(18.206.238.77) 您好!臺灣時間:2021/05/17 18:07
字體大小: 字級放大   字級縮小   預設字形  
回查詢結果

詳目顯示:::

我願授權國圖
: 
twitterline
研究生:陳致光
研究生(外文):Chih-Kuang Chen
論文名稱:以逆微乳膠法調控奈微米級碳酸鈣之晶貌
論文名稱(外文):Crystal Morphology Control of Nano-/Micro-sized Calcium Carbonate using Reverse Microemulsion Technique
指導教授:戴怡德戴怡德引用關係
指導教授(外文):Clifford Yi-Der Tai
學位類別:碩士
校院名稱:國立臺灣大學
系所名稱:化學工程學研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2004
畢業學年度:92
語文別:中文
論文頁數:186
中文關鍵詞:晶貌碳酸鈣逆微乳膠法
外文關鍵詞:Calcium carbonateparticle morphologyreverse microemulsion
相關次數:
  • 被引用被引用:6
  • 點閱點閱:205
  • 評分評分:
  • 下載下載:0
  • 收藏至我的研究室書目清單書目收藏:0
摘要
碳酸鈣為地球上豐富的資源,同時也是工業界使用量最大的無機填充材料,其廣泛的運用於橡塑膠、造紙、塗料、醫藥、封裝材料等行業。碳酸鈣粉體之粒徑、晶貌及晶型為影響基材性能之重要因素。奈米碳酸鈣已被證實可有效的降低填充體積同時提高基材之機械強度,目前市售之奈米碳酸鈣以立方型為主,本研究希望在奈微米尺度下調控粒子晶貌,使碳酸鈣分散在等向性基材中可形成具方向性性質的複合材料,而大幅提升基材之性能。
  本研究以二逆微乳膠法調控奈微米級碳酸鈣之晶貌,所使用的逆微乳膠系統為AOT/Isooctane/Water,AOT為界面活性劑,Isooctane為油相,水相反應物則分別為氯化鈣與碳酸鈉。我們主要探討逆微乳膠系統中ω值(水/界面活性劑,莫耳比)、S值(水/異辛烷,莫耳比)、無機及有機添加劑效應、總莫耳比(R值)、反應溫度(T值)對碳酸鈣粒徑與晶貌上的影響,同時分析製程再現性及粉體之物理性質。
  本實驗已成功合成具圓盤片狀、六角片狀、甜甜圈狀、菱形體、紡錘狀、類球狀、雙辦花、條狀、絲狀晶貌之碳酸鈣。類球狀粒徑最小可至100~200nm,圓盤片狀、菱形體、紡錘狀最小可至200~300nm,六角片狀、甜甜圈狀則可控制於1~1.5μm。甜甜圈狀碳酸鈣比表面積高達42m2/g,預期可做為高效能吸收劑。


Abstract
Calcium carbonate, one of the most abundant resources on earth, which is massively used for inorganic filler in various industrial fields, including rubber, plastic, painting, pharmacy, seal etc.. Particle size, particle morphology and crystal morphology of calcium carbonate affect the performance of matrix materials strongly. Nano-sized calcium carbonate has been proved to reduce its usage and to improve the mechanical strength of matrix materials effectively. Cubic shape is the general form of commercial nano-sized calcium carbonate. The Objective of this study is to control particle morphology of nano-/micro-sized calcium carbonate using the two-reverse-microemulsion technique. Therefore, a composite formed by mixing a matrix with calcium carbonate of distinctive shape may possess high mechanical strength due to the well-aligned structure.
The AOT/isooctane/water reverse microemulsion system was selected in this research. The water phases of the two emulsions are CaCl2 and Na2CO3 aqueous solution, respectively. When the two reverse microemulsions are mixed together, calcium carbonate will precipitate. The effects of several operating variables, including ω values(molar ratio of water/surfactant), S values(molar ratio of water/oil), type and concentration of additives, R values(total molar ratio) and reaction temperature on the particle size and morphology of calcium carbonate were investigated.
This study has successfully synthesized CaCO3 particle with disk, hexagonal plate, rhombohedron, sphere-like, spindle, twin-rosette, doughnut, rods and filament in shapes. The size of the sphere-like particle can be reduced to 100~200nm, of the disk, rhombohedron, and spindle particles,to 200~300nm, of doughnut particle to 1~1.5μm. Doughnut-like particle has a specific surface area as high as 42m2/g, which is expected to be a high-performance absorbent.


