林金福臺灣大學：材料科學與工程學研究所潘漢聰Pan, Han-ChungHan-ChungPan2007-11-262018-06-282007-11-262018-06-282004http://ntur.lib.ntu.edu.tw//handle/246246/55200本文研究之目的是探討矽酸鹽層包覆界面活性劑(Cetyltrimethylammonium bromide，CTABr)奈米複合材料的製程、結構和物性。利用界面活性劑CTABr和矽酸鹽的系統作為討論的基礎。在界面活性劑CTABr和矽酸鹽的系統中，改變不同比率的cetyltrimethylammonium bromide 、tetramethoxysilane、水和溶液中的pH值，作為surface-templated mseostructure silicate film此微胞結構形成的討論基礎。 界面活性劑CTABr形成的微胞(micelle) 與silicate互相作用的關係有三項的主要因素: 一為界面活性劑的濃度效應。當界面活性劑濃度超過CMC時，會形成微胞。二為pH效應。當鹽酸加入越多時，微胞和silicate愈易作用，因此微胞聚集的程度就越嚴重，常會有凝膠(gel)的情形出現。三為silicate的濃度效應。聚合性矽酸鹽silicate可視為陰離子的聚電解質(polyelectorolyte)，會和帶正電荷溴離子的界面活性劑CTABr形成的微胞作用。而silicate會進一步地切割界面活性劑CTABr形成的微胞，而產生10 nm大小左右的奈米管結構。我們將把此一溶液系統乾燥成粉末，進一步地利用不同的實驗方法如小角度散射、TEM、XRD、BET、AFM來觀察此微結構的孔洞大小及分布。 我們另外加入螢光劑pyrene進一步研究CTABr、矽酸鹽和pyrene的聚集情形。由於pyrene的螢光性質顯示出強烈的溶劑效應。在pyrene分子的五個特徵波峰中，其強度隨溶劑環境的偶極矩和介電常數而變化。因此我們利用pyrene分子的第三根特徵波峰和第一根特徵波峰的強度比值，來探測微胞周圍環境的變化、決定界面活性劑的極端微胞濃度(critical micelle concentration)和研究pyrene excimer的行為。The main purpose of this research was to study the processing, structure and physical properties of cetyltrimethylammonium bromide (CTABr) templated nano-porous silicate material. We altered the ratios of cetyltrimethylammonium bromide, tetramethoxysilane, water and pH value in the formulations to investigate the suitable condition for the the formation of micelles and their templated mesostructural silicate film. There are three factors for the formation of surfactant-templated nano-porous structure needed to be considered. First, the concentration effect of the surfactant: when the concentration of the surfactant exceeds CMC, surfactant molecules can aggregate to form micelles. Second, the effect of the pH value: when the amount of HCl is increased, micelles interact wih silicate stronger, resulting in severe aggragation between micelles and silicate. Third, the concentration effect of the silicate: silicate is regarded as an anionic polyelectorolyte which can interact with micelles through the cationic amine groups of CTABr. The concentration of silicate should be high enough to cover the surface of micelles and further divide the aggregate of micelles into an array of nanotubes. After freeze-drying the solution into powders, we calcinated the powders and used small angle x-ray scattering, TEM, XRD, BET, AFM to investigate their meso-porous structures and estimate their pore size distribution. Besides, we attempted to employ pyrene as a fluorescence sensor to investigate the micelle formation and their aggregation condition after the incorporation of silicate. Because the fluorescence properties of pyrene show strong solvation effects, we could use it to determine the critical micelle concentration of the surfactant as well as to study the initial formation of mesoporous structure in solutions.目錄 中文摘要------------------------------------------------------------------------------------------2 英文摘要------------------------------------------------------------------------------------------3 目錄------------------------------------------------------------------------------------------------4 表索引---------------------------------------------------------------------------------------------6 圖索引---------------------------------------------------------------------------------------------7 第一章 緒論 1.1前言----------------------------------------------------------------------------------13 1.2 界面活性劑簡介--------------------------------------------------------------------------16 1.3界面活性劑之文獻回顧與理論發展---------------------------------------------------18 1.3.1界面活性劑之理論發展----------------------------------------------------------------18 1.3.2微胞的結構-------------------------------------------------------------------------------------21 1.3.3臨界微胞濃度(CMC)和微胞之熱力學--------------------------------------------------22 1.3.4矽酸鹽界面活性劑奈米管之文獻回顧----------------------------------------------23 1.4 pyrene簡介---------------------------------------------------------------------------------26 1.4.1在同質溶劑中的螢光-------------------------------------------------------------------27 1.4.2在微胞環境下的pyrene螢光---------------------------------------------------------28 1.5 本文目的-----------------------------------------------------------------------------------------28 第二章 實驗部分 2.1 實驗材料-----------------------------------------------------------------------------------30 2.2 實驗儀器-----------------------------------------------------------------------------------30 2.3實驗方法------------------------------------------------------------------------------------32 電導測量與分析-------------------------------------------------------------------------------32 表面張力測量----------------------------------------------------------------------------------33 silicate的製備----------------------------------------------------------------------------------33 silica-surfactant的溶液的製備--------------------------------------------------------------34 surfactant-pyrene溶液silica-surfactant-pyrene溶液的製備----------------------------34 PL光譜-------------------------------------------------------------------------------------------35 粉末的配置-------------------------------------------------------------------------------------35 結構觀察----------------------------------------------------------------------------------------36 孔洞分布測量----------------------------------------------------------------------------------37 第三章 結果和討論 3.1 測量界面活性劑CTABr的臨界微胞濃度(CMC)----------------------------------39 3.1.1 利用表面張力測量臨界微胞濃度(CMC)------------------------------------------39 3.1.2 利用電導值測量臨界微胞濃度(CMC)---------------------------------------------39 3.1.3 利用螢光光譜探測測量臨界微胞濃度(CMC)------------------------------------40 3.2 利用PL光譜探測分析界面活劑CTABr和pyrene分子的聚集情形-----------41 3.2.1在CMC附近(8*10-4M)的PL光譜探測---------------------------------------------41 3.2.2在CMC之上(8*10-4M)的PL光譜探測---------------------------------------------42 3.2.3 比CMC高一點的濃度(9*10-4 M)，加入更入的pyrene，使一個微胞中包含更多的pyrene分子的PL光譜探測-------------------------------------------------42 3.2.4 探討exmimer和界面活性劑及silicate之關係-----------------------------------43 3.3孔徑分佈------------------------------------------------------------------------------------45 3.4結構觀察 -----------------------------------------------------------------------------------46 第四章 結論------------------------------------------------------------------------------------47 參考文獻----------------------------------------------------------------------------------------49 圖-------------------------------------------------------------------------------------------------542236971 bytesapplication/pdfen-US矽酸鹽tetramethoxysilanesilicacetyltrimethylammonium bromidethesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/55200/1/ntu-93-R91527019-1.pdf