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研究生： 曾士豪
論文名稱： 單壁奈米碳管量產及其光聲響性質之研究
Large-scale Production and Photoacoustic Effect of Single Wall Carbon Nanotubes
指導教授： 戴念華
口試委員:
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學工程學系
Materials Science and Engineering
論文出版年： 2005
畢業學年度： 93
語文別： 中文
論文頁數： 194
中文關鍵詞： 單壁奈米碳管 、懸浮觸媒法 、光聲響 、垂直爐管 、燃燒 、聲波 、氧化 、奈米碳球 、二茂鐵
外文關鍵詞： single wall carbon nanotube, floating catalyst method, photoacoustic, vertical furnace, ignition, acoustic wave, oxidation, carbon nanocapsule, ferrocene
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    • 本實驗以水平式懸浮觸媒法製備高純度單壁奈米碳管絨球，研究單壁奈米碳管絨球經照光產生氧化以及光聲響的效應。本實驗發現所生產之單壁奈米碳管絨球照光會產生聲波並伴隨碳氧化反應與Fe2SiO4顆粒狀產物的出現，改變照光氣氛 (包含真空與惰性氣氛下)可進一步確認此產物的出現是由於氧化所造成。本實驗同時也利用二茂鐵去推論絨球照光後的表面溫度，並發現Fe2SiO4出現與否與催化劑的存在具有相當大的關聯，而出現燃燒或是氧化結果主要是因為催化劑含量的多寡所致，這可以奈米碳球照光的結果做進一步的驗證。同時在光聲響頻譜量測方面也發現單壁奈米碳管的聲波強度遠大於相關的碳材料，可高達0.0045 pa，藉此也推測出聲波的出現與結構的變化乃是由於光聲響機制所造成。
    另一方面，本實驗進一步以自組裝垂直式爐管量產單壁奈米碳管，實驗結果證實產量可達到200 mg/10 min以上，並可發現單壁奈米碳管確實可纏繞於收集器的旋轉軸上，此一維束狀結構未來可應用於複合材料以及相關強化材。

    The high purity fluffy SWNT ball was synthesized through the floating catalyst method in a horizontal tube furnace. Ignition and photoacoustic effects of SWNT ball due to flash exposure were investigated. Acoustic wave accompanied with formation of Fe2SiO4 particles was detected. This phenomenon can be further verified as rapid expansion of surrounding air and carbon oxidation. Ferrocene on fluffy SWNT ignited after flashing, which indicates that the surface temperature of carbon nanotubes after flashing exceeds burning temperature of ferrocene. It also found that the appearance of Fe2SiO4 was related to the existence of iron catalyst. Depending on the catalyst amount in SWNTs, the fluffy ball may ignite or oxidize, according to the response of carbon nanocapsules after flash exposure. The acoustic intensity of fluffy SWNT ball is stronger than that of other carbon materials such as MWNT, carbon fiber, carbon powders etc. Based on the results, it is concluded that the structure transformation of fluffy ball is due to the photoacoustic effect.
    Moreover, this work established a vertical tube furnace to synthesize the SWNTs with large scale production rate, and a production rate high up to 200 mg/10 min can be achieved. This one dimension SWNT rope can be applied to composite and reinforced materials in the future.

    中文摘要..................................................Ⅰ 英文摘要..................................................Ⅱ 致謝......................................................Ⅲ 總目錄....................................................Ⅳ 圖表目錄..................................................Ⅸ 第一章 緒論...............................................1 1.1簡介................................................1 1.2奈米碳管結構與性質..................................1 1.3奈米碳管製程........................................3 1.3.1 電弧放電法 (arc-discharge)....................3 1.3.2 雷射蒸發法（laser ablation）..................4 1.3.3 化學氣相沉積法(chemical vapor deposition).....4 1.3.4 研究目的與動機................................5 第二章 文獻回顧..........................................12 2.1高溫裂解碳氫化合物製備奈米碳管.....................12 2.1.1多孔隙矽基板成長奈米碳管......................12 2.1.2化學氣相沉積懸浮觸媒法........................12 2.1.3熱燈絲化學氣相沈積法(HFCVD)...................14 2.1.4量產及收集單壁奈米碳管........................14 2.2 光聲響效應 (photoacoustic effect).................15 2.3 單壁奈米碳管光聲響及燃燒..........................19 2.3.1 單壁奈米碳管燃燒的發現.......................19 2.3.2 單壁奈米碳管的來源...........................22 2.4 奈米碳球製造方法..................................23 第三章 研究方法與實驗步驟................................39 3.1 研究方法..........................................39 3.2 實驗方法及步驟....................................39 3.2.1 水平式懸浮觸媒法成長單壁、雙壁、多壁奈米碳管及奈碳球.....................................................39 3.2.2 光聲響實驗...................................42 3.2.3 閃光實驗.....................................43 3.2.3.1空氣下閃光.................... ........43 3.2.3.2 真空下閃光............................44 3.2.3.3 惰性氣體下閃光........................44 3.3 單壁奈米碳管純化..................................44 3.4 半連續式奈米碳管收集量產..........................45 3.5 使用及分析儀器....................................48 3.5.1 水平式CVD....................................48 3.5.2 垂直式CVD....................................49 3.5.3閃光燈........................................51 3.5.4 掃瞄穿遂式電子顯微鏡.........................51 3.5.5 穿透式電子顯微鏡.............................52 3.5.6 拉曼光譜儀...................................52 3.5.7 X光繞射儀...................................54 第四章 結果與討論........................................55 4.1水平式懸浮觸媒法成長單壁、多壁奈米碳管與奈米碳球...55 4.1.1 單壁奈米碳管的製備...........................55 4.1.2 奈米碳球的製備...............................58 4.1.3 多壁奈米碳管製備.............................58 4.2 閃光燈照光........................................59 4.2.1 奈米碳管照光.................................60 4.2.2 奈米碳管絨球照光氧化.........................60 4.2.3 單壁奈米碳管絨球巨觀結構變化.................61 4.2.4 單壁奈米碳管絨球微觀結構變化.................63 4.2.5 單壁奈米碳管與多壁奈米碳管薄膜微觀結變化.....65 4.2.6 奈米碳管照光後產物的鑑定.....................65 4.2.6.1 SEM及EDS分析..........................65 4.2.6.2 TEM及EDS分析..........................68 4.2.6.3 Xray分析..............................70 4.2.6.4 Raman光譜分析.........................70 4.2.7 純化後單壁奈米碳管照光.......................71 4.2.8 真空氣氛下照光...............................72 4.2.9 Ar氣氛下照光.................................73 4.2.10 單壁奈米碳管絨球加上二茂鐵照光..............74 4.2.11 奈米碳球照光................................76 4.2.12 奈米碳球照光後產物結構分析..................77 4.2.12.1 SEM及EDS分析.........................77 4.2.12.2 TEM分析..............................78 4.2.12.3 X-ray分析............................79 4.3 單壁奈米碳管氧化熱處理............................80 第五章 光聲響量測及機制.................................155 5.1 光聲響量測.......................................155 5.2 空白實驗.........................................155 5.3 單壁奈米碳管光聲響量測...........................156 5.4 相關碳材料光聲響量測.............................157 5.5 光聲響機制.......................................158 第六章 垂直爐管式量產單壁奈米碳管.......................176 第七章 結論.............................................188 第八章 參考文獻.........................................191

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