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Register a new userVitrification, relaxation and free volume in glycerol-water binary liquid mixture: Spin probe ESR studies
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Glass transition and relaxation of the glycerol-water binary mixture system are studied over the glycerol concentration range of 5 - 85 mol% using the highly sensitive technique of spin probe ESR. For the water rich mixture the glass transition, sensed by the spin probe, arises from the vitrified mesoscopic portion of the binary system. The concentration dependence of the glass transition temperature manifests a closely related molecular level cooperativity in the system. A drastic change in the mesoscopic structure of the system at the critical concentration of 40 mol% is confirmed by an estimation of the spin probe effective volume in a temperature range where the tracer reorientation is strongly coupled to the system dynamics.
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First systematic spin probe ESR study of water freezing has been conducted using TEMPOL and TEMPO as the probes. The spin probe signature of the water freezing has been described in terms of the collapse of narrow triplet spectrum into a single broad line. This spin probe signature of freezing has been observed at an anomalously low temperature when a milimoler solution of TEMPOL is slowly cooled from room temperature. A systematic observation has revealed a spin probe concentration dependence of these freezing and respective melting points. These results can be explained in terms of localization of spin probe and liquid water, most probably in the interstices of ice grains, in an ice matrix. The lowering of spin probe freezing point, along with the secondary evidences, like spin probe concentration dependence of peak-to-peak width in frozen limit signal, indicates a possible size dependence of these localizations/entrapments with spin probe concentration. A weak concentration dependence of spin probe assisted freezing and melting points, which has been observed for TEMPO in comparison to TEMPOL, indicates different natures of interactions with water of these two probes. This view is also supported by the relaxation behavior of the two probes.
We present an accurate equation of state for water based on a simple microscopic Hamiltonian, with only four parameters that are well-constrained by bulk experimental data. With one additional parameter for the range of interaction, this model yields a computationally efficient free-energy functional for inhomogeneous water which captures short-ranged correlations, cavitation energies and, with suitable long-range corrections, the non-linear dielectric response of water, making it an excellent candidate for studies of mesoscale water and for use in ab initio solvation methods.
In this paper we calculate the interfacial resistances to heat and mass transfer through a liquid-vapor interface in a binary mixture. We use two methods, the direct calculation from the actual non-equilibrium solution and integral relations, derived earlier. We verify, that integral relations, being a relatively faster and cheaper method, indeed gives the same results as the direct processing of a non-equilibrium solution. Furthermore we compare the absolute values of the interfacial resistances with the ones obtained from kinetic theory. Matching the diagonal resistances for the binary mixture we find that kinetic theory underestimates the cross coefficients. The heat of transfer is as a consequence correspondingly larger.
A gold-capped Janus particle suspended in a near-critical binary liquid mixture can self-propel under illumination. We have immobilized such a particle in a narrow channel and studied the nonequilibrium dynamics of a binary solvent around it, using experiment and numerical simulations. For the latter we consider both a purely diffusive and a hydrodynamic model. All approaches indicate that the early time dynamics is purely diffusive and characterized by composition layers traveling with a constant speed from the surface of the colloid into the bulk. Subsequently, hydrodynamic effects set in and the transient state is destroyed by strong nonequilibrium concentration fluctuations, which arise as a result of the temperature gradient and the vicinity of the critical point of the binary liquid mixture. They give rise to a complex, permanently changing coarsening patterns. For a mobile particle, the transient dynamics results in propulsion in the direction opposite to that observed after the steady state is attained.
The force-level Elastically Collective Nonlinear Langevin Equation theory of activated relaxation in glass-forming free-standing thin films is re-visited to improve its treatment of collective elasticity effects. The naive cut off of the isotropic bulk displacement field approximation is improved to explicitly include spatial anisotropy with a modified boundary condition consistent with a step function liquid-vapor interface. The consequences of this improvement on dynamical predictions are quantitative but of significant magnitude and in the direction of further speeding up dynamics and further suppressing Tg. The theory is applied to thin films and also thick films to address new questions for three different polymers of different dynamic fragility. Variation of the vitrification time scale criterion over many orders of magnitude is found to have a minor effect on changes of the film-averaged Tg relative to its bulk value. The mobile layer length scale grows strongly with cooling and correlates in a nearly linear manner with the effective barrier deduced from the corresponding bulk isotropic liquid alpha relaxation time. The theory predicts a new type of spatially inhomogeneous dynamic decoupling corresponding to an effective factorization of the total barrier into its bulk temperature-dependent value multiplied by a function that only depends on location in the film. The effective decoupling exponent grows as the vapor surface is approached. Larger reductions of the absolute value of Tg shifts in thin polymer films are predicted for longer time vitrification criteria and more fragile polymers. Quantitative no-fit-parameter comparisons with experiment and simulation for film-thickness-dependent Tg shifts of PS and PC are in reasonable accord with the theory, including a nearly 100 K suppression of Tg in 4 nm PC films. Predictions are made for polyisobutylene thin films.
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