Martin Medebach

Electrophoresis of colloidal dispersions in the low-salt regime

We study the electrophoretic mobility of spherical charged colloids in a low-salt suspension as a function of the colloidal concentration. Using an effective particle charge and a reduced screening parameter, we map the data for systems with different particle charges and sizes, including numerical simulation data with full electrostatics and hydrodynamics and experimental data for latex dispersions, on a single master curve. We observe two different volume fraction-dependent regimes for the electrophoretic mobility that can be explained in terms of the static properties of the ionic double layer.

Phenomenology of colloidal crystal electrophoresis

We studied the motion of polycrystalline solids comprising of charged sub-micron latex spheres suspended in deionized water. These were subjected to a low frequency alternating square wave electric field in an optical cell of rectangular cross section. Velocity profiles in X and Y direction were determined by Laser Doppler Velocimetry. The observed complex flow profiles are time dependent due to the combined effects of electro-osmosis, electrophoresis, crystal elasticity, and friction of the crystals at the cell wall. On small time scales elastic deformation occurs. On long time scales channel formation is observed. At intermediate times steady state profiles are dominated by a solid plug of polycrystalline material moving in the cell center. At large field strengths the plug shear melts. Mobilities in the shear molten state are on the order of (6.5±0.5) 10−8 m2 V−1 s−1 and connect continuously with those of the equilibrium fluid. The apparent mobility of the plug is much larger than of the fluid and like...

Drude-type conductivity of charged sphere colloidal crystals : Density and temperature dependence

We report on extensive measurements in the low-frequency limit of the ac conductivity of colloidal fluids and crystals formed from charged colloidal spheres suspended in de-ionized water. Temperature was varied in a range of 5 degrees C < Theta < 35 degrees C and the particle number density n between 0.2 and 25 microm(-3) for the larger, respectively, 2.75 and 210 microm(-3) for the smaller of two investigated species. At fixed Theta the conductivity increased linearly with increasing n without any significant change at the fluid-solid phase boundary. At fixed n it increased with increasing Theta and the increase was more pronounced for larger n. Lacking a rigorous electrohydrodynamic treatment for counterion-dominated systems we describe our data with a simple model relating to Drudes theory of metal conductivity. The key parameter is an effectively transported particle charge or valence Z(*). All temperature dependencies other than that of Z(*) were taken from literature. Within experimental resolution Z(*) was found to be independent of n irrespective of the suspension structure. Interestingly, Z(*) decreases with temperature in near quantitative agreement with numerical calculations.

Colloidal crystal motion in electric fields

Abstract We report on the short and long time flow behaviour of colloidal crystals subjected to a homogeneous electrical square wave a.c.-field in closed cells of rectangular cross section. Local velocities are determined from Laser Doppler velocimetry, sample structure and morphology were observed by time resolved polarisation microscopy. We observe a complex time dependence of the flow behaviour. After each field reversal we find a transition from an initial parabola-like flow to a final plug-like flow. On the time scale of minutes to hours channel narrowing occurs, i.e. flow initially restricted by the cell walls becomes restricted to the cell centre by wall based stationary crystals. Within the narrowed channel, however, a qualitatively similar time dependence of flow is observed.

Slow dynamics in dense oil?water emulsions studied using dynamic light scattering

The 3D-echo-DLS (dynamic light scattering) flat cell light scattering instrument (3D-echo-DLS-FCLSI) presents the possibility of measuring slow dynamics of turbid and concentrated colloidal systems. It combines a modified 3D-DLS component and an echo-DLS component with the flat cell light scattering instrument. While the 3D-DLS suppresses multiple scattering, the echo-DLS allows measurements of slow dynamics or even on non-ergodic systems. The advantage of the thin flat cell is that it increases the transmission and reduces multiple scattering; i.e., singly scattered light that is required by the 3D-DLS is still available from dense turbid systems. In the first part of this contribution the 3D-echo-DLS-FCLSI is introduced and the instrumental performance is presented. The second part of the paper is concerned with the ageing behavior of dense fluids in a flat cell, and with confinement effects. Here, we show that ageing is strongly influenced by the process of filling of the flat cell. In some cases complementary methods can be utilized to measure special properties of the system; e.g., the multispeckle method is most appropriate for measuring heterogeneity effects. In the last part of the paper we compare glass transition measurements of an index-matched emulsion carried out using the 3D-echo-DLS-FCLSI and using the multispeckle instrument. We still find an α-relaxation in the glassy state.

Influence of structure in heterodyne electrophoretic light scattering.

Heterodyne light scattering is employed to probe the electrophoretic flow behavior of a concentrated, deionized model colloidal suspension. Both for the fluid and crystalline regime, the power spectra are well described as velocity distributions, which let assume that the power spectra are dominated by the self-dynamic structure factor. Furthermore, all measured power spectra show an increase of the frequency integrated intensity with the electric field. Since the number of particles should remain constant this finding is unexpected. These effects are rationalized on the basis of a new theoretical model including the influence of the structure factor and of the mobility polydispersity on the power spectra.