Surface Freezing Research Articles

Effect of Geometrical Confinement on the Nucleation and Crystallization Behavior of n-Alkane Mixtures

The condensed structure of normal alkane (n-alkane) mixtures in confined geometry is an interesting topic concerning the difference in crystallization behavior of odd and even alkanes. In the present work, the crystallization of mixtures of normal octadecane (n-C18H38) and normal nonadecane (n-C19H40) in microcapsules with narrow size distribution was investigated using the combination of differential scanning calorimetry (DSC) and X-ray diffraction (XRD). A surface freezing monolayer for microencapsulated n-C18H38, n-C19H40, and their mixture was detected by DSC, which for the mixture is a mixed homogeneous crystalline phase with continuous change in the composition. A more stable rotator phase (RI) was observed for the microencapsulated n-C18H38/n-C19H40 = 95/5 (molar ratio) mixture, confirmed by an increased supercooling of the transition from RI to stable phase compared to that of the mixture in bulk. Two nucleation mechanisms were speculated as "liquid-to-solid" heterogeneous nucleation and "solid-to-solid" homogeneous nucleation, which occur at different crystallization stages in microcapsules and might be attributed to the surface effect and confinement effect, respectively, in the confined geometry.

Crystallization Behaviors of n-Octadecane in Confined Space: Crossover of Rotator Phase from Transient to Metastable Induced by Surface Freezing

In this paper, the confined crystallization and phase transition behaviors of n-octadecane in microcapsules with a diameter of about 3 microm were studied with the combination of differential scanning calorimetry (DSC), temperature dependent Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The main discovery is that the microencapsulated n-octadecane crystallizes into a stable triclinic phase via a mestastable rotator phase (R I), which emerges as a transient state for the bulk n-octadecane and is difficult to be detected by the commonly used characterization methods. As evident from the DSC measurement, a surface freezing monolayer, which is formed at the interface between the microcapsule inner wall and n-octadecane, induces the crossover of the R I from transient to metastable. We argue that the existence of the surface freezing monolayer decreases the nucleating potential barrier of the R I phase, and consequently the lower relative nucleation barrier in the confined geometry turns the transient R I phase into a metastable one.

Estimating apparent thermal diffusivity using temperature time series: A comparison of temperature data measured in KMA boreholes and NGMN wells

Two different time series data sets, shallow ground temperatures of 58 synoptic stations of the Korea Meteorological Administration (KMA) and groundwater temperatures of 67 wells of the National Groundwater Monitoring Network (NGMN), were analyzed to estimate the apparent thermal diffusivity by using the analytical solution of the one-dimensional heat conduction equation. The KMA temperature data measured at 1–5 m depths illustrated values of the phase delay and the amplitude decay coincident with their theoretical relationship, indicating that the conductive heat transport should prevail over the nonconductive processes. On the contrary, some of the estimates from temperatures at a depth of 0.5 m were away from the theoretical values. It is most likely that the deviation would be caused by the effects of latent heat associated with freezing and thawing of the near ground surface. In contrast to KMA data, results obtained from the NGMN data highly deviated from the theoretical ones, and thereafter yielded unacceptably high values of thermal diffusivities as compared to the representative values of soils and rocks. Implication of the discrepancy between two data sets was discussed in conjunction with perturbation of the conductive heat transport by free convection of water and air occurring in large diameter wells as well as the convective heat transport by groundwater flow.

