臺灣博碩士論文加值系統

高表面能的奈米碳管會發生團聚現象，必須對其進行改質。一般酸洗過程相當普遍，但這會破壞電子結構而產生缺陷。為了符合工業安全，我們結合高分子與超音波震盪的搭配，使PVP以物理方式吸附於碳管表面。改質的碳管經過敏化活化作為基板，利用無電鍍技術析鍍出鎳合金。改變操作條件如劑量、時間、溫度等，以TEM觀察粒子成長的情形，因為靜磁吸引效應，粒子會沿著某一軸向排列。EDX顯示出磷的含量控制在2 ~ 3 wt%，並且以VSM量測其磁滯曲線。由於鎳在傳導電子途徑上是不錯的選擇，因此以高分子樹脂當作連續相，鍍上鎳合金的碳管則是導電填料，經由物理攪拌方式製成複合膜。以不同的添加比例測量表面電阻值，當基材為丙烯酸樹脂，電阻值始終無法下降維持109 Ω/sq；當基材為環氧樹脂，含量在4 wt%以內，約在108 Ω/sq；在9 wt%時，才降低至4.9×105 Ω/sq。

Fabrication and characteristics of polymer resin blended with carbon nanotubes (CNT) decorated with electroless nickel were attempted in this work to give an economic method to produce polymer conductive composites. Carbon nanotubes are inclined to agglomerate due to their high surface energy. Hence, before nickel could be electrolessly deposited onto CNT surface, it is necessary that surface modification on CNTs, commonly in severe acidic environment, has to be undertaken priorly to render active sites that nickel can be deposited subsequently. Instead of acidic treatment, a safe and convenient method using PVP and ultrasonification was found to be able to fulfill the function. Effects of concentration, deposition time and temperature on resulted electroless nickel decorated CNT (Ni-CNT) were investigated as well. The phosphorus content of these electroless nickel alloys is about 2 ~ 3 wt%. Owing to magnetism of nickel, the Ni-CNT appeared preferably with a 1D-order orientation. Magnetic hysteresis was measured by VSM, which revealed the saturation magnetization and remnant magnetization are around 15 and 2.5 emu/g sample. The acrylic resin and epoxy resin were used in preparing polymer conductive composites. It was found that the surface resistivity is still as high as 109 Ω/sq, when matrix is acrylic resin, and lowered to 4.9×105 Ω/sq, when 9 wt% of Ni-CNT were blended with epoxy resin.

摘要 I
Abstract II
致謝 III
目錄 IV
表目錄 VI
圖目錄 VII
第一章 緒論 1
第二章 理論與簡介 4
2-1 奈米碳管的簡介 4
2-1-1 奈米碳管的結構 4
2-1-2 奈米碳管的性質 5
2-1-3 奈米碳管的改質 8
2-2 無電鍍的簡介與原理 15
2-2-1 簡介 15
2-2-2 反應機制的探討 19
2-3 導電複合材料的簡介 23
2-3-1 導電複材的應用 23
2-3-2 導電複材的導電原理 26
2-3-3 導電黏著劑 29
第三章 實驗 33
3-1 實驗藥品 33
3-2 實驗儀器 33
3-3 實驗方法與步驟 34
3-3-1 奈米碳管的前處理 34
3-3-2 無電鍍鎳合金於碳管的製備 35
3-3-3 膜的製備 35
3-4 磁滯現象的簡介 35
第四章 結果與討論 39
4-1 以雙氧水改質的碳管作為基板 39
4-1-1 於鎳磷鍍液中反應 39
4-1-2 於鎳鎢磷鍍液中反應 41
4-2 使用界面活性劑或高分子來改質碳管 43
4-3 以PVP改質的碳管作為基板 44
4-3-1 碳管經由不同的敏化活化條件之影響 44
4-3-2 反應有無進行 46
4-3-3 鍍液中沒有添加穩定劑 46
4-3-4 錯合劑劑量的影響 48
4-3-5 反應隨時間的變化 49
4-3-6 反應隨溫度的變化 52
4-4 膜的製備 56
4-4-1 以丙烯酸樹脂為基材 56
4-4-2 以Epon 828為基材 58
第五章 結論 61
參考文獻 62
自述 67

Ang L-M, Hor TSA, Xu G-Q, Tung C-H, Zhao S, Wang JLS. Electroless plating of metals onto carbon nanotubes activated by a single-step activation method. Chem Mater. 1999;11:2115–2118.

Bal S, Samal SS. Carbon nanotube reinforced polymer composites–A state of the art. Bull Mater Sci. 2007;30:379–386.

Charbonnier M, Romand M. Tin-free electroless metallization of glass substrates using different PACVD surface treatment processes. Surf Coat Technol. 2002;162:19–30.

Chen BH, Hong L, Ma Y, Ko TM. Effects of surfactants in an electroless nickel-plating bath on the properties of Ni-P alloy deposits. Ind Eng Chem Res. 2002;41:2668–2678.

Chen H, Jacobs O, Wu W, Rüdiger G, Schädel B. Effect of dispersion method on tribological properties of carbon. Polym Test. 2007;26:351–360.

Chen J, Hamon MA, Hu H, Chen Y, Rao AM, Eklund PC, Haddon RC. Solution properties of single-walled carbon nanotube. Science. 1998;282:95–98.

Chen X, Xia J, Peng J, Li W, Xie S. Carbon-nanotube metal-matrix composites prepared by electroless plating. Compos Sci Technol. 2000;60:301–306.

