Advertisement

Swelling pressure equilibrium of swollen crosslinked systems in an external field. II: The determination of molecular parameters of gelatin/water gels from the swelling pressure-concentration curves

  • -G. Holtus
  • H. Cölfen
  • W. Borchard
Conference paper
Part of the Progress in Colloid & Polymer Science book series (PROGCOLLOID, volume 86)

Abstract

Physically crosslinked watery gels of a dialyzed pigskin gelatin of type A are investigated by means of equilibrium runs at 10 and 20°C. From the data of the Schlieren patterns the swelling pressure-concentration curves can be calculated. It can be shown that equilibria are achieved in all cases and that the swelling pressure which is calculated for a given concentration is independent of the rotational speed selected for the experiment if all other conditions are kept constant. The results are described by the swelling equation of the Flory-Huggins type where the interaction paramter x is allowed to depend linearly on the polymer concentration. Thus, two interaction constants and the network parameter have been calculated for each network by means of a nonlinear numerical iteration due to the Gauss-Jordan procedure. With these constants the swelling pressure-concentration curves are well described. The x-parameter at low initial concentration of the polymer is very close to the value which has been experimentally determined in polymer solutions in the highly diluted range above the coil-helix transition range. Both x-values reveal the influence of a highly branched structure of the polymer network. The calculated elastic modulus has nearly the same order of magnitude as that which has been obtained from the experimentally determined real part of the complex shear modulus of the same gel.

