Search

We investigated the impact of sample preparation on the glassy dynamics of thin films of poly(4-chlorostyrene), a polymer whose molecular mobility is particularly sensitive to changes in the specific volume. Samples were obtained by spincoating, the technique most commonly used to prepare thin organic layers, which consists of pouring dilute polymer solutions onto a plate rotating at a high rate. Our experimental results demonstrate that filtering the solutions before spincoating affects the value of the segmental relaxation time of the as-prepared films. Thin polymer layers obtained via filtered solutions show accelerated segmental dynamics upon confinement at the nanoscale level, once below 100nm, while the samples obtained via unfiltered solutions exhibit bulk-like dynamics down to 15-20nm. We analyzed these results by means of the cooperative free volume rate model, considering a larger free volume content in thin films obtained via filtered solutions. The validity of the model predictions was finally verified by measurements of irreversible adsorption, confirming a larger adsorbed amount, corresponding to a higher specific volume, in the case of samples obtained via unfiltered solutions. Our results prove that filtering is a crucial step in the preparation of thin films, and it could be used to switch on and off nanoconfinement effects. Graphical abstract: [Figure not available: see fulltext.]., SCOPUS: ar.j, info:eu-repo/semantics/published

The critical region in the phase diagram of condensed matter systems such as fluids or fluid mixtures is characterized by the anomalous behaviour of specific thermodynamic properties. Here, we discuss the progress of understanding the behaviour of two intimately related properties, the dielectric constant ɛ and the refractive index n, when approaching the liquid-liquid critical point in binary liquid mixtures. Phenomenological scaling approaches, in particular, complete scaling formulation, are highlighted. In addition, experimental evidence provided by dielectric spectroscopy and optical measurements supporting the asymmetry-related critical features in ɛ and n in the one- and two-phase regions is assessed. We revisit recent experimental data and point out peculiar patterns of behaviour of polar-polar liquid mixtures as compared to (much more frequently studied) polar-non-polar mixtures. We point the necessity of additional research efforts towards the study of polar-polar mixtures, which would shed light into the influence of (microscopic) system-dependent parameters on asymmetry-related features of liquid-liquid criticality. Graphical abstract: [Figure not available: see fulltext.]., SCOPUS: re.j, info:eu-repo/semantics/published

This paper describes the European Space Agency (ESA) experiments devoted to study thermodiffusion of fluid mixtures in microgravity environment, where sedimentation and convection do not affect the mass flow induced by the Soret effect. First, the experiments performed on binary mixtures in the IVIDIL and GRADFLEX experiments are described. Then, further experiments on ternary mixtures and complex fluids performed in DCMIX and planned to be performed in the context of the NEUF-DIX project are presented. Finally, multi-component mixtures studied in the SCCO project are detailed. Graphical abstract: [Figure not available: see fulltext.]., 0, SCOPUS: re.j, info:eu-repo/semantics/published