Glass polymorphism in glycerol-water mixtures: II. Experimental studies

Abstract

We report a detailed experimental study of (i) pressure-induced transformations in glycerol-water mixtures at T = 77 K and P = 0-1.8 GPa, and (ii) heating-induced transformations of glycerol-water mixtures recovered at 1 atm and T = 77 K. Our samples are prepared by cooling the solutions at ambient pressure at various cooling rates (100 K s-1-10 K h-1) and for the whole range of glycerol mole fractions, χg. Depending on concentration and cooling rates, cooling leads to samples containing amorphous ice (χg ≥ 0.20), ice (χg ≤ 0.32), and/or "distorted ice" (0 < χg ≤ 0.38). Upon compression, we find that (a) fully vitrified samples at χg ≥ 0.20 do not show glass polymorphism, in agreement with previous works; (b) samples containing ice show pressure-induced amorphization (PIA) leading to the formation of high-density amorphous ice (HDA). PIA of ice domains within the glycerol-water mixtures is shown to be possible only up to χg ≈ 0.32 (T = 77 K). This is rather surprising since it has been known that at χg < 0.38, cooling leads to phase-separated samples with ice and maximally freeze-concentrated solution of χg ≈ 0.38. Accordingly, in the range 0.32 < χg < 0.38, we suggest that the water domains freeze into an interfacial ice, i.e., a highly-distorted form of layered ice, which is unable to transform to HDA upon compression. Upon heating samples recovered at 1 atm, we observe a rich phase behavior. Differential scanning calorimetry indicates that only at χg ≤ 0.15, the water domains within the sample exhibit polyamorphism, i.e., the HDA-to-LDA (low-density amorphous ice) transformation. At 0.15