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Surface melting of ice crystals proceeds below the melting point (0 °C) and forms thin liquid water layers, called quasi-liquid layers (QLLs), which govern a wide variety of phenomena in nature. Hence, many studies have been performed so far; however, the lowest temperature above which QLLs exist on ice crystal surfaces varied from −90 to −1 °C. To reveal the cause of such significant variations, here we show, by laser confocal microscopy combined with Michelson interferometry, the behavior of QLLs on polycrystalline ice thin films that include a large amount of grain boundaries and defects. We found that the QLLs can exist stably on the polycrystalline ice thin films even at −16.2 °C (the lowest temperature adopted in this study), although the QLLs on ice single crystals disappear at temperature lower than −2.4 ± 0.5 °C. These results emphasize the importance of grain boundaries and defects for the presence of QLLs. In addition, we also found that critical water vapor pressure above which the QLLs can gr...

We measured the velocity Vstep of isolated elementary spiral steps and the distance Leq between adjacent equivalent spiral steps on ice basal faces by advanced optical microscopy. We determined the step kinetic coefficient β from Vstep measured under various supersaturations. We performed similar experiments under various temperatures T, and determined the temperature dependence of β of ice basal faces, for the first time, in the temperature range of −26.0 to −2.7 °C. When −6.2 ≤ T ≤ −2.7 °C, the value of β decreased significantly with decreasing T. In contrast, when −15.0 ≤ T ≤ −6.2 °C, the value of β increased with decreasing T, and had the maximum at T ≈ −15 °C. When −26.0 ≤ T ≤ −15.0 °C, the value of β decreased monotonically with decreasing T. Such complicated temperature dependence of β strongly implies the existence of unknown phenomena in the temperature range examined. To obtain a clue to the complicated behavior of β, we also measured dependence of Leq on surface supersaturation Δμsurf. When −13...

Ice is one of the most abundant materials on the earth's surface, and its growth governs various natural phenomena. Hence, the molecular-level understanding of ice crystal surfaces is crucially important. However, it is generally acknowledged that the molecular-level observation of ice crystal surfaces by ordinary microscopy techniques, such as atomic force microscopy and scanning electron microscopy, is very difficult at temperatures near the melting point (0 °C). To overcome such difficulties, we have developed laser confocal microscopy combined with differential interference contrast microscopy (LCM-DIM). We proved that LCM-DIM can visualize individual elementary steps (0.37 nm in thickness) on a basal face by observing two-dimensional nucleation growth. Then we found by LCM-DIM that spiral steps on a basal face exhibit a double-spiral pattern, which can be expected from ice's crystallographic structure. In addition, we revealed that temperature dependence of growth kinetics of elementary spiral steps on a basal face exhibits complicated behaviors, which show the presence of unknown phenomena in the growth kinetics. Furthermore, we proved that surface diffusion of water admolecules on a basal face plays a crucially important role in the lateral growth of elementary steps when the distance between adjacent spiral steps is smaller than 15 µm. These findings will provide a clue for unlocking growth kinetics of ice crystals. In addition, through the use of LCM-DIM much progress has been made in studies on the surface melting of ice and the interaction between ice and atmospheric gasses.

It has been implicitly assumed that ices on grains in molecular clouds and proto planetary disks are formed by homogeneous layers regardless of their composition or crystallinity. To verify this assumption, we observed the H2O deposition onto refractory substrates and the crystallization of amorphous ices (H2O, CO2, and CO) using an ultra-high-vacuum transmission electron microscope. In the H2O-deposition experiments, we found that three-dimensional islands of crystalline ice (Ic) were formed at temperatures above 130 K. The crystallization experiments showed that uniform thin films of amorphous CO and H2O became three-dimensional islands of polyhedral crystals; amorphous CO2, on the other hand, became a thin film of nano crystalline CO2 covering the amorphous H2O. Our observations show that crystal morphologies strongly depend not only on the ice composition, but also on the substrate. Using experimental data concerning the crystallinity of deposited ices and the crystallization timescale of amorphous ices, we illustrated the criteria for ice crystallinity in space and outlined the macroscopic morphology of icy grains in molecular clouds as follows: amorphous H2O covered the refractory grain uniformly, CO2 nano-crystals were embedded in the amorphous H2O, and a polyhedral CO crystal was attached to the amorphous H2O. Furthermore, a change in the grain morphology in a proto-planetary disk is shown. These results have important implications for the chemical evolution of molecules, non-thermal desorption, collision of icy grains, and sintering., 60 pages, 18 figures, 3 tables, published in ApJ

A microscopic understanding of crystal-melt interfaces, inseparably involved in the dynamics of crystallization, is a long-standing challenge in condensed matter physics. Here, using an advanced optical microscopy, we directly visualize growing interfaces between ice basal faces and quasiliquid layers (QLLs) during ice crystal growth. This system serves as a model for studying the molecular incorporation process of the crystal growth from a supercooled melt (the so-called melt growth), often hidden by inevitable latent heat diffusion and/or the extremely high crystal growth rate. We reveal that the growth of basal faces inside QLLs proceeds layer by layer via two-dimensional nucleation of monomolecular islands. We also find that the lateral growth rate of the islands is well described by the Wilson-Frenkel law, taking into account the slowing down of the dynamics of water molecules interfaced with ice. These results clearly indicate that, after averaging surface molecular fluctuations, the layer by layer stacking still survives even at the topmost layer on basal faces, which supports the kink-step-terrace picture even for the melt growth.

