High-density amorphous ice: Nucleation of nanosized low-density amorphous ice

Abstract

The pressure dependence of the crystallization temperature of different forms of expanded high-density amorphous ice (eHDA) was scrutinized. Crystallization at pressures 0.05-0.30 GPa was followed using volumetry and powder x-ray diffraction. eHDA samples were prepared via isothermal decompression of very high-density amorphous ice at 140 K to different end pressures between 0.07-0.30 GPa (eHDA0.07-0.3). At 0.05-0.17 GPa the crystallization line T x (p) of all eHDA variants is the same. At pressures >0.17 GPa, all eHDA samples decompressed to pressures <0.20 GPa exhibit significantly lower T x values than eHDA0.2 and eHDA0.3. We rationalize our findings with the presence of nanoscaled low-density amorphous ice (LDA) seeds that nucleate in eHDA when it is decompressed to pressures <0.20 GPa at 140 K. Below ∼0.17 GPa, these nanosized LDA domains are latent within the HDA matrix, exhibiting no effect on T x of eHDA<0.2. Upon heating at pressures 0.17 GPa, these nanosized LDA nuclei transform to ice IX nuclei. They are favored sites for crystallization and, hence, lower T x. By comparing crystallization experiments of bulk LDA with the ones involving nanosized LDA we are able to estimate the Laplace pressure and radius of ∼0.3-0.8 nm for the nanodomains of LDA. The nucleation of LDA in eHDA revealed here is evidence for the first-order-like nature of the HDA → LDA transition, supporting water's liquid-liquid transition scenarios.