Long term trend of chemical oxygen demand in Saroma-ko Lagoon, Japan; possible effects of climatic warming

A trend of shortening duration of ice coverage has been reported in many rivers, ponds and lakes around the world due to climatic warming. The shortening will have much influence on organic production due to the greater supply of light intensity and hence on water quality. Chemical Oxygen Demand (COD), a useful measure of water quality, has been monitored over the past thirty years in Saroma-ko Lagoon, a boreal lake in Japan characterized by wintertime ice coverage. Here the data set of water quality in the lagoon is analyzed to reveal long-term trends in COD and the influence of climatic warming on such trends. There has been a significant increasing trend, caused primarily by an abrupt increase in the early 1990s. However, the increase could not be explained by the increased load of organic matter on the lagoon from the river basin and organic production in the lagoon. On the other hand, periods of freezing of the entire surface have tended to be shorter with inevitable thinning of ice over the past forty years, probably due to climatic warming. Ice and planktonic algae are exposed to the low light intensity in situ, which is not optimum for the algal production of organic matter. The shortening and thinning should thus bring an improvement in ambient light conditions for algae, resulting in an increase of organic matter in winter. Most of the organic matter possibly remains even after spring because of the low water temperature. It is highly possible that climatic warming promotes deterioration in water quality in ice-covered lakes.

Long term trend of chemical oxygen demand in Saroma-ko Lagoon, Japan; possible effects of climatic warming

AbstractA trend of shortening duration of ice coverage has been reported in many rivers, ponds and lakes around the world due to climatic warming. The shortening will have much influence on organic production due to the greater supply of light intensity and hence on water quality. Chemical Oxygen Demand (COD), a useful measure of water quality, has been monitored over the past thirty years in Saroma-ko Lagoon, a boreal lake in Japan characterized by wintertime ice coverage. Here the data set of water quality in the lagoon is analyzed to reveal long-term trends in COD and the influence of climatic warming on such trends. There has been a significant increasing trend, caused primarily by an abrupt increase in the early 1990s. However, the increase could not be explained by the increased load of organic matter on the lagoon from the river basin and organic production in the lagoon. On the other hand, periods of freezing of the entire surface have tended to be shorter with inevitable thinning of ice over the past forty years, probably due to climatic warming. Ice and planktonic algae are exposed to the low light intensity in situ, which is not optimum for the algal production of organic matter. The shortening and thinning should thus bring an improvement in ambient light conditions for algae, resulting in an increase of organic matter in winter. Most of the organic matter possibly remains even after spring because of the low water temperature. It is highly possible that climatic warming promotes deterioration in water quality in ice-covered lakes.

Influence of Molecular and Supramolecular Structure on the Gas−Liquid Interfacial Reactivity of Hydrocarbon Liquids with O(3P) Atoms

We have investigated the interfacial reactivity of gas-phase O(3P) atoms with a representative range of long-chain liquid hydrocarbons. These consisted of two branched molecules, squalane (C30H62, 2,6,10,15,19,23-hexamethyltetracosane) and pristane (C19H40, 2,6,10,14-tetramethylpentadecane), and three linear ones, n-docosane (C22H46), n-tetracosane (C24H50) and n-octacosane (C28H58). This represents the first systematic investigation of reactions of this type for molecules other than squalane. The O(3P) atoms were generated by 355-nm laser photolysis of a low pressure of NO2 above the liquid surface. The nascent gas-phase OH radical products were detected by laser-induced fluorescence (LIF). Measurements for the linear hydrocarbons were constrained by their vapor pressures to single temperatures slightly (∼1 K) above their respective melting points. Pristane was studied at the lowest temperature practically achievable. Squalane was compared as a reference at the full set of temperatures. Appearance profiles for all of the liquids showed similar characteristic differences between OH v‘=0 and 1. LIF excitation spectra were obtained for each of the vibrational levels at both the rising edge and peak of the appearance profiles. We conclude that the observed variations in rotational temperatures are consistent with dual contributions to the reaction mechanism for all the liquids, involving both direct escape and trapping-desorption components of the observed OH, as has previously been proposed for squalane. The relative yields of OH showed some surprising dependences on the liquid, including an unexpectedly strong variation with linear hydrocarbon chain length. These cannot all be explained by the relative reactivity of primary, secondary, and tertiary H−C units. We discuss the possibility that the known “surface freezing” phenomenon for linear hydrocarbons may play a role.

