Thermodiffusion of polymer solutions and colloidal dispersions in mixed solvents

Two-color optical measurements of thermodiffusion in ternary mixtures frequently suffer from ill-conditioned contrast factor matrices, whose inversion leads to very large experimental errors. In this contribution, we show how the error amplification can be avoided in situations where a priori knowledge about the directions of the eigenvectors of the diffusion matrix is available. We present optical beam deflection experiments on solutions of the polymer polystyrene of M_w = 4880 g/mol in a mixed solvent of toluene and cyclohexane. In this system, the two diffusion eigenvalues differ by almost one order of magnitude. The large eigenvalue can be attributed to the interdiffusion of the two solvents and the small one to the polymer diffusion relative to the mixed solvent. The pre-selection of the eigenvectors renders the method stable against fluctuations of the experimental parameters. Both the diffusion and the Soret coefficients attributed to the two modes agree very well with the respective values of corresponding binary mixtures.