臺灣博碩士論文加值系統

本研究主要探討前處理(包括離子交換、研磨插層等)對烷基銨鹽插層蒙脫石之研究，以台灣樟原黏土為主要研究對象並與市售蒙脫石比較，目的使蒙脫石之層間距離均勻增大，期使成為聚合物/蒙脫石奈米複合材料之優質前導物。研究結果指出，台東樟原黏土經充分的前處理後可有效提高其品位，得到以蒙脫石為主之產品。經一價金屬陽離子交換之蒙脫石與烷基銨鹽類反應後，得到之有機蒙脫石，層間距離隨濃度增加而增大，可達市售蒙脫石之品位。
為使純化後之蒙脫石成為優質前導物，將蒙脫石添加不同碳鏈之烷基銨鹽(C12NH3+ 和 C18NH3+)進行研磨插層試驗，藉由X光繞射儀(XRD)、紅外線光譜儀(FTIR)及穿透式電子顯微鏡(TEM)等觀察其材料結構及性質之變化，結果顯示研磨插層72小時以上，X光繞射圖在2θ=2-10°間並無明顯繞射峰出現，由Bragg’s公式計算層間距離應超過4.41 nm，以穿透式電子顯微鏡觀察濕式研磨96小時之有機蒙脫石發現，平均兩層間之距離約4.5 nm。
在不同研磨液之研磨影響比較中發現，經Na離子交換之蒙脫石在水基系統中，6小時之研磨插層雖未達到完全之脫層 (2θ=2-10°無繞射峰)，但與未離子交換48小時之研磨插層結果相當，有效縮短研磨處理時間，證實離子交換有助於烷基銨鹽之研磨插層。在油基系統中，研磨6小時C18-NH3+蒙脫石，以TEM觀察層間距離約為4.5 nm，部分邊緣高翹曲(curvature)或呈現V型處之距離高達5 nm以上增大，故研磨插層可使有機蒙脫石層間距離有效增大達到研究目的。

An experimental study has been conducted to evaluate the changes of montmorillonite under various conditions, such as different chemical ion exchange, alkylammonium, solvent (water and kerosene), intercalation by mixing and stirred ball-milling. Initial montmorillonite sample was prepared from raw bentonite/clay mined in Taitung, Eastern Taiwan. By the purification processes, it belongs to good grade in general clay resources.
For the different alkylammonium conditions, the final organic montmorillonite has been obtained via two different straight-chain organic alkylammonium of treatment, namely: C12NH3+ and C18NH3+. The microstructure of the raw material and the products were examined by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The X-ray (XRD) results show that stirred ball-milling is an effective physical operation for breaking down the size of the clay particles and facilitating the intercalation of ammonium ions. The degree of the final products is noted that the increase in the layer space, from about 1.50 nm to 4.5 nm, and no obvious peak shape at 2θ = 2–10° over 72 hours.
In order to achieve the commercial purpose, study on the effect of solvent (water and kerosene), intercalation by mixing and stirred ball-milling. The final product of exfoliated organic montmorillonite was obtained by treatment in water and kerosene systems. The optimum duration for stirred ball-milling was 6 h in both systems. In water the basal spacing increased gradually from 1.27 nm to 2.41 nm with dodecylammonium ions in the case of mixing and from 3.19 to 4.55 nm for dodecylammonium and hexadecylammonium ions during 2 h of ball-milling, respectively.

摘要　　　　　　　　　　　　　　　　　I
Abstract　　　　　　　　　　　　　　　II
致謝　　　　　　　　　　　　　　　　　III
圖目錄　　　　　　　　　　　　　　　　VI
表目錄　　　　　　　　　　　　　　　　IX
第一章 緒論　　　　　　　　　　　　　　1
　1-1前言　　　　　　　　　　　　　　　1
　1-2前人研究　　　　　　　　　　　　　4
　1-3研究目的　　　　　　　　　　　　　9
第二章 理論基礎　　　　　　　　　　　　11
　2-1蒙脫石之晶體結構　　　　　　　　　11
　2-2離子交換理論及能力　　　　　　　　14
　2-3插層劑吸附機制　　　　　　　　　　17
　2-4攪拌研磨作用　　　　　　　　　　　19
第三章 黏土純化與插層試驗　　　　　　　22
　3.1前言　　　　　　　　　　　　　　　22
　3.2實驗方式　　　　　　　　　　　　　23
　　3.2.1實驗樣品　　　　　　　　　　　23
　　3.2.2實驗試劑　　　　　　　　　　　23
　　3.2.3實驗之主要設備　　　　　　　　24
　3.3實驗方法與步驟　　　　　　　　　　27
　　3.3.1黏土之純化　　　　　　　　　　27
　　3.3.2離子交換　　　　　　　　　　　28
　　3.3.3有機蒙脫石之製備　　　　　　　28
　3.4結果與討論　　　　　　　　　　　　30
　　3.4.1蒙脫石純化結果　　　　　　　　30
　　3.4.2熱性質分析　　　　　　　　　　35
　　3.4.3陽離子交換　　　　　　　　　　38
　　3.4.4插層劑對黏土之變化　　　　　　40
　3.5小結　　　　　　　　　　　　　　　47
第四章 研磨處理對蒙脫石插層之影響　　　48
　4.1前言　　　　　　　　　　　　　　　48
　4.2實驗方式　　　　　　　　　　　　　50
　　4.2.1實驗樣品　　　　　　　　　　　50
　　4.2.2實驗試劑　　　　　　　　　　　50
　　4.2.3實驗之主要設備　　　　　　　　50
　　4.2.4蒙脫石插層試驗　　　　　　　　51
　4.3結果與討論　　　　　　　　　　　　53
　　4.3.1烷基銨鹽插層蒙脫石　　　　　　53
　　4.3.2蒙脫石濕式研磨之影響　　　　　54
　　4.3.3濕式研磨插層　　　　　　　　　57
　　4.3.4球磨之效應　　　　　　　　　　63
　　4.3.5紅外線光譜　　　　　　　　　　64
　　4.3.6 TEM構造觀察　　　　　　　　　70
　4.4小結　　　　　　　　　　　　　　　72
第五章 研磨環境對蒙脫石插層之影響　　　73
　5.1前言　　　　　　　　　　　　　　　73
　5.2實驗方式　　　　　　　　　　　　　75
　　5.2.1蒙脫石樣品來源　　　　　　　　75
　　5.2.2實驗試劑　　　　　　　　　　　75
　　5.2.3實驗之主要設備　　　　　　　　75
　　5.2.4蒙脫石有機化程序　　　　　　　75
　5.3結果與討論　　　　　　　　　　　　78
　　5.3.1離子交換與烷基銨鹽插層　　　　78
　　5.3.2水基研磨插層　　　　　　　　　79
　　5.3.3油基研磨插層　　　　　　　　　83
　　5.3.4烷基銨鹽對研磨插層之影響　　　85
　　5.3.5 TEM結構觀察　　　　　　　　　87
　5.4小結　　　　　　　　　　　　　　　89
第六章 結論　　　　　　　　　　　　　　90
參考文獻　　　　　　　　　　　　　　　 92

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