Colloid and Polymer Science

, Volume 283, Issue 1, pp 24–32 | Cite as

Hydrogels in aqueous phases of polyvinylalcohol (PVA), surfactants and clay minerals

Original Contribution


Aqueous solutions of synthetic clay minerals have been studied in the presence of surfactants and water-soluble polyvinylalcohol (PVA). The PVAs (PVA 1, PVA 2) had a molecular weight of about 105 Dalton and a degree of hydrolysis of 82%. The PVA-samples were surface active and lowered the surface tension to 43 mN/m. As a consequence of their amphiphilic nature the PVA molecules bind strongly to clay mineral particles. On saturation the clay mineral particles adsorb the fivefold weight of PVA of their own weight. It is concluded that the thickness of the adsorbed layers on both sides of the clay mineral is in the range of the hydrodynamic diameter of the PVA-coils in the bulk phase.

When the clay mineral particles are not saturated with PVA, they act as cross-linking agents for the PVA. The whole systems are physically cross-linked and assume gel-like properties. Rheological measurements show that samples behave like soft matter with a yield stress value. All of them have a frequency independent storage modulus which is an order of magnitude larger than the loss modulus. The hydrogels become stronger as PVA concentration increases.

Small amounts of cationic surfactants bind on the clay mineral. The interface of the clay mineral becomes more hydrophobic and the binding of the PVA on the clay mineral is strengthened. With rising concentration of the surfactant the surfactant molecules bind on PVA and the PVA becomes hydrophilic. As a consequence the PVA can no longer bind on the clay mineral and the gels transform to viscous and turbid solutions. Small amounts of cationic surfactants therefore stiffen the hydrogels while larger amounts cause phase separation and a solution with low viscosity. Anionic surfactants like SDS do not bind on the clay mineral, but strongly on the PVA. With increasing SDS concentration, the hydrogels become stiffer at first but thereafter they break and transform to viscous fluids.

In PVA-solutions without the clay minerals both cationic and anionic surfactants bind to the PVAs in the aqueous solution. With increasing concentration of surfactant, the viscosities of the solutions pass over a maximum. In this respect the PVAs behave like hydrophobically modified water soluble polymers. The surfactants bind to the hydrophobic microdomain and thereby crosslink the polymer molecules. On saturation the polyvinyl alcohol with anionic surfactant become hydrophilic and the network character disappears to a certain extent.


Hydrogels Clay minerals Polyviny lalcohol Polymer surfactant interaction 



The authors would like to thank Wacker Polymer Systems GmbH & Co. KG in Burghausen (Germany) for supplying the compounds for this investigation and, in particular for the financial support for Dr. Jing Liu.


  1. 1.
    Matsunaga S (2002) Jpn Kokai Tokkyo Koho 12Google Scholar
  2. 2.
    Vaia RA, Vasudevan S, Krawiec W, Scanlon LG, Giannelis EP (1995) Adv Mater 7:154Google Scholar
  3. 3.
    Banin A, Kafleat U (eds) (1980) Agrochem. Soils. Pergamon, OxfordGoogle Scholar
  4. 4.
    Williams-Daryn S, Thomas RK, Castro MA, Becerro A (2002) J Colloid Interface Sci 256(2):314–324CrossRefGoogle Scholar
  5. 5.
    Sesta S, La Mesa C (2002) Curr Top Colloid Interface Sci 5:261–270Google Scholar
  6. 6.
    Goddard ED, Ananthapadmanabhan KP (ed) (1993) Interactions of surfactants with polymers and proteins. CRC Press, Boca RatonGoogle Scholar
  7. 7.
    Jonsson B, Lindman B, Holmberg K, Kronberg B (eds) (1998) Surfactants and polymers in aqueous solutions. Wiley, New YorkGoogle Scholar
  8. 8.
    Cabane B, Duplessix R (1982) J Phys (Paris) 43(10):1529–1542Google Scholar
  9. 9.
    Yamaguchi Y, Hoffman H (1997) Colloids Surf A Physicochem Eng Aspects 121(1):67–80CrossRefGoogle Scholar
  10. 10.
    Schmidt G, Nakatani AI, Butler PD, Karim A, Han CC (2000) Macromolecules 33(20):7219–7222CrossRefGoogle Scholar
  11. 11.
    Greenland DJ (1963) J Colloid Sci 18:647Google Scholar
  12. 12.
    Mangravite FJ Jr, Leitz CR, Galick PE (1986) Proc Eng Found Conference (Meeting Date 1985), pp 139–58Google Scholar
  13. 13.
    Breen C, Moronta AJ (2001) Clay Miner 36(4)L467–472Google Scholar
  14. 14.
    Torn LH, de Keizer A, Koopal LK, Lyklema J (2003) J Colloid Interface Sci 260(1):1–8CrossRefPubMedGoogle Scholar
  15. 15.
    Anderson VJ, de Hoog EHA, Lekkerkerker HNW (2002) Phys Rev E Stat Nonlinear Soft Matter Phys 65(011403)Google Scholar
  16. 16.
    Lagaly G, Schultz O, Zimehl R (1997) Dispersionen und Emulsionen. Steinkopf, Darmstadt, p 147Google Scholar
  17. 17.
    Piculell L, Lindman B, Karlstrom G (1998) Surfactant Science Series 77 (Polymer-Surfactant Systems), pp 65–141Google Scholar
  18. 18.
    Muller AJ, Garces Y, Torres M, Scharifleer B, Saez AE (2003) Prog Colloid Polym Sci 122:73–78Google Scholar
  19. 19.
    Krishnan C (1992) J Colloid Interface Sci 151(1):294–296Google Scholar
  20. 20.
    Hoffmann H, Huber G (1989) Colloids Surf 40:181–193CrossRefGoogle Scholar
  21. 21.
    Diamant H, Andelman D (2000) Macromolecules 33(21):8050–8061CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2004

Authors and Affiliations

  1. 1.Physical Chemistry IUniversity of BayreuthBayreuthGermany

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