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.     

功率超声在结晶过程中应用的进展

功率超声在结晶过程中的应用研究促进了结晶技术的发展,丰富了功率超声学和相关学科相互交叉的学术内容。以实例陈述了超声强化溶液结晶过程在化工、食品和制药行业中的应用,从熔融结晶和电结晶两方面阐述了超声改善金属结晶,综述了高分子材料和生物大分子等聚合物结晶过程中超声波的应用,总结了超声波对纳米晶型材料制备和性能的影响,着重说明了功率超声在食品冷冻中冰结晶过程的研究现状和发展方向。最后,总结了超声对结晶的强化机理。     

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.     

静电场对红细胞悬液冻结特性的影响

本文以红细胞悬液为研究模型,通过在对其进行慢速冻结的过程中引入静电场,具体研究了静电场对降温过程中红细胞悬液冻结特性的影响。实验结果表明:静电场在一定程度上改变了冰晶的形成与生长特性,抑制了晶核的形成, 使晶枝出现不对称生长,并减缓了冰晶的生长速度,这些影响随着场强的增加而逐渐加强。在较强的静电场的影响下,冰晶明显变粗,最终成为块状,细胞也不再与冰晶分离而是完全融入粗大的冰晶之中,在冻结的末期,细胞不再受到冰晶挤压,从而减少了其所受的机械性损伤。     

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.     

On the dynamics of contact line freezing of water droplets on superhydrophobic carbon soot coatings

Despite the opportunity to manipulate the water freezing via superhydrophobic materials, their commercial use for passive icing protection is still questioned, since the combined effect of surface morphology, air cushion arrangement, roughness, chemistry and film thickness on the icephobic properties of a given non-wettable solid remains unexplored. This article addresses the existing research gaps by studying the ice nucleation dynamics at the contact line of various superhydrophobic soot-based surfaces, potentially applicable in cryobiology for enhancing the existing cryopreservation technologies. We examine the freezing time and freezing temperature of water droplets settled on three groups of soot coatings with divergent morphochemical features, adjusted by modifying the samples with alcohol, fluorocarbon and/or silver hydrogen fluoride. Our results demonstrate the appearance of a new “contour” freezing mode, where the droplet shell crystallizes simultaneously with the contact interface, whilst the soot's chemical bonds along with some of its physical characteristics govern the ice formation.     

Effect of ultrasound-assisted freezing on the physico-chemical properties and volatile compounds of red radish

Power ultrasound, which can enhance nucleation rate and crystal growth rate, can also affect the physico-chemical properties of immersion frozen products. In this study, the influence of slow freezing (SF), immersion freezing (IF) and ultrasound-assisted freezing (UAF) on physico-chemical properties and volatile compounds of red radish was investigated. Results showed that ultrasound application significantly improved the freezing rate; the freezing time of ultrasound application at 0.26 W/cm² was shorten by 14% and 90%, compared to IF and SF, respectively. UAF products showed significant (p < 0.05) reduction in drip loss and phytonutrients (anthocyanins, vitamin C and phenolics) loss. Compared to SF products, IF and UAF products showed better textural preservation and higher calcium content. The radish tissues exhibited better cellular structures under ultrasonic power intensities of 0.17 and 0.26 W/cm² with less cell separation and disruption. Volatile compound data revealed that radish aromatic profile was also affected in the freezing process.     

Investigations in physical mechanism of ultrasound-assisted antisolvent batch crystallization of lactose monohydrate from aqueous solutions

Sonication is known to enhance crystallization of lactose from aqueous solutions. This study has attempted to reveal the mechanistic features of antisolvent crystallization of lactose monohydrate from aqueous solutions. Experiments were conducted in three protocols, viz. mechanical stirring, mechanical stirring with sonication and sonication at elevated static pressure. Mechanical stirring provided macroconvection while sonication induced microconvection in the system. Other experimental parameters were initial lactose concentration and rate of antisolvent (ethanol) addition. Kinetic parameters of crystallization were coupled with simulations of bubble dynamics. The growth rate of crystals, rate of nucleation, average size of crystal crop and total lactose yield in different protocols were related to nature of convection in the medium. Macroconvection assisted nucleation but could not give high growth rate. Microconvection comprised of microstreaming due to ultrasound and acoustic (or shock) waves due to transient cavitation. Sonication at atmospheric static pressure enhanced growth rate but reduced nucleation. However, with elimination of cavitation at elevated static pressure, sonication enhanced both nucleation and growth rate resulting in almost complete lactose recovery.     

