Etsuro Yokoyama

We demonstrate the oscillatory phenomenon for the twisting growth of a triclinic crystal through in situ observation of the concentration field around the growing tip of a needle by high-resolution phase-shift interferometry.

We measured velocities V-step of lateral displacement of individual elementary steps on an ice basal face, for the first time, by advanced optical microscopy, under various bulk water vapor pressure p(H2O)(infinity). Distances L between adjacent spiral steps exhibited considerable variation under constant p(H2O)(infinity). Hence, we analyzed V-step as functions of L and p(H2O)(infinity). Then we found that (1) under a constant p(H2O)(infinity), V-step decreased with decreasing distances L when L <= 15 mu m and that V-step remained constant when L >= 15 mu m. We named V-step of L >= 15 mu m (isolated steps) V-step(int) and analyzed dependencies of V-step(int) on p(H2O)(infinity). Then we found that (2) the slope of the V-step(int) vs p(H2O)(infinity) plot gradually decreased with increasing p(H2O)(infinity). We proposed a model that took into account both the volume diffusion of water vapor molecules and the surface diffusion of water admolecules on a terrace. Our model could explain result (1) mainly by the competition of adjacent spiral steps for water admolecules diffusing on a terrace but could not explain the result (2) satisfactorily.

The two-dimensional (2D) distributions of surface supersaturation of sodium chlorate crystals with and without solutal convection have been measured by means of a multidirectional interferometry (MDI) technique coupled with the principles of three-dimensional (3D) computer tomography. When solutal convection was present over a top face, the supersaturation at the center of the face was depleted by a factor of &gt;0.9 with reference to the value at the edges of the crystal. When the convection was suppressed using an upside-down geometry, the depletion of supersaturation at the center of the face was much smaller, &lt;0.4. Therefore, the supersaturation difference between the edges and the face center, which is responsible for the morphological stability due to volume diffusion for the solute, becomes less important compared to the effect of convection due to hydrodynamic reasons. This result should give us a key to solve why the crystal quality is sometimes better in convection-free microgravity conditions because of improved stability of a crystal face caused by more homogeneous distribution of supersaturation over the crystal surface.

An ice crystal growth experiment was performed on board the International Space Station. The experiment was repeated 134 times with various undercooling conditions. Dendrite crystal growth velocity and tip radius were precisely measured by using a newly developed software. The results are compared with those obtained previously on the ground as well as with those reported by Glicksman et al. for Succinonitrile (SCN). The plot of the dimensionless velocity V as a function of the dimensionless undercooling Delta under microgravity revealed values that were consistently lower than those obtained under 1-G which indicates that thermal convection was suppressed. The plot of the dimensionless radius R-0 as a function of Delta showed a less scattered value. The stability factor sigma* became close to that of SCN when it was calculated using the geometrical mean radius.

An ice crystal growth experiment was performed on board the International Space Station. The experiment was repeated 134 times with various undercooling conditions. Dendrite crystal growth velocity and tip radius were precisely measured by using a newly developed software. The results are compared with those obtained previously on the ground as well as with those reported by Glicksman et al. for Succinonitrile (SCN). The plot of the dimensionless velocity V as a function of the dimensionless undercooling Delta under microgravity revealed values that were consistently lower than those obtained under 1-G which indicates that thermal convection was suppressed. The plot of the dimensionless radius R-0 as a function of Delta showed a less scattered value. The stability factor sigma* became close to that of SCN when it was calculated using the geometrical mean radius.

