An NMR study of the freezing of emulsion-containing drops

Various nuclear magnetic resonance (NMR) techniques were used to monitor the freezing behaviour of suspended 2-mm-diameter drops. The drops were composed of hydrocarbon oils emulsified in either water or water/sucrose mixtures. As such they were good model systems for the study of spray freezing, sharing structural similarities with potential products such as ice cream. In particular, simple 1H NMR spectroscopy was used to monitor and individually quantify the freezing or solidification behaviour of the various constituent species of the drops. In addition, the effect of freezing on the emulsion droplet size distribution (and hence emulsion stability) was also measured based on NMR self-diffusion measurements. The effect of freeze/thaw cycling was also similarly studied. The nucleation temperature of the emulsion droplets was found to depend on the emulsion droplet size distribution: the smaller the droplets, the lower the nucleation temperature. Emulsion droplet sizing indicated that oil-in-sucrose-solution emulsions were more stable, showing minimal coalescence, whereas oil-in-water emulsions showed significant coalescence during freezing and freeze/thaw cycling.     

The usage of computer-aided cooling curve thermal analysis to optimise eutectic refiner and modifier in Al–Si alloys

Bismuth, antimony and strontium concentrations were optimised to alter the eutectic Al?CSi phase in a commercial Al?CSi?CCu?CMg alloy by way of computer-aided cooling curve thermal analysis. The results show that the eutectic growth temperature shifted to lower temperatures for all three inoculants. However, addition of Sr resulted in more depression of growth temperature compared with Bi and Sb. No further significant changes were observed with increasing the concentrations to more than 1, 0.5 and 0.04?wt% of Bi, Sb and Sr, respectively. The recalescence of these concentrations, meanwhile, showed a significant increase of magnitude. A good correlation was found between the results of thermal and microstructural analysis. For Bi and Sb, the eutectic depression temperature can be used as an individual criterion to gauge optimal levels of content in the refinement of Si, whereas for Sr, both depression temperature and recalescence magnitude must be considered. Based on the observed depression in eutectic growth temperature and recalescence, it can be concluded that the optimal concentrations to refine the eutectic Al?CSi phase with Bi and Sb and to modify it with Sr at the given solidification conditions were 1, 0.5 and 0.04?wt%, respectively.     

Weight loss and isotopic shifts for water drops frozen on a liquid nitrogen surface

A liquid nitrogen freezing method was used to collect raindrops for the determination of isotope-size distribution. Water drops that fall onto a surface of liquid nitrogen stay suspended for 10 to 20 s, until their temperature reaches the Leidenfrost point (126 K). As their temperature falls to the freezing point, they release their heat by thermal conduction. At the freezing point, latent heat of fusion is released, along with a significant loss of water. After freezing completely, the ice droplets stay suspended, cooling by thermal conduction until they reach the Leidenfrost point. They then lose buoyancy and start sinking. Consistent isotopic changes of 1.5 +/- 0.4 and 0.33 +/- 0.05 per thousand for hydrogen and oxygen, respectively, were found for droplets with radii between 1.0 and 1.5 mm. Isotope fractionation appeared to occur at the same time as water loss, as the droplets were freezing, in what was probably a kinetic effect.     

Nanosecond freezing of water under multiple shock wave compression: optical transmission and imaging measurements

Water samples were subjected to multiple shock wave compressions, generating peak pressures of 1-5 GPa on nanosecond time scales. This loading process approximates isentropic compression and leads to temperatures where the ice VII phase is more stable than the liquid phase above 2 GPa. Time resolved optical transmission and imaging measurements were performed to determine the solidification rate under such conditions. Freezing occurred faster at higher pressures as water was compressed further into the ice VII phase, in agreement with classical micleation theory. Water consistently froze when in contact with a silica window, whereas no solidification occurred in the presence of sapphire windows. The transition was determined to be a surface initiated process--freezing began via heterogeneous nucleation at the water/window interface and propagated over thicknesses greater than 0.01 mm. The first optical images of freezing on nanosecond time scales were obtained. These images demonstrate heterogeneous nucleation and irregular solid growth over 0.01-0.10 mm lateral length scales and are consistent with latent heat emission during the transformation. The combination of optical transmission and imaging measurements presented here provide the first consistent evidence for freezing on short time scales.     

