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標題: Functionalizing Carbon Nanotube by Poly(oxyalkylene)aminefor Enhancing Dispersing Properties
作者: Lin, Sung-Tso
關鍵字: carbon nanotube;奈米碳管;Poly(oxyalkylene)amine;surface organic modification;聚醚胺類高分子;有機化表面改質
出版社: 化學工程學系
(1) 依照文獻中所提及之混合酸(H2SO4/HNO3)方式,於長時間下進行超音波震盪改質,氧化奈米碳管表面生成具有反應性之羧酸官能基。並利用商業化聚醚胺(Jeffamine® poly(oxyalkylene)amine) 於三種不同反應下(Direct Thermal Amidation,Acylation-mediated Amidation, Dicyclohexylcarbodiimide-coupling Amidation) 與羧酸官能基接合,生成醯胺化鍵結,進而延長碳管表面高分子鏈段與其他溶劑或基材之接觸面積,使相容性更為提升。
(2) 利用傅立葉紅外線光譜與熱重分析方式,判斷碳管表面所帶有之有機高分子結構以及各式反應鍵結所得不同聚醚胺類重量,進而計算彼此反應於碳管表面與聚醚胺類之醯胺化比例,得到相對高效率之奈米碳管表面醯胺化方式。
(3) 在兩階段改質步驟中,經醯胺化鍵結得到表面帶有親水性或親油性聚醚胺之奈米碳管。藉由分散於極性或非極性溶劑中,以巨觀方式分析其間相容性的差異。發現碳管因表面生成羧酸官能基,於極性溶劑中可達到均勻分散的效果,且因鍵結上鏈段長度不同之親油性聚丙烯醚胺後,進而衍生具有雙性或親油特質。
(4) 除了分散性改變之外,在微觀觀察下,以單、雙官能基及長短鏈段作區別之親水、親油性聚醚胺反應下所衍生之奈米碳管,藉助穿透式與場發射式電子顯微鏡觀察,展現出不同型態之多條奈米碳管網狀交聯排列或微奈米尺寸下之黏聚情形,清楚定義各式聚醚胺類所形成之獨特奈米碳管型態。並也由動態原子力顯微鏡間接證實了聚醚胺類確實鍵結於碳管表面之證據及其單根碳管存在時之現象。

In this dissertation, the carbon nanotube(CNT)/polymer hybrids were prepared. CNTs have received a great deal of attentions because of its unique potential applications, and high worth in electronic/photonic technology. But the carbon bonding and geometric
shape make the material hard to be well-dispersed in polymer matrix. Modifying CNT surface in order to enhance the miscibility is the main purpose of this research.
In part one, CNT has been reported that could be oxidized to carboxylic acid derivatives by using nitric acid/sulfuric acid under ultrasonic. Furthermore, amide derivatives were prepared from the reaction of CNT-acid and amines in three different methods (direct thermal, acylation-mediated, dicyclohexylcarbondiimide-coupling amidation). The resultant CNT derivatives had an increased solubility and miscibility due to the presence of polyamido-amine chain grafted on the surface.
In part two, we provided evidences for the CNT derivative with the tethering amine functionally by using Fourier transform infrared and thermal gravimetric analysis. After calculating the graft ratio of amidation reaction, the efficiency of three amidation reactions could be compared.
In part three, a series of solubility of MWNT derivatives in several organic solvents was compared. The properties of hydrophilic, hydrophobic, or amphiphilic nature for different MWNT derivatives have been characterized and correlated to the attachment of polyoxyethylene and polyoxypropylene segments on the nanotube surface in altering the solubility in polar or non-polar solvents.
In part four, the tethering polyamido-amine by polyoxyalkylene-amide linkage is not only changing the interface properties of MWNT derivatives but also influencing the dispersion ability. The various morphologies of cross-linked and micro scale aggregation was directly judged be using a transmission electron microscopy analysis and field emission-scanning electron microscopy. To further realizing the polymer morphology on the surface of MWNT, we analyze the morphology of the single-tube of MWNT derivatives by using atomic force microscopy phase image analysis.
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