On Viscoelastic, Birefringent, and Swelling Properties of Laponite Clay Suspensions: Revisited Phase Diagram

Abstract

Relations between thermodynamics, structural, and mechanical properties of Laponite suspensions were recently discussed in the literature. One important issue concerning the liquid/gel transition of the Laponite suspensions is to understand why a mechanical gel appears concomitantly with what appears as an incomplete nematic transition. To get some insight, we first give a more extended characterization of the viscoelastic properties of these suspensions near the liquid/gel transition. For this purpose, stress relaxation experiments are compared to direct determinations of the viscoelastic modulus in the frequency domain. This permits the following of viscoelastic properties, in the linear regime, on a very extended scale, from 10-5 to 102 rad/s. The data show that the relaxation mechanisms are very slow and are compatible with the presence of a large scale structural organization compared to the elementary particle size. The elastic modulus follows the power law: G‘ = A(C − C0)α. Only the concentration threshold varies with the ionic strength. In a second part, we compare, on the same system, how the osmotic pressure and the birefringent properties are correlated. As already shown by Gabriel et al., three optical domains can be defined, an isotropic liquid, an isotropic gel, and a birefringence gel, where numerous threadlike defects highly reminiscent of nematic texture are observed. An interesting new result is seen, a line that separates the isotropic and the birefringent gel coincides with the line where the plateau of the osmotic pressure ends up. Recalling that the osmotic plateau starts just at the liquid/solid transition, we propose a more complete phase diagram exhibiting a pseudobiphasic region with no macroscopic phase separation.