Freezing transition of interfacial water at room temperature under electric fields

The freezing of liquid water into ice was studied inside a gap of nanometer spacing under the control of electric fields and gap distance. The interfacial water underwent a sudden, reversible phase transition to ice in electric fields of 10(6) V m(-1) at room temperature. The critical field strength for the freezing transition was much weaker than that theoretically predicted for alignment of water dipoles and crystallization into polar cubic ice (>10(9) V m(-1)). This new type of freezing mechanism, occurring in weak electric fields and at room temperature, may have immediate implications for ice formation in diverse natural environments.     

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.     

Optical and structural investigation of a-plane GaN layers on r-plane sapphire with nucleation layer optimization

Nonpolar a-plane GaN epilayers are grown on several r-plane sapphire substrates by metal organic chemical vapour deposition using different nucleation layers:(A) a GaN nucleation layer deposited at low temperature(LT);(B) an AlN nucleation layer deposited at high temperature;or(C) an LT thin AlN nucleation layer with an AlN layer and an AlN/AlGaN superlattice both subsequently deposited at high temperature.The samples have been characterized by Xray diffraction(XRD),atomic force microscopy and photoluminescence.The GaN layers grown using nucleation layers B and C show narrower XRD rocking curves than that using nucleation layer A,indicating a reduction in crystal defect density.Furthermore,the GaN layer grown using nucleation layer C exhibits a surface morphology with triangular defect pits eliminated completely.The improved optical property,corresponding to the enhanced crystal quality,is also confirmed by temperature-dependent and excitation power-dependent photoluminescence measurements.     

Antifreeze glycoproteins from the antarctic fish Dissostichus mawsoni studied by differential scanning calorimetry (DSC) in combination with nanolitre osmometry

This study investigates in detail the freezing events during cooling of solutions of various size classes of antifreeze glycoproteins. Differential scanning calorimetry and nanolitre osmometry were used to observe ice growth at temperatures within the hysteresis gap between the melting point and non-equilibrium freezing point (hysteresis freezing point) of solutions of the various sized antifreeze glycoproteins (AFGPs). The ice growth within the hysteresis gap is presumably due to both the expression of primary or near primary prism planes and also some growth at the basal plane. The binding of the AFGPs to the ice causes a particular ice crystal morphology. With the smaller AFGPs, substantial microscopic ice growth was observed in the form of a hexagonal bipyramids within the hysteresis gap.     

Survival of freezing by free-living Antarctic soil nematodes

Free-living microbivorous nematodes become numerically dominant in Antarctic terrestrial faunas as environmental conditions become more severe, while also reaching very high levels of abundance in moist, vegetated habitats. Nematodes have little resistance to freezing via exogenous ice nucleation, such as would occur as their microhabitat freezes. We report the results of experiments testing the ability of seven maritime Antarctic nematode taxa to survive freezing in small water droplets at high sub-zero temperatures. Isolated individuals of these species possessed supercooling characteristics similar to those previously reported (supercooling points -6 to -25 degree C). When frozen in water at -3 to -6 degree C, most showed high (> 70%) survival both (i) after rapid cooling (1 degree C/min) to c. -60 degree C followed by immediate rewarming, and (ii) when held for 7-12 h at either -10 or -30 degree C, although the proportions surviving varied between species. We propose that the ability to survive freezing while fully hydrated at high sub-zero temperatures is one of the most important aspects of these species' survival tactics.     

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 particle image velocimetry method in the study of the dynamics of phase transitions induced by high pressures in triolein and oleic acid

