就是未 發生熱裂解的碳源層91。 較佳地，該步驟⑴的基材9是一電木板。 較佳地，該步驟⑴的碳源層91的材質是紛甲盤樹脂。 較佳地，該步驟⑴的導電層92的材質是銅。 較佳地，該步驟（ii)的導電層92在通以電流後的溫度是 9 201014788 介於700°C至1000。(：之間。更佳地，是介於7〇〇。(：至800°c 之間。 當該導電層92的材質是銅時’較佳地，該步驟（丨丨）的電 流密度是介於4.9x104 A/cm2至6.2x104 A/cm2之間。更佳地 ，是介於 5.2xl04A/cm2 至 5.9xl04A/cm2 之間。 較佳地’該奈米碳材是管狀奈米碳纖維（carb〇n nan〇fiber)、奈米碳膜（carbon nanosheets)，或此等之一組 合。 較佳地’該奈米碳膜的厚度是介於5〇 nm至2〇〇 nm之 〇 間，且寬度可達數十微米。 較佳地’該管狀奈米碳纖維的直徑是介於5〇 nm至300 nm之間’且長度是介於2微米至15微米之間。 需特別說明的是，該碳源層上所形成的奈米碳材的型 態會和該碳源層的溫度有關，而該碳源層的溫度會和該導 電層的材質、其通電流的時間及其所通的電流密度有關， 且距離該導電層越遠的區域，其溫度會因與加熱源（即導 電層）的距離變遠而降低，因此，與該導電層不同距離的❹ 碳源層上所形成的奈米碳材的型態是不相同的。以本案之 具體實施例為例，當使用導電層的材質為銅且通以一強度 介於5.5A至6.2A之間的電流（其電流密度相當於5 2χ1〇4 A/cm2〜5·9χ1〇4 A/cm2) 30秒時，與該導電層的水平距離介 於〇微米至200微米之間的碳源層上所形成的奈米碳材是 以奈米碳膜為主；與該導電層的水平距離介於2〇〇微米至 3〇〇微米之間時的碳源層上所形成的奈米碳材是以管狀奈米 10 201014788 破纖維為主。 由此可知’操作者可以藉由使用不同材質的導電層及 控制通過該導電層的電流密度來調控該碳源層上所形成的 奈米碳材的型態。本案發明人猜測其機制應是熱裂解後的 碳會飄到導電層四周圍的碳源層上，進而形成奈米碳材， 而且，接近導電層的溫度較高的碳源層上會生成奈米碳膜 ，而遠離導電層的溫度較低的碳源層上會生成管狀奈米碳 纖維。 鲁 本案之具體實施例中所使用的基材是源自於一市售的 感光電木板，亦即本案發明人是藉由將該市售的感光電木 板經過一特殊處理，進而製得一含有一碳源層及一導電層 的基材。更詳細地，本案發明人使用一曝光機及一具有一 疋形狀的預疋光罩在購得的感光電木板上曝出一與該預定 光罩相同形狀的圖形，再經顯影及蝕刻，以製得該基材。 接著，依需求並參照上面所述的操作參數，藉由控制電流 密度，進而調控該碳源層的溫度’以製備出不同型態的奈 ® 米碳材。 上述的感光電木板經表面線路化後即為目前市面上所 稱之印刷電路板，此印刷電路板為一般電子產品之基本元 件。此等產品通常在使用後，就會被當作廢棄物丟棄，然 ，本發明製備方法除了可使用市售的感光電木板，亦可利 用廢棄的感光電木板作為基材，由此可知，本發明製備方 法不但是具有製程簡易的優點，還有具有環保的功效。 在本案之具體實施例中，該預定光罩是由二個正方形 11 201014788 部分及-個位於該等正方形部分之間的長條形部分所組成 的，然，並不應以此為限，該光罩可以是任何形狀。、 本發明製備奈米碳材的方法是以與本發明製備含有奈 米碳材的基板相似的方法製備，不同之處在於：本發明= 備奈米碳材的方法還包含一在該步驟⑼之後的步驟㈤）， 其係將該奈米碳材自該步驟（ii)的底層上移除，進而得 奈米碳材。 上述移除的方式可以是任何已知的移除方式，例如： 用刮勺輕刮底層表面。 如圖3所示’本發明含有奈米碳材的高分子膜2的一 具體例係包含-高分子層21，及-形成於該高分子層21上 的奈米碳材20’且該高分子膜2是藉由如下所述之方法所 製得的。 本發月製備含有奈米碳材的高分子膜2的方法係包含 以下步驟：⑷提供一基材9 ’如圖4所示，該基材9包括一 '層91形成於該碳源層91之部份表面上的導電層 92,及—可撕離地附著於該碳源層91之鄰近該導電層92 © 的部为表面上的高分子層21 ’且該碳源層91的材質是選自 於紛甲盤樹脂、聚對苯二甲酸丁二醋、聚四氣乙稀、偏氟 稀聚乙缔醇、聚丙烯、聚乙烯°比°各燒酮，或此等之一 組合二該導電層92的材質是選自於銅、鐵、鈷、錄，或此 等之弋合，及該高分子層21包含-玻璃轉換溫度高於 的门刀子，（b)對該導電層92通以一電流，使該碳源 表面進行熱裂解並使該奈米碳材20形成於該高分子 12 201014788 層21之表面上；以及（c)使該高分子層2i脫離該碳源層91 之表面’進而得製得一含有一高分子層21及一形成於該高 分子層21上的奈米碳材2〇的高分子膜2。 較佳地’該步驟（a)的高分子層的高分子的玻璃轉換溫 度是介於200。(：至4001之間。但適用於本案的高分子並 不以具有上述玻璃轉換溫度範圍者為限，只要是該高分子 的玻璃轉換溫度夠高’使其在導電層通電加熱後仍可維 持穩疋型態並作為奈米碳材成長之基地者皆可適用。更 佳地’該步驟（a)的高分子層的高分子是聚醯亞胺（ polyimide ;簡稱pj )。在本案之一具體實施例中，該步驟 (a)的高分子層即是一聚醯亞胺薄膜（以下簡稱pl膜）。 附註說明的是，該步驟（b)中所指的高分子層21之表面 上是指遠離該碳源層91的表面上。 該步驟（a)的碳源層的材質及導電層的材質的較佳選擇 ’以及該步驟（b)的導電層在通以電流後的溫度範圍，都與 製備含有奈米碳材的基板的方法中所述的相同，故不在此 資述。同樣地，該奈米碳材的型態亦與製備含有奈米碳材 的基板的方法中所述的相同，故也不再贅述。 另本發明製備含有奈米碳材的尚分子媒的具體實施 例中所使用的基材與製備含有奈米碳材的基板的具體實施 例中所使用的基材的來源是相同的，不同的是，在此製備 方法中，發明人進一步在經顯影及蝕刻後的基材之部分表 面上貼覆上一高分子層。 實施例 13 201014788 本發明將就以下實施例來作進一步說明，但應瞭解的 是’該等實施例僅為例示說明之用，而不應被解釋為本發明 實施之限制。 <儀器設備> 1. 鑽石切割機：購自於尚偉；型號為LECO VC-50。 2. 掃描式電子顯微鏡（SEM):購自於je〇l ;型號為JSM_ 6700F 。 3. 穿透式電子顯微鏡（TEM):購自於JE〇L ;型號為jem_ 1200CXII ; JEM-2010。 ❹ 4. X光繞射儀（XRD):購自於Rigaku;型號為D/MAX_ 2200PC。 5. 熱電偶（thermocouple):購自於峰昌電機；型號為CSG_ 321T-K-2A 〇 <製備例1 > 本製備例是取一市售的長度為3〇 cm、寬度為15 £111及 厚度為1.6 mm之感光電木板（購自於金金電子；型號： PS1530-1.0，其表面已塗有光阻劑），/並使用曝光機將該感❹ 光電木板上曝出和一預定光罩相同形狀的圖形，該預定光 罩是由二個5 mmx 5 mm正方形部分及一個位於該等正方形 部分之間且尺寸為i cmx 300 μίη的長條形部分所組成。曝 光完後，將該經曝光的感光電木板浸入一含有wt%顯影 劑（構自於金金電子）的水溶液内均勻搖晃至該圖形顯現 出來’接著’再將其置於i刻液中’歷時3〇分鐘，進而 得到一含有一碳源層及一銅導電層的基材。 14 201014788 <實施例1> 本實施例是先以鑽石切割機將製備例丨 〈暴材切割成 一尺寸為2.5 cmx 7 mm的測試基材後， 付到一測試基松201014788 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method for preparing a nano carbon material, and more particularly to a method for preparing a nano carbon material by using electric heating, and preparing the carbon nanomaterial. Method for substrate and polymer film and application thereof. [Prior Art] In recent years, nano carbon materials such as carbon nanotubes and nano carbon fibers have been used in many fields due to their light weight, large surface area, and electrical properties such as conductivity, for example, M battery bipolar materials. , biomaterials, fuel cells, biosensors, field emission components and hydrogen storage materials. • At present, the methods for preparing nano carbon materials mainly include arc discharge (arc_ discharge), laser evaporation method 〇aser vap〇dzati〇n zip (4), and chemical vapor deposition (chemical vap〇r dep〇siti〇n). Among the three methods, although the nano-carbon material produced by the arc discharge method has good quality and the carbon tube is straight, but the output is small and needs to be immersed under the dish at a high π 卞 degree of two or three thousand tangs, and the laser