A new method for the simultaneous determination of the size and shape of pores: the thermoporometry

A thermodynamic study of the liquid—solid phase transformations in porous materials provides the relationships between the size of the pores in which solidification takes place and the temperature of the triple point of the divided liquid, on the one hand, and between this temperature and the apparent solidification energy on the other hand.The experimental study of the phase transformations, carried out by means of a microcalorimeter, gives the values of the parameters necessary to calculate the free solid = liquid interphase extension energy γ_ls at different temperatures. A formula γ_ls  f(T) is given for water and benzene. Once this factor is known, it is possible to study the numerical relationship between pore-radius and freezing energy at the equilibrium temperature.By using these relations together with the solidification thermogram (the recording of the power evolved by the solidification of a capillary condensate during a linear decrease of temperature) the authors have been able to determine pore distribution curves. An emphasis is put on the comparison between this method, thermoporometry, and the B.J.H. method.Last of all the comparison of the experimental data for solidification and melting provide information concerning pore shape by means of the evaluation of a thermodynamic shape factor or by a method of simulation of porous material.     

On the solidification of a supercooled liquid droplet lying on a surface

We model the solidification and subsequent cooling of a supercooled liquid droplet that is lying on a cold solid substrate after impact. It is assumed that solidification occurs for a given fixed droplet shape. The shapes used by the model are a sphere, truncated spheres, and an experimentally registered droplet shape. The freezing process is conduction-dominant and is modeled as a one-phase Stefan problem. This moving boundary problem is reformulated with the enthalpy method and then solved numerically with an implicit finite-difference technique. The numerical results for the simple case of a spherical droplet touching a surface are similar to those of a freely freezing spherical droplet and are well confirmed by the 1D asymptotic analytical model of Feuillebois et al. (J. Colloid Interface Sci. 169 (1995) 90). A freezing water droplet is considered as an example. The numerical results for full freezing time, subsequent cooling time, and last freezing point coordinate for the various droplets shapes are fitted by analytical functions depending on supercooling, thermal resistance of the target surface (expressed by Biot number), and spreading parameter. These functions are proposed for direct application, thus avoiding the need to solve the full freezing and cooling problem.     

Effect of cooling rate on the microstructure and solidification characteristics of Al2024 alloy using computer-aided thermal analysis technique

The aim of this work was to investigate the effect of different cooling rates on the microstructure and solidification parameters of 2024 aluminum alloy. Solidification characteristics are recognized from the cooling curve and its first and second derivative curves which have been plotted using thermal analysis technique. In this study, a mold having high cooling rate was designed and used to simulate the direct-chill casting process. The results of thermal analysis show that the characteristic parameters of Al2024 alloy are influenced by cooling rate. The cooling rates used in the present study range from 0.4 to 17.5 °C s^?1. Increasing the cooling rate affects the undercooling parameters both in liquidus and eutectic solidification regions. Investigations showed that solidification parameters such as nucleation temperature, recalescence undercooling temperature, and range of solidification temperature are influenced by variation of cooling rates. Microstructural evaluation was carried out to present the correlation between the cooling rate and dendrite arm spacing.     

聚合物 分散液晶体系的相分离结构对温度依赖性的研究

在不同温度下采用紫外光引发相分离法制备了聚合物分散液晶样品．用光学显微镜及扫描电镜研究了样品的相分离结构．采用对样品施加电压观察其微结构轮廓，或测量液晶微粒相变点的简单方法研究了聚合温度对相分离结果的影响．结果表明，在一定温度范围内，随着温度的增高，液晶微粒的平均尺寸趋于减小，而且形成的液晶微粒也逐渐变纯．作者给出了这些测试结果并进行了讨论．     

Effects of temperature and physical state on heterogeneous oxidation of oleic acid droplets with ozone

The heterogeneous reactions of pure micrometer-sized oleic acid droplets with ozone were studied as a function of temperature and physical state. Oxidation reactions were monitored using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FT-IR) and UV-vis spectrometry. Variations in droplet morphology due to the extent of oxidation were monitored using an optical microscope. Oleic acid droplets were maintained in either solid or liquid state at 9.0 °C. The physical state of the aerosol was determined from the IR absorbance spectra. Oxidation of solid state oleic acid with ozone at 9.0 °C was rapidly converted to the liquid state, which was most likely due to the presence of oxidation products on the surface of the droplets. The fast melting process that resulted from exposure of solid-phase droplets to ozone produced an oxidation rate similar to that for liquid-phase droplets exposed to ozone at the same temperature. Analysis of the carboxylic IR absorbance ratio for esters vs carboxylic acids indicates that the larger ester C═O-to-carboxylic acid C═O ratios at higher temperature appeared to correspond to the production of α-acyloxyalkyl hydroperoxide oligomers and polymers. The wide variation in product yields will result in vastly different physical properties of aerosol particles under different ambient environmental conditions.     

