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Phase Transitions

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Emulsion Science

Part of the book series: Springer Tracts in Modern Physics ((STMP,volume 181))

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Abstract

Attractive interactions between droplets may induce reversible phase transitions or flocculation and depending upon the densities of the solvent and the droplets, sedimentation or creaming occurs. Flocculation is a process in which emulsion droplets aggregate, without rupture of the stabilizing film between them. Flocculation occurs when the total pair interaction between the droplets becomes appreciably attractive at some separation. If the depth of the attractive well is of the order of kT, then the droplets form aggregates which coexist with single Brownian droplets. The thermal energy allows an equilibrium state to be reached, with continual exchange between aggregated and free droplets. On the macroscopic scale, after a few hours of settling, the emulsion undergoes a phase separation into a concentrated cream or sediment and a dilute phase. When the depth of the attractive well is large compared with kT (i.e. more than 10kT), the droplets are strongly bound to the aggregates and cannot be redispersed by thermal motion. After a short period of time, all the droplets are entrapped within large, tenuous clusters that fill the whole space. The contraction of this gel-like network may take a very long time, especially in concentrated emulsions. In this section, we shall describe reversible flocculation phenomena, while irreversible flocculation phenomena and their associated gel structures will be presented in Sect. 3.2.

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References

  1. S. Asakura, J. Oosawa: Interaction between particles suspended in solutions of macromolecules, J. Polym. Sci. 32, 183 (1958)

    Article  Google Scholar 

  2. M. P. Aronson: The role of free surfactont in destabilizing oil-in-water emulsions, Langmuir 5, 494 (1989)

    Article  CAS  Google Scholar 

  3. J. Bibette, D. Roux, F. Nallet: Depletion interactions and fluid-solid equilibrium in emulsions, Phys. Rev. Lett. 65, 2470 (1990).

    Article  CAS  Google Scholar 

  4. J. Bibette: Depletion interactions and fractionated crystallization for polydisperse emulsion purification, J. Colloid Interface Sci. 147, 474 (1991)

    Article  CAS  Google Scholar 

  5. J. Bibette, D. Roux, B. Pouligny: Creaming of emulsions: the rote of depletion forces induced by surfactant, J. Phys. II (France) 2, 401 (1992)

    Article  CAS  Google Scholar 

  6. A. Meller, J. Stavans: Stability of emulsions with nonadsorbing polymers, Langmuir 12, 301 (1996)

    Article  CAS  Google Scholar 

  7. U. Steiner, A. Meller, J. Stavans: Entropy driven phase Separation in binary emulsions, Phys. Rev. Lett. 74, 4750 (1995)

    Article  CAS  Google Scholar 

  8. V. Digiorgio, R. Piazza, M. Corti, C. Minero: Critical properties of nonionic micellar solutions, J. Chem. Phys. 82, 1025 (1984)

    Article  Google Scholar 

  9. J. N. Israelachvili: Intermolecular and Surface Forces (Academic Press, New York 1992)

    Google Scholar 

  10. F. Leal-Calderon, B. Gerhardi, A. Espert, F. Brossard, V. Alard, J. F. Tranchant, T. Stora, J. Bibette: Aggregation phenomena in Water-in-Oil emulsions, Langmuir 12, 872 (1996)

    Article  CAS  Google Scholar 

  11. B. P. Binks, P. D. I. Fletcher, D. I. Horsup: Effect of microemulsified surfactant in destabilizing water-in-oil emulsions containing C12E4, Colloids Surf. 61, 291 (1991)

    Article  CAS  Google Scholar 

  12. F. Leal-Calderon, O. Mondain-Monval, K. Pays, N. Royer, J. Bibette: Water-in-Oil emulsions: Role of the solvent molecular size an droplet interactions, Langmuir 13, 7008 (1997)

    Article  CAS  Google Scholar 

  13. P. G. De Gennes: Scaling Concepts in Polymer Physics (Cornell University Press, London 1979)

    Google Scholar 

  14. J. P. Hansen, I. R. McDonald: Theory of Simple Liquids (Academic Press, London 1991)

    Google Scholar 

  15. P. N. Pusey, W. van Megen: Phase behaviour of concentrated suspensions of nearly hard colloidal spheres, Nature 320, 340 (1986)

    Article  CAS  Google Scholar 

  16. A. P. Gast, C. K. Hall, W. B. Russel: Polymer-induced phase separations in non-aqueous colloidal suspensions, J. Colloid Interface Sci. 96, 251 (1983)

    Article  CAS  Google Scholar 

  17. B. Vincent, J. Edwards, S. Emmett, R. Croot: Phase Separation in dispersions of weakly interacting particles in solutions of non adsorbing polymer, Colloids Surf. 31, 267 (1988)