evaporates the main Single-walled carbon nanotubes, but the equipment used in the Angbei, resulting in high cost of the process, as for the chemical vapor deposition method, although the lack of carbon fiber can be used === amount, but the product is more #壁的纳米碳材, and its preparation process is cumbersome, it is necessary to control the flow rate of gas by a plurality of flow control valves. In addition, the above preparation methods need to be carried out under vacuuming conditions, so there is still a need to send a kind of j There is a need to develop a method for preparing a nanocarbon material which is simple in process and low in cost. Therefore, the first object of the present invention is to provide a method for preparing a nanocarbon material which is simple in process and low in cost, 201013788. Therefore, the method for preparing a nano carbon material of the present invention comprises the following steps: (1) providing a substrate comprising a carbon source layer and a conductive layer formed on a portion of the surface of the carbon source layer, and the carbon The material of the source layer is selected from the group consisting of phenol-formaldehyde resin, polybutylene terephthalate (PBT), polyvinyl pyrrolidone (PVP), and polytetrafluoroethylene. Polytetrafluoroethylene (PTFE), vinylidene fluoride-trifluoroethylene copolymer; P (VDF-TrFE), polyethylene glycol (p〇iyVinyi aic〇h〇l) Or a combination of the ones, the conductive layer is selected from the group consisting of copper, iron, cobalt, nickel, or a combination thereof; (ii) a current is applied to the conductive layer to surface the carbon source layer Thermally cracking to obtain a substrate comprising a bottom layer and a nano carbon material forming the bottom layer; and (in) removing the nano carbon material from the bottom layer of the crucible, thereby obtaining a Nano carbon material. So 'this hair A second object is to provide a method for preparing a substrate containing a nano carbon material which is simple in process and low in cost. The method of preparing a substrate containing a nano carbon material according to the present invention comprises the following steps: (1) providing a substrate comprising: a carbon source layer and a conductive layer formed on a portion of the surface of the rabbit source layer, and the material of the carbon source layer is selected from the group consisting of carboxylic acid resin and polybutylene terephthalate Diester, polyvinylpyrrolidone, polytetrafluoroethylene, vinylidene fluoride/trifluoroethylene copolymer, polyvinyl alcohol, or a combination thereof, the conductive layer is selected from the group consisting of copper, iron, cobalt, Nickel, or a combination thereof; and (π) passing a current to the conductive layer to thermally crack the surface of the carbon source layer, thereby producing a bottom layer and a layer formed on the bottom layer A substrate for a carbonaceous material. A third object of the present invention is to provide a substrate containing a nanocarbon material which is simple in process and low in cost, which is obtained by the method as described above. Purpose, that is, providing a simple process and cost The method for preparing a polymer film containing a nano carbon material. The method for preparing a polymer film containing a nano carbon material according to the present invention comprises the steps of: (a) providing a substrate comprising a carbon source layer, a conductive layer formed on a portion of the surface of the carbon source layer, and a polymer layer detachably attached to a portion of the carbon source layer adjacent to the conductive layer, and the material of the carbon source layer is Selected from phenol formaldehyde resin, polybutylene terephthalate, polytetrafluoroethylene, vinylidene fluoride, polyvinyl alcohol, polypropylene, polyvinylpyrrolidone, or a combination thereof, the material of the conductive layer is selected From copper, iron, cobalt, nickel, or a combination thereof, and the polymeric layer comprises a glass transition temperature of greater than 200. (a polymer, (b) a current is applied to the conductive layer, the surface of the carbon source layer is thermally cracked and the nano-material is formed on the surface of the polymer layer; and (c) The south molecular layer is separated