Surface melting of ice crystals forms quasi-liquid layers (QLLs) on ice surfaces, and affects a wide variety of natural phenomena. Since QLLs enhance various chemical reactions in ice clouds, the formation of QLLs by atmospheric gases has been studied intensively. However, such studies were performed using spectroscopy techniques, which have low spatial resolution. Here we show the first direct visualization of QLLs on ice basal faces in the presence of hydrogen chloride (HCl) gas (model atmospheric gas) by advanced optical microscopy, which can visualize individual 0.37 nm-thick elementary steps on ice crystal surfaces. We found that the HCl gas induced the appearances of QLLs with a droplet shape in the temperature range from −15.0 to −1.5 °C, where no QLL appears in the absence of HCl gas. This result indicates that HCl gas adsorbed on ice crystal surfaces probably changed the surface structure of ice crystals and then induced the subsequent melting of ice surfaces. We also observed the movement, shape...

The spiral growth of crystals, mediated by their screw dislocations, is a general crystal-growth mechanism observed over a large variety of crystalline solids. Despite its general nature, direct observations of the spiral growth of ice have been rarely reported so far. Here, with the aid of advanced optical microscopy, we succeed in making in situ observations of the perfect spiral growth during the vapor growth of ice. We find that the spiral steps observed are well described by the classical Burton--Cabrera--Frank theory, taking into account surface diffusion of water admolecules between adjacent steps. This is distinct from the dominant growth mode that we have assigned as spiral in our recent studies, which accompanies fluctuations of the adjacent step interval. We also successfully capture the birth of a screw dislocation and the ensuing spiral growth, originating in the lattice mismatch arising from the coalescence of single ice crystals. Furthermore, we demonstrate that the nucleation of quasi-liquid layers (QLLs) takes place at the spiral center immediately after the birth of the dislocation, which suggests a link between screw dislocations and the generation of QLLs near the ice melting point.

Since the pioneering prediction of surface melting by Michael Faraday, it has been widely accepted that thin water layers, called quasi-liquid layers (QLLs), homogeneously and completely wet ice surfaces. Contrary to this conventional wisdom, here we both theoretically and experimentally demonstrate that QLLs have more than two wetting states and that there is a first-order wetting transition between them. Furthermore, we find that QLLs are born not only under supersaturated conditions, as recently reported, but also at undersaturation, but QLLs are absent at equilibrium. This means that QLLs are a metastable transient state formed through vapor growth and sublimation of ice, casting a serious doubt on the conventional understanding presupposing the spontaneous formation of QLLs in ice–vapor equilibrium. We propose a simple but general physical model that consistently explains these aspects of surface melting and QLLs. Our model shows that a unique interfacial potential solely controls both the wetting and thermodynamic behavior of QLLs.

The existence of more than two liquid states in a single-component substance and the ensuing liquid-liquid transitions (LLTs) has attracted considerable attention because of its counterintuitive nature and its importance in the fundamental understanding of the liquid state. Here we report direct experimental evidence for a genuine (isocompositional) LLT without macroscopic phase separation in an aqueous solution of glycerol. We show that liquid I transforms into liquid II by way of two types of kinetics: nucleation and growth, and spinodal decomposition. Although liquid II is metastable against crystallization, we could access both its static and dynamical properties experimentally. We find that liquids I and II differ in density, refractive index, structure, hydrogen bonding state, glass transition temperature and fragility, and that the transition between the two liquids is mainly driven by the local structuring of water rather than of glycerol, suggesting a link to a plausible LLT in pure water.

We have experimentally determined the surface tension-to-shear viscosity ratio (the so-called characteristic velocity) of quasiliquid layers (QLLs) on ice crystal surfaces from their wetting dynamics. Using an advanced optical microscope, whose resolution reaches the molecular level in the height direction, we directly observed the coalescent process of QLLs and followed the relaxation modes of their contact lines. The relaxation dynamics is known to be governed by the characteristic velocity, which allows us to access the physical properties of QLLs in a noninvasive way. Here we quantitatively demonstrate that QLLs, when completely wetting ices, have a thickness of 9 +/- 3 nm and an approximately 200 times lower characteristic velocity than bulk water, whereas QLLs, when partially wetting ices, have a velocity that is 20 times lower than the bulk. This indicates that ice crystal surfaces significantly affect the physical properties of QLLs localized near the surfaces at a nanometer scale.

A test method to evaluate the complex permittivity of materials with thin configuration (thickness of 50–300μm) is presented. We evaluate the complex permittivity of materials with various mechanical and electrical characteristics (films, powders, and liquids) at frequencies from 100 MHz to 20 GHz and at temperatures from 293 to 353 K using an experimental method presented in this paper. We have developed a fixture having a circular parallel-plate capacitor which is suitable for the measurement of materials with thin configuration. Our method is based on theoretical consideration of wave propagation in the capacitor, which is associated with multiple reflections along the diameter of the sample. The consideration of time delay in the sample section makes it possible to evaluate the permittivity of high dielectric constant materials in the frequency range up to 20 GHz. In addition, some examples for the measurements show that the resolution with tanδ is as low as 0.001. Our method is powerful to understand...