Information Guidance System for Rotary Snowplow on Sidewalk to Improve Operation Ability

In winter, the northern part of Japan has very deep and heavy snow, and faces the problem of freezing of the road surface. People have difficulty to walk along a sidewalk and to move from place to place in winter. This study aims to achieve efficient wintertime sidewalk administrator by applying developed ITS technologies to the snowplow. This paper describes the analysis of snow removal task on sidewalk, the mechanical type of rotary snowplow, and proposes information guidance system using Head-Up-Display, which is expected to be practically used in the near future.

冬季道路における路面温度・凍結予測モデルの構築

In the present study,the author attempted to establish the forecast model of the road surface temperatures and the road surface freezing after three hours which would enable anti-icing work before the road surface freezes using a neural network.The results of the present study revealed that the road surface temperatures and the road surface freezing in three hours can be predicted with considerable precision.

Interfacial phase transitions in conducting fluids

We present a review, largely based on recent experimental work of our group, on phase transitions at interfaces of fluid metals, alloys and ionic liquids. After a brief analysis of possible experimental errors and limitations of surface sensitive methods, we first deal with first-order wetting transitions at the liquid/vapour and liquid/wall interface in systems such as Ga-based alloys, K-KCl melts, and fluid Hg. The following chapter refers to surface freezing or surface induced crystallization in different metal alloys. The respective surface phase diagrams are discussed in comparison with their bulk counterpart. In the last part we present very recent investigations of ionic liquid interfaces, including order-disorder transitions at the liquid/vapour interface and examples of two-dimensional phase transitions at the electrified ionic liquid/metal interface. Finally, a simple electrowetting experiment with an ionic liquid droplet under vacuum is described which gives new insight into the contact angle saturation problem. The article ends up with a few perspective remarks on open problems and potential impact of interfacial phenomena on applied research.

Thermal stability of surface freezing films in Ga-based alloys: An x-ray photoelectron spectroscopy and scanning tunneling microscopy study

We have investigated the thickness and surface structure of surface freezing films in Ga-Bi and Ga-Pb alloys over a wide temperature range between room temperature and the respective surface freezing transitions by x-ray photoelectron spectroscopy (XPS) and scanning tunnelling microscopy (STM). For the example of a Ga-Bi alloy dilute in Bi, XPS measurements show that the surface freezing film has a nearly constant value of approximately 25 A between the surface freezing temperature of 130 degrees C and room temperature if the sample is cooled slowly (5 Kh). On heating to 130 degrees C the film thickness exhibits a clear hysteresis on melting. On quenching the alloy sample (>100 Kh) the film thickness increases by almost a factor of 10. These observations indicate that the surface freezing films are metastable. The surface structure of the surface freezing films of various Ga-rich Ga-Bi and Ga-Pb alloys has been probed for the first time by STM at different temperatures below and above the bulk eutectic point. Atomically resolved STM images show the surface structures of pure Bi (0001) and Pb (111), respectively, at room temperature. On heating above the eutectic temperature the surface structure of the films does not change significantly as judged from the size and thickness of Pb or Bi terraces. These observations together with the film thickness variation with temperature indicate that the surface freezing films behave like a metastable independent surface phase. These results together with the wetting characteristics of these alloys suggest that surface freezing in these systems is a first order surface phase transition between wetting and metastable surface freezing films. The energy barrier for nucleation is strongly reduced due to a lowering of the interfacial energy if the nucleus is completely immersed in the respective wetting layer.

Mathematical modelling of the diffusion of ascorbic acid during water blanching of surface frozen potato strips

Summary Partial freezing is a promising technique in producing good quality french fries, especially for potatoes stored for an extended period and containing large amounts of reducing sugars. The cell damage of the potato strip caused by surface freezing facilitates surface leaching of reducing sugars and other soluble solids like ascorbic acid, preventing undesirable dark colour in the finish-fried products. A theoretical study to describe the diffusion of ascorbic acid during the water blanching at 50°C of surface frozen potato strips (10 x 10 x 80 mm) is developed. Ascorbic acid profiles as a function of blanching time, position in the potato strip and thickness of the frozen layer are shown as well as average retention as a function of blanching time, frozen layer thickness, apparent diffusion coefficient and mass transfer coefficient of ascorbic acid. Significant changes in the ascorbic acid concentration during blanching are produced in the frozen layer. Ascorbic acid average retention is mainly influenced by frozen layer thickness and temperature, and the mass transfer coefficient is less important.