Key words

Thermoreversible gelation physical network swelling pressure ultracentrifugation Flory-Huggins equation 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Posnjak E (1912) Koll Chem Beiheft 3:417Google Scholar
  2. 2.
    Lloyd DJ, Moran T (1934) Proc Roy Soc 147A:382Google Scholar
  3. 3.
    Pennings AJ, Prins WJ (1961) Polymer Science 49Google Scholar
  4. 4.
    van de Kraats EJ (1968) Rec Trav Chim Pays Bas 87:1137Google Scholar
  5. 5.
    Borchard W (1966) Dissertation, AachenGoogle Scholar
  6. 6.
    Brochard W, Emberger A, Schwarz J (1978) Die Angewandte Makromolekulare Chemie 66, Nr. 986:43Google Scholar
  7. 7.
    Borchard W (1975) Progr Colloid Polym Sci 57:39CrossRefGoogle Scholar
  8. 8.
    Svedberg T, Pedersen KO (1940) Die Ultrazentrifuge, Steinkopff, DresdenGoogle Scholar
  9. 9.
    Johnson P (1964) Proc Royal Soc A 278:527CrossRefGoogle Scholar
  10. 10.
    Johnson P, Metcalfe JC (1967) Europ Polym J 3:423CrossRefGoogle Scholar
  11. 11.
    Johnson P, King RW (1968) J Photograph Sci 16:82Google Scholar
  12. 12.
    Johnson P (1971) J Photograph Sci 19:49Google Scholar
  13. 13.
    Johnson P (1970) Velocity and equilibrium aspects of the sedimentation of agar gels in Photographic Gelatin I, Academic Press, London:13Google Scholar
  14. 14.
    Richard AJ (1983) Biopolymers 22(3):935CrossRefGoogle Scholar
  15. 15.
    Richard AJ (1984) Biopolymers 23(7):1307CrossRefGoogle Scholar
  16. 16.
    Richard AJ, Westkaemper RB (1986) Biopolymers 25(10):2017CrossRefGoogle Scholar
  17. 17.
    Lange H (1986) Colloid Polym Sci 264:488CrossRefGoogle Scholar
  18. 18.
    Holtus G, Borchard W (1989) Colloid Polym Sci 267:1333CrossRefGoogle Scholar
  19. 19.
    Holtus G (1990) Dissertation, DuisburgGoogle Scholar
  20. 20.
    Cölfen H (1991) Diplomarbeit, DuisburgGoogle Scholar
  21. 21.
    Cölfen H, Borchard W this issueGoogle Scholar
  22. 22.
    Borchard W thsis issueGoogle Scholar
  23. 23.
    Flory PJ (1942) J Chem Phys 10:51CrossRefGoogle Scholar
  24. 24.
    Huggins ML (1943) Ann NY Acad Sci 44:431CrossRefGoogle Scholar
  25. 25.
    Staverman AJ (1962) Thermodynamics of Polymers in flügge S (1962) Encyclopedia of Physics/Handbuch der Physik, Springer Berlin-Göttingen-Heidelberg 1962Google Scholar
  26. 26.
    Borchard W (1975) Habilitation, ClausthalGoogle Scholar
  27. 27.
    Dusek K, Prins W (1968) Adv Polym Sci 6:58Google Scholar
  28. 28.
    Candau S, Bastide J, Delsanti M (1982) Structural Elastic and Dynamic Properties of Swollen Polymer Networks in Dusek K (1982) Polymer Networks Springer Berlin-Heidelberg-New York 27Google Scholar
  29. 29.
    Graessley WW (1975) Macromolecules 8:186, 865CrossRefGoogle Scholar
  30. 30.
    Edwards SF (1971) The Statistical Mechanics of Rubbers in Chömpff & Newman (1971) Polymer Network Structure and Mechanical Properties, Plenum Press, New York-LondonGoogle Scholar
  31. 31.
    Kilian HG, Schenk H, Wolff S (1987) Colloid Polym Sci 265 Nr. 5:410CrossRefGoogle Scholar
  32. 32.
    Scholte TG (1971) J Polym Sci 9A2:1553Google Scholar
  33. 33.
    Staverman AJ (1982) Properties of Phantom Networks and Real Networks in Dusek K (1982) Polymer Networks, Springer Berlin-Heidelberg-New York 1982:73Google Scholar
  34. 34.
    Rehage G (1964) Kolloid-Z u Z Polymere 194:16 and 196:57CrossRefGoogle Scholar
  35. 35.
    Koningsveld R, Kleintjens LA (1971) Macromolecules 4:5, 637CrossRefGoogle Scholar
  36. 36.
    Haase R (1956) Thermodynamik der Mischphasen, Springer Berlin-Göttingen-HeidelbergGoogle Scholar
  37. 37.
    Adames W, Michalczyk A, Borchard W (1989) Europ Polym J 25 Nr. 9:951CrossRefGoogle Scholar
  38. 38.
    Candau F, Strazielle C, Benoit H (1976) Europ Polym J 12:95CrossRefGoogle Scholar
  39. 39.
    Boedtker H, Doty P (1954) J Phys Chem 58:968CrossRefGoogle Scholar
  40. 40.
    Fietzek PP, Kühn K (1975) Cellular Biochem 8:141CrossRefGoogle Scholar
  41. 41.
    ter Meer HU (1985) Thermoreversible Gelierung: Carrageenan; Agarose; Alginate and Pektin in Burchard W (1985) Polysaccharide, SpringerGoogle Scholar
  42. 42.
    Stauffer D, Coniglio A, Adam M (1982) Gelation and Critical Phenomena in Dusek K (1982) Polymer Networks, Springer Berlin-Heidelberg-New York 103Google Scholar
  43. 43.
    Keese AS (1978) Diplomarbeit, ClausthalGoogle Scholar
  44. 44.
    Borchard W, Keese A (1979) presented at the IUPAC Meeting MainzGoogle Scholar
  45. 45.
    Borchard W, Bergmann K, Rehage G (1976) Investigations of Gelation Phenomena in Aqueous Gelatin Solutions in Photographic Gelatin II, Academic Press, London:57Google Scholar
  46. 46.
    Borchard W, Bergmann K, Emberger A, Rehage G (1976) Progr Colloid Polym Sci 60:20Google Scholar
  47. 47.
    Burg B (1988) Dissertation, DusiburgGoogle Scholar
  48. 48.
    Burg B, Borchard W (1988) Optical and Viscoelastic Properties of Gelatin-Water During Gelation in Lemstra PJ & Kleintjens LA (1988) Integration of Fundamental Polymer Science And Technology 3, Elseiver Applied Science London-New York 323Google Scholar
  49. 49.
    Borchard W, Burg B (1990) Progr Colloid Polym Sci 83:200Google Scholar
  50. 50.
    Emberger A (1975) Diplomarbeit, ClausthalGoogle Scholar
  51. 51.
    Rose PI (1987) in Encyclopedia of Polymer Science and Engineering, Volume 7, 2nd Edition, John Wiley & Sons:499Google Scholar

Copyright information

© Dr. Dietrich Steinkopff Verlag GmbH & Co. KG 1991

Authors and Affiliations

  • -G. Holtus
    • 1
  • H. Cölfen
    • 1
  • W. Borchard
    • 1
  1. 1.Angewandte Physikalische ChemieUniversität-GH-DuisburgDuisburg 1FRG

Personalised recommendations