本實驗在討論以鋯的醇氧化合物(alkoxide)經由溶膠凝膠法，製備納米(nano)級的微孔型氧化鋯薄膜的方法。有別於常見的氧化鋯溶凝膠製程，本實驗利用乙酸與丁醇進行酯化反應產生的水，與鋯之醇氧化合物進行水解反應。由於乙酸也具有螯合物(chelating agent)的功能，因此可以降低醇氧化合物的高水解速度，避免快速沉澱,可製備出均相的氧化鋯溶膠。經由氣相層析/質譜(GC/Mass)分析，乙酸丁酯的生成證實了酯化反應的發生。溶膠的FT-IR分析也證實乙酸在反應中扮演螯合物的角色。加入硝酸或水對溶膠進行peptization，可以得到pH值分別為1以及5.5的兩種溶膠。利用旋轉塗佈法將各溶膠塗佈於Whatman公司出品的氧化鋁薄膜上，在控制濕度及溫度的條件下乾燥，最後在500℃煆燒後，可以由XRD分析推斷氧化鋯可能為正方晶與立方晶之混合晶相。
由SEM的觀察發現，以硝酸進行peptization之溶膠可以在載體上完整的披覆一層氧化鋯薄膜。由氮氣滲透法估算薄膜之流量平均孔徑(flow average pore diameter)約為3.63nm。未支撐(unsupported)的氧化鋯由氮氣吸附法可得孔徑大小在1.5~3.5nm間。利用薄膜分離黃豆油與正己烷，可以得到37%的阻隔率(rejection)，比未塗佈的載體高出許多。TEM觀察粒徑大小約在5~10nm。然而以水進行peptization所得之溶膠有膠化(gelation)的趨勢。以此溶膠製成的薄膜，表面有少數的裂縫產生，會造成載體結構的破壞，不但使得氣體滲透法出現反常的結果，進行黃豆油混合液分離時，得到的阻隔率為負值。

The objective of this study is to synthesize nano-pore zirconia membranes using Zr alkoxide via sol-gel route. Unlike the traditional technique, the hydrolyzing water is provided by the esterification of butanol and acetic acid. In addition, acetic acid also serves as chelating agent to stabilize the hydrolysis-condensation process so that the agglomeration of zirconia is minimized. Esterification is verified by the product, butyl acetate, determined by a GC/Mass. The chelating complex is evidenced from FTIR spectrum. The peptization is performed either adding HNO3 or H2O resulting two different sols with pH values, ~1 and ~ 5.5, respectively. Such sols are spin-coated on Whatman anodic discs, dried in controlled temperature and humidity, then calcined at 500℃ to remove organic compounds. Zirconia is transformed to the mixture of tetragonal and cubic forms which is confirmed by XRD pattern.
SEM micrograph shows a uniform layer on disc which using sol peptized by HNO3. The flow average pore size of membrane is estimated 3.63 nm by nitrogen gas permeation. The pore size distribution of un-supported zirconia ranges from 1.5 to 3.5 nm measured by nitrogen adsorption.The rejection of soybean oil / hexane mixture reaches 37% which is much better than that of bare disc. TEM shows that average particle size is near 5~10 nm. Gelation occurs in the sol peptized by H2O when setting for a period of time. Membrane prepared from H2O peptized sol can develop a few cracks, which cause the destruction of disc resulting anomalous gas permeation and the negative rejection of soybean oil / hexane.