Ice crystal growth experiments in heavy water were carried out under microgravity to investigate the morphological transition from a disk crystal to a dendrite. Surprisingly, however, no transition was observed, namely, the disk crystal or dendrite maintained its shape throughout the experiments, unlike the results obtained on the ground. Therefore, we introduce a growth model to understand disk growth. The Gibbs-Thomson effect is taken into account as a stabilization mechanism. The model is numerically solved by varying both an interfacial tension of the prism plane and supercooling so that the final sizes of the crystals can become almost the same to determine the interfacial tension. The results are compared with the typical experimental ones and thus the interfacial tension is estimated to be 20 mJ/m(2). Next, the model is solved under two supercooling conditions by using the estimated interfacial tension to understand stable growth. Comparisons between the numerical and experimental results show that our model explains well the microgravity experiments. It is also found that the experimental setup has the capability of controlling temperature on the order of 1/100 K.

Ice crystal growth experiments in heavy water were carried out under microgravity to investigate the morphological transition from a disk crystal to a dendrite. Surprisingly, however, no transition was observed, namely, the disk crystal or dendrite maintained its shape throughout the experiments, unlike the results obtained on the ground. Therefore, we introduce a growth model to understand disk growth. The Gibbs-Thomson effect is taken into account as a stabilization mechanism. The model is numerically solved by varying both an interfacial tension of the prism plane and supercooling so that the final sizes of the crystals can become almost the same to determine the interfacial tension. The results are compared with the typical experimental ones and thus the interfacial tension is estimated to be 20 mJ/m(2). Next, the model is solved under two supercooling conditions by using the estimated interfacial tension to understand stable growth. Comparisons between the numerical and experimental results show that our model explains well the microgravity experiments. It is also found that the experimental setup has the capability of controlling temperature on the order of 1/100 K.

The growth of single ice crystals from supercooled heavy water was studied under microgravity conditions in the Japanese Experiment Module "KIBO" of the International Space Station (ISS). The velocities of dendrite tips parallel to the a axis and the growth rates of basal faces parallel to the c axis were both analyzed under supercooling ranging from 0.03 to 2.0 K. The velocities of dendrite tips agree with the theory for larger amounts of supercooling when the growth on the basal faces are not zero. At very low supercooling there is no growth on the basal faces. With increasing supercooling the basal faces start to grow, the growth rate changing as a function of supercooling with a power law with an exponent of about 2, with the exponent approaching 1 as supercooling increases further. We interpret the growth on the basal faces as being controlled by two-dimensional nucleation under low supercooling, with a change in the growth kinetics to spiral growth with the aid of screw dislocations with increasing supercooling then to a linear growth law. We discuss the combined effect of tip velocity and basal face kinetics on pattern formation during the growth of ice.

The growth of single ice crystals from supercooled heavy water was studied under microgravity conditions in the Japanese Experiment Module "KIBO" of the International Space Station (ISS). The velocities of dendrite tips parallel to the a axis and the growth rates of basal faces parallel to the c axis were both analyzed under supercooling ranging from 0.03 to 2.0 K. The velocities of dendrite tips agree with the theory for larger amounts of supercooling when the growth on the basal faces are not zero. At very low supercooling there is no growth on the basal faces. With increasing supercooling the basal faces start to grow, the growth rate changing as a function of supercooling with a power law with an exponent of about 2, with the exponent approaching 1 as supercooling increases further. We interpret the growth on the basal faces as being controlled by two-dimensional nucleation under low supercooling, with a change in the growth kinetics to spiral growth with the aid of screw dislocations with increasing supercooling then to a linear growth law. We discuss the combined effect of tip velocity and basal face kinetics on pattern formation during the growth of ice.

A barred-olivine (BO) chondrule usually has an olivine rim that covers the chondrule surface. Numerous experiments have been carried out to reproduce the BO texture. However, the rim structure could be reproduced only in a few studies reported in the literature. The difficulty in reproducing the rim structure lies in the fact that its formation condition has not been constrained experimentally or theoretically. In the present paper, we have carried out numerical simulations of crystal growth of a highly-supercooled melt droplet of pure forsteritic composition (Mg2SiO4), and succeeded in reproducing the double structure, i.e. the rim and the dendrite. The droplet cools from the surface, the temperature of which should be cooler than the center of the droplet. Since a crystal grows faster along the cooler surface than across the hotter center, the rim was found to be formed when the temperature difference between the center of the droplet and its surface is large enough. From our results, both from numerical simulations and analytical consideration, we found that the double structure of rim and the dendrite could be formed only when the cooling rate is within a narrow range, which depends upon the degree of supercooling. Our results, for the first time, could explain why the formation of rim of BO texture was hardly reproduced in the previous experiments reported in the literature to date.

