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博碩士論文 etd-0726100-180133 詳細資訊
Title page for etd-0726100-180133
論文名稱
Title
含矽鋁之CTAB水溶液中形成的中尺度結構相, MCM-41與三水鋁石
Microstructures of Mesophases, MCM-41 and Gibbsite Formed in CTAB/Water System with Negatively Charged Silicate and Aluminate Species
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
162
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2000-07-17
繳交日期
Date of Submission
2000-07-26
關鍵字
Keywords
溴化十六烷基三甲基銨、高嶺土、穿透式電子顯微鏡
Kaolinite, Cetyltrimethyl ammonium brombide (CTAB)
統計
Statistics
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中文摘要
本論文主要是利用一個陽離子界面活性劑溴化十六烷基三甲基銨(CTAB)當模板和矽酸鈉、鋁酸鈉在pH=10的情況下來合成MCM-41分子篩和層狀相。

第第Ⅰ部份分別以鋁酸鈉(最高達0.25莫耳比例)和矽酸鈉當作Al 和Si的先驅物;在第Ⅱ部分則以高嶺土Al4[Si4O10](OH)8當作先驅物。溶液置於鐵氟龍封住的不?袗?容器中在100℃反應72小時後,所得固體物經過濾,在560℃鍛燒或用乙醇沖洗之後,以X光繞射、偏光顯微鏡、掃瞄式電子顯微鏡或穿透式電子顯微鏡來觀察其顯微構造並討論中尺度結構相的形成機構。

第Ⅰ部份:
乙醇清洗鍛燒和顯示皆可以成功地去除模板,得到的MCM-41小顆粒會合併(coalesced);而長條狀物長到某一程度就會彎曲。六角形堆積(2-D hexagonal)的MCM-41,其管與管的間距是4.5-5.4 nm、管壁厚度在1.9-3.7 nm之間,二者隨著鋁酸鈉/矽酸鈉的比例(高至0.1莫耳比例)的增加而增加。此外管的直徑亦隨著Al/Si的比例增加。MCM-41具有{100}晶癖面和結實的非晶管壁,顯示MCM-41之形成是由附著了含鋁矽無機物的稈狀微胞,依最密堆積面,排列而成。管中管超過一長度後(典型是1μm)會起皺折和彎曲。

第Ⅱ部分:
發現 高嶺土/CTAB/水 系統(以KCH代表)在pH=10會形成含水的凝膠(gel),到最後還是會脫水。此凝膠最後會轉變成板狀三水鋁石及樹枝狀的含鋁酸鹽的層狀相。而在CTAB/水 系統中,則長出板狀及樹枝狀的CTAB液晶或結晶相。

Abstract
Abstract
Cationic surfactant cetyltrimethyl ammonium brombide (CTAB) was used as template to synthesize aluminosilicate MCM-41 (plane group P6m, hexagonal array of uniform mesopores derived from crystalline colloidal array (CCA)) molecular sieve and lamellar phases in colloidal solution with negatively charged silicate and aluminate species at pH=10. In the first part, sodium aluminate (up to 0.25 molar ratio) and sodium silicate were the precursor of Al and Si, respectively; in the second part, kaolinite (Al4[Si4O10](OH)8) was used instead. The hydrothermally reacted (100oC in a Teflon sealed container) materials subject to room temperature drying, calcination (540oC) or ethanol rinsing were studied by X-ray diffraction (XRD), optical microscopy under plane polarized light or transmission electron microscopy (TEM) with emphasis on the microstructures and formation mechanism of mesophases, MCM-41, and gibbsite (Al(OH)3) at a relatively low CTAB/water ratio and the effect of Al/Si ratio on micelle interspacing in terms of micelle size and aluminosilicate wall thickness.