from the surface of the carbon source layer to obtain a polymer film comprising a polymer layer and a nano carbon material formed on the polymer layer. The fifth object of the present invention is to provide a The polymer film containing nano-obstruction material which is simple in process and low in cost is obtained by the method as described above. The preparation method of the invention utilizes a pair of a carbon source layer and a conductive layer 7 201014788 . a method of applying a motor to form a nano carbon material on the carbon source layer or the same sub-layer, and further, the method utilizes energization of the conductive layer and converts the electric moon b The heat energy is generated, so that the carbon source layer has sufficient heat to be thermally cracked, thereby providing carbon required for forming the nano carbon material, and therefore, the process of the prior preparation method is simple and low in cost, so that the invention can be achieved. [Effects] Examined in the past equipped with nano carbon materials The method is not to add a catalyst, such as chemical chaos [> children's product method, that is, it is necessary to prepare a crystalline nano carbon material in a high temperature environment of two or three thousand degrees, such as an arc discharge method, and the existing preparation of nai The technology of rice carbon material is almost always improved in the known preparation method. Therefore, the inventor of the present case skipped the existing idea and thought about the principle of the existing method for preparing nano carbon material, and then developed a kind of Different from the preparation method of the prior art. The principle of the known method for preparing the nano carbon material is mainly two: one, there is a carbon source (earbon SQUlxe); second, there is a heating source to provide sufficient heat to make The carbon source pyrolysis (py kiss sis) produces carbon, so the present invention uses a method of applying a current to a substrate containing a carbon source layer and a conductive layer to prepare a nano carbon material, thereby making the carbon source The layer has sufficient heat to undergo thermal cracking, wherein the carbon source layer is the carbon source, the conductive layer is the heating source, and the nano carbon material is formed on the surface of the substrate. The foregoing and other technical contents of the present invention , characteristics and efficacy, in In the following detailed description of the two preferred embodiments of the reference circle, it will be clearly shown. 201014788 Before the present invention is described in detail, it is noted that in the following description, similar elements are identical. As shown in FIG. 1 , a specific example of the substrate 1 containing the nano carbon material of the present invention comprises a bottom layer 11 and a nano carbon material 10 ′ formed on the bottom layer 11 and the substrate 1 The method for preparing the substrate 1 containing the nano carbon material comprises the following steps: (1) providing a substrate 9, as shown in FIG. 2, the substrate 9 comprises a a carbon source layer 91 and a conductive layer 92 formed on a portion of the surface of the carbon source layer 91, and the material of the carbon source layer 91 is selected from the group consisting of phenol formaldehyde resin, polybutylene terephthalate, and poly 4 a combination of vinyl fluoride, vinylidene fluoride, polyvinyl alcohol, polypropylene, polyvinylpyrrolidone, or the like, the conductive layer 92 is selected from the group consisting of copper, iron, cobalt, nickel, or a combination thereof; And (ϋ) passing a current to the conductive layer 92 to make the surface of the carbon source layer 91 Line pyrolysis, further comprising a substrate to prepare an underlayer 11 and a bottom layer formed on the nano-carbon material 10 is u 1. Preferably, the step (π) further removes a portion of the substrate 9 containing the conductive layer 92 by cutting, thereby producing the substrate of the present invention. Note that the underlayer Π in the substrate 含有 containing the nano carbon material of the present invention is the carbon source layer 91 derived from the substrate 9 in the step (1), that is, the carbon source layer 91 in which thermal cracking