A barred-olivine (BO) chondrule usually has an olivine rim that covers the chondrule surface. Numerous experiments have been carried out to reproduce the BO texture. However, the rim structure could be reproduced only in a few studies reported in the literature. The difficulty in reproducing the rim structure lies in the fact that its formation condition has not been constrained experimentally or theoretically. In the present paper, we have carried out numerical simulations of crystal growth of a highly-supercooled melt droplet of pure forsteritic composition (Mg2SiO4), and succeeded in reproducing the double structure, i.e. the rim and the dendrite. The droplet cools from the surface, the temperature of which should be cooler than the center of the droplet. Since a crystal grows faster along the cooler surface than across the hotter center, the rim was found to be formed when the temperature difference between the center of the droplet and its surface is large enough. From our results, both from numerical simulations and analytical consideration, we found that the double structure of rim and the dendrite could be formed only when the cooling rate is within a narrow range, which depends upon the degree of supercooling. Our results, for the first time, could explain why the formation of rim of BO texture was hardly reproduced in the previous experiments reported in the literature to date.

Chondrules are submillimeter-sized and spherical-shaped crystalline grains consisting mainly of silicate material observed in chondritic meteorites. We numerically simulated pattern formation of a forsterite (Mg(2)SiO(4))-chondrule in the melt droplet using a phase-field method. Because of the large surface-to-volume ratio, the surface cooling term was introduced in the framework of this method. We reproduced an unique crystal growth pattern inside the droplet composed of two distinguishable parts; the rim that covers whole droplet surface, and dendrite inside the droplet. It was found that the rim was formed when there is a large temperature difference of similar to 100 K between the center and surface of the droplet due to the large cooling flux at the surface. In order to obtain the temperature difference, we derived temperature distribution of the droplet analytically, and concluded that the rim was formed only when the droplet cools rapidly at a rate of R(cool) similar to 10(3) K s(-1). However, when the surface cooling was so large as the temperature at the droplet center still remains above the melting point, no dendrite was obtained, though the rim was formed. The double structure captures the distinctive features of barred-olivine textures observed in natural chondrules. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3504655]

Chondrules are submillimeter-sized and spherical-shaped crystalline grains consisting mainly of silicate material observed in chondritic meteorites. We numerically simulated pattern formation of a forsterite (Mg2 SiO 4) -chondrule in the melt droplet using a phase-field method. Because of the large surface-to-volume ratio, the surface cooling term was introduced in the framework of this method. We reproduced an unique crystal growth pattern inside the droplet composed of two distinguishable parts the rim that covers whole droplet surface, and dendrite inside the droplet. It was found that the rim was formed when there is a large temperature difference of ∼100 K between the center and surface of the droplet due to the large cooling flux at the surface. In order to obtain the temperature difference, we derived temperature distribution of the droplet analytically, and concluded that the rim was formed only when the droplet cools rapidly at a rate of Rcool ∼ 103 K s-1. However, when the surface cooling was so large as the temperature at the droplet center still remains above the melting point, no dendrite was obtained, though the rim was formed. The double structure captures the distinctive features of barred-olivine textures observed in natural chondrules. © 2010 American Institute of Physics.