Particle image velocimetry (PIV) is an optical measurement method capable of providing visualisation of velocity field of particle flow in fluids. After analysis of data acquired in the form of an image sequence, it is possible to retrieve information about flow parameters as mean values of velocity, vorticity, shear and normal strain. This paper presents the results of high pressure experiments using this method applied to triolein and oleic acid samples in their phase transition region. A high pressure optical chamber, He–Ne laser and light-sheet optics together with a digital camera and image acquisition computer allow us to study the motion of particles in high pressure conditions. The set-up was similar to that presented in Özmutlu et al. [Momentum and energy transfer during phase change of water under high hydrostatic pressure, Innov. Food Sci. Emerg. Technol. 7(3) (2006), pp. 161–168] and Kulisiewicz et al. [Visualization of pressure-shift freezing and thawing of concentrated aqueous sucrose solutions, High Press. Res. 27(2) (2007), pp. 291–297]. The analysis of phase transition dynamics in triolein and oleic acid is an extension to the work presented in Tefelski et al. [The investigation of the dynamics of the phase transformation in triolein and oleic acid under pressure, J. Phys.: Conf. Ser. 121(142004) (2008), pp. 1–6]. Oleic acid is a monounsaturated fatty acid and has a bent rod shape. Triolein is a triglyceride and has a “chair”-like shape. It is the base particle of many vegetable oils, especially olive oil. Triolein consists of three chains of oleic acid bound by a glycerol part. Information obtained by the study of phase transitions dynamics is important for food science and food technology processes which involve high pressure treatment. The PIV method shows differences in the solidification process of both substances in time, the existence of inhomogeneities (layers of different densities in the observed flow) and allows us to calculate the parameters of flow using the PIVview2C software from PIVTEC GmbH.     

Analytical considerations and dimensionless analysis for a description of particle interactions in high pressure processes

High pressures of up to several hundreds of MPa are utilized in a wide range of applications in chemical, bio-, and food engineering, aiming at selective control of (bio-)chemical reactions. Non-uniformity of process conditions may threaten the safety and quality of the resulting products because processing conditions such as pressure, temperature, and treatment history are crucial for the course of (bio-)chemical reactions. Therefore, thermofluid-dynamical phenomena during the high pressure process have to be examined, and numerical tools to predict process uniformity and to optimize the processes have to be developed. Recently applied mathematical models and numerical simulations of laboratory and industrial scale high pressure processes investigating the mentioned crucial phenomena are based on continuum balancing models of thermofluid dynamics. Nevertheless, biological systems are complex fluids containing the relevant (bio-)chemical compounds (enzymes and microorganisms). These compounds are particles that interact with the surrounding medium and between each other. This contribution deals with thermofluid-dynamical interactions of the relevant particulate (bio-)chemical compounds (enzymes and microorganisms) with the surrounding fluid. By consideration of characteristic time and length scales and particle forces, the motion of the (bio-)chemical compounds is characterized.     

Desorption and crystallization kinetics in nanoscale thin films of amorphous water ice

The amorphous to crystalline ice phase transition is studied by measuring the water desorption rate from nanoscale thin films of water vapor deposited on Au(111) and Ru(001) single crystal metallic substrates. The desorption kinetics are substrate dependent and suggest strongly that the film morphology is governed by the hydrophilicity of the substrate. The crystallization kinetics are independent of substrate but depend strongly on both temperature and film thickness and are consistent with a spatially random nucleation and isotropic growth model.     

Effects of AlN nucleation layer thickness on crystal quality of AlN grown by plasma-assisted molecular beam epitaxy

In this paper,the effects of thickness of AlN nucleation layer grown at high temperature on AlN epi-layer crystalline quality are investigated.Crack-free AlN samples with various nucleation thicknesses are grown on sapphire substrates by plasma-assisted molecular beam epitaxy.The AlN crystalline quality is analysed by transmission electron microscope and x-ray diffraction (XRD) rocking curves in both (002) and (102) planes.The surface profiles of nucleation layer with different thicknesses after in-situ annealing are also analysed by atomic force microscope.A critical nucleation thickness for realising high quality AlN films is found.When the nucleation thickness is above a certain value,the (102) XRD full width at half maximum (FWHM) of AlN bulk increases with nucleation thickness increasing,whereas the (002) XRD FWHM shows an opposite trend.These phenomena can be attributed to the characteristics of nucleation islands and the evolution of crystal grains during AlN main layer growth.     

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.     

An experimental investigation into the icing and melting process of a water droplet impinging onto a superhydrophobic surface

The freezing and melting process of a small water droplet on a superhydrophobic cold surface was investigated using the Laser Induced Fluorescence (LIF) technique. The superhydrophobic surface was prepared using a sol-gel method on a red copper test plate. From the obtained fluorescence images, the phase transition characteristics during the freezing and melting process of a water droplet were clearly observed. It was found that, at the beginning of the droplet freezing process, liquid water turned into ice at a very fast rate. Such phase transition process decreased gradually with time and the volume of frozen ice approached a constant value at the end of the icing process. In addition, the freezing time was found to reduce with the decrease of the test plate temperature. Besides, when the test plate temperature is relatively high, the effect of droplet volume on the freezing time is very significant. Over all, we provide some tentative insights into the microphysical process related to the icing and melting process of water droplets.