Ice nucleation of water droplet containing solid particles under weak ultrasonic vibration

Water with small volume (a few microlitres or less) often maintains its liquid state even at temperatures much lower than 0 °C. In this study, we examine the onset of ice nucleation in micro-sized water droplets with immersed solid particles under weak ultrasonic vibrations. The experimental results show that ice nucleation inside the water droplets can be successfully induced at relatively high temperatures. The experimental observations indicate that the nucleation sites are commonly encountered in the region between the particle and the substrate. A numerical study is conducted to gain insight into the possible underlying phenomenon for ice nucleation in such systems. The simulation results show that the collapse of cavitation bubbles in the crevice at the particle surface is structure sensitive with the hemisphere-shape crevice generating pressures as high as 1.63 GPa, which is theoretically suitable for inducing ice nucleation.     

The sonocrystallisation of ice in sucrose solutions: primary and secondary nucleation

Two investigations of the sonocrystallisation of ice are reported for solutions in the concentration range of 0-45 wt.% sucrose. The first, carried out at 20 kHz using a commercial sonicator shows clear evidence of the stimulation of primary nucleation, by increasing the temperature at which nucleation takes place. The nucleation temperature is also increased as the ultrasonic power output level or duty cycles are increased. The second uses a novel measurement cell which permits the direct visualisation of the crystallisation and cavitation with a light microscope while different levels of alternating pressures at a frequency of 67 kHz are applied to the sample, whose heating and cooling is carefully controlled and monitored. This provides confirmation of the fragmentation of ice dendrites growing in a sucrose solution to produce smaller new ice crystals (secondary nucleation). These observations show that the primary and secondary nucleation of ice are both possible during the sonocrystallisation of ice.     

Thermodynymic analysis of the mechanism of deep supercooling of tissue water in winter-hardy plants

The temperature at which ice grows through narrow, hydrophilic capillary is known to be depressed. Further, the nucleation temperature near a hydrophilic surface varies with the size, geometry and the properties of a particle. In this paper we show how these two effects are additive for the water that freezes on the wall of a capillary without the presence of pre-existing ice. The combined effect is a substantial lowering of nucleation temperature that could, if this analysis is correct, have important cryobiological consequences.     

In situ investigation of ice formation on surfaces with representative wettability

In this work, we have prepared a series of samples with five representative surface wettabilities: i.e. superhydrophilic, hydrophilic, critical, hydrophobic and superhydrophobic. These samples were in situ observed the freezing process of water droplets on clean and artificially contaminated surfaces to investigate the relationship between surface wettability and ice formation. Ice accretion was also tested by spraying supercooled water to samples at different horizontal inclination angles (HIA). Surface topography was proved to be essential to the icing through heterogeneous nucleation. However, the correlation between surface wettability and ice formation was not observed. Finally, we found that the superhydrophobic surface clearly exhibited reduced ice accumulation in the initial stage of ice formation associated with the lower sliding angle (SA) of water droplets.     

Suppression of ice nucleation in supercooled water under temperature gradients

Understanding the behaviours of ice nucleation in non-isothermal conditions is of great importance for the preparation and retention of supercooled water. Here ice nucleation in supercooled water under temperature gradients is analyzed thermodynamically based on classical nucleation theory (CNT). Given that the free energy barrier for nucleation is dependent on temperature, different from a uniform temperature usually used in CNT, an assumption of linear temperature distribution in the ice nucleus was made and taken into consideration in analysis. The critical radius of the ice nucleus for nucleation and the corresponding nucleation model in the presence of a temperature gradient were obtained. It is observed that the critical radius is determined not only by the degree of supercooling, the only dependence in CNT, but also by the temperature gradient and even the Young's contact angle. Effects of temperature gradient on the change in free energy, critical radius, nucleation barrier and nucleation rate with different contact angles and degrees of supercooling are illustrated successively. The results show that a temperature gradient will increase the nucleation barrier and decrease the nucleation rate, particularly in the cases of large contact angle and low degree of supercooling. In addition, there is a critical temperature gradient for a given degree of supercooling and contact angle, at the higher of which the nucleation can be suppressed completely.     