目錄
中文摘要
英文摘要
圖索引
表索引

第一章、 緒論……………………………………………………………1
1-1 前言………………………………………………………………….1
1-2 研究目的…………………………………………………………….2

第二章、 文獻回顧………………………………………………………4
2-1 微乳膠原理………………………………………………………….4
 2-1-1 界面活性劑種類與性質……………………………………….4
 2-1-2 微胞之性質與結構……………………………………………11
2-1-3 微乳膠系統及穩定性………………………………………...19
2-2 碳酸鈣微粉體的特性與製備……………………………………...28
2-2-1 碳酸鈣的結構與性質………………………………………...28
2-2-2 碳酸鈣微粉之分類與製程…………………………………...31
2-2-3 奈微米級特殊晶貌碳酸鈣粉體之應用……………………...35
2-2-4 以逆微乳膠系統合成碳酸鈣………………………………...39
2-3 碳酸鈣之晶貌及其控制…………………………………………47
2-3-1 晶體之晶貌與形態………………………………………….47
2-3-2 水溶液組成對碳酸鈣晶型及晶貌之影響…………………..48
2-3-3 無機鹽類及離子性金屬對晶體成核與成長的影響………..51
2-3-4 片狀碳酸鈣相關文獻整理…………………………………...53
2-4 生物礦化行為 …………………………………………………….64
2-4-1 含碳酸鈣之仿生材料………………………………………...64
 2-4-2 可溶物對碳酸鈣晶貌之調控………………………………...67
2-4-3 不可溶性基材對碳酸鈣晶貌之調控………………………...70

第三章、實驗原理與方法………………………………………………71
3-1 實驗藥品…………………………………………………………...71
3-2 實驗裝置…………………………………………………………...74
3-3 分析儀器…………………………………………………………...75
3-4 實驗原理與步驟…………………………………………………...76

第四章、結果與討論
4-1逆微乳膠系統之選擇………………………………………………80
4-1-1CTAB/Hexanol/Water系統…………………………………….80
4-1-2 Aerosol OT/isooctane/Water 系統…………………………….86
4-2 影響碳酸鈣晶貌與粒徑的主要操作變數……………………….95
4-3 總莫耳比對碳酸鈣晶貌與粒徑的影響………………………….98
4-4 逆微乳膠組成對碳酸鈣晶貌與粒徑的影響……………………102
4-5 金屬離子及磷酸鹽濃度對碳酸鈣晶貌與粒徑的影響………….108
4-6 胺類化合物及高分子對碳酸鈣晶貌與粒徑的影響…………….122
4-7 反應溫度對碳酸鈣晶貌與粒徑的影響………………………….139
4-8 再現性實驗及特殊晶貌產品之性質分析……………………….153
4-9各種碳酸鈣合成法之比較………………………………………..172

第五章、結論………………………………………………………….177
參考文獻………………………………………………………………180








參考文獻
Addadi L.,S.Weiner,Proc.Natl.Acad.Sci.USA,82,pp,4110(1985)

Andelman D., M. E. Cates, D. Roux, S. A. Safran, “Theory of microemulsions: comparison with experimental behavior”,Langmuir, 4,pp.802~806(1988)

Arriagada F. J., K. Ossed-Asare, “Synthesis of Nanosize Silica in
Aerosol OT Reverse Microemulsions, Journal of colloid and interface
science, 170,pp.8~17(1995)

Belcher A. M., X. H. Wu, R. J. Christensen, P. K. Hansma and G. D.
Stucky, “ Control of crystal phase switching and orientation by soluble
mollusc-shell proteins”, Nature,381,pp.56(1996)

Bommarius A. S.,J. F. Holzwarth. D. I. C. Wang and T. A. Hatton,
“Coalescence and Solubilizate Exchange in Cationic Four Component
Reverse Micellar System”, J. Phys. Chem.,94,pp.7232(1990)

