Equilibrium fluid-crystal interfacial free energy of bcc-crystallizing aqueous suspensions of polydisperse charged spheres

The interfacial free energy is a central quantity in crystallization from the meta-stable melt. In suspensions of charged colloidal spheres, nucleation and growth kinetics can be accurately measured from optical experiments. In previous work, from this data effective non-equilibrium values for the interfacial free energy between the emerging bcc-nuclei and the adjacent melt in dependence on the chemical potential difference between melt phase and crystal phase were derived using classical nucleation theory. A strictly linear increase of the interfacial free energy was observed as a function of increased meta-stability. Here, we further analyze this data for five aqueous suspensions of charg…

Solidification Experiments in Single-Component and Binary Colloidal Melts

Phase behaviour of deionized binary mixtures of charged colloidal spheres.

We review recent work on the phase behaviour of binary charged sphere mixtures as a function of particle concentration and composition. Both size ratios and charge ratios are varied over a wide range. By contrast to hard spheres the long ranged Coulomb interaction stabilizes the crystal phase at low particle concentrations and shifts the occurrence of amorphous solids to particle concentrations considerably larger than the freezing concentration. Depending on size- and charge ratios we observe upper azeotrope, spindle, lower azeotrope and eutectic types of phase diagrams, all known well from metal systems. Most solids are of body centred cubic structure. Occasionally stoichiometric compound…

Colloids as model systems for liquid undercooled metals

Physical review / E 79(1), 4 (2009). doi:10.1103/PhysRevE.79.010501

Nucleation and crystal growth in a suspension of charged colloidal silica spheres with bi-modal size distribution studied by time-resolved ultra-small-angle X-ray scattering

A suspension of charged colloidal silica spheres exhibiting a bi-modal size distribution of particles, thereby mimicking a binary mixture, was studied using time-resolved ultra-small-angle synchrotron X-ray scattering (USAXS). The sample, consisting of particles of diameters d(A) = (104.7 ± 9.0) nm and d(B) = (88.1 ± 7.8) nm (d(A)/d(B) ≈ 1.2), and with an estimated composition A(0.6(1))B(0.4(1)), was studied with respect to its phase behaviour in dependance of particle number density and interaction, of which the latter was modulated by varying amounts of added base (NaOH). Moreover, its short-range order in the fluid state and its eventual solidification into a long-range ordered colloidal…

Competition between heterogeneous and homogeneous nucleation near a flat wall

We studied the competition between heterogeneous and homogeneous nucleation of an aqueous suspension of charged colloidal spheres close to the container walls. Samples of equilibrium crystalline structure were shear-melted and the metastable melt left to solidify after the cessation of shear. The crystallization kinetics was monitored using time-resolved scattering techniques: at low particle number densities n we applied an improved static light scattering method while at large particle concentrations ultra-small-angle x-ray scattering was applied for the first time. Our results show some unexpected behavior: the heterogeneous nucleation at the container walls is delayed in comparison to t…