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 microscopic visualisation of the sonocrystallisation of ice using a novel ultrasonic cold stage

This work reports dynamic video images of the influence of ultrasonic cavitation on the sonocrystallisation of ice at a microscopic level. This has been achieved through the construction of a unique ultrasonic system for an optical microscope. The system consists of (1). an ultrasonic cold stage, (2). a temperature control system, and (3). a microscope and imaging setup. This allows the temperature of a sample to be systematically controlled while it is subjected to simultaneous excitation with alternating pressures in the ultrasonic frequency range. Both the amplitude of excitation and the frequency can be varied. Experiments on ice crystals in pure water and sucrose solutions were conducted. Three distinct phenomena were observed. Firstly, there is a tendency for cavitation bubbles to form at the grain boundaries between ice crystals. Secondly, there is a progressive melting of ice by cavitation bubbles which appear to eat their way into the ice phase. Thirdly, the dendritic ice structures may fragment under the influence of ultrasound, thus increasing the number of nuclei which may subsequently grow (secondary nucleation). These observations form the basis of a significantly enhanced understanding and exploitation of the sonocrystallisation of ice.     

Use of enantiomeric properties of sodium chlorate to assess primary and secondary nucleation under sonication

Ultrasound is known to promote crystal nucleation, but despite significant research there remains uncertainty about how the mechanisms are affected. Despite the proposal of various primary nucleation theories, most studies provide no way to quantify or observe the extent to which primary nucleation is taking place, leaving open the possibility that sonocrystallisation is occurring by a secondary nucleation-driven mechanism. By utilising the widely reported enantiomeric properties of sodium chlorate, the extent to which ultrasound can induce primary nucleation can clearly be observed. It was demonstrated during seeded cooling crystallisation that when stirring the seed similarity was 99.3% on average, indicating secondary nucleation had almost exclusively taken place. The application of ultrasound however, decreased the seed similarity to 85.8% and 92.4% when applying 98 kHz and 200 kHz ultrasound respectively, clearly showing that primary nucleation had been induced and indicating the frequency dependency of the induced primary nucleation. This frequency dependency suggests a link between crystal nucleation and high intensity cavitation collisions and collapses, and the potential existence of a collapse/collision intensity threshold required to induce primary nucleation. In addition, secondary nucleation rate was investigated using anti-solvent crystallisation and was observed to increase with the application of ultrasound, though it appeared frequency independent (between 98 kHz & 200 kHz), suggesting that higher energy cavitational events are less important in inducing secondary nucleation or that a lower cavitation intensity threshold exists compared to primary nucleation.     

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.     

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.     

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.     

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.     

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.     

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.     

Visualization of pressure-shift freezing and thawing of concentrated aqueous sucrose solutions

A visualization of pressure-shift freezing of 0.7 w/w sucrose solutions was carried out at three temperatures 268, 253 and 235 K by release of pressure from 200 MPa to atmospheric value. Furthermore, pressure-shift freezing at 268 K and additionally pressure-shift thawing was carried out for a solution of 0.2 sucrose mass fraction. The solid phase observed at 268 K in the case of solution with 0.2 w/w sucrose fraction was ice I. The phase changes of 0.7 w/w sucrose solutions at 253 K and 235 K resulted in formation of spherical solids which are hypothesized to be eutectics, i.e. crystals with structure containing sucrose hydrates and water. The visual evaluation revealed differences in size and distribution of spherical crystals. The solids formed at 235 K were more numerous, more homogenously distributed and finally smaller than those observed at 253 K. It is explained by the higher supercooling of the solution in the former case, which provided higher driving force for nucleation and crystal growth.