第一章、緒論 1
第二章、文獻回顧 3
2-1溶凝膠法製備氧化鋯薄膜 3
2-1-1以鋯之水合物製備薄膜 3
2-1-2以鋯之醇氧化合物製備薄膜 3
2-2 pH值對溶凝膠的影響 7
2-3 塗佈方法 8
2-4薄膜分離程序 10
2-4-1微過濾與超過濾 11
2-4-2逆滲透 12
2-4-3透析與電透析 12
第三章、實驗內容 13
3-1反應基本原理 13
3-2藥品與載體材料 15
3-3實驗設備 15
3-4實驗步驟 16
3-4-1溶膠製備 16
3-4-2溶膠之旋轉塗佈 17
3-4-3薄膜的乾燥與煆燒 17
3-4-4氣相層析-質譜分析(GC-Mass) 19
3-4-5傅利葉轉換紅外線光譜(FTIR)分析 19
3-4-6熱重及熱差分析(TGA/DTA) 19
3-4-7氮氣吸(脫)附測定孔徑分佈 19
3-4-8 X-ray繞射法(XRD) 20
3-4-9 氣體滲透法 21
3-4-10 掃瞄式電子顯微鏡(SEM) 23
3-4-11 穿透式電子顯微鏡(TEM) 23
3-4-12 黃豆油與正己烷混合液的分離 24
第四章、結果 26
4-1 GC-Mass分析 26
4-2 FTIR分析 27
4-3 TGA/DTA分析 28
4-4氮氣吸附法測量孔徑分佈 30
4-5 XRD表面分析 32
4-6 氣體滲透率測試 35
4-7 SEM觀察表面 38
4-7-1 以硝酸peptize之溶膠 39
4-7-2 以水peptize之溶膠 41
4-8 TEM觀察結構 45
4-9 黃豆油與正己烷混合液的分離 48
第五章、討論 51
5-1 氣體滲透法估算薄膜流動平均孔徑51
5-1-1 以硝酸peptize溶膠塗佈的薄膜51
5-1-2以水peptize溶膠塗佈的薄膜 54
5-1-3 各種方法估算薄膜孔徑之比較56
5-2 塗佈薄膜在黃豆油與正己烷混合液分離上的應用 57
5-3 影響溶膠製備的因素 60
5-3-1 手套箱內的水氣對實驗的影響60
5-3-2 乙酸在溶膠製備過程中扮演的角色60
5-3-3 乙酸/醇氧化合物 的比例對溶膠的影響62
5-3-4 以硝酸及水進行peptization後的溶膠比較 62
第六章、結論 64
參考文獻 65
附錄 68

Accelerated surface area and porosimetry system operator’s
manual (201-42801), Appendix C13-36 , Micromeritics Co. (1995)
Chen. B.T, “Investigation of the solvent-evaporation effect on
spin coating of the film”, Polym. Eng. Sci. , vol.23, 379
(1983)
Debslikdar. J. C,”Transparent zirconia gel-monolith from
zirconium alkoxide,” J. Non-cryst. Solid, vol. 86,231-241
(1986)
Etienne. J, A. Larbot, A.Julbe,C.Guizard and L.Cot,”A
microporous zirconoa membrane prepared by the sol-gel process
from zirconyloxalate,” J. Mem. Sci. ,vol.86,95-102(1994)
Guizard. C, N.Cygankiewicz, A.Larbot and L.Cot.”Sol-gel
transition in zirconia systems using physical and chemical
processes,” J. Non-cryst. Solid,vol.82,86-91(1986)
Jeffrey Brinker. C, George W.Scherer, Sol-gel science, Academic
Press,Inc. (1990)
Jones. R. W, Fundamental principles of sol-gel technology, The
institute of metals(1989)
Julbe. A, C. Guizard, A. Larbot, L. Cot and A. Giroir
Fendler, ”The sol-gel approch to prepare candidate miro
porous inorganic membrane reactor”, J. Mem. Sci.,vol.77, 137-
153 (1983)
Kamiya. K, S.Sakka, J. Non-cryst. Solid, vol.52, 357(1982)
Larbot. A, M.J.Munoz-Aguado, M.Gregorkiewitz, “Sol-gel
synthesis of the binary oxide (Zr,Ti)O2 from the alkoxides
and acetic acid in alcoholic medium,” Chem. Res. Bull,
vol.27, 87-97(1992)
Lijzenga. C,.”Nanostructure characterization of titania
membranes ,” Key Eng. Materials ,vol.61༖,379-382(1991)
Lijzenga. C, ”Zirconia-coated gamma-alumina membrane
toplayer,” Key Eng. Materials,vol.61༖,383-386(1991)
Lin. Y. S, A. J. Burggraaf ,”Experimemtal studies on pore size
change of porous ceramic membranes after modification”,
J.Mem.Sci. ,vol.79, 65-82(1993)
Lin. Y. S, A.J. Burggraaf , “Preparation and characterization
of high-temperature thermally stable composite membrane”, J.
