PhD Thesis Defenses

Optical and x-ray studies of ice growth in water


The key purpose of this thesis is to study the structure of metastable water and its transformation into ice upon deep supercooling using x-ray scattering as well as optical microscopy. In all experiments, micrometer-sized water droplets were evaporatively cooled in vacuum and probed either by x-rays or optical illumination. In addition to these, an infrared (IR) heating pulse was employed in one of the experiments to introduce a temperature jump in water droplets and achieve ultrafast calorimetry, which can measure specific heat capacity upon supercooling. The second peak of the structure factor presented a maximum at 236 K. The anomalous decrease in peak positions below 236 K was related to a repeat spacing in the tetrahedral network, associated with the intermediaterange correlations in water. The decrease in temperature makes the paircorrelation function change in a similar manner to that of low-density amorphous ice (LDA), meaning that the structure moves towards a less dense local ordering. This is in consistency with a low-density pentamer-bonded tetrahedral network that shifts continuously towards an LDA structure as it cools down. The x-ray scattering data showed that there is a maximum in the specific heat capacity of water at about 229 K and it increases from 88 J/mol/K at 244 K to 218 J/mol/K at 229 K upon cooling. Homogeneous ice nucleation showed that there is a mechanism of freezing based on the rates at which different frozen stages, i.e., partially frozen, liquid extrusion and fractured droplets, are seen in the microscopic images. Experimental nucleation data at temperatures as low as ∼230 K resulted in a nucleation fitting curve that shows a slower nucleation rate increase upon supercooling. Using self-diffusion data that was experimentally measured through wide-angle x-ray scattering and ultrafast calorimetry, we can assess the interfacial energy as a function of temperature. This resulted in a minimum in interfacial energy at around 236 K. Moreover, within the droplet, ice tends to form different structures after it has nucleated based on where in the droplet it is growing. It was observed that for crystals inside the bulk and close to the center of the droplets, ice crystallizes with hexagonal structure whereas on the surface it crystallizes with stacking-disorder containing a considerable amount of cubic structure. This can come from the fact that planar growth of crystals at the surface breaks down into a faulty structure that needs to accommodate the curvature of the droplet’s surface.