臺灣博碩士論文加值系統

本實驗主要是以溶膠-凝膠法(Sol-gel)合成出具規則性排列之奈米中孔洞(mesopore)白榴石牙科瓷，實驗分成四個部份探討，分別是界面活性劑含量改變造成孔洞形成的影響因素，溫度的作用下探討孔洞的規則性現象，熟化環境溫度的變化是否能影響孔洞狀態及pH值對孔洞狀態的影響。
實驗結果顯示，可由XRD圖得知在900℃以上熱處理得到白榴石晶體。以三區塊共聚高分子作為天然模板，於室溫環境合成下可產出中孔洞粉末，由吸/脫附曲線圖形的趨勢走向，可以知道本實驗所製備的粉末內部有序中孔洞為圓柱狀通道孔洞型態，藉由恆溫吸/脫附儀的量測並配合BET與BJH理論，顯示所具有的中孔洞平均孔洞尺寸大小在7~8 nm之間，此外其他的結果，如界面活性劑添加量的多寡，可清楚顯示微胞堆積情況會影響中孔洞材料的結構，在P123莫爾分率為0.38孔洞數量最多且排列最佳。熱處理溫度對孔洞型態影響顯著，在650℃孔洞將完全被破壞。當60℃恆溫熟化在界面活性劑添加量為0.17~0.25莫爾比時有助於孔洞排列規則性，反之則不利。利用小角度繞射圖的結果分析後，可清楚得知熱處理溫度確實是具有明顯控制孔洞排列的能力。當鹽酸水溶液濃度增加時孔徑縮短，比表面積下降。由穿透式電子顯微鏡影像圖觀察證明，本實驗所製備的中孔洞粉末其孔洞型態為圓柱狀通道，孔洞排列方式則為二維-六角堆積型結構(2D-hexagonal)，是屬於對稱p6mm點群。最後在奈米銀填充所形成之奈米銀與中孔洞樣品複合粉末有抑菌效果，且奈米銀粒子粒徑大小為7~8 nm。

The purpose of this study was tried to fabricate the leucite porcelain with ordered mesoporous structure. We have four topics in this plan to discuss. A study amount on the basis of the interactions between inorganic-organic to form meso-structured composites.The reaction temperature is relatively order of mesostructure. The pore structures of mesoporous materials depend on the temperature changing and pore condition of mesoporous materials depend on the pH value of micells formation.
The results shown the temperature of calcination over 900℃ leucite crystal was obtained. The triblock copolymer surfactant (P123) was employed as the structure agents for synthesizing the mesopore leucite at room temperature. According to the isothermal nitrogen adsorption-desorption curve and the Barrett- Emmett-Teller (BET) and Barrett-Joyner-Halanda (BJH) theories, the results shown that the mesoporous structure with the pore size of 7~8 nm. The concentration of the surfactant low micelle formation is difficult to great shape. P123 was 0.38 mol ratio to obtaine the best amount and order of mesopore. Pores were break down when the temperature of calcination were over 650℃.Decreasing surfactant mol ratio was helpful for order mesostructure formation when aging at 60℃.But it could be opposite when increasing surfactant. Then, poer size and the BET value were decreased with the increasing pH value. These results were confirmed by TEM and reveal a highly ordered 2D-hexagonal arrangement of one-dimensional channel with a symmetry p6mm space group.

摘要 I
ABSTRACT .II
誌謝 III
目錄 IV
表目錄 VI
圖目錄 .. VII
第一章 緒論 1
1.1 前言 1
1.2 研究背景 4
1.3 研究方向與目的 4
第二章 理論基礎與文獻回顧 5
2.1 牙科材料 5
2.1.1 白榴石介紹 5
2.1.2 義齒清潔及損壞 ….... 9
2.2 中孔洞材料介紹 .. 9
2.2.1 中孔洞材料的研究與發展 .15
2.2.2 自組合反應法簡介 .17
2.2.3 界面活性劑性質介紹 .20
2.3 奈米銀性質介紹 .25
2.3.1 奈米銀合成 .25
2.3.2 奈米銀抗菌 .27
第三章 實驗方法與步驟 .28
3.1 材料 .28
3.2 白榴石合成步驟 .29
3.3 中孔洞白榴石合成步驟 .29
3.3.1 中孔洞白榴石實驗參數 .31
3.4 中孔洞填充奈米銀 .31
3.4.1 熱裂解法 .31
3.4.2 光化學法 .32
3.4.3 固態抗菌分析 .32
3.5 材料性質分析 .32
第四章 結果與討論 .35
4.1 白榴石之合成及性質 .35
4.2 中孔洞結構白榴石之合成 .37
4.2.1 界面活性劑含量對中孔洞白榴石合成之影響 .37
4.2.2 熱處理溫度對中孔洞白榴石結構之影響 .53
4.2.3 恆溫熟化對中孔洞白榴石結構之影響 .60
4.2.4 不同鹽酸水溶液濃度對中孔洞白榴石合成之影響 .65
4.3 中孔洞白榴石填充奈米銀 .75
第五章 結論…. .77
參考文獻 .78

[1]葉瑞明，奈米科技導論，高立，2004，127-130。
[2]M. Zukalová, A. Zukal, L. Kavan, M. K. Nazeeruddin, P. Liska and M. Grätzel, “Organized mesoporous TiO2 films exhibiting greatly enhanced performance in dye-sensitized solar cells”, Nano Lett., 2005, 5, 1789-1792.
