本篇研究係合成一種陰離子型共聚物: 聚二(二甲基丙烯酯)乙基磺酸鈉鹽/丙烯醯胺 (PMESA )，作為鈦酸鋇漿體(BT)的分散劑，探討在不同pH值下PMESA對於BT漿體中分散性質的影響。
PMESA是由二(二甲基丙烯酯)乙基磺酸鈉鹽(MES)和丙烯醯胺(AM)經自由基反應聚合而得。本研究利用1H-NMR 和 FT-IR光譜儀來量測確認共聚物的化學結構，以GPC量測聚合物的分子量，經由電位滴定估算PMESA中所含各單體的比例。
PMESA對鈦酸鋇漿體分散性質的影響主要經由漿體黏度、沈降體積、粒徑分佈、表面電位等實驗結果來探討；另外，並量測鈦酸鋇漿體中Ba2+的溶出量。
結果顯示出，添加PMESA能夠分散穩定水溶液系統的鈦酸鋇漿體，其效果與PMAAN相當；PMESA中所含有的MES比例愈多，對BT漿體分散效果愈好；其中以添加0.3 wt% PMESA(MES/AM=9/1)在pH=9時的漿體有最好的分散穩定效果。另外，添加PMESA能有效降低漿體中鋇離子的溶出。

This study has prepared of an anionic water-soluble copolymer, Poly (2-(2-methyl-acryloyloxy)ethylsulfonate-acrylamide) (PMESA) as a dispersant for barium titanate (BT) powder in water. The effects of this polymer on the dispersion properties of BT aqueous suspensions at various pH values were investigated.
PMESA was prepared from sodium 2-(2-methyl-acryloyloxy)ethyl sulfonate (MES) and acrylamide (AM) through a free radical polymerization. The chemical structure of PMESA were verified from their 1H-NMR and FT-IR spectra; the molecular weight of this polymer was measured by GPC; the monomer ratio in PMESA was determined by a potential titration method. The dispersion ability of PMESA on BT suspensions was evaluated from the results of viscosity, sedimentation, particle size, zeta potential and adsorption measurements. Besides, the amount of leached Ba2+ ions from BT particles in suspensions was also measured.
The result shows that incorporation of PMESA will reduce the viscosity and stabilize the BT suspensions. The dispersion property of this polymer is as good as PMAAN. PMESA with increasing MES moiety is more effective. It appears that incorporating 0.3 wt% PMESA with MES/AM=9/1 is most effective in making stable BT suspensions at pH=9. Additionally, PMESA could reduce the leached Ba2+ ions from solid particles in BT suspensions.

1. X. Wang, B. I. Lee,and L. Mann, “Dispersion of Barium Titanate with Polyaspartic Acid in Aqueous Media”, Colloids Surf. A : phy. Eng. Asp. 202 (2002) 71-80

2. W. J. Tseng and S. Li, “Rheology of Colloidal BaTiO3 Suspension with Ammonium Polyacrylate as a Dispersant”, Mat. Sci. Eng. A: 333 (2002) 314-319

3. S. Chio, and Y. Jung,, “The Effect of Electrostatic Repulsive Forces on the Stability of BaTiO3 Particles Suspended in Non-aqueous Media ”, Colloids Surf. A : phy. Eng. Asp. 135 (1998) 77-88

4. J.H. Jean, H.R. Wang, “Dispersion of Aqueous Barium Titanate Suspensions with Ammonium Salt of Poly(methacrylic acid)”, J. Am. Ceram. Soc. 81 (1998) 1589~1599

5. C. Gόmez-Yáňez, H. Balmori-Ramírez, and F. Martínez,”Colloidal Processing of BaTiO3 Using Ammonium Polyacrylate as Dispersant”, Ceram. Inte. 26 (2000) 609-616