has not occurred. Preferably, the substrate 9 of the step (1) is an electric board. Preferably, the material of the carbon source layer 91 of the step (1) is a striated resin. Preferably, the conductive layer 92 of the step (1) is made of copper. Preferably, the temperature of the conductive layer 92 of the step (ii) after passing the current is 9 201014788 between 700 ° C and 1000. (: between. More preferably, it is between 7 〇〇. (: to 800 ° c. When the material of the conductive layer 92 is copper) Preferably, the current density of the step (丨丨) is It is between 4.9 x 104 A/cm2 and 6.2 x 104 A/cm2. More preferably, it is between 5.2 x 104 A/cm2 and 5.9 x 104 A/cm2. Preferably, the nano carbon material is tubular nano carbon fiber ( Carb〇n nan〇fiber), carbon nanosheets, or a combination of these. Preferably, the thickness of the nanocarbon film is between 5 〇 nm and 2 〇〇 nm. And the width can be several tens of micrometers. Preferably, the diameter of the tubular nano carbon fiber is between 5 〇 nm and 300 nm and the length is between 2 μm and 15 μm. The type of the nanocarbon material formed on the carbon source layer is related to the temperature of the carbon source layer, and the temperature of the carbon source layer and the material of the conductive layer, the time of the current flowing therethrough, and the passage thereof The current density is related, and the farther away from the conductive layer, the temperature is lowered due to the distance from the heating source (ie, the conductive layer), and therefore, the conductive layer The shape of the nano carbon material formed on the carbon source layer at the same distance is different. Taking the specific embodiment of the present invention as an example, when the conductive layer is made of copper and the intensity is between 5.5A and The current between 6.2A (the current density is equivalent to 5 2χ1〇4 A/cm2~5·9χ1〇4 A/cm2). At 30 seconds, the horizontal distance from the conductive layer is between 〇μm and 200μm. The nano carbon material formed on the carbon source layer is mainly a nano carbon film; the naphthalene formed on the carbon source layer when the horizontal distance of the conductive layer is between 2 〇〇 micrometer and 3 〇〇 micrometer The rice carbon material is mainly composed of tubular nano 10 201014788 broken fiber. It can be seen that the operator can control the formation of the carbon source layer by using a conductive layer of different materials and controlling the current density through the conductive layer. The type of rice carbon material. The inventor of this case speculated that the mechanism should be that the carbon after thermal cracking will float to the carbon source layer around the conductive layer, thereby forming nano carbon material, and the temperature close to the conductive layer is higher. A carbon film is formed on the carbon source layer, and a lower temperature carbon source layer away from the conductive layer The tubular nanofiber is produced. The substrate used in the specific embodiment of the Ruben case is derived from a commercially available photosensitive bakelite, that is, the inventor of the present invention passes a special treatment by the commercially available photosensitive bakelite. Further, a substrate comprising a carbon source layer and a conductive layer is prepared. In more detail, the inventor of the present invention uses an exposure machine and a pre-dawning cover having a shape to expose a commercially available photosensitive wood board. The pattern of the same shape as the predetermined mask is developed and etched to obtain the substrate. Next, the temperature of the carbon source layer is controlled by controlling the current density according to the operation parameters as described above and referring to the above. 