奈米結晶氧化鋯合成與分散

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姓名

王藪勳(Sho-Hsun Wang) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

奈米結晶氧化鋯合成與分散

相關論文

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★ 四氯化鈦之控制水解研究	★ 具環氧基矽烷包覆奈米粒子之研究
★ 具再分散性之奈米級氧化鋯結晶粒子之合成研究	★ 塑膠表面抗磨層之研究

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摘要(中)

奈米氧化鋯粒子表面殘留保護劑時，會對於分散性測試的結果有很大的影響。因此，本研究開發無添加任何保護劑之合成奈米氧化鋯之方法。奈米氧化鋯主要是透過碳酸鋯和氫氧化鈉經低溫水熱法所製備且具有較高的氧化鋯濃度佔整體系統中的25 wt%。奈米氧化鋯的晶相和結晶大小可根據「純鈉比」來進行調控，其「純鈉比」被定義為([Na]-2[CO3])。當「純鈉比」大於0.3時，則可得立方晶之奈米氧化鋯。當「純鈉比」從1.6增加到13.7時，其結晶大小會約從8奈米降至3奈米。
此外，本研究也利用DLVO (Derjaguin-Landau-Verwey-Overbeek)理論來探討表面修飾兩種不同類型改質劑之奈米氧化鋯粒子的分散行為。第一種為表面螯合不同長短碳鏈的有機酸。第二種為表面同時具有疏水性的有機酸和親水性的矽烷。當表面螯合長碳鏈有機酸時，奈米氧化鋯可被分散到介電常數小於7.5的有機溶劑。經固態核磁共振碳譜證實沒有額外的化學物殘留氧化鋯表面。本研究利用「軟鏈接枝模型」分析分散性測試的結果發現有機酸碳鏈的長度必須要大於0.28 nm才能使滲透勢能和彈性勢能在凡德瓦爾勢能變強之前進行抵銷。
奈米氧化鋯可以透過配位體交換法讓表面螯合具有疏水性的有機酸和親水性的矽烷。當表面具有1.90 mmol/g的丁酸和1.34 mmol/g的3-(甲基丙烯酰氧)丙基三甲氧基矽烷時，奈米氧化鋯則具有非常廣泛的分散範圍從非極性有機溶劑的苯到極性有機溶劑的異丙醇。根據DLVO理論的計算，經表面修飾奈米氧化鋯的靜電勢能遠小於位能障礙 (61.72×10-21焦耳，15KBT在298K)即使分散在高介電常數的有機溶劑。因此，奈米氧化鋯能夠具有非常廣泛的分散範圍主要是立體障礙的貢獻。在雙改質劑系統中，選擇適當相對長度的改質劑是一件非常重要的事情，因為當相對長度差距太大時，較短改質劑的性質則會被較長改質劑遮蔽。最後，經表面修飾的氧化鋯可與商用壓克力樹脂混摻且製作出折射率為1.725之奈米複合材料。因此，這樣的奈米粒子技術將可被應用在光學膜領域。

摘要(英)

