Colloid and Polymer Science

, Volume 291, Issue 5, pp 1201–1210 | Cite as

Colloidal crystallization of cationic gel spheres of lightly cross-linked poly(2-vinylpyridine) in the deionized aqueous suspension

  • Tsuneo OkuboEmail author
  • Syuji Fujii
  • Kodai Aono
  • Yoshinobu Nakamura
  • Akira Tsuchida
Original Contribution


Colloidal crystallization of deionized suspensions of the cationic gel spheres of lightly cross-linked poly(2-vinylpyridine) (PEGMA-P2VP) has been studied from the microscopic observation, morphology, phase diagram, and elastic property. Critical concentrations of melting coexisted with ion-exchange resins were low compared with those without resins and increased but slightly as the degree of cross-linking decreased. The densities of the gel spheres, i.e., weight percent of the gel spheres divided by the corresponding volume percent, were between 0.7 and 0.9 and rather insensitive to the degree of cross-linking of the spheres examined from 0.1 to 1 mol%. This means that the gel spheres are rather dense. The closest inter-sphere distances of the crystals were much longer than the hydrodynamic diameters of the gel spheres especially at low sphere concentrations. Fluctuation parameters evaluated from the rigidities of the crystals of PEGMA-P2VP were similar to those of colloidal crystals of typical hard spheres. Mono-layered adsorption of cationic gel spheres at the nearest-neighbored layer from a cover glass of the cell was observed microscopically. The stable ordered layers, however, formed beyond the monolayer in the suspension phase. These experimental findings support the important role of the extended electrical double layers around the cationic gel spheres in addition to the excluded volume effect of the sphere themselves on the crystallization.


Cationic gels Poly(2-vinyl pyridine) Reflection spectroscopy Electrical double layer Colloidal crystal Lattice spacing 



The research funds from AMX Co. (Tokyo) to T.O. are appreciated greatly. Financial supports for Scientific Research (B) to T.O. and A.T. from Japan Society for the Promotion of Science are greatly acknowledged. S.F. acknowledges Grant-in-Aid for Challenging Exploratory Research (project no. 24655212) for Japan Society for Promotion of Science and Grant-in-Aid for Scientific Research on Innovative Areas “Molecular Soft Interface Science” from the Ministry of Education, Culture, Sports, Science, and Technology of Japan.