'To prepare different types of nanometer carbon materials. The above-mentioned photosensitive electric board is surface-lined and is the currently known printed circuit board on the market, and the printed circuit board is a basic component of general electronic products. These products are usually discarded as waste after use. However, in the preparation method of the present invention, in addition to commercially available photosensitive bakelite, waste photosensitive wood boards can be used as a substrate, and it is known that The preparation method of the invention not only has the advantages of simple process, but also has environmental protection effects. In a specific embodiment of the present invention, the predetermined reticle is composed of two squares 11 201014788 portions and a long strip portion located between the square portions, but should not be limited thereto. The photomask can be of any shape. The method for preparing a nano carbon material of the present invention is prepared by a method similar to the method for preparing a nano carbon material-containing substrate of the present invention, except that the method of the present invention = preparing a nano carbon material further comprises a step (9) Subsequent step (5)), which removes the nano carbon material from the bottom layer of the step (ii) to obtain a nano carbon material. The manner of removal described above can be any known removal means, such as: Scrubbing the underlying surface with a spatula. As shown in FIG. 3, a specific example of the polymer film 2 containing the nanocarbon material of the present invention includes a polymer layer 21, and a nanocarbon material 20' formed on the polymer layer 21, and the height is high. The molecular film 2 was obtained by the method described below. The method for preparing the polymer film 2 containing the nano carbon material in the present month comprises the following steps: (4) providing a substrate 9' as shown in FIG. 4, the substrate 9 comprising a 'layer 91 formed on the carbon source layer 91 a portion of the conductive layer 92 on the surface, and a portion of the carbon source layer 91 adjacent to the conductive layer 92 © is a polymer layer 21 ′ on the surface and the material of the carbon source layer 91 is It is selected from the group consisting of a variety of resin, polybutylene terephthalate, polytetraethylene, defluorinated polyethylene glycol, polypropylene, polyethylene ° ° each burning ketone, or a combination of these two The material of the conductive layer 92 is selected from the group consisting of copper, iron, cobalt, recording, or the like, and the polymer layer 21 includes a door knife having a glass transition temperature higher than (b) the conductive layer 92. The surface of the carbon source is thermally cracked by an electric current to form the nano carbon material 20 on the surface of the layer 12 of the polymer 12 201014788; and (c) the polymer layer 2i is separated from the carbon source layer 91. The surface 'further, a polymer film 2 comprising a polymer layer 21 and a nano carbon material 2〇 formed on the polymer layer 21 is obtained. Preferably, the glass transition temperature of the polymer of the polymer layer of the step (a) is 200. (: to 4001. However, the polymer suitable for this case is not limited to the above glass transition temperature range, as long as the glass transition temperature of the polymer is high enough to maintain the conductive layer after being electrically heated It is suitable for use as a base for the growth of nano carbon materials. More preferably, the polymer of the polymer layer in step (a) is polyimine (polyimide; pj). In this case In a specific embodiment, the polymer layer of the step (a) is a polyimide film (hereinafter referred to as a pl film). Note that the surface of the polymer layer 21 referred to in the step (b) is on the surface. It means to be away from the surface of the carbon source layer 91. The material of the carbon source layer of the step (a) and the material of the conductive layer are preferably selected, and the temperature range of the conductive layer of the step (b) after the current is passed. It is the same as described in the method of preparing a substrate containing a nano carbon material, and therefore is not described herein. Similarly, the form of the nano carbon material is also in the method of preparing a substrate containing a nano carbon material. The description is the same, so it will not be described again. The invention also contains nano carbon. The substrate used in the specific embodiment of the molecular medium is the same as the source used in the specific embodiment for preparing the substrate containing the nano carbon material, except that in the preparation method, the invention The person further applies a polymer layer on a portion of the surface of the developed and etched substrate. Embodiment 13 201014788 The present invention will be further illustrated by the following examples, but it should be understood that the examples are only The description is for illustrative purposes and should not be construed as limiting the implementation of the invention. <Instrument Equipment> 1. Diamond cutting machine: purchased from Shang Wei; model number is LECO VC-50. 