Thermal characterization of the interaction of poly(3-hydroxybutyrate) with maleic anhydride

In this research, the effects of Al–5Ti–1B grain refiner and Al–10Sr modifier were studied on solidification characteristics and microstructural features of 319 aluminum alloy. Important solidification events such as recalescence and nucleation undercooling temperature and aluminum–silicon eutectic depression temperature have been evaluated using cooling curve and its first derivative curve obtained from thermal analysis of a sample. The aim of this article is to show the ability of the thermal analysis technique to predict some key parameters controlling solidification and casting process. It has been found that the thermal analysis is the identified method for a rapid on-line monitoring of metallurgical characteristics of aluminum alloy melts without conventional metallographic examination.     

Freezing of water and aqueous NaCl droplets coated by organic monolayers as a function of surfactant properties and water activity

This study presents heterogeneous ice nucleation from water and aqueous NaCl droplets coated by 1-nonadecanol and 1-nonadecanoic acid monolayers as a function of water activity (a(w)) from 0.8 to 1 accompanied by measurements of the corresponding pressure-area isotherms and equilibrium spreading pressures. For water and aqueous NaCl solutions of ~0-20 wt % in concentration, 1-nonadecanol exhibits a condensed phase, whereas the phase of 1-nonadecanoic acid changes from an expanded to a condensed state with increasing NaCl content of the aqueous subphase. 1-Nonadecanol-coated aqueous droplets exhibit the highest median freezing temperatures that can be described by a shift in a(w) of the ice melting curve by 0.098 according to the a(w)-based ice nucleation approach. This freezing curve represents a heterogeneous ice nucleation rate coefficient (J(het)) of 0.85 ± 0.30 cm(-2) s(-1). The median freezing temperatures of 1-nonadecanoic acid-coated aqueous droplets decrease less with increasing NaCl content compared to the homogeneous freezing temperatures. This trend in freezing temperature is best described by a linear function in a(w) and not by the a(w)-based ice nucleation approach most likely due to an increased ice nucleation efficiency of 1-nonadecanoic acid governed by the monolayer state. This freezing curve represents J(het) = 0.46 ± 0.16 cm(-2) s(-1). Contact angles (α) for 1-nonadecanol- and 1-nonadecanoic acid-coated aqueous droplets increase as temperature decreases for each droplet composition, but absolute values depend on employed water diffusivity and the interfacial energies of the ice embryo. A parametrization of log[J(het)(Δa(w))] is presented which allows prediction of freezing temperatures and heterogeneous ice nucleation rate coefficients for water and aqueous NaCl droplets coated by 1-nonadecanol without knowledge of the droplet's composition and α.     

Induction of instability in water-in-oil-in-water double emulsions by freeze-thaw cycling

Individual water-in-oil-in-water (W1/O/W2) double-emulsion globules loaded with fluorescently labeled bovine serum albumin (FITC-BSA) were optically monitored within cylindrical capillaries during freeze-thaw cycling. Coalescence of internal aqueous droplets (W1) and external aqueous phase (W2), termed external coalescence, was not observed before or during freezing of the oil phase (O). On the other hand, this instability mechanism was readily promoted during thawing. This realization confirms the previously suggested potential of W1/O/W2 double emulsions to trigger release upon oil thawing and demonstrates that it is a direct result of globule breakage through external coalescence. The presented results also identified a threshold in the relative W1 droplet size above which instability occurred, while smaller droplets remained unperturbed and therefore indicate that optimization of the delivery can be achieved by tuning the size of W1 droplets. In addition, we propose a possible explanation for the occurrence of instability during oil thawing and its dependence on the size of W1 droplets. Because this alternative globule-breakage mechanism simply uses temperature increase (solid-to-liquid-phase transition) as external stimulus, W1/O/W2 double-emulsion delivery systems can be easily tailored by choosing an oil phase with the appropriate phase-transition temperature.     