6. J. Tsubaki, M. Kato, M. Miyazawa, T. Kuma, and H. Mori, “The Effects of the Concentration of a Polymer Dispersant on Apparent Viscosity and Sedimentation Behavior of Dense Slurries”, Chem. Eng. Sci. 56 (2001) 3021-3026

7. D.Völtzke, H.P. Abicht,J. Woltersdorf,and E. Pippel, “Surface Modification of Pre-sintered BaTiO3 Particles”, Mat. Chem. Phy. 73 (2002) 274-280

8. S. Chibowski and M. Wiśniewska, “Study of Electrokinetic Properties and Structure of Adsorbed Layers of Polyacrylic Acid and Polyacrylamide at Fe2O3-polymer Solution Interface”, Colloids Surf. A : phy. Eng. Asp. 208 (2002) 131-145
9. S. Baklouti, M. R. B. Romdhane, S. Boufi, C. Pagnoux, T. Chartier,and J. F. Baumard, “Effect of Copolymer Dispersant Structure on the Properties of Alumina Suspensions”, J. Eur. Ceram. Soc. 23 (2003) 905-911

10. D.Guo, K. Cai, L. Li,and Z. Gui,” Application of Gelcasting to the Fabrication of Piezoelectric Ceramic Parts” , J. Eur. Ceram. Soc. 23 (2003) 1131-1137

11. M. R. B. Romdhanea, S. Bakloutia, J. Bouaziza,and T. Chartier,” Dispersion of Al2O3 Concentrated Suspensions with New Molecules able to Act as Binder”, J. Eur. Ceram. Soc. 24 (2004) 2723~2731

12. W. J. Wei, S. J. Lu,and B. K. Yu, “Characterization of Submicron Alumina Dispersions with Poly(methacrylic acid) Polyelectrolyte”, J. Eur. Ceram. Soc. 15 (1995) 155-164

13. J. Cesarano, I. A. Aksay, “Processing of Highly Concentrated Aqueous α-Alumina Suspensions Stabilized with Polyelectrolytes”, J. Am. Ceram. Soc. 71 (1988) 1062-67

14. W. Tseng, C. Lin, “Effect of Dispersants on Rrheological Behavior of BaTiO3 Powders in Eethanol-isopropanol Mixtures”, Mat. Chem. Phy. 80 (2003) 232-238

15. P. F. Luckham, and S Rossi,”The Colloidal and Rheological Properties of Bentonite Suspensions”, Adv. Colloid Inte. Soc. 82 (1999) 43~92

16. B. V. Velamakanni, F. F. Lange, F. W. Zok, and D. S. Pearson, “Influence of Interparticle Forces on the Rheological Behavior of Pressure-Consolidated Alumina Particle Slurries”, J. Am. Ceram. Soc. 77 (1994) 216~220

17. J. A. Lewis, “Colloidal Processing of Ceramics”, J. Am. Ceram. Soc. 83 [10] (2000) 2341~2359

18. P. Sarkar. and S.Patrick.,”Electrophoretic Deposition (EPD) :Mechansims, Kinetics, and Application to Ceramic”, J. Am. Ceram. Soc. 79 (1996) 1987~2002

19. R.G. Horn., “Surface Forces and Their Action in Ceramic Materials”, J. Am. Ceram. Soc. 73 (1990) 1117~1135

20. M.C. B. Lo pez , B. Rand, F.L. Riley,”Polymeric Stabilisation of Aqueous Suspensions of Barium Titanate. Part I: Effect of pH”, J. Eur. Ceram. Soc. 20 (2000) 1579~1586

21. J. Davies, J.G.P. Binner, “The role of Ammonium Polyacrylate in Dispersing Concentrated Alumina Suspensions”, J. Eur. Ceram. Soc. 20 (2000) 1539~1553

22. J. Cesarano and I. A. Aksay,”Stability of ,Aqueous a-Al203 Suspensions with Poly(methacry1ic acid) Polyelectrolyte”, J. Am. Ceram. Soc.71 (1988) 250~255