To the problem of first order phase transition at the fluid–fluid interface

The thermodynamic analysis is developed to describe both the surface freezing and the surface melting in various systems. The key physico-chemical parameters determining the shift of the freezing temperature in boundary phases in comparison to the temperature of corresponding bulk phase transition are discussed.

Freezing transition of Langmuir-Gibbs alkane films on water

We show that adding CTAB (CTAB, hexadecyltrimethylammonium bromide) in sub-millimolar bulk concentrations to water reduces its surface tension (ST) to a level where spontaneous surface spreading of a monolayer of medium-sized alkane (C n H 2 n+2 , 12 ≤ n ≤ 17) occurs. ST and X-ray reflectivity (XR) measurements are used to show that the quasi two-dimensional (2D) liquid monolayer can be driven through a reversible surface freezing phase transition upon cooling. Grazing incidence diffraction (GID) shows that the frozen monolayer is crystalline, hexagonally packed, with surface-normal molecules, and a crystalline coherence length of at least a few hundred Å, very similar to the structure of surface-frozen (SF) monolayers at the surface of similar-length alkane melts.

Monitoring Temperatures on a Real Box-Girder Bridge and Energy Budget Analysis for Basic Information on Bridge Cooling and Surface Freezing

A prestressed concrete (PC) box-girder bridge was instrumented to enable monitoring of its surface and body temperature. The daily variations of temperature in the pavement and upper beam of the bridge were greater the deeper from the surface. During daytime on a fine day, bridge surface temperatures were higher than air temperatures, and at nighttime on a fine night, temperatures at the surface were lower than air temperatures. It is well known that sensible heat transfers depend on wind speed and surface temperature. The wind speed measured at the bridge and on the road revealed that the wind speed at the bridge was higher than at the road due to their topography. This wind effect during the daytime causes the surface temperature at the bridge to be lower than that at the road. Thus, the reason why only bridge surfaces may freeze while roads do not can be explained by the fact that the surface temperatures of bridges are usually lower than those of roads, which can be attributed to their energy budget patterns caused by the wind speed differences between bridges and roads.

Growth mechanism of diamond-like carbon film based on the simulation model of atomic motion

Molecular dynamics simulations are performed to study the growth of diamond-like carbon (DLC) films on the atomic scale. The behaviors of incident atoms on the surface are classified into four categories: surface freezing, migration, implantation and rebounding, according to the atomic movement. The behaviors of incident atoms have an important impact on microstructure and growth mode of DLC film. The transverse migration of the atoms is the main route of film relaxation. The competition between atomic implantation and migration determines the growth mode and final structures of the film. Energy dependence of surface behaviors of deposited atoms and film structures is analyzed statistically, which deepens the understanding of DLC film growth mechanism.

Disturbance, colonization and development of Antarctic benthic communities.

