The anomalous melting behavior of water in aqueous PVME solutions

The Wertheim lattice thermodynamic perturbation theory is used to predict the liquid-liquid and solid-liquid coexistence data for a model polymer solution. The theory predicts bimodal LCST phase behavior and an unusual step with composition in the solid-liquid equilibrium of the solvent.The theoretical solid-liquid equilibrium calculations are used to interpret experimental data obtained for aqueous solutions of poly(vinyl methyl ether) (PVME), which is known to show bimodal LCST phase behavior. An experimental method is proposed, employing Fourier transform infrared (FTIR) spectroscopy to determine the equilibrium melting line of water in the presence of PVME. In addition, the complete melting line of water is obtained by partial integration of the melting endotherm observed using modulated temperature differential scanning calorimetry (MTDSC). Both, the FTIR and MTDSC methods are in good agreement, experimentally confirming the predicted step with composition in the solid-liquid equilibrium. This peculiar concentration dependence of the melting curve of ice provides a new explanation for the inhibited crystallization of water in aqueous PVME solutions, since the actual supercooling (at high polymer concentration) is smaller than it could be anticipated for a conventional course of the melting curve. Hence, the vicinity of the glass transition region in these highly concentrated polymer mixtures leads to a dramatic slowing down of the nucleation rate and thus the subsequent crystallization. Moreover, the atypical shape of the equilibrium melting line also provides a new explanation for the double melting endotherm observed in (MT)DSC experiments, which is conventionally attributed to the melting at different temperatures of bound and free water.