2. Scanning electron microscope ( SEM): purchased from je〇l; model number is JSM_ 6700F. 3. Transmission electron microscope (TEM): purchased from JE〇L; model is jem_ 1200CXII; JEM-2010. ❹ 4. X-ray diffractometer (XRD): purchased from Rigaku; model is D/MAX_ 2200PC. 5. Thermocouple: purchased from Fengchang Motor; model number CSG_321T-K-2A 〇<Preparation Example 1 > Preparation Example It is a commercially available sensitizer with a length of 3〇cm, a width of 15 £111 and a thickness of 1.6 mm. Wood board (purchased from Jinjin Electronics; model: PS1530-1.0, the surface of which has been coated with a photoresist), and using an exposure machine to expose the sensible photoelectric board to a pattern of the same shape as a predetermined mask, The predetermined mask is composed of two 5 mm x 5 mm square portions and a long strip portion between the square portions and having a size of i cm x 300 μίη. After exposure, the exposed photosensitive wood board is immersed. An aqueous solution containing wt% of the developer (from gold-gold electrons) was evenly shaken until the pattern appeared 'then' and then placed in the engraving solution for 3 minutes, thereby obtaining a layer containing a carbon source. And a substrate of a copper conductive layer. 14 201014788 <Example 1> In this embodiment, a test piece of a test material of 2.5 cm x 7 mm was cut with a diamond cutter to give a test base.
，如圖5所示，該測試基材9含有一碳源 T 、久—鋼導· ® 層92,且該銅導電層92包括二個正方形部分 々i及_個< 於該等正方形部分之間的長條形部分922。 131 伐暫’將一直汽As shown in FIG. 5, the test substrate 9 includes a carbon source T, a long-steel-conductive layer 92, and the copper conductive layer 92 includes two square portions 々i and _ a square portion. A long strip portion 922 between. 131 cutting temporary will be always steam
電電流供應器8的正負極81、82分別與該銅導電層 92的二個正方形部分921接觸以導通電，且將電流控制在 5.5A至6.2A之間，歷時i分鐘，進而製得—含有奈米碳 的測試基板。需特別說明的是，此時通過該鋼導；層 條形部分的溫度是介於7〇〇乞至8〇〇。〇之間。 <實施例2至4 > 實施例2至4是以與實施例i相同的方式製備含有太 米碳材的測試基板，㈣之處在於：通電的時間依序改為1 分40秒、2分鐘及2分15秒。 <實施例5 > 本實施例是在實施例1製得的測試基材的表面上貼上 -尺寸為4靡！ —ρι膜’以得到一貼覆有贝膜的測 試基材。而後續的操作步驟収以與實施们相似的步驟 製備奈米碳材，不同之處在於：通電的時間改》i分鐘， 且本實施例還包含—將含有奈米碳材的pi膜從該測試基材 的表面上撕離的步驟，進而得到—含有奈米碳材的ρι膜。 奈米碳材之型態圖 歹施例1至4 15 201014788 發明人以掃描式電子顯微鏡（SEM)及穿透式電子顯微 鏡（TEM)分別觀察實施例1至4之經通電處理的測試基 板’發現與該銅導電層水平距離不同的碳源層區塊上所形 成的奈米碳材是不同型態的，於是發明人將該碳源層依照 不同型態的奈米碳材的分布區域裁成二個試片，與該銅導 電層水平距離介於〇微米至2〇〇微米的區塊裁成第一試片 :與該銅導電層水平距離200微米至3〇〇微米的區塊裁成 第二試片。The positive and negative electrodes 81, 82 of the electric current supply 8 are respectively in contact with the two square portions 921 of the copper conductive layer 92 to conduct electricity, and the current is controlled between 5.5A and 6.2A for one minute, thereby producing - A test substrate containing nanocarbon. It should be specially noted that the steel guide is passed at this time; the temperature of the strip portion is between 7 〇〇乞 and 8 。. Between 〇. <Examples 2 to 4 > Examples 2 to 4 were prepared in the same manner as in Example i, in which the test substrate containing the carbon steel material was used. (4) The time of energization was changed to 1 minute and 40 seconds, 2 minutes and 2 minutes and 15 seconds. <Example 5> This example was attached to the surface of the test substrate prepared in Example 1 - the size was 4 靡! - ρι膜' to obtain a test substrate coated with a shell film. The subsequent operation steps were carried out in a similar manner to the implementation of the preparation of the nano carbon material, except that the time of energization was changed to "i minutes", and the present embodiment further included - the pi film containing the nano carbon material from the The step of tearing off the surface of the test substrate, thereby obtaining a ρ film containing a nano carbon material. Types of Nano Carbon Materials 歹 Examples 1 to 4 15 201014788 The inventors observed the electrically-treated test substrates of Examples 1 to 4 by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. It is found that the nano carbon material formed on the carbon source layer block having different horizontal distance from the copper conductive layer is of different types, so the inventor cuts the carbon source layer according to the distribution area of the different types of nano carbon material. Forming two test pieces, the block having a horizontal distance of 〇 micrometers to 2 〇〇 micrometers with the copper conductive layer is cut into a first test piece: a block with a horizontal distance of 200 micrometers to 3 micrometers from the copper conductive layer Into the second test piece.