[3]X. S. Zhao, X. Y. Bao, W. Guo and F. Y. Lee, “Immobilizing catalysts on porous materials”, Materials Today, 2006, 9, 32-39.
[4]X. X. Yan, C. Z. Yu, X. F. Zhou, J. W. Tang and D. Y. Zhao, “Highly Ordered Mesoporous Bioactive Glasses with Superior In Vitro Bone-Forming Bioactivities”, Angewandte Chemie - International Edition , 2004, 43, 5980.
[5]T. Wagner, T. Waitz, J. Roggenbuck, M. Fröba, C.-D. Kohl and M. Tiemann, “Ordered mesoporous ZnO for gas sensing”, Thin Solid Films, 2007, 515, 8360-8363.
[6]K. J. Anusavice: “Dental ceramics”, Phillips’ Science of DentalMaterials/10th edition, 1996, pp. 583-618.
[7]G. J. de A. A. Soler-Illia, and P. Innocenzi, “Mesoporous Hybrid Thin Films: The Physics and Chemistry Beneath”, Chemistry - A European Journal, 2006, 12, 4478 – 4494.
[8]G. J. de A. A. Soler-Illia, E. L. Crepaldi, D. Grosso and C. Sanchez, “Block copolymer-templated mesoporous oxides”, Current Opinion in Colloid and Interface Science, 2003, 8, 109–126.
[9]IUPAC Manual of Symbols and Terminology, Appendix 2, Part 1, Colloid and Surface Chemistry. Pure and Applied Chemistry, 1972, 31, 578.
[10]楊家銘，奈米孔洞材料之物理吸脫附分析，科儀新知，第二十六卷，第六期，2005，32-38。
[11]G. Q. Lu and X. S. Zhao, “Nanoporous Materials:Science and Engineering”, Imperial College Press, 2004, 317-364.
[12]王明光，王敏昭，實用儀器分析，合記，2003，125-159。
[13]M. Kruk and M. Jaroniec, “Gas Adsorption Characterization of Ordered Organic-Inorganic Nanocomposite Materials”, Chemistry of Materials, 2001, 13, 3169-3183.
[14]C. T. Kresge, M. E. Leonowicz, W. J. Roth; J. C. Vartuli; J. S. Beck “Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism.” Nature, (London, United Kingdom) 1992, 359, 710-712.
[15]J. S. Beck; J. C. Vartuli; W. J. Roth; M. E. Leonowicz; C. T. Kresge; K. D. Schmitt; C. T. W. Chu; D. H. Olson; E. W. Sheppard; et al “A new family of mesoporous molecular sieves prepared with liquid crystal templates.” Journal of the American Chemical Society, 1992, 114, 10834-10843.
[16]J. C. Vartuli; C. T. Kresge; W. J. Roth; S. B. McCullen; J. S. Beck; K. D. Schmitt; M. E. Leonowicz; J. D. Lutner; E. W. Sheppard “Designed synthesis of mesoporous molecular sieve systems using surfactant-directing agents.” Advanced Catalysts and Nanostructured Materials, 1996, 1-19.
[17]D. Zhao; Q. Huo; J. Feng; B. F. Chmelka; G. D. Stucky “Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous silica structures.” Journal of the American Chemical Society, 1998, 120, 6024-6036.
[18]D. Zhao; J. Feng; Q. Huo; N. Melosh; G. H. Frederickson; B. F. Chmelka; G. D. Stucky “Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores.” Science, (Washington, D.C.) 1998, 279, 548-552.
[19]M. Imperor-Clerc; P. Davidson; A. Davidson “Existence of a microporous corona around the mesopores of silica-based SBA-15 materials templated by triblock copolymers.” Journal of the American Chemical Society, 2000, 122, 11925-11933.
