Diffusion processes in homogeneous and phase-separated binary fluid mixtures

Diffusion processes in dynamically asymmetric binary fluid mixtures made of monodisperse polystyrene (PS) and a rodlike nematogen molecule (5CB) are studied by pulsed-field gradient spin echo NMR in the vicinity of the phase-separation/phase-dissolution temperature. The phase-separation process and the loss of mobility of polymer chains at Tg take place simultaneously evidencing the strong effect of elasticity on the sample morphology. Below the instability point of the mixture, two self-diffusion coefficients, named Dfast and Dslow, are observed and assigned to mobile molecules i) dissolved in the polymeric matrix and ii) phase-separated in isolated or interconnected domains, respectively. The temperature dependence of Dfast exhibits an Arrhenius-like behaviour when the mixture is submitted to a slow cooling rate whereas a Vogel–Fulcher–Tamman–Hesse law is obeyed for deep quenches. These results show the dynamic heterogeneities existing in the PS/5CB system below the UCST. Characteristic length scales are estimated from modelling echo attenuation curves exhibiting diffraction-like patterns.