Ame. Ceramic Soci. , vol.74, 219-224( 1991)
Livage.J , S.Doeuff, M.Henry, C.Sanchez, “Hydrolysis of
titanium alkoxides: modification of he molecular precursor by
acetic acid,” J. Non-cryst. Solid, vol. 89, 206-216(1987)
Nerant. M and L. C. Klein,”Durability of porous zirconia
powders in caustic”, Key Eng.Materails ,vol.61༖,137-142
(1991)
Okubo. T and Hakuaiinoue, ”Introduction of specific gas
selectivity to porous glass membranes by treatment with
tetraethoxysiliane,” J.Mem. Sci.,vol.42,109-117(1989)
Osada. Y, T. Nakagawa, “Membeane science and technology”
Chapter8, New York(1992)
Pflanz. K, N.stroh, R.Riedel, “Flat ceramic ultrafiltration
membranes and modules coated by sol-gel technique”, to be
published
Pflanz.K, R.Riedel and H.Chmiel, “Preparation of spinel
ultrafiltration membranes”, Adv. Materials, vol. 4, No. 10,
662-665(1992)
Ramesh R,Bhave,Ph.D,Inorganic membranes synthesis
characteristics and applications,Van nostrand Reinhold,New
York(1991)
“TEM specimen preparation of materials by ion millering”,
Gatan Co.,(Nov. 1991)
Uhlhorn. R.J.R, M.H.B.J. Huis in’t Veld, K.Keizer and
A.J.Burggraaf,“Synthesis of ceramic membranes. Part 1.
Synthesis of non-supported and supported γ-alumina
membrane without defects”, J. Mater. Sci. ,vol.27, 527(1992)
Wolf.C, C.Russel,”Sol-gel formation of zirconia:
preparation,structure and rheology of sols”, J. Mater. Sci.,
vol.27,3749-3755(1992)
Yamada. K, T.Y.Chow,T.Horihata and M.Nagata,”A low temp
synthesis of zirconium oxide coating using chelating agents,”
J.Non-cryst. Solid,vol.100,316-320(1988)
Yazawa. T, H. Nakamichi ,K.Eguchi and O. Yamaguchi,”
Preparation of heat and water vapor resistant composite
porous glass membrane coated on porous alumina tubing by sol-
gel method”, J. Ceram. Soc. Japan, Int Edition, vol 99,1234-
1236(1991)
Yazawa.T,H. Nakamichi , Takuji, “Preparation of water and
durable porous glass membrane coated on porous alumina by sol-
gel method,” J. Mem. Sci. ,vol.60,307-317(1991)
王志達, “旋轉塗佈之研究”, 國立台灣大學 化工研究所 博士學位論
文(1996)
李恩賢, “微孔陶瓷磨在超微過濾之應用研究- 分離黃豆油/正己烷混
合液”, 國立台灣大學 化工研究所 碩士學位論文(1997)
郭文正, 曾添文, “薄膜分離”第二章,高立圖書(1991).
陳立俊等，”材料電子顯微鏡學” , ch.4, 國科會精儀中心(1994)
陳世爵，陳潤卿，楊培, “黃豆資料全集”, 90(1986)
黃君強, “溶凝膠法製備微孔型氧化鋯薄膜”, 國立台灣大學 化工研
究所 碩士學位論文(1996)