Relationships between cold hardiness, and ice nucleating activity, glycerol and protein contents in the hemolymph of caterpillars, Aporia crataegi L

Insects in Siberia must tolerate some of the coldest conditions on earth. The relationship between hemolymph ice nucleating activity, glycerol and total protein concentrations, and cold hardiness was explored in Aporia crataegi L. (Lepidoptera: Pieridae). Cold-hardened overwintering caterpillars were collected at a time of year when temperatures are regularly below -50 degree C, and warm-acclimated at +22 degree C, to see how changes in the physical and chemical properties of the hemolymph influence their cold hardiness potential. Warm acclimation led to a decrease in glycerol and proteins content in the hemolymph, which was associated with the decrease in ice nucleating activity and dramatic loss of cold hardiness potential of the caterpillars. It is suggested that one of the effects of cryoprotection in the freeze tolerant insects, caused by glycerol, might be associated with its ability to form larger aggregates of ice nucleating polypeptides that initiate the ice nucleation at high subzero temperatures. Such ice nucleating structures seem to ensure a high probability of ice nucleation at relatively high temperatures, which may contribute to the extraordinary cold hardiness of A. crataegi caterpillars, which may tolerate temperatures below -85 degree С.     

A study on the primary and secondary nucleation of ice by power ultrasound

Several different investigations have been carried out to study the primary and secondary nucleation of ice by sonocrystallisation. Firstly, the primary nucleation of discrete ice crystals in a supercooled sucrose solution has been observed. For increasing concentrations of sucrose solutions from 0 to 45 wt%, the nucleation temperature consistently occurs at a higher nucleation temperature in the presence of ultrasound. The nucleation temperature also increases as the power output and duty cycle of a commercial ultrasonic horn are increased. Snap shot images of the bubble clouds obtained from the ultrasonic horn also show that the number of bubbles appears to increase as the ultrasonic output is increased. This suggests that the nucleation of ice is related to the power output and number of cavitation bubbles. The effect of a single bubble on the sonocrystallisation of ice is discussed. High-speed movies (1120 fps) have shown that the crystallisation appears to occur in the immediate vicinity of the single bubble. In most cases, many crystals are observed and it is not known whether a single ice crystal is being fragmented by the bubble or whether many crystals are being initiated. The bubble appears to undergo a dancing regime, frequently splitting and rejoining and also emitting some small microbubbles. A study on the secondary nucleation of ice in sucrose solutions has been carried out using a unique ultrasonic cold stage device. Images taken using a microscope system show that the pre-existing ice dendrite crystals can be broken up into smaller fragments by an ultrasonic field. Cavitation bubbles appear to be important during the fragmentation process, possibly melting any ice crystals in their path. Flow patterns around cavitation bubbles have also been observed, and these may be responsible for the fragmentation of ice crystals.     

The effect of antifreeze proteins and poly(vinyl alcohol) on the nucleation of ice: a preliminary study

Three substances have been tested for ice nucleation inhibition. These were an antifreeze protein AFP III from the fish Macrozoarces americanus, an antifreeze glycoprotein AFGP from the fish Dissostichus mawsoni, and an 80% hydrolysed poly(vinyl alcohol) with a molecular weight of 9 to 10 kD. A nucleation spectrometer was used to test nucleation inhibition at a range of concentrations against two types of ice nuclei: those present in tap water and a bacterial nucleator from Pseudomonas syringae. The PVA reduced the nucleation temperature of tap water and the bacterial dispersions at all the concentrations which were tested. The AFGP reduced the nucleation temperature of tap water but enhanced the nucleation activity of the bacterial nucleators. At low concentrations the AFP III reduced the nucleation temperature of both tap water and the bacterial nucleator. At high concentrations the AFP III enhanced the nucleation temperature of the bacterial nucleator and broadened the nucleation spectrum of the tap water to encompass the nucleation spread of the control. The possible mechanisms of nucleation suppression and enhancement are discussed.     