  1. 1.
    Okubo T (1996) Colloid Surf A 109:77CrossRefGoogle Scholar
  2. 2.
    Schaefer DW (1977) J Chem Phys 66:3980CrossRefGoogle Scholar
  3. 3.
    Alexander S, Chaikin PM, Grant P, Morales Gm Pincus P, Hone D (1984) J Chem Phys 80:5776CrossRefGoogle Scholar
  4. 4.
    Okubo T (1993) Prog Polym Sci 18:481CrossRefGoogle Scholar
  5. 5.
    Garbow N, Evers M, Palberg T, Okubo T (2004) J Phys Condens Matter 16:3835CrossRefGoogle Scholar
  6. 6.
    Vanderhoff W, van de Hul HJ, Tausk RJM, Overbeek JTG (1970) In: Goldfinger G (ed) Clean surfaces: their preparation and characterization for interfacial studies. Dekker, New York, pp 15–44Google Scholar
  7. 7.
    Hiltner PA, Papir YS, Krieger IM (1971) J Phys Chem 75:1881CrossRefGoogle Scholar
  8. 8.
    Kose A, Ozaki M, Takano K, Kobayashi Y, Hachisu S (1973) J Colloid Interf Sci 44:330CrossRefGoogle Scholar
  9. 9.
    Williams R, Crandall RS, Wojtowicz PJ (1976) Phys Rev Lett 37:348CrossRefGoogle Scholar
  10. 10.
    Mitaku S, Ohtsuki T, Enari K, Kishimoto A, Okano K (1978) Jap J Appl Phys 17:305CrossRefGoogle Scholar
  11. 11.
    Lindsay HM, Chaikin PM (1982) J Chem Phys 76:3774CrossRefGoogle Scholar
  12. 12.
    Pieranski P (1983) Contemp Phys 24:25CrossRefGoogle Scholar
  13. 13.
    Ottewill RH (1985) Ber Bunseng Phys Chem 89:517CrossRefGoogle Scholar
  14. 14.
    Aastuen DJW, Clark NA, Cotter LK, Ackerson BJ (1986) Phys Rev Lett 57:1733CrossRefGoogle Scholar
  15. 15.
    Pusey PN, van Megen W (1986) Nature 320:340CrossRefGoogle Scholar
  16. 16.
    Okubo T (1988) Acc Chem Res 21:281CrossRefGoogle Scholar
  17. 17.
    Sood AK (1991) Solid State Phys 45:2Google Scholar
  18. 18.
    Okubo T (1988) J Chem Soc Faraday Trans 1 84:1163CrossRefGoogle Scholar
  19. 19.
    Lowen H, Palberg T, Simon R (1993) Phys Rev Lett 70:1557CrossRefGoogle Scholar
  20. 20.
    Okubo T (1994) Macro-ion characterization. From dilute solutions to complex fluids. ACS Symp Ser 548. ACS, Washington, DC, pp 364–380Google Scholar
  21. 21.
    Okubo T, Tsuchida A (2002) Forma 17:141Google Scholar
  22. 22.
    Okubo T (2002) In: Hubbard A (ed) Encyclopedia of surface and colloid science. Marcell Dekker, New York, pp 1300–1309Google Scholar
  23. 23.
    Okubo T (2005) In: Kinoshita S, Yoshioka S (eds) Structural colors in biological systems. Osaka University Press, Osaka, p 267Google Scholar
  24. 24.
    Okubo T (2008) Polym J 40:882CrossRefGoogle Scholar
  25. 25.
    Russel WB (1990) Phase Transition 21:127CrossRefGoogle Scholar
  26. 26.
    Dhont JKG, Smits C, Lekkerkerker HNW (1992) J Colloid Interf Sci 152:386CrossRefGoogle Scholar
  27. 27.
    Verhaeghe NAM, van Blaaderen A (1994) Langmuir 10:1427CrossRefGoogle Scholar
  28. 28.
    Butler S, Harrowell P (1995) Phys Rev E 52:6424CrossRefGoogle Scholar
  29. 29.
    Okubo T, Tsuchida A (2002) Colloid Polym Sci 280:438CrossRefGoogle Scholar
  30. 30.
    Shibayama M, Tanaka T (1993) Adv Polym Sci 109:1CrossRefGoogle Scholar
  31. 31.
    Shibayama M (1998) Macromol Chem Phys 199:1CrossRefGoogle Scholar
  32. 32.
    Holtz JH, Asher SA (1997) Nature 389:829CrossRefGoogle Scholar
  33. 33.
    Pelton R (2000) Adv Colloid Interf Sci 85:1CrossRefGoogle Scholar
  34. 34.
    Xia Y, Cates B, Yin Y, Lu Y (2000) Adv Mater 12:693CrossRefGoogle Scholar
  35. 35.
    Hellweg T, Dewhurst CD, Bruckner E, Kratz K, Eimer W (2000) Colloid Polym Sci 278:972CrossRefGoogle Scholar
  36. 36.
    Debord JD, Lyon LA (2000) J Phys Chem B 104:6330CrossRefGoogle Scholar
  37. 37.
    Xia Y (2001) Adv Mater 13:369CrossRefGoogle Scholar
  38. 38.
    Gao J, Hu Z (2002) Langmuir 18:1360CrossRefGoogle Scholar
  39. 39.
    Okubo T, Hase H, Kimura H, Kokufuta E (2002) Langmuir 18:6783CrossRefGoogle Scholar
  40. 40.
    Okubo T, Mizutani T, Okamoto J, Kimura K, Tsuchida A, Tauer K, Khrenov V, Kawaguchi H, Tsuji S (2006) Colloid Polym Sci 285:351CrossRefGoogle Scholar
