Phase separation in bimodal dispersions of sterically stabilized silica particles

Binary mixtures of suspended, nearly hard-sphere, sterically stabilized colloidal silica particles of diameter ratio 6 were observed to phase-separate at comparable volume fractions of the two particle species. The occurrence of phase separation as a function of the particle concentrations was studied visually and by small-angle light scattering. The results support recent predictions by Biben and Hansen

Tilt order parameters, polarity and inversion phenomena in smectic liquid crystals

The order parameters for the phenomenological description of the smectic-{\it A} to smectic-{\it C} phase transition are formulated on the basis of molecular symmetry and structure. It is shown that, unless the long molecular axis is an axis of two-fold or higher rotational symmetry, the ordering of the molecules in the smectic-{\it C} phase gives rise to more than one tilt order parameter and to one or more polar order parameters. The latter describe the indigenous polarity of the smectic-{\it C} phase, which is not related to molecular chirality but underlies the appearance of spontaneous polarisation in chiral smectics. A phenomenological theory of the phase transition is formulated by means of a Landau expansion in two tilt order parameters (primary and secondary) and an indigenous polarity order parameter. The coupling among these order parameters determines the possibility of sign inversions in the temperature dependence of the spontaneous polarisation and of the helical pitch observed experimentally for some chiral smectic-{\it $C^{\ast}$} materials. The molecular interpretation of the inversion phenomena is examined in the light of the new formulation.Comment: 12 pages, 5 figures, RevTe

Theory of asymmetric non-additive binary hard-sphere mixtures

We show that the formal procedure of integrating out the degrees of freedom of the small spheres in a binary hard-sphere mixture works equally well for non-additive as it does for additive mixtures. For highly asymmetric mixtures (small size ratios) the resulting effective Hamiltonian of the one-component fluid of big spheres, which consists of an infinite number of many-body interactions, should be accurately approximated by truncating after the term describing the effective pair interaction. Using a density functional treatment developed originally for additive hard-sphere mixtures we determine the zero, one, and two-body contribution to the effective Hamiltonian. We demonstrate that even small degrees of positive or negative non-additivity have significant effect on the shape of the depletion potential. The second virial coefficient $B_2$, corresponding to the effective pair interaction between two big spheres, is found to be a sensitive measure of the effects of non-additivity. The variation of $B_2$ with the density of the small spheres shows significantly different behavior for additive, slightly positive and slightly negative non-additive mixtures. We discuss the possible repercussions of these results for the phase behavior of binary hard-sphere mixtures and suggest that measurements of $B_2$ might provide a means of determining the degree of non-additivity in real colloidal mixtures

Free energy changes on freezing and melting ductile metals

The variation in Landau free energy while melting platinum was investigated at a number of temperatures using computer simulation with a model potential. The technique used was to apply a biasing potential in a Monte Carlo simulation with umbrella sampling. From the Landau free energy curves one can determine the difference in free energies between the solid and liquid phases easily and accurately, the thermodynamic melting point (Tm), and the limit of metastability of the crystalline phase. The latter occurs at approximately 1·2Tm. It was difficult to freeze the material, but, using a suitable order parameter, this was achieved. Unlike earlier results on a soft sphere system, there was no evidence for nucleation of a metastable body-centred-cubic phase. One possible reason is the existence of local icosahedral order in the liquid phase of the metal. The surface free energy of the solid-liquid surface was estimated from the free energy barrier to melting. Model rhodium behaved in a very similar way