Inversion of thermodiffusive properties of ionic colloidal dispersions in water-DMSO mixtures probed by forced Rayleigh scattering

Thermodiffusion properties at room temperature of colloidal dispersions of hydroxyl-coated nanoparticles (NPs) are probed in water, in dimethyl sulfoxide (DMSO) and in mixtures of water and DMSO at various proportions of water, . In these polar solvents, the positive NPs superficial charge imparts the systems with a strong electrostatic interparticle repulsion, slightly decreasing from water to DMSO, which is here probed by Small Angle Neutron Scattering and Dynamic Light Scattering. However if submitted to a gradient of temperature, the NPs dispersed in water with ClO4 - counterions present a thermophilic behavior, the same NPs dispersed in DMSO with the same counterions present a thermophobic behavior. Mass diffusion coefficient and Ludwig-Soret coefficient are measured as a function of NP volume fraction at various . The -dependence of is analyzed in terms of thermoelectric and thermophoretic contributions as a function of . Using two different models for evaluating the Eastman entropy of transfer of the co- and counterions in the mixtures, the single-particle thermophoretic contribution (the NP's Eastman entropy of transfer) is deduced. It is found to evolve from negative in water to positive in DMSO. It is close to zero on a large range of values, meaning that in this -range largely depends on the thermoelectric effect of free co- and counterions.