Resolving nanoscale dynamics during a liquid-liquid transition in supercooled glycerol-water solutions

• It is proposed that a liquid-liquid transition (LLT), related to the hypothesized transition between high- and low-density liquids (HDL, LDL) in pure water, also exists in supercooled aqueous mixtures. However, experimental observations of the LLT in the supercooled solution is often complicated by the overlap with freezing. Here, we conducted an experiment probing the hypothesized LLT in deeply supercooled 16.5 mol% glycerol-water solution, combining X-ray photon correlation spectroscopy (XPCS), ultra small-angle X-ray scattering (USAXS) and wide-angle X-ray scattering (WAXS). This approach allows us to capture simultaneous, discontinuous structural and dynamic changes within the supercooled liquid following quenching to cryogenic temperatures (172-182 K). We observe changes in the inter-atomic liquid structure (from WAXS) as well as in the nanoscale structure and dynamics (from USAXS/XPCS), resembling a first-order LLT between HDL-like to LDL-like liquid. Importantly, we find that the LLT precedes the onset of ice crystalliization, which we can distinguish based on the advent of ice bragg peaks in WAXS. In addition, analysis of the two-time correlation (TTC) function from XPCS enables us to follow the dynamics during the LLT, which indicates super-diffusive ballistic-like motion and a gradual slowdown towards an arrested state upon freezing, consistent with an LLT via spinodal decomposition. We conclude that these results indicate the existence of a first-order LLT in supercooled glycerol-water solutions at intermediate glycerol concentrations, similar to that hypothesized for pure water at elevated pressures.

Ämnesord

NATURVETENSKAP  -- Fysik (hsv//swe)

NATURAL SCIENCES  -- Physical Sciences (hsv//eng)

NATURVETENSKAP  -- Fysik -- Den kondenserade materiens fysik (hsv//swe)

NATURAL SCIENCES  -- Physical Sciences -- Condensed Matter Physics (hsv//eng)

Nyckelord

Water

Aqueous solutions

X-ray scattering

X-ray photon correlation spectroscopy

kemisk fysik

Chemical Physics

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