圖6至8分別為實施例i至3之第一試片的SEM圖， 從該等圖式可以明顯看出不同實施例的第一試片之表面上 生成的奈米碳材是以二維結構的奈米碳膜為主，且當通電 時間為1分40秒時’如圖7所示，該第一試片的表面上已 經着不到奈米碳纖維，其所呈現的型態是眾多緊貼在一起 的奈米碳膜，而當通電時間為達2分鐘時，如圖8所示， 該第-試片的表面上出現的型態則是由多數聚集在一起的 奈米碳膜所形成的三維結構的奈米碳花（⑽时η&η〇ίι_6 to 8 are SEM images of the first test pieces of Examples i to 3, respectively, from which it is apparent that the nano carbon material produced on the surface of the first test piece of the different embodiments is two-dimensional. The structure of the nano carbon film is dominant, and when the energization time is 1 minute and 40 seconds, as shown in Fig. 7, the surface of the first test piece is not covered with nano carbon fiber, and the form exhibited by the first test piece is numerous. The carbon film is in close contact with each other, and when the energization time is 2 minutes, as shown in Fig. 8, the pattern appearing on the surface of the first test piece is a nano carbon film which is mostly gathered together. The three-dimensional structure of the nanocarbon flower formed ((10) η&η〇ίι_
)由此可知，通電加熱時間的長短對生成的奈米碳材的 量及型態有一定程度的影響。 圖9為實施例1之第二試片的SEM ®，由此可見， 第二試片之表面上所生成的奈米碳材的型態是奈米碳鑛 丄且絕大部分是呈中空的管狀奈米碳纖維，但是也會有 刀的實心奈米碳纖維生成。$，經量測後得知其直徑大 約爪刚疆，而實施例2至4之第二試片之表面上所生 的奈米奴材也疋如圖9戶斤示的奈米碳纖維，只是隨著通 16 201014788 時間愈長’其所生成的奈米碳纖維的直徑也愈大。 女施例5- 發明人以掃描式電子顯微鏡觀察實施例5之PI膜上所 生成的奈米碳材的型態，並依照不同型態的奈米碳材的分 布區域裁成二個試片，與該銅導電層水平距離介於〇微米 至200微米的區塊裁成第一試片；與該銅導電層水平距離 200微米至300微米的區塊裁成第二試片。如圖所示， 可以發現鄰近銅導電層的區塊（即第一試片）内所看見的 型態為奈米碳膜，而如圖11所示，離銅導電層較遠的區域 (即第二試片）内所看見的型態則是奈米碳纖維。 進一步將PI膜上所形成的奈求碳纖維與電木板上的奈 米碳纖維做比較時，可以發現PI膜上所形成的奈米碳纖維 的排列是比較凌亂且密集，而電木板上的奈米碳纖維的排 列則是比較整齊。 機制推測 §發明人以TEM/EDS分析奈米碳膜與管狀奈米碳纖維 的組成時，發現其中含有極少量的銅，由於在許多文獻中 有提及銅可作為觸媒’因此發明人不排除銅做為觸媒的可 能性’而銅的來源推測是銅導電層在通電加熱時，有部分 揮發所產生，發明人將在往後的時間做更深入的探討。 然’不論本發明製備方法的生成機制為何，综上所述 ’本發明使用簡單的設備·電源供應器對該導電層通電，即 可將電能轉換成熱能’使該碳源層有足夠的熱量發生熱裂 解’進而在其表面上形成該奈米碳材，因此，明顯可知其 17 201014788 比現有的製備方法的製程都來得簡易且成本低，此外，操 作者還可以直接拿廢棄的電木板來作為製備用的基材，所 以不但成本低還兼具環保的功效，故確實能達到本發明之 功效。 惟以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明中請專利 範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 圖1疋-立體圖’說明本發明含有奈米碳材的基板； 圖2疋一立體圖，說明用以製備本發明含有奈米碳材 的基板的基材； 圖3疋纟體圖，說明本發明含有奈米碳材的高分子 膜； ® 4是一立體圖’說明用以製備本發明含有奈米破材 的高分子膜的基材； 圖5是-立體圖，說明用以製備本發明含有奈米碳材@ 的基板的裝置； 圖6是一 SEM圖， 生成的奈米碳材的型態， 圖7是一 SEM圖， 生成的奈米碳材的型態， 圖8是一 SEM圖， 生成的奈米碳材的型態， 顯示實施例1之第一試片的表面上 其放大倍率為1〇〇〇 X; 顯示實施例2之第一試片的表面上 其放大倍率為650 X; 顯示實施例3之第一試片的表面上 其放大倍率為1500 X ; 18 201014788 圖9是一 SEM圖，顯示實施例1之第二試片的表面上 生成的奈米碳材的型態，其放大倍率為900 x ; 圖10是一 SEM圖，顯示實施例5之第一試片的表面 上生成的奈米碳材的型態’其放大倍率為1 〇〇〇 x ;及 圖11是- SEM ®，顯示實施例5之第二試片的表面 上生成的奈米碳材的型態，其放大倍率為15〇〇χ。From this, it can be seen that the length of the energization heating time has a certain influence on the amount and type of the produced nanocarbon material. 9 is a SEM ® of the second test piece of Example 1, and it can be seen that the type of the nanocarbon material formed on the surface of the second test piece is a nanocarbon ore and most of them are hollow. Tubular nano-carbon fiber, but also the solid nano-carbon fiber of the knife. $, after measurement, it is found that the diameter is about Cangjiang, and the nano-nano material produced on the surface of the second test piece of Examples 2 to 4 is also as shown in Figure 9. With the longer the time of 2010-16788, the diameter of the nanocarbon fiber produced by it is also larger. Female Example 5 - The inventors observed the morphology of the nanocarbon material formed on the PI film of Example 5 by a scanning electron microscope, and cut two test pieces according to the distribution area of the different types of nano carbon materials. The block having a horizontal distance of 〇 micrometers to 200 micrometers with the copper conductive layer is cut into a first test piece; a block horizontally spaced from the copper conductive layer by 200 micrometers to 300 micrometers is cut into a second test