Diandra LLP, Reuben DR. Magnetic properties of nanostructured materials. Chem. Mater. 1996;8:1770–1783.

Fiedler B, Gojny FH, Wichmann MHG, Nolte MCM, Schulte K. Fundamental aspects of nano-reinforced composites. Compos Sci. Technol. 2006;66:3115–3125.

Hilding J, Grulke EA, Zhang ZG, Lockwood F. Dispersion of carbon nanotubes in liquids. J Dispers Sci Technol. 2003;24(1):1–41.

Kim JA, Seong DG, Kang TJ, Youn JR. Effects of surface modification on rheological and mechanical properties of CNT/epoxy composites. Carbon. 2006;44:1898–1905.

Kim YJ, Shin TS, Choi HD, Kwon JH, Chung Y-C, Yoon HG. Electrical conductivity of chemically modified multiwalled carbon nanotube/epoxy composites. Carbon. 2005;43:23–30.

Li C-C, Lin J-L, Huang S-J, Lee J-T, Chena C-H. A new and acid-exclusive method for dispersing carbon multi-walled nanotubes in aqueous suspensions. Colloid Surface Physicochem Eng Aspect. 2007;297:275–281.

Li Q-Q, Fan S-S, Han W-Q, Sun C-H, Liang W-J. Coating of carbon nanotube with nickel by electroless plating method. Jpn J Appl Phys. 1997;36:L501–L503.

Li Y, Wong CP. Recent advances of conductive adhesives as a lead-free alternative in electronic packaging: Materials, processing, reliability and applications. Mater Sci Eng R. 2006;51:1–35.

Li ZH, Wang XQ, Wang M, Wang FF, Ge HL. Preparation and tribological properties of the carbon nanotubes–Ni–P composite coating. Tribol Int. 2006;39:953–957.

Liong S, Wong CP. Development of thermoplastic isotropically conductive adhesive. Electronic Components and Technology Conference, 2001.

Mallory GO, Hajdu JB, editors. Electroless plating: Fundamentals and applications. American Electroplaters and Surface Finishers Society, 1990.

Moisala A, Li Q, Kinloch IA, Windle AH. Thermal and electrical conductivity of single- and multi-walled carbon nanotube-epoxy composites. Compos Sci Technol. 2006;66:1285–1288.

O’Connell MJ, Boul P, Ericson LM, Huffman C, Wang Y, Haroz E, Kuper C, Tour J. Reversible water-solubilization of single-walled carbon nanotubes by polymer wrapping. Chem Phys Lett. 2001;342:265–271.

Peng Y, Liu H. Effects of oxidation by hydrogen peroxide on the structures of multiwalled carbon nanotubes. Ind Eng Chem Res. 2006;45:6483–6488.

Rina S-C, Yael L-K, Einat N-R, Rachel Y-R. Generic approach for dispersing single-walled carbon nanotubes: The strength of a weak interaction. Langmuir. 2004;20:6085–6088.

Sandler J, Shaffer MSP, Prasse T, Bauhofer W, Schulte K, Windle AH. Development of a dispersion process for carbon nanotubes in an epoxy matrix and the resulting electrical properties. Polymer. 1999;40:5967–5971.

Shan L, Verghese KNE, Robertson CG, Reifsnider KL. Effect of network structure of epoxy dgeba-poly(oxypropylene)diamines on tensile behavior. J Polym Sci Part B: Polym. Phys. 1999;37:2815–2819.

Tasis D, Tagmatarchis N, Georgakilas V, Prato M. Soluble carbon nanotubes. Chem Eu. J. 2003;9:4000–4008.

Vaisman L, Wagner HD, Marom G. The role of surfactants in dispersion of carbon nanotubes. Adv Colloid Interface Sci. 2006;128-130:37–46.

Vigolo B, Pénicaud A, Coulon C, Sauder C, Pailler R, Journet C, Bernier P, Poulin P. Macroscopic fibers and ribbons of oriented carbon nanotubes. Science. 2000;290:1331–1334.

Wang F, Arai S, Endo M. The preparation of multi-walled carbon nanotubes with a Ni–P coating by an electroless deposition process. Carbon. 2005;43:1716–1721.

Xie X-L, Mai Y-W, Zhou X-P. Dispersion and alignment of carbon nanotubes in polymer matrix: A review. Mater Sci Eng R. 2005;49:89–112.

Yang Z, Xu H, Shi Y-L, Li M-K, Huang Y, Li H-L. The fabrication and corrosion behavior of electroless Ni–P-carbon nanotube composite coatings. Mater Res Bull. 2005;40:1001–1009.

Yin X, Hong L, Chen BH. Role of a Pb2+ stabilizer in the electroless nickel plating system: A theoretical exploration. J Phys Chem B. 2004;108:10919–10929.

Youngs IJ. Exploring the universal nature of electrical percolation exponents by genetic algorithm fitting with general effective medium theory, J Phys D: Appl Phys. 2002;35:3127–3137.

Yu ZJ, Kang ET, Neoth KG. Electroless plating of copper on polyimide films modified by surface grafting of tertiary and quaternary amines polymers. Polymer. 2002;43:4137–4146.

Yuan XY, Xie T, Wu GS, Lin Y, Meng GW, Zhanga LD. Fabrication of Ni–W–P nanowire arrays by electroless deposition and magnetic studies. Physica E. 2004;23:75–80.


黃仁豪, 抗靜電/靜電消散之導電塑膠材料及應用簡介, 工業材料 (1995)

莊萬發, 科學用書 無電解鍍金–化學鍍金技術, 復漢出版社 (2000)