[20]C. J. Brinker, Y. Lu, A. Sellinger and H. Fan, “Evaporation-Induced Self-Assembly :Nanostructures Made Easy”, Advanced Materials, 1999, 11, 579-585.
[21]P. Yang, D. Zhao, D. I. Margolese, B. F. Chmelka and G. D. Stucky, Generalized syntheses of large-pore mesoporous metal oxide with semicrystalline frameworks, Nature, 396, 152-155 (1998).
[22]D. Grosso, G. J. A. A. Soler-Illia, E. Crepaldi and C. Sanchez, Nanocrystalline transition metal oxide spheres with controlled multi-scale porosity, Adv. Funct. Mater., 13, 37-42 (2003).
[23]G. J. de A. A.Soler-Illia, E. L. Crepaldi, D. Grosso and C. Sanches, Block copolymer-templated mesoporous oxides, Curr. Opin. Colloid Interface Sci., 8, 109-126 (2003).
[24]F. Schüth, Kenneth S. W. Sing, Jens WeitKamp, Handbook of Porous Solids, WILEY-VCH, vol 3, 2002, 1313-1315.
[25]王世榮, 李祥高, 劉東志, 表面活性劑化學, 化學工業, 2005, 1-26.
[26]張驊, 胡耿源, 表面活性劑化學, 浙江大學, 1996, 173-182.
[27]Y. Wan and D. Zhao “On the Controllable Soft-Templating Approach to Mesoporous Silicates”, Chemical Reviews, 2007, Vol. 107, No. 7.
[28]B. Lindman and H. Wennerström, Micelles : Amphiphile Aggregation in Aqueous Solution, Springer-Verlag, Heidelberg, 1980.
[29]J. N. Israelachvili, S. Marcelja, R. G. Horn, Q. Rev. Biophys, 1980, 13, 121.
[30]D. J. Mithchell, B. W. Ninham, J. Chem. Soc., Faraday, Trans. II., 1981, 77, 1264.
[31]D. Zhao, Q. Huo, J. Feng, B. F. Chmelka, G. D. Stucky, J. Am. Chem. Soc., 1998, 120, 6024.
[32]汪山, 陳繼健, 陳奇. 載銀型可溶性玻璃抗菌材料的研究與應用. 玻璃與陶瓷,2000 ,28(5) :46∼50。
[33]吳躍輝, 徐麗金. 銀殺菌材料及其殺菌作用. 江西化工,2001 ,3 :8∼10。
[34]蘇品書，超微粒子材料技術，復漢出版社(1989)。
[35]Y. H. Chen, C. S. Yeh, Laser ablation method: use of surfactants to form the dispersed Ag nanoparticles, Colloids and surfaces, 197, 133 (2002).
[36]A. D. Russell, W. B. Hugo 1994. Antinmicrobial activity and action of nanoparticles and nanocomposites. Prog Polym Sci 33: 40-112.
[37]Y-S E Lin, R. D. Vidic, J. E. Stout, V. L. Yu 1996. Individual and combined effects of copper and silver ions on inactivation of Legionella pneumophila,. Water Res 30(8): 1905-13.
[38]M. A. Del Nobile, M. Cannarsi, C. Altieri, M. Sinigaglia, P. Favia, G. Iacoviello, D’Agostono R. 2004. Effect of Ag-containing nano-composite active packaging system on survival of Alicyclobacillus acidoterestris., J Food Sci69: 379-383.
[39]K. H Cho, J. H. Park, T. Osaka, S. G. Park, 2005. The study of antimicrobial activity and preservative effects of nanosilver ingredient. Electrochimica Acta 51: 956-960.
[40]行政院科技年鍵奈米網，我國產業應用奈米科技現況http://nano.nac.gov.tw。
[41]周開平，陳郁文。2005。二氧化鈦光觸媒的應用。科學期刊。395: 66-69。
[42]Q. L. Feng, T. N. Kim, J. Wu, E. S. Park, J. O. Kim, D. Y. Lim, F. Z. Cui 1998. Antibacterial effects of Ag-Hap thin films on alumina substrates. Thin Solid Films 335: 214-219.
[43]J. M. Schierholz, L. J. Lucas, A. Rump, G. Pulverez 1998. Efficacy of silver-coated medical device. Rev J Hosp Inf 40: 257-262.
[44]L. L. Hench and J. K. West, “The Sol-Gel Process”, Chemical Reviews, 1990, 90, 33-72.
[45]U. Schubert and N. Husing, “Synthesis of Inorganic Materials”, Wiley-VCH, 2005, 196-221.