Chen J. F., Y. H. Wang, F. Guo, X. M. Wang and C. Zheng, “Synthesis of Nanoparticles with Novel Technology: High-Gravity Reactive Precipitation”, Ind. Eng. Chem. Res.,39, pp.948~954(2000)

Davis J. T. and E. K. Rideal, “Interfacial Phenomena”, Academic Press, New York(1961)

Fletcher P. D. I., A. M. Howe and B. H. Robinson, Journal of the Chemical Society, Faraday Transactions,83,pp.985(1987)

Giannimaras E. K., P. G. Koutsoukos, “Precipitation of Calcium Carbonate in Aqueous Solution in the Presence of Oxalate Anions, Langmuir, 4,pp.855(1988)

Gleiter H., “Nanocrystalline Materials”, Progress in materials science,33, pp.223~345(1989)


Gower L.A., D.A. Tirrell, “Calcium Carbonate Films and Helices Grown
in Solutions of Poly(aspartate), Journal of Crystal Growth,
191,pp.153~160(1998)

Gower L.B., D.J. Odom, “Deposition of Calcium Carbonate Films by a
Polymer-Induced Liquid-Precursor (PILP) Process, Journal of Crystal
Growth, 210,pp.719~734(2000)

Griffin W. C., “Encyclopedia of Chemical Technology”,5, Interscience Encyclopedia, Inc., New York(1950)

Hatton T. A., “Surfactant-Based Sepparation Process”, Marcel Dekker, New York,(1989)

Hayashi C., “Ultrafine Particles”, Physics today,12,pp.44(1987)

Heywood B. R., S. Mann, “Template-directed Nucleation and Growth
of Inorganic Materials, Advanced Materials, 6,pp.9~20(1994)

Hiemenz P. C., “Principles of Colloid and Surface Chemistry”, Marcel Dekker, New York, 2nd ed.(1986)

Hirai T., S. Hariguchi, I. Komasawa, R.J Davey, “Biomimetic
Synthesis of Calcium Carbonate Particles in a Pseudovesicular Doble
Emulsion”, Langmuir,13,6650(1997)

Hostomsky J. and A. G. Jones, “Calcium Carbonate Crystallization,
Agglomeration and Form during Continuous Precipitation from
Solution”,J. Phys. D:Appl. Phys.,24,pp.165(1991)

Hunter R. J., “Foundations of Colloid Science Volume 2”, Oxford,
New York(1989)

Ishikawa H., K. Noda and T. Oka, in “Enzyme Eng. 8”, Ann. Acad. Sci., 104,pp.4659(1990)



Jada A., J. Lang, R. Zana, R. Makhloufi, E. Hirsch, S. J. Candau,
“Ternary water in oil microemulsions made of cationic surfactants, water,
and aromatic solvents. 2. Droplet sizes and interactions and exchange of
material between droplets”, J. Phys. Chem. 94,pp.387~395(1990)

Kandori K., K. Kon-No, A. Kitahara, “Dispersion Stability of
Nonaqueous Calcium Carbonate Dispersion Prepared in Water Core W/O
Microemulsion”, J. of Colloid and Interface Sci.115,pp.579~582(1987)

Kandori K., K. Kon-No, A. Kitahara, “Formation of Ionic water/oil
Microemulsions and Their Application in the Preparation of CaCO3
Particles”, J. of Colloid and Interface Sci.,122,pp.78~82(1988)

Kato T., T. Suzuki, T. Amamiya, H. Yui, “Effects of Macromolecules
on the Crystallization of CaCO3 the Formation of Organic/Inorganic
Composites, Supramolecular Science, 5,pp.411~415(1998)

Kato T. Ayae Sugawara, Naoya Hosoda, Calcium
carbonate-organic hybrid materials, Advanced Materials
14,pp.869~877(2002)

Katsifaras A., N. Spanos, “Effect of Inorganic Phosphate Ions on the
Spontaneous Precipitation of Vaterite and on the Transformation of
Vaterite to Calcite, J. of Crystal Growth,204,183-190(1999)

Katz J. L., R.E. Herzog, Q. Shi, J. N. “Patial, Magnetic Water Treatment: The Effect of Iron on Calcium Carbonate Nucleation and Growth, Langmuir, 5,pp.861(1989)