Ultrasonic-induced nucleation of ice in water containing air bubbles

Cavitation induced by ultrasonic vibrations can cause nucleation of ice in supercooled water. In this study, the time required for ultrasonic-induced nucleation of ice was measured for water containing two different size distributions of air bubbles. When the water was supersaturated with air bubbles, there was a time lag of about 0.5 s between the onset of ultrasonic irradiation and the onset of ice nucleation, and the probability of ice nucleation was unusually high within 0.5-1.1 s after the onset of ultrasonic irradiation. These results cannot be explained by conventional models alone, in which the collapse of a cavitation bubble triggers the nucleation of ice. Secondary effects appear to also influence ice nucleation.     

Substances which inhibit ice nucleation: a review

There are a number of substances described in the published literature which inhibit ice nucleation. Certain bacterial strains, mostly found among the nonfluorescent pseudomonade species, release material into the growth medium which reduces the nucleation temperature of water droplets to below that of distilled water. Extracts from the seeds of food crops including apricot, peach and plum can reduce the nucleation temperature of water droplets and dispersions of silver iodide. Antifreeze glycoproteins can reduce the nucleation temperature of saline solutions. Antifreeze proteins can inhibit the activity of some biological ice nucleators but not others. Certain novel polymers have been shown to inhibit the nucleation activity of dispersions of silver iodide and ice-nucleating bacteria.     

The growth of ice clusters on the Si(100)(2 × 1)-H(D) surface: Electron energy loss spectroscopy and thermal desorption studies

The growth of ice clusters on the Si(100)(2 × 1)-H surface has been investigated mainly by the use of high-resolution electron energy loss spectroscopy and thermal desorption spectroscopy. At 90 K, H₂O molecules are adsorbed on the (2 × 1)-H surface to form ice clusters by the hydrogen-bonding interaction. Four H₂O peaks are observed at 165, 185, 215 and 270 K in the thermal desorption spectra for the ice-covered surface. The peaks at 165 and 185 K correspond to the ice clusters and the peaks at 215 and 270 K to the strongly-bound H₂O species which play a role as the nucleation centers of the ice clusters desorbing as H₂O at 185 and 165 K, respectively.     

Can secondary nucleation exist in ice banding of freezing colloidal suspensions?

The formation mechanism of ice banding in the system of freezing colloidal suspensions, which is of significance in frost heaving, ice-templating porous materials and biological materials, is still a mystery. Recently, the theory of secondary nucleation and growth of ice has been proposed to explain the emergence of a new ice lens. However, this theory has not been quantitatively examined. Here, we quantitatively measure the initial interfacial undercooling of a new ice lens and the nucleation undercoolings of suspensions. We find that the interfacial undercooling cannot satisfy the nucleation undercooling of ice and hence disprove the secondary nucleation mechanism for ice banding.     

Nucleation-limited dewetting of ice films on Pt(111)

Quantifying dewetting phenomena at the microscopic level is the key to deciphering how a balance between kinetic and equilibrium effects determines ice-film morphology on Pt(111). Overcoming the difficulty of imaging nominally insulating ice multilayers with scanning tunneling microscopy allowed us to track the dewetting process. The results show that the rate at which new layers nucleate, and not surface diffusion, determines how fast individual crystallite shapes equilibrate. Applying nucleation theory to measured growth rates versus crystallite size, we obtain new bounds on the energetics both of step formation on ice and of the Pt-ice interface.     

基于改进格子Boltzmann焓法模型的霜层生长数值研究

采用介观尺度格子Boltzmann方法数值研究壁面的表面特性对霜层生长的影响.将成核概率模型和改进的焓法相变模型相耦合，建立基于成核概率理论的霜层生长过程格子Boltzmann模型.该模型能够在宏观尺度上模拟霜层生长的加密加厚过程，也可以从微观尺度上描述局部的冰枝生长导致的霜层结构的动态变化，应用该模型能够获得霜层平均厚度、平均密度、结霜量等内部非稳态物理量.开展冷壁面上霜层形成及生长过程的数值研究，获得霜层的拓扑结构时空演化特性，得到不同时刻下结霜量以及霜层的平均厚度、平均密度、平均固相体积分数，探讨冷壁面温度、相对湿度、冷表面浸润性能对结霜的影响.     