In the first part, both calcination and ethanol rinsing were shown to remove the template successfully. The resultant MCM-41 particulates were more or less coalesced and the elongated ones tended to be folded. The hexagonal MCM-41 has a tube interspacing 4.5-5.4 nm and tube wall thickness 1.9-3.7 nm, both generally increasing with the increase of sodium aluminate/sodium silicate ratio up to 0.1 molar. ratio. The tube diameter also increased slightly presumably because of competitive electrostatic coordination of the hydrophilic head of CTAB with the negatively charged aluminate (AlO2-) vs. silicate (SiO4-4) species stable at pH=10. The MCM-41 particulates have well-developed {100} faces, the close-packed plane of 2-D hexagonal structure, and rigid amorphous tube walls, suggesting interface-controlled assembly of rod-like CTAB micelles with their polar head already incorporated with aluminosilicate. Tubules-within-a-tubule were corrugated and folded when extended beyond a certain persistence length, typically 1 mm. Spherical particles with disordered mesopores (typically ca. 4 nm in mesh size) due to entanglement of micelles under semi-dilute condition were also formed.

In the second part, the CTAB-saturated solution at pH=10 was separated from mud-like kaolinite to form translucent hydrous gel. Upon drying on a glass slide at room temperature, the gel became whitish because of the following crystallization events. First, whitish gibbsite nucleated preferentially at gel/air and gel/glass interface to form spherulites. The spiral and lateral growth of plate-like gibbsite crystal with {100} and {110} growth front was rapid enough to entrap solution droplets. Subsequently, dendritic lamellar (basal spacing ca. 2.6 nm according to XRD and TEM observations) mesophase exhibiting length fast and clino-extinction with extinction angle 42o was formed via 2-D growth near the edge of the drying gel. This lamellar phase was incorporated with aluminate according to TEM-EDX analysis. Finally, explosive nucleation and dendritic growth of isotropic phase concluded the crystallization. This final event involved surface nucleation as best exhibited at the droplets trapped in gibbsite host. Upon calcination to remove the surfactant, the aluminosilicate MCM-41 retained while aluminate-incorporated lamellar mesophase disappeared as indicated by XRD. In an additional experiment to understand the crystallization behavior of CTAB in drying water, we found that the plate-like and then dendritic monoclinic lamellar phase (space group P21/c) with optical extinction angle of 37o was formed as the growth dimensionality decreased toward the edge of the gel. This nucleation and growth process is analogous to the CTAB/water system with negatively charged silicate and aluminate species derived from kaolinite at pH=10.


目次 Table of Contents
Contents

Abstract
Contents
List of Figures
Introduction

Part I
Formation of lamellar phase and MCM-41 in CTAB/water
dissolved with sodium silicate and sodium aluminate
I .1. More about M41S and MCM-41 Material and
motivation of this research
I. 2 Experimental
I.2.1 Calcination route
I.2.2 Dissolution route
I.2.3 Adjusting Al/Si ratio to regulate the tubule's spacing
I.3 Results
I.3.1 Calcination route
(A). XRD
(B). SEM
(C). TEM
I.3.2 Dissolution route
(A). XRD
(B). SEM
(C). TEM
I.3.3 Tube spacing change as a function of the Al/Si ratio
(A). XRD
(B). SEM
(C). TEM
I. 4 Discussion
I.4.1 Effect of Al/Si ratio on the shape of micelle
I.4.2 Effect of Al/Si ratio on tube spacing of MCM-41
I.4.3 Formation mechanism of hexagonal liquid crystal and tubules
I.4.4 Flexibility of tubular aluminosilicate MCM-41
I.4.5 Aluminosilicate framework relaxation upon template removal via disolution route

Figures


Part Ⅱ.
Formation of mesophases, MCM-41 and gibbsite in kaolinite CTAB/water system–gelation and devitrification of colloidal solution
Ⅱ.1 Outline and background
Ⅱ.2 Experimental
Ⅱ.3 Results
Ⅱ.3.1 CTAB/H2O system
Ⅱ.3.2 CTAB/water /kaolinite system
Ⅱ.4 Discussion
Ⅱ.4.1 Kaolinite and gibbsite in equilibrium with charged species at pH=10
Ⅱ.4.2 CTAB/H2O/aluminosilicate mixture gel
Ⅱ.4.3 Crystallization path of dehydroxylating gel upon dehydroxylation
Ⅱ.4.4 Template-assisted crystallization of gibbsite and alumina/CTAB lamellar phase
Ⅱ.4.5 Effect of growth dimensionality on the morphology of lamellar phase

Figures

Conclusions

References


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