Katz J. L., S. Takasaki, K. I. Parsiegla, “Calcite Growth and the Inhibiting effect of Iron, Journal of crystal growth,143,pp.261(1994)

Kojima Y., A. Sadotomo, T. Yasue, and Y. Arai, Control of crystal
shape and modification of calcium carbonate prepared by precipitation
from calcium hydrogencarbonate solution, J.Ceram.Soc.Jpn.
,100,pp.1128~1135(1992)


Kojima Y., N. Endo, T. Yasue, and Y. Arai, Morphological Controls
of Calcium Carbonate Hexahydrate and Its Dehydrating Substance,
J.Ceram.Soc.Jpn.,103,pp.1268~1274(1995)

Kralj D., L. Brecevic, and A. E. Nielson, “Vaterite growth and
dissolution in aqueous solution”, J. Crystal Growth, 104, pp.793 (1990)

Kunieta H., K. Shinoda, “Solition behavior of Aerosol OT/Water/oil”,
J. Colloid Interface Sci.,70,pp.577~583(1979)

Langevin D., “ Microemulsions. Interfacial aspects”, Advances in Colloid and Interface Science,34,pp.583~595(1991)

Lin R. Y., J. Y. Zhang, P. X. Zhang, “Nucleation and Growth Kinetics in Synthesizing Nanometer Calcite, J. of Crystal Growth, 245, pp.309~320(2002)

Litivin A. L., S. Valiyaveettil, D. L. Kaplan, S. Mann, “ Template-directed
Synthesis of Aragonite under Supermolecular Hydrogen-bonded
Langmuir Monolayers”,Advanced Materials, 9,pp.124(1997)

Lufimpadio, N., Nagy, J. B., and Derouane, E. G., :Preparation of
Colloidal Iron Boride Particles in the CTAB-n-Hexanol-Water Reversed
Micellar System, in Surfactants in Solution, vol. 3, ed. K. L. Mittal, B.
Lindman, Pleum Press, New York, pp. 1483~1497 (1984)

Mann S., B.R. Heywood, S. Rajam, J. D. Birchall, “Controlled
Crystallization of CaCO3 under Stearic Acid Monolayers, Nature,
334,pp.692~695(1988)

Mann S., J. M. Didymus, N. P. Sanderson, B. R. Heywood, E. J. A.
Samper, Journal of the Chemical Society, Faraday Transactions,
86,pp.1873(1990)

Mann S., D. Walsh, B. Lebeau, “Morphosynthesis of Calcium
Carbonate(Vaterite) Microspomges”, Advanced Materials,11,
pp.324~328(1999)
Mann S., M. Li, “Emergent Nanostructure:Water-Induced Mesoscale
Transformation of Surfactant-Stabilized Amorphous Calcium Carbonate
Nanoparticles in Reverse Microemulsion”, Advanced Functional
Materials,12,773(2002)

Meyer H. J., “The Influence of Impurities on the Growth Rate of Calcite, J. of Crystal Growth, 66,pp.639(1984)

Ota Y., N. Goto, I. Motoyama, T. Iwashita, K. Nomura, USA patent
publication, No.4857291(1989)

Pach L.,S. Duncan,R. Roy,S. Komameni, “Morphological Control of
Precipitated Calcium Carbonates and Phosphates by Colloidal Additives,
Journal of Materials Science,31,pp.6565~6569(1996)

Penninger J. M. L., “Supercritical Fluid Technology”, Amsterdam, Elsevier, New York(1985)

Pileni M. P., “Structure and Reactivity in Reverse Micelles”, Plenium, New York(1984)

Pileni M. P., “ Reverse micelles as microreators”, Journal of Physical Chemistry, 97,pp.6961~6973(1993)

Porter M. R., “Handbook of Surfactants”, 2nd ed., Chapman & Hall,
New York(1994)

Qi L., J. Li, J. Ma, Biomimetic Morphogenesis of Calcium Carbonate
in Mixed Solutions of Surfactants and Double-hydrophilic Block
Copolymers, Advanced Materials,14,pp.300~303(2002)

Randolph A. D. and M. A. Larson, “Theory of Particulate
Processes”,Academic press,Inc.,2nd(1988)