Neutrons for probing the ice nucleation on atmospheric soot particles

Soot resulting from combustion of kerosene in aircraft engines can act as condensation nuclei for water/ice in the atmosphere and promote the formation of contrails that turn into artificial cirrus clouds and affect the climate. The mechanisms of nucleation of water/ice particles are not well identified. Studies ??in situ?? are difficult to realize, so we try to determine by neutron diffraction the nucleation of water/ice adsorbed on soot collected at the outlet of an aircraft engine combustor within the conditions of the upper troposphere. The results are compared with those obtained on model laboratory soot. The comparison highlights the role of chemical impurities and structural defects of original aircraft engine soot on the nucleation of water/ice in atmospheric conditions.     

The effect of ultrasonic waves on the nucleation of pure water and degassed water

In order to clarify the mechanism of nucleation of ice induced by ultrasound, ultrasonic waves have been applied to supercooled pure water and degassed water, respectively. For each experiment, water sample is cooled at a constant cooling rate of 0.15 °C/min and the ultrasonic waves are applied from the water temperature of 0 °C until the water in a sample vessel nucleates. This nucleation temperature is measured. The use of ultrasound increased the nucleation temperature of both degassed water and pure water. However, the undercooling temperature for pure water to nucleate is less than that of degassed water. It is concluded that cavitation and fluctuations of density, energy and temperature induced by ultrasound are factors that affect the nucleation of water. Cavitation is a major factor for sonocrystallisation of ice.     

Theoretical model of ice nucleation induced by inertial acoustic cavitation. Part 2: Number of ice nuclei generated by a single bubble

In the preceding paper (part 1), the pressure and temperature fields close to a bubble undergoing inertial acoustic cavitation were presented. It was shown that extremely high liquid water pressures but quite moderate temperatures were attained near the bubble wall just after the collapse providing the necessary conditions for ice nucleation. In this paper (part 2), the nucleation rate and the nuclei number generated by a single collapsing bubble were determined. The calculations were performed for different driving acoustic pressures, liquid ambient temperatures and bubble initial radius. An optimal acoustic pressure range and a nucleation temperature threshold as function of bubble radius were determined. The capability of moderate power ultrasound to trigger ice nucleation at low undercooling level and for a wide distribution of bubble sizes has thus been assessed on the theoretical ground.     

Evaluation of the ice ratio formed during quasi-adiabatic pressure shift freezing

Abstract

Pressure shift freezing consists in cooling a biological substance (mainly containing water) under pressure without phase change followed by a sudden release of the pressure. The high supercooling obtained during the quasi adiabatic depressurisation permits to achieve a rapid and uniform ice nucleation. The ice fraction formed during the pressure release of a sample of pure water has been calculated using a mathematical model. In addition, this fraction was experimentally evaluated by isothermal calorimetry. The calculations and measurements were carried out at 3 different initial points of the ice I melting curve. A relatively good agreement is observed between the experimental and calculated ice ratio which were between 0.117 and 0.402 (kg ice/kg ice-water mixture) for an initial temperature-pressure values of -10°C/1 15 MPa and -21°C/210 MPa respectively.     

A theoretical model for ice primary nucleation induced by acoustic cavitation

The modelling and simulation of ice nucleation triggered by acoustic cavitation was addressed in this study. The objective was to evaluate the number of nuclei generated by a single gas bubble and afterwards by a multi-bubble system as function of the acoustic pressure (ultrasound wave amplitude) and supercooling level (liquid temperature). According to our calculations, the nucleation could be initiated with moderated acoustic pressure amplitude (around one bar) even at low supercooling levels (around few degrees). These results may provide a sound basis for the control of ice crystal size and morphology which is a key issue in industrial freezing and freeze-drying processes.     

Nucleation of crystalline phases of water in homogeneous and inhomogeneous environments

We employ two-body and three-body bond-orientational order-parameters, in conjunction with non-Boltzmann sampling to calculate the free energy barrier to nucleation of crystalline phases of water. We find that, as the coupling between the successive peaks of the direct correlation function increases, the free energy barrier to nucleation decreases. On this basis we explain the important parameters that govern the nucleation rate involving crystalline phases of water in different homogeneous and inhomogeneous environments, giving a "unified picture" of ice nucleation in water.