Due to the abundance of ice on earth, the phase transition of ice plays crucially important roles in various phenomena in nature. Hence, the molecular-level understanding of ice crystal surfaces holds the key to unlocking the secrets of a number of fields. In this study we demonstrate, by laser confocal microscopy combined with differential interference contrast microscopy, that elementary steps (the growing ends of ubiquitous molecular layers with the minimum height) of ice crystals and their dynamic behavior can be visualized directly at air-ice interfaces. We observed the appearance and lateral growth of two-dimensional islands on ice crystal surfaces. When the steps of neighboring two-dimensional islands coalesced, the contrast of the steps always disappeared completely. We were able to discount the occurrence of steps too small to detect directly because we never observed the associated phenomena that would indicate their presence. In addition, classical two-dimensional nucleation theory does not support the appearance of multilayered two-dimensional islands. Hence, we concluded that two-dimensional islands with elementary height (0.37 and 0.39 nm on basal and prism faces, respectively) were visualized by our optical microscopy. On basal and prism faces, we also observed the spiral growth steps generated by screw dislocations. The distance between adjacent spiral steps on a prism face was about 1/20 of that on a basal face. Hence, the step ledge energy of a prism face was 1/20 of that on a basal face, in accord with the known lower-temperature roughening transition of the prism face.

Due to the abundance of ice on earth, the phase transition of ice plays crucially important roles in various phenomena in nature. Hence, the molecular-level understanding of ice crystal surfaces holds the key to unlocking the secrets of a number of fields. In this study we demonstrate, by laser confocal microscopy combined with differential interference contrast microscopy, that elementary steps (the growing ends of ubiquitous molecular layers with the minimum height) of ice crystals and their dynamic behavior can be visualized directly at air-ice interfaces. We observed the appearance and lateral growth of two-dimensional islands on ice crystal surfaces. When the steps of neighboring two-dimensional islands coalesced, the contrast of the steps always disappeared completely. We were able to discount the occurrence of steps too small to detect directly because we never observed the associated phenomena that would indicate their presence. In addition, classical two-dimensional nucleation theory does not support the appearance of multilayered two-dimensional islands. Hence, we concluded that two-dimensional islands with elementary height (0.37 and 0.39 nm on basal and prism faces, respectively) were visualized by our optical microscopy. On basal and prism faces, we also observed the spiral growth steps generated by screw dislocations. The distance between adjacent spiral steps on a prism face was about 1/20 of that on a basal face. Hence, the step ledge energy of a prism face was 1/20 of that on a basal face, in accord with the known lower-temperature roughening transition of the prism face.

We investigate a simple experimental system using candles; stable combustion is seen when a single candle burns, while oscillatory combustion is seen when three candies burn together. If we consider a set of three candles as a component oscillator, two oscillators, that is, two sets of three candles, can Couple with each other, resulting in both in-phase and antiphase synchronization depending on the distance between the two sets. The mathematical model indicates that the oscillatory combustion in a set of three candles is induced by a lack of oxygen around the burning point. Furthermore, we suggest that thermal radiation may be an essential factor of the synchronization.

We investigate a simple experimental system using candles; stable combustion is seen when a single candle burns, while oscillatory combustion is seen when three candies burn together. If we consider a set of three candles as a component oscillator, two oscillators, that is, two sets of three candles, can Couple with each other, resulting in both in-phase and antiphase synchronization depending on the distance between the two sets. The mathematical model indicates that the oscillatory combustion in a set of three candles is induced by a lack of oxygen around the burning point. Furthermore, we suggest that thermal radiation may be an essential factor of the synchronization.

Antifreeze glycoproteins (AFGPs) are a necessary tool for the survival of fish that live in subfreezing environments [Yeh, Y.; Feeney, R. E. Antifreeze proteins-Structures and mechanisms of function. Chem. Rev. 1996, 96 (2), 601-617]. Although scientists agree that these proteins arrest ice crystal growth by a surface adsorption mechanism, the exact nature of the interaction remains an open question. Here, we study the adsorption kinetics of AFGPs during solution ice crystal growth using confocal fluorescence microscopy within and just below the freezing-melting temperature hysteresis region. The AFGP kinetics at the ice surface reveal a two-step inhibition process: (i) incomplete adsorption or a weak interaction that modifies the surface for (ii) a stronger interaction to achieve the complete adsorption necessary to halt growth. The growth is modified from a rough interface to a faceted one, and growth is halted at supercoolings less than 0.05 degrees C. However, growth resumes, and the proteins desorb, return to the solution phase, and are not incorporated into the ice crystal as previously proposed. Our findings are contrary to an AFGP mechanism described by the Gibbs-Thomson model. We argue that an alternative explanation must include a solvated protein interacting with a solvated ice surface. While thermodynamics considerably alter the interfacial region, antifreeze action is a purely kinetic phenomenon.