    Article  CAS  Google Scholar 

  18. H. N. W. Lekkerkerker, W. C. K. Poon, P. N. Pusey, A. Stroobants, P. B. Warren: Phase behaviour of colloid and polymer mixtures, Europhys. Lett. 20, 59 (1992)

    Article  Google Scholar 

  19. M. H. J. Hagen, D. Frenkel: Determination of phase diagrams for the hord-core attractive Yukawa System, J. Chem. Phys. 101, 4093 (1994)

    Article  CAS  Google Scholar 

  20. P. R. Sperry: Morphology and mechanism in latex flocculated by volume restriction, J. Colloid Interface Sci. 99, 97 (1984)

    Article  CAS  Google Scholar 

  21. B. Vincent: The Stability of non-aqueous dispersions of weakly interacting particles, Colloids Surf. 24, 269 (1987)

    Article  CAS  Google Scholar 

  22. F. Leal-Calderon, J. Bibette, J. Biais: Experimental phase diagrams of polymer and colloid mixtures, Europhys. Lett. 23, 653 (1993)

    Article  Google Scholar 

  23. W. C. K. Poon, S. M. Ilet, P. N. Pusey: Phase bahaviour of colloid-polymer mixture, Il nuovo cimento D 116, 1127 (1994)

    Article  Google Scholar 

  24. S. Sanyal, N. Easwear, S. Ramaswamy, et al.: Phase separation in binary nearly-hard-sphere colloids: evidence for the depietion force, Europhys. Lett. 18, 107 (1993)

    Article  Google Scholar 

  25. R. Jullien, R. Botet, Aggregation and Fractal Aggregates (World Scientific, Singapore 1987)

    Google Scholar 

  26. M. Carpineti, M. Giglio: Spinodal-type dynamics in fractal aggregation of colloidal clusters, Phys. Rev. Lett. 68, 3327 (1992)

    Article  CAS  Google Scholar 

  27. J. Bibette, T. G. Mason, H. Gang, D. A. Weitz: Kinetically induced ordering in gelation of emulsions, Phys. Rev. Lett. 69, 981 (1992)

    Article  CAS  Google Scholar 

  28. J. Bibette, T. G. Mason, H. Gang, D. A. Weitz, P. Poulin: Structure of adhesive emulsions, Langmuir 9, 3352 (1993)

    Article  CAS  Google Scholar 

  29. D. J. Robinson, J. C. Earnshaw: Long range order in two dimensional fractal aggregation, Phys. Rev. Lett. 71, 715 (1993)

    Article  CAS  Google Scholar 

  30. A. Hasmy, E. Anglaret, M. Foret, J. Pellows, R. Jullien: Small-angle neutron-scattering investigation of long-range correlations in silica aerogels: Simulations and experiments, Phys. Rev. B 50, 6006 (1994)

    Article  CAS  Google Scholar 

  31. A. Hasmy, R. Jullien: Sol-gel process simulation by cluster-cluster aggregation, J. Non-Cryst. Solids 186, 342 (1995)

    Article  CAS  Google Scholar 

  32. A. E. Gonzalez, G. Ramirez-Santiago: Spatial Ordering and Structure Factor Scaling in the Simulations of Colloid Aggregation, Phys. Rev. Lett. 74, 1238 (1995)

    Article  CAS  Google Scholar 

  33. F. Sciortino, P. Tartaglia: Structure Factor Scaling during Irreversible Cluster-Cluster Aggregation, Phys. Rev. Lett. 74, 282 (1995)

    Article  CAS  Google Scholar 

  34. P. Poulin, J. Bibette, D. A. Weitz: From colloidal aggregation to spinodal decomposition in sticky emulsions, Eur. J. Phys. B 9, 3352 (1999)

    Google Scholar 

  35. J. M. Gunton, M. San Miguel, P. S. Sahni, In: C. Domb, J. L. Lebowitz (Eds.): Phase Transition and Critical Phenomena (Academic Press, London 1983), Vol. 8, p. 267

    Google Scholar 

  36. J. W. Cahn, J. E. Hilliard: Free Energy of a Nonuniform system. I. Interfacial Free Energy, J. Chem. Phys. 28, 258 (1958)

    Article  CAS  Google Scholar 

Download references

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© 2002 Springer-Verlag Berlin Heidelberg

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(2002). Phase Transitions. In: Emulsion Science. Springer Tracts in Modern Physics, vol 181. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-70820-0_3

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  • DOI: https://doi.org/10.1007/3-540-70820-0_3

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  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-43682-9

  • Online ISBN: 978-3-540-70820-9

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