23. J. Yu, H. Liu, and J. Chen,” Flocculation and Characterization of Protein by Anionic Copolymer Containing Reactive Functional Groups”, Colloids Surf. A : phy. Eng. Asp. 163 (2000) 225~232

24. C.W. Chiang, and J. H. Jean, “Effects of Barium Dissolution on Dispersing Aqueous Barium Titanate Suspensions”, Mat. Chem. Phy. 80 (2003) 647~655

25. P. Ungyu ,”Influence of Solids Concentration on the Isoelectric Point of Aqueous Barium Titanate”, J. Am. Ceram. Soc. 83 (2000) 2381~2384

26. M. C. B. Lopez, F. L. Riley,and B. Rand,”The Properties of Aqueous Phase Suspensions of Barium Titanate”, J. Eur. Ceram. Soc. 17 (1997) 281~287

27. S. Lee, U. Paik, V. A. Hackley, Y. G. Jung,and K.J.Yoon.,”Microstructure and Permittivity of Sintered BaTiO3: Influence of Particle Surface Chemistry in an Aqueous Medium”, Mat. Res. Bull. 39 (2004) 93~102

28. G. H. Kirby, D. J. Harris, Qi Li, and J. A. Lewis, ”Poly(acrylic acid)–Poly(ethylene oxide) Comb Polymer Effects on BaTiO3 Nanoparticle Suspension Stability”, J. Am. Ceram. Soc. 87 (2004) 181~186
29. H. Mahdjoub, P. Roy, C. Filiatre, G. Bertrand,and C. Coddet, “The Effect of the Slurry Formulation Upon the Morphology of Spray-dried Yttria Stabilized Zirconia Particles”, J. Eur. Ceram. Soc. 23 (2003) 1637-1648

30. M. R. B. Romdhane, S. Boufi, S. Baklouti, T. Chartier ,and J. F. Baumard , “Dispersion of Al2O3 Suspension with Acrylic Copolymers Bearing Carboxylic Ggroups”, Colloids Surf. A : phy. Eng. Asp. 212 (2003) 271~283

31. K. Vermohlen, H. Lewandowski, H.-D. Narres,and M.J. Schwuger, “Adsorption of Ppolyelectrolytes onto Oxides — The Influence of Ionic Strength, Molar Mass, and Ca2+ Ions”, Colloids Surf. A : phy. Eng. Asp. 163 (2000) 45~53

32. A. Malgat, J.P. Boisvert,and C. Daneault, “Specific Influence of Univalent Cations on The Ionization of Alumina-Coated TiO2 Particles and on the Adsorption of Poly(acrylic) Acid”, J. Colloids Inte. Sci. 269 (2004) 320~328

33. S. Farrokhpay, G. E. Morris, D. Fornasiero,and P. Self, “Effects of Chemical Functional Groups on The Polymer Adsorption Behavior onto Titania Ppigment Particles”, J. Colloids Inte. Sci. 274 (2004) 33~40

34. 陳志豪，”高分子分散劑的合成以及對於鈦酸鋇粉末的分散性質” 國立台
灣師範大學化學研究所碩士論文，2005。

35. G. Bertrand, C. Filiatre, H. Mahdjoub, A. Foissy, and C. Coddet,”Influence of Slurry Characteristics on The Morphology of Spray-Dried Alumina Powders”, J. Eur. Ceram. Soc. 23 (2003) 263~271

36. 吳俊賢,“水系氧化鋁懸浮液之酸鹼度對沈降、流變行為與電泳披覆影響之研究”,中國文化大學材料科學與製造研究所碩士論文,2001

37. H. Bouhamed, S. Boufi, and A. Magnin, “Alumina Interaction with AMPS-MPEG Random Copolymers Ι. Adsorption and Electrokinetic Behavior”, J. Colloids Inte. Sci. 261 (2003) 264~272