Antifreeze glycoproteins (AFGPs) are a necessary tool for the survival of fish that live in subfreezing environments [Yeh, Y.; Feeney, R. E. Antifreeze proteins-Structures and mechanisms of function. Chem. Rev. 1996, 96 (2), 601-617]. Although scientists agree that these proteins arrest ice crystal growth by a surface adsorption mechanism, the exact nature of the interaction remains an open question. Here, we study the adsorption kinetics of AFGPs during solution ice crystal growth using confocal fluorescence microscopy within and just below the freezing-melting temperature hysteresis region. The AFGP kinetics at the ice surface reveal a two-step inhibition process: (i) incomplete adsorption or a weak interaction that modifies the surface for (ii) a stronger interaction to achieve the complete adsorption necessary to halt growth. The growth is modified from a rough interface to a faceted one, and growth is halted at supercoolings less than 0.05 degrees C. However, growth resumes, and the proteins desorb, return to the solution phase, and are not incorporated into the ice crystal as previously proposed. Our findings are contrary to an AFGP mechanism described by the Gibbs-Thomson model. We argue that an alternative explanation must include a solvated protein interacting with a solvated ice surface. While thermodynamics considerably alter the interfacial region, antifreeze action is a purely kinetic phenomenon.

Ice crystal growth in a supercooled solution containing proteins such as anti-freeze glycoproteins (AFGPs) is inhibited by its adsorption at the ice/water interface. Although these proteins have dramatic consequences for natural biological processes and technological applications, little is known about the dynamic mechanism of ice growth inhibition. One-directional growth experiments were carried out to observe the pattern formation at the ice/water interface growing from an aqueous AFGP solution. Typical zigzag patterns composed of flat prismatic (10 $(1) over bar $0) interfaces were observed in the final quasi-stable growth state. By analyzing the zigzag patterns, we were able to directly determine the interfacial kinetic supercooling, delta T, at the interfaces of prismatic faces as a function of growth rate. delta T linearly increased with increasing growth rate in the range below a critical growth rate, but its dependence showed the reversed relationship above the critical growth rate. This growth rate dependency of delta T was qualitatively explained by the interaction between the rejection and incorporation rates of AFGP molecules at the growing interface. (c) 2004 Elsevier B.V. All rights reserved.

Ice crystal growth in a supercooled solution containing proteins such as anti-freeze glycoproteins (AFGPs) is inhibited by its adsorption at the ice/water interface. Although these proteins have dramatic consequences for natural biological processes and technological applications, little is known about the dynamic mechanism of ice growth inhibition. One-directional growth experiments were carried out to observe the pattern formation at the ice/water interface growing from an aqueous AFGP solution. Typical zigzag patterns composed of flat prismatic (10 $(1) over bar $0) interfaces were observed in the final quasi-stable growth state. By analyzing the zigzag patterns, we were able to directly determine the interfacial kinetic supercooling, delta T, at the interfaces of prismatic faces as a function of growth rate. delta T linearly increased with increasing growth rate in the range below a critical growth rate, but its dependence showed the reversed relationship above the critical growth rate. This growth rate dependency of delta T was qualitatively explained by the interaction between the rejection and incorporation rates of AFGP molecules at the growing interface. (c) 2004 Elsevier B.V. All rights reserved.