Rock M.L., L.J. Tranchitella, R.S. Pilato, “Control of Calcium
Carbonate Particle Size and Shape by Precipitation from
CTAB/alcohol/hexadecane Mixtures, Colloid Polymer
Sci.,275,pp.893(1997)
Roques H. and A. Girou, “Kinetics of the Formation Conditions of
Carbonate Tartars”, Water Res.,8,pp.907(1974)

Sabbibes T. G., P. G. Koustoukos, “Effect of Orthophosphate on the Crystallization of Calcium Carbonate in High Ionic Strength Media, Industrial crystallization 93, Warsaw, Poland,2-123(1993)

Shaw D. J., “Introduction to Colloid and Surface Chemistry”, 4nd ed., Butterworths, London(1992)

Sohnel O. and J. W. Mullin, “Precipitation of Calcium Carbonate”, J. of Crystal Growth, 60, pp.239(1982)

Sugihara H.,K. Ono,K. Adachi,Y. Setoguchi,T. Ishihara,Y.
Takita,Synthesis of disk-like calcium carbonate(part1), J.Ceram. Soc.
Jpn.,104,pp.832~836(1996)

Sugihara H., T. Anan, K. Adachi, A. Baba, N. Egashira, H.
Nishiguchi, T. Ishihara, H. Sugihara, T. Anan, K. Adachi, A. Baba, N.
Egashira, H. Nishiguchi, T. Ishihara, Y. Takita, “Synthesis of Disk-like
Calcium Carbonate(part2)”, J.Ceram. Soc. Jpn.,105,pp.886~890(1997)

Tai C. Y., and Chen F. B., “Polymorphism of CaCO3 Precipitated in a Constant-composition Environment, AIChE J.,44,pp.1790(1998)

Tai C. Y., Lee, M.-H., and Wu Y.-C., Control of Zirconia Particle Size by Using Two-emulsion Precipitation Technique, Chem. Eng. Sci. 56, pp.2389 (2001).

Vacassy R., J. Lemaitre, H. Hofmann and J. H. Gerlings, “Calcium
Carbonate Precipitation Using New Segmented Flow Tubular Reactor”
AIChE J, 46, pp.1241~1252(2000)

Watabe N.,J.Ultrastruct. Res.,12,pp.351(1965)

Winsor P. A., Trans. Faraday Soc.,44,pp.376(1948)


Wray J. L. and F. Daniels, “Precipitation of Calcium and Aragonite”, J.
Am. Chem. Soc.,79(9),pp.2031(1957)

Xiang L.,Y. Wen, and Y. Jin., “Synthesis of Plate-like Calcium
Carbonate via Carbonation Route”, Materials letters,57,2565(2003)

Xyla A. G. Xyla, P. G. Koutsoukos, “Quantitative Analysis of Calcium Carbonate Polymorphs by Infared Spectroscopy, Colloids and surface,53,pp.241(1991)

Yagi H., A. Iwazawa, R. Sonobe, T. Matsubara and H. Hikita,
“Crystallization of Calcium Carbonate Accompanying chemical
adsorption”,Ind. Eng. Chem. Fundam.,23,pp.153(1984)

Yu J., M. Lei, B. Cheng, X. Zhao, “Facile Preparation of Calcium
Carbonate Particles with Unusual Morphologies by Precipitation
Reaction,Journal of Crystal Growth, 261,pp.566~570(2004)

李嘉甄, “奈米碳酸鈣的性質與應用” ,產業奈米技術應用資訊園地,
No. 1,pp.19(June,2003)
奈米級碳酸鈣應用產業聯結高階主管座談會,August,2003(台北)
曹恆光、王順程、曾文良,”微乳液的簡介”,化工,47,3,pp.53~67(2000)
廖建勛,奈米結構生物材料,化工,Vol.50,No.6,pp.94~104(Dec,2003)
趙承琛,界面科學基礎,復文書局(1994)
廖明隆,界面化學與界面活性劑,復文書局(1994)
陳復邦,”以定組成法探討碳酸鈣多晶型之形成”,碩士學位論文,台大化工所(1995)




QRCODE
 
 
 
 
 
                                                                                                                                                                                                                                                                                                                                                                                                               
第一頁 上一頁 下一頁 最後一頁 top