38. M. C. B. Lopez, F. L. Riley, and B. Rand, “Polymeric Stabilization of Aqueous Suspensions of Bbarium Ttitanate PartⅠ: Effect of pH”, J. Eur. Ceram. Soc. 20 (2000) 1579~1586

39. D. Houivet, J. E. Fallah, and J. M. Haussonne,”Dispersion and Grinding of Oxide Powders into an Aqueous Slurry”, J. Am. Ceram. Soc. 85 (2002) 321~328

40. B.P. Singh, S. Bhattacharjee, L. Besra,”Optimisation of Performance of Dispersants in Aqueous Plasma Dissociated Zircon Suspension”, Ceram. Int. 28 (2002) 413~417

41. B. P. Singh, R. Menchavez, C. Takai, M. Fuji, and M. Takahashi, “Stability of Dispersions of Colloidal Alumina Particles in Aqueous Suspensions”, J. Colloids Inte. Sci. 291 (2005) 181~186

42. C. Miot, C. Proust,and E. Husson, “Dense Ceramics of BaTiO3 Produced from Powders Prepared by a Chemical Process”, J. Eur. Ceram. Soc.15 (1995)1163-1170

43. S. Chibowski , E. O. Mazur,and J. Patkowski, ”Influence of the Ionic Strength on The Adsorption Properties of The System Dispersed Aluminium Oxide–Polyacrylic Acid”, Mat. Chem. Phy. 93 (2005) 262~271

44. M. Balastre,J. Persello,A. Foissy,,and J-F. Argillier, “Binding and Ion-Exchange Analysis in the Process of Adsorption of Anionic Polyelectrolytes on Barium Sulfate”, J. Colloids Inte. Sci. 219 (1999) 155–162
45. A. Neubrand, R. Lindner, and P. Hoffmann, ”Room-Temperature Solubility Behavior of Barium Titanate in Aqueous Media”, J. Am. Ceram. Soc. 83 (2000) 860~864

46. Y. Kan, P. Wang, Y. Li,Y. B. Cheng, and D. Yan,”Properties of Aqueous Bismuth Titanate Suspensions Stabilized by Acrylic Acid/Acrylic Ester Copolymer”, J. Am. Ceram. Soc. 86 (2003) 2203~2205

47. D. H. Yoon and B. I. Lee, ”Effects of Excess Barium Ions on Aqueous Barium Titanate Tape Properties”, J. Am. Ceram. Soc. 87 (2004) 1066~1071

48. Z. C. Chen,T. A. Ring, and J. Lemaitre, “Stabilization and Processing of Aqueous BaTiO3 Suspension with Polyacrylic Acid”, J. Am. Ceram. Soc. 75 (1992) 3201~3208

49. J. S. Reed, “Introduction to the Principles of Ceramic Processing”, Singapore, John Wiley & Sons (1989)

50. 陳龍賓，“分散劑的合成以及對於鈦酸鋇漿體分散性能的評估” 國立台灣師
範大學化學研究所碩士論文， 2002。

51. K. L. Ying, T. E. Hsieh, Sintering Behaviors and Dielectric Properties of
Nanocrystalline Barium Titanate, Mat. Sci. Eng. B 138 (2007) 241–245

52. C. H. Chen and K. C. Hsu, “Dispersion Properties of BaTi4O9/ Ba3Ti9O20 Colloids with Amphoteric Polyelectrolytes”, J. Eur. Ceram. Soc.27 (2007) 463~468

53. B. Y. Yu, W. C. Wei, and K. C. Hsu, “Study of Adsorption Mechanism of Amphoteric Polyelectrolyte in BaTiO3 Colloids Suspension “, J. Ceram. Proc. Res. 5 (2004) 163~170

54. 吳杏璇，“添加陰離子型分散劑之鈦酸鋇漿體在不同pH值下的分散行為”
國立台灣師範大學化學研究所碩士論文， 2004。