A decade has yielded much progress in understanding polar disturbance and community recovery-mainly through quantifying ice scour rates, other disturbance levels, larval abundance and diversity, colonization rates and response of benthos to predicted climate change. The continental shelf around Antarctica is clearly subject to massive disturbance, but remarkably across so many scales. In summer, millions of icebergs from sizes smaller than cars to larger than countries ground out and gouge the sea floor and crush the benthic communities there, while the highest wind speeds create the highest waves to pound the coast. In winter, the calm associated with the sea surface freezing creates the clearest marine water in the world. But in winter, an ice foot encases coastal life and anchor ice rips benthos from the sea floor. Over tens and hundreds of thousands of years, glaciations have done the same on continental scales-ice sheets have bulldozed the seabed and the zoobenthos to edge of shelves. We detail and rank modern disturbance levels (from most to least): ice; asteroid impacts; sediment instability; wind/wave action; pollution; UV irradiation; volcanism; trawling; non-indigenous species; freshwater inundation; and temperature stress. Benthic organisms have had to recolonize local scourings and continental shelves repeatedly, yet a decade of studies have demonstrated that they have (compared with lower latitudes) slow tempos of reproduction, colonization and growth. Despite massive disturbance levels and slow recolonization potential, the Antarctic shelf has a much richer fauna than would be expected for its area. Now, West Antarctica is among the fastest warming regions and its organisms face new rapid changes. In the next century, temperature stress and non-indigenous species will drastically rise to become dominant disturbances to the Antarctic life. Here, we describe the potential for benthic organisms to respond to disturbance, focusing particularly on what we know now that we did not a decade ago.

Fate of Cryptosporidium Oocysts and Giardia Cysts in the Norwegian Aquatic Environment over Winter

We investigated the survival of Cryptosporidium oocysts and Giardia cysts during winter in an aquatic environment (approximate temperature measurements between 1 and 7 degrees C) in Norway, using morphology and uptake of dyes as indicators of viability. Previous research has shown that in the terrestrial environment, shear forces caused by freeze and thaw cycles probably cause the parasites to be inactivated. Such forces occurred infrequently in the aquatic environment, as freezing of the water around the parasites was not observed during the study period (although freezing of the water surface did occur). The rate of decline in viability (log(10) N (t)/N (0)) was similar in control and experimental environments for both parasites; no Cryptosporidium oocysts with viable morphology were detected after approximately 20 weeks and no Giardia cysts with apparently viable morphology could be detected after 1 month. These results suggest that infection with these parasites in Norway is not usually from transmission stages that have over-wintered in the Norwegian environment.

Perturbation theory for traveling droplets

The motion of chemically driven droplets is analyzed by applying a solvability condition of perturbed hydrodynamic equations affected by the adsorbate concentration. Conditions for traveling bifurcation analogous to a similar transition in activator-inhibitorsystems are obtained. It is shown that interaction of droplets leads to either scattering of mobile droplets or the formation of regular patterns, respectively, at low or high adsorbate diffusivity. The same method is applied to droplets running on growing terrace edges during surface freezing.

Field measurements and analyses for a hybrid system for snow storage/melting and air conditioning by using renewable energy

This paper aims to propose a hybrid system for snow storage/melting and air conditioning by using renewable energy-resources, and clarify the effects of an actual realized application. First, the outline of the system installed at an office building, which was completed in Sapporo, Japan in 2001, is shown. The hybrid system is composed of an underground thermal utility for snow melting by using vertical earth heat-exchangers and space cooling through seasonal cold storage of snow-and-ice cryogenic energy. Second, at the comparatively severe climatic conditions (the lowest outside air-temperature −9.2 °C and the amount of daily snowfall 8.1 cm), it was found that the underground thermal utilization system contributes to preventing freezing of a road surface, and that the road-surface exposure rate was approximately 90%. The effectiveness of this system on energy conservation, environmental protection and cost was verified through numerical analyses. Also, as a result of measuring snow-storage characteristics and space-cooling performance, the effective amount of snow stored on the first day of the space-cooling period was approximately 74%, which gave comparatively good agreement with the predicted value.

Surface Segregation in Polymer Blends Driven by Surface Freezing

-1 as a function of temperature for blends with b of 0.000023 (a), 0.00023 (b), 0.0023 (c), and 0.023 (d). The (0) and (O) are for cooling and heating cycles, respectively. Also shown are the Ts,22 (vertical dashed lines) and the Ts,18 (vertical dotted lines). The black and gray lines are for transition temperature measured for the homopolymers in the heating and cooling cycles. The inset of (a) shows the chemical structure of alkyl side chain acrylate polymer of side chain length “ n”. 7467