  41. 41.
    Crassous JJ, Ballauff M, Drechsler M, Schmidt J, Talmon Y (2006) Langmuir 22:2403CrossRefGoogle Scholar
  42. 42.
    Crassous JJ, Wittemann A, Siebenburger M, Schrinner M, Drechsler M, Ballauff M (2008) Colloid Polym Sci 286:805CrossRefGoogle Scholar
  43. 43.
    Crassous JJ, Rochette CN, Wittemann A, Schrinner M, Ballauff M (2008) Langmuir 25:7862CrossRefGoogle Scholar
  44. 44.
    Okubo T, Suzuki D, Yamagata T, Katsuno A, Sakurai M, Kimura H, Tsuchida A (2011) Colloid Polym Sci 289:291CrossRefGoogle Scholar
  45. 45.
    Okubo T, Suzuki D, Yamagata T, Horigome K, Shibata K, Tsuchida A (2011) Colloid Polym Sci 289:1273CrossRefGoogle Scholar
  46. 46.
    Suzuki D, Horigome K, Yamagata T, Shibata K, Tsuchida A, Okubo T (2011) Colloid Polym Sci 289:1799CrossRefGoogle Scholar
  47. 47.
    Suzuki D, Yamagata T, Horigome K, Shibata K, Tsuchida A, Okubo T (2012) Colloid Polym Sci 290:107CrossRefGoogle Scholar
  48. 48.
    Okubo T, Suzuki D, Tsuchida A (2012) Colloid Polym Sci. doi: 10.1007/s00396-012-2770-3.
  49. 49.
    Okubo T, Suzuki D, Shibata K, Tsuchida A (2012) Colloid Polym Sci 290:1403Google Scholar
  50. 50.
    Dupin D, Fujii S, Armes SP, Reeve P, Baxter SM (2006) Langmuir 22:3381CrossRefGoogle Scholar
  51. 51.
    Okubo T, Fujii S, Aono K, Nakamura Y, Tsuchida A (2012) Colloid Polymer Sci. doi: 10.1007/s00396-012-2825-5
  52. 52.
    Okubo T (1986) J Chem Soc Faraday Trans 1(82):3163Google Scholar
  53. 53.
    Fujii S, Kameyama S, Armes SP, Dupin D, Suzaki M, Nakamura Y (2010) Soft Matter 6:635CrossRefGoogle Scholar
  54. 54.
    Okubo T (1987) Ber Bunsenges Phys Chem 91:1064Google Scholar
  55. 55.
    Okubo T (1988) J Colloid Interf Sci 125:380CrossRefGoogle Scholar
  56. 56.
    Baker JA, Henderson D (1967) J Chem Phys 47:2856CrossRefGoogle Scholar
  57. 57.
    Wadachi M, Toda M (1972) J Phys Soc Jpn 32:1147CrossRefGoogle Scholar
  58. 58.
    Hachisu S, Kobayashi Y, Kose A (1973) J Colloid Interf Sci 42:342CrossRefGoogle Scholar
  59. 59.
    Brenner SL (1976) J Phys Chem 80:1473CrossRefGoogle Scholar
  60. 60.
    Takano K, Hachisu S (1977) J Chem Phys 67:2604CrossRefGoogle Scholar
  61. 61.
    Okubo T (1988) J Chem Soc Faraday Trans 1 84:1171CrossRefGoogle Scholar
  62. 62.
    Okubo T (1988) J Chem Soc Faraday Trans 1 84:1949CrossRefGoogle Scholar
  63. 63.
    Okubo T (1988) J Chem Soc Faraday Trans 1 84:4161CrossRefGoogle Scholar
  64. 64.
    Crandall RS, Williams R (1977) Science 198:293CrossRefGoogle Scholar
  65. 65.
    Mitaku S, Ohtsuki T, Okano K (1980) Jpn J Appl Phys 19:439CrossRefGoogle Scholar
  66. 66.
    Mitaku S, Ohtsuki T, Kishimoto A, Okano K (1980) Biophys Chem 71:411CrossRefGoogle Scholar
  67. 67.
    Stoeber W, Fink A, Bohn E (1968) J Colloid Interf Sci 26:62CrossRefGoogle Scholar
  68. 68.
    Okubo T, Okamoto J, Tsuchida A (2010) Colloid Polym Sci 288:189CrossRefGoogle Scholar
  69. 69.
    Okubo T, Suzuki D, Yamagata T, Katsuno A, Mizutani M, Kimura H, Tsuchida A (2011) Colloid Polym Sci 289:807CrossRefGoogle Scholar
  70. 70.
    Okubo T, Suzuki D, Tsuchida A (2012) Colloid Polym Sci 290:411CrossRefGoogle Scholar
  71. 71.
    Okubo T, Suzuki D, Tsuchida A (2012) Colloid Polym Sci 290:867Google Scholar
  72. 72.
    Okubo T, Suzuki D, Tsuchida A (2012) Colloid Polym Sci. doi: 10.1007/s00396-012-2727-6

Copyright information

© Springer-Verlag Berlin Heidelberg 2012

Authors and Affiliations

  • Tsuneo Okubo
    • 1
    Email author
  • Syuji Fujii
    • 2
  • Kodai Aono
    • 2
  • Yoshinobu Nakamura
    • 2
  • Akira Tsuchida
    • 3
  1. 1.Institute for Colloidal OrganizationUjiJapan
  2. 2.Department of Applied ChemistryOsaka Institute of TechnologyOsakaJapan
  3. 3.Department of Applied Chemistry, Faculty of EngineeringGifu UniversityGifuJapan

Personalised recommendations