Glass polymorphism in Glycerol–water mixtures: II. Experimental studies

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 s1–10 K h1) and for the whole range of glycerol mole fractions, wg. Depending on concentration and cooling rates, cooling leads to samples containing amorphous ice (wg Z 0.20), ice (wg r 0.32), and/or ‘‘distorted ice’’ (0 o wg r 0.38). Upon compression, we find that (a) fully vitrified samples at wg Z 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 wg E 0.32 (T = 77 K). This is rather surprising since it has been known that at wg o 0.38, cooling leads to phase-separated samples with ice and maximally freezeconcentrated solution of wg E 0.38. Accordingly, in the range 0.32 o wg o 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 wg r 0.15, the water domains within the sample exhibit polyamorphism, i.e., the HDA-to-LDA (low-density amorphous ice) transformation. At 0.15 o wg r 0.38, samples contain ice, interfacial ice, and/or HDA domains. All samples (wg r 0.38) show: the crystallization of amorphous ice domains, followed by the glass transition of the vitrified glycerol–water domains and, finally, the melting of ice at high temperatures. Our work exemplifies the complex ‘‘phase’’ behavior of glassy binary mixtures due to phase-separation (ice formation) and polyamorphism, and the relevance of sample preparation, concentration as well as cooling rates. The presence of the distorted ice (called ‘‘interphase’’ by us) also explains the debated ‘‘drift anomaly’’ upon melting. These results are compatible with the high-pressure study by Suzuki and Mishima indicating disappearance of polyamorphism at P E 0.03–0.05 GPa at wg E 0.12–0.15 [J. Chem. Phys., 2014, 141, 094505]

Glass polymorphism in glycerol–water mixtures: I. A computer simulation study

We perform out-of-equilibrium molecular dynamics (MD) simulations of water–glycerol mixtures in the glass state. Specifically, we study the transformations between low-density (LDA) and high-density amorphous (HDA) forms of these mixtures induced by compression/decompression at constant temperature. Our MD simulations reproduce qualitatively the density changes observed in experiments. Specifically, the LDA–HDA transformation becomes (i) smoother and (ii) the hysteresis in a compression/ decompression cycle decreases as T and/or glycerol content increase. This is surprising given the fast compression/decompression rates (relative to experiments) accessible in MD simulations. We study mixtures with glycerol molar concentration wg = 0–13% and find that, for the present mixture models and rates, the LDA–HDA transformation is detectable up to wg E 5%. As the concentration increases, the density of the starting glass (i.e., LDA at approximately wg r 5%) rapidly increases while, instead, the density of HDA remains practically constant. Accordingly, the LDA state and hence glass polymorphism become inaccessible for glassy mixtures with approximately wg 4 5%. We present an analysis of the molecular-level changes underlying the LDA–HDA transformation. As observed in pure glassy water, during the LDA-to- HDA transformation, water molecules within the mixture approach each other, moving from the second to the first hydration shell and filling the first interstitial shell of water molecules. Interestingly, similar changes also occur around glycerol OH groups. It follows that glycerol OH groups contribute to the density increase during the LDA–HDA transformation. An analysis of the hydrogen bond (HB)-network of the mixtures shows that the LDA–HDA transformation is accompanied by minor changes in the number of HBs of water and glycerol. Instead, large changes in glycerol and water coordination numbers occur. We also perform a detailed analysis of the effects that the glycerol force field (FF) has on our results. By comparing MD simulations using two different glycerol models, we find that glycerol conformations indeed depend on the FF employed. Yet, the thermodynamic and microscopic mechanisms accompanying the LDA–HDA transformation and hence, our main results, do not. This work is accompanied by an experimental report where we study the glass polymorphism in glycerol–water mixtures prepared by isobaric cooling at 1 ba