piece. As shown in the figure, it can be found that the pattern seen in the block adjacent to the copper conductive layer (ie, the first test piece) is a nano carbon film, and as shown in FIG. 11, the region far from the copper conductive layer (ie, The type seen in the second test piece) is nano carbon fiber. Further comparing the carbon fiber formed on the PI film with the nano carbon fiber on the electric board, it can be found that the arrangement of the nano carbon fibers formed on the PI film is relatively messy and dense, and the nano carbon fiber on the electric board The arrangement is relatively neat. Mechanism speculation § The inventors analyzed the composition of nano carbon film and tubular nano carbon fiber by TEM/EDS, and found that it contains a very small amount of copper. Since copper is mentioned as a catalyst in many literatures, the inventors do not rule out The possibility of copper as a catalyst' and the source of copper is presumed to be caused by partial volatilization of the copper conductive layer when it is energized and heated, and the inventors will conduct a more in-depth discussion in the future. However, regardless of the mechanism of the preparation method of the present invention, in summary, the present invention uses a simple device and a power supply to energize the conductive layer, thereby converting electrical energy into heat energy, so that the carbon source layer has sufficient heat. The thermal cracking occurs, and the nanocarbon material is formed on the surface thereof. Therefore, it is apparent that 17 201014788 is simpler and less expensive than the conventional preparation method, and the operator can directly take the discarded bakelite. As a substrate for preparation, it is not only low in cost but also environmentally friendly, so that the effects of the present invention can be achieved. However, the above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent change and modification according to the scope of the patent and the description of the invention in the present invention. All remain within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A is a perspective view showing a substrate containing a nano carbon material according to the present invention; and FIG. 2 is a perspective view showing a substrate for preparing a substrate containing a nano carbon material of the present invention; FIG. 5 is a perspective view showing a substrate for preparing a polymer film containing a nano-material according to the present invention; FIG. 5 is a perspective view showing a structure for illustrating a polymer film containing a nano carbon material according to the present invention; The apparatus for preparing a substrate containing nano carbon material@ of the present invention; Fig. 6 is an SEM image, the type of the formed nanocarbon material, and Fig. 7 is an SEM image, the type of the produced nano carbon material, Fig. 8 Is an SEM image, the type of the resulting nanocarbon material, showing that the magnification of the first test piece of Example 1 is 1 〇〇〇X; on the surface of the first test piece showing Example 2 The magnification was 650 X; the magnification of the surface of the first test piece of Example 3 was shown to be 1500 X; 18 201014788 Fig. 9 is an SEM image showing the nanoparticle formed on the surface of the second test piece of Example 1. The carbon material has a magnification of 900 x; FIG. 10 is an SEM image showing the fifth embodiment. The morphology of the nanocarbon material produced on the surface of the test piece was 1 〇〇〇x; and FIG. 11 is - SEM ® , showing the carbon carbon formed on the surface of the second test piece of Example 5. The type of material has a magnification of 15 〇〇χ.
19 201014788 【主要元件符號說明】19 201014788 [Main component symbol description]
1 …基板 82 ·· -----負極 10...... …奈米碳材 …·基材 11····· …底層 9 1 4· K « V 4 …"礙源層 2…… …基板 9 2..... •-…導電層 …奈米礙材 921 · •…正方形部分 21 ··* …高分子層 922… —•長條形部分 b H * λ * b …電源供應器 8 1——… …正極 201 ... substrate 82 · · ----- negative electrode 10 ... ... nano carbon material ... · substrate 11 · · · · ... ... bottom layer 9 1 4 · K « V 4 ... " barrier layer 2...... ...substrate 9 2..... •-...conductive layer...nano barrier material 921 ·•...square portion 21 ··* ...polymer layer 922...-•long strip portion b H * λ * b ...power supply 8 1 -... positive 20