The capping agents remained on the surface of the zirconia nanocrystals have an extensive effect on the dispersion test of nanoparticle. In this study, we developed a method for synthesizing zirconia nanocrystals without any capping agents. The zirconia nanocrystals was processed through zirconium carbonate basic hydrate and sodium hydroxide under the low temperature hydrothermal method. The amount of zirconia obtained per batch was as high as 25 wt%. The crystalline and grain size of zirconia was controlled by the net-Na ratio, defined as ([Na]-2[CO3]) with the produced cubic zirconia larger than 1.6, while the grain size decreased from ~8 nm to ~3 nm between net-Na/Zr=1.6 to 13.7.
In addition, the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was employed for explaining the dispersion behavior of nanoparticles grafted with two types of modifier. The first modifier contains different carbon chain length of carboxylic acid chelated on zirconia surfaces. The second modifier comprises hydrophobic carboxylic acid and hydrophilic silane. When the surface chelated with long chain carboxylic acid, the zirconia nanoparticles can be dispersed in dielectric constant less than 7.5 solvents. According to the solid state 13C NMR spectrum, no additional residues remained on the surface of zirconia nanocrystals. The soft-brush model was used to analyze the dispersion test of nanoparticles. According to the model, the length of the ligands must be longer than 0.28 nm in order for the osmotic and elastic repulsion to offset the van der Waals attraction before the latter becomes too strong.
Zirconia nanocrystals grafted with hydrophobic and hydrophilic groups can be prepared by ligand exchange method. When zirconia nanocrystals grafted with 1.90 mmol of BA and 1.34 mmol of 3-trimethoxysilyl-propyl-methacrylate (MPS) per gram zirconia, they can be dispersed from non-polar solvent such as benzene to polar solvent such as IPA. Base on DLVO calculation, the electrostatic potential was far smaller than the energy barrier of 15KBT even in high dielectric constant solvents; thus, our modified zirconia nanoparticles that can be dispersed in broad range of solvents was due to steric effect. Selecting the relative length is very important to the dispersion behavior in dual modified system because when the relative length becomes large, the short modifier would be shielded by the long modifier. Finally, the modified zirconia nanocrystals can blend with the commercial acrylic resin to produce nanocomposite with high refractive index of 1.725. Therefore, this technology of nanoparticle dispersion can be applied effectively to the research of optical film field.

關鍵字(中)

★ 氧化鋯
★ 分散
★ 表面改質

關鍵字(英)

★ Zirconia
★ Dispersion
★ Surface modification

論文目次

摘要 i
Abstract ii
Table of Contents iv
List of figures vii
List of tables xii
Chapter 1 1
Preliminary study on the dispersion of zirconia nanocrystals 1
1.1 Introduction 1
1.2 Problems to be solved 9
1.3 Organization of the thesis 11
1.4 References 19
Chapter 2 26
The synthesis of dispersible ZrO2 nanocrystals without organic capping agent 26
2.1 Introduction 26
2.1.1 Synthesis of ZrO2 nanocrystals 26
2.1.2 Raman spectroscopic analysis of the zirconia phases 30
2.1.3 Zirconia as catalyst support 31
2.1.4 The productivity of the process 32
2.1.5 The scope of this chapter 32
2.2 Experimental 34
2.2.1 Chemicals 34
2.2.2 Synthesis of ZrO2 nanocrystals 35
2.2.3 Post-treatment 36
2.2.4 Characterization 38
2.3 Results and Discussion 39
2.3.1 The formation of cubic zirconia in ZBC/NaOH system 39
2.3.2 The formation of cubic zirconia in Zr(OH)2/NaCO3/NaOH system 41
2.3.3 The formation of tetragonal phase in ZBC/KOH system 41
2.3.4 The grain size of the zirconia nanocrystals 42
2.3.5 Calcination of the Na-stabilized cubic zirconia 44
2.4 Summary 48
2.5 References 80
Chapter 3 89
Dispersion of carboxylic acid capped zirconia nanocrystals 89
3.1 Introduction 89
3.2 Experimental 94
3.2.1 Chemicals 94
3.2.2 Capping of ZrO2 nanocrystals with carboxylic acid 94
3.2.3 Characterization 95
3.3 Results and Discussion 96
3.3.1 Physicochemical properties of carboxylate capped zirconia 96
3.3.2 The dispersion of carboxylate capped ZrO2 nanocrystals in nonpolar solvents with low dielectric constant (<7.5) 97
3.3.3 Determination of the Flory-Huggins interaction parameter 98
3.3.4 Analysis based on the soft-brush model 100
3.4 Summary 106
3.5 References 124
Chapter 4 128
Dispersion of zirconia nanocrystals with carboxylate-silane dual-ligand 128
4.1 Introduction 128
4.2 Experimental 131
4.2.1 Chemicals 131
4.2.2 Partial exchange of carboxylic ligand with silane 131
4.2.3 Characterization 132
4.3 Results and Discussion 133
4.3.1 Physicochemical properties 133
4.3.2 Analysis of the solvent dispersion behavior 137
4.4 Summary 143
4.5 References 162
Chapter 5 165
Conclusion 165

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指導教授

蔣孝澈(† Anthony Shiaw-Tseh Chiang)

審核日期

2014-8-1

推文