Temperature-induced protein release from water-in-oil-in-water double emulsions

A model water-in-oil-in-water (W1/O/W2) double emulsion was prepared by a two-step emulsification procedure and subsequently subjected to temperature changes that caused the oil phase to freeze and thaw while the two aqueous phases remained liquid. Our previous work on individual double-emulsion globules1 demonstrated that crystallizing the oil phase (O) preserves stability, while subsequent thawing triggers coalescence of the droplets of the internal aqueous phase (W1) with the external aqueous phase (W2), termed external coalescence. Activation of this instability mechanism led to instant release of fluorescently tagged bovine serum albumin (fluorescein isothiocyanate (FITC)-BSA) from the W 1 droplets and into W2. These results motivated us to apply the proposed temperature-induced globule-breakage mechanism to bulk double emulsions. As expected, no phase separation of the emulsion occurred if stored at temperatures below 18 degrees C (freezing point of the model oil n-hexadecane), whereas oil thawing readily caused instability. Crucial variables were identified during experimentation, and found to greatly influence the behavior of bulk double emulsions following freeze-thaw cycling. Adjustment of these variables accounted for a more efficient release of the encapsulated protein.     

Synthesis and evolution of novel hollow ZnO urchins by a simple thermal evaporation process

Delicate hollow ZnO urchins have been fabricated by thermal evaporation of metallic zinc powders in a tube furnace without the use of additive, high temperature, or low pressure. The phase transformation, morphologies, and photoluminescence evolution of the ZnO products were carefully studied and investigated with X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), and photoluminescence (PL) spectra. These studies indicated that the growth of hollow ZnO urchins involves the vaporization of Zn powder, solidification of liquid droplets, surface oxidation, sublimation, and self-catalytic growth of one-dimensional nanowires.     

The ammonia-hydrogen system under pressure

Binary mixtures of hydrogen and ammonia were compressed in diamond anvil cells to 15 GPa at room temperature over a range of compositions. The phase behavior was characterized using optical microscopy, Raman spectroscopy, and synchrotron X-ray diffraction. Below 1.2 GPa we observed two-phase coexistence between liquid ammonia and fluid hydrogen phases with limited solubility of hydrogen within the ammonia-rich phase. Complete immiscibility was observed subsequent to the freezing of ammonia phase III at 1.2 GPa, although hydrogen may become metastably trapped within the disordered face-centered-cubic lattice upon rapid solidification. For all compositions studied, the phase III to phase IV transition of ammonia occurred at ~3.8 GPa and hydrogen solidified at ~5.5 GPa, transition pressures equivalent to those observed for the pure components. A P-x phase diagram for the NH(3)-H(2) system is proposed on the basis of these observations with implications for planetary ices, molecular compound formation, and possible hydrogen storage materials.     

Effect of oil phase transition on freeze/thaw-induced demulsification of water-in-oil emulsions

Recently, there has been an increasing interest in the breakage of water-in-oil (W/O) emulsions by the freeze/thaw method. Most of the previous works focused on the phase transition of the water droplet phase. This paper emphasizes the effect of continuous oil phase transition. A series of oils with different freezing points were used as oil phases to produce model emulsions, which were then frozen and thawed. The emulsion whose oil phase froze before the water droplet phase did (OFBW) on cooling was readily demulsified with a dewatering ratio as high as over 80%, but the emulsion whose oil phase did not freeze when the water droplet phase did (NOFBW) was relatively hard to break. The difference in demulsification performance between them resulted from the distinction between their demulsification mechanisms via the analyses of the emulsion stability, emulsion crystallization/melting behaviors, oil phase physical properties, and wettability of the frozen oil phase, etc. For the OFBW emulsion, the first-frozen oil phase was ruptured by the volume expansion of the subsequently frozen droplet phase, and meanwhile, some liquid droplet phase was drawn into the fine gaps/crevices of the frozen oil phase to bridge droplets, which were considered to be essential to the emulsion breakage, whereas for the NOFBW emulsion, the demulsification was attributed to the collision mechanism proposed in our previous work. The findings may provide some criteria for selecting a proper oil phase in the emulsion liquid membrane (ELM) process and then offer an alternative approach to recycle the oil phase for continuous operation. This work may also be useful for emulsion stability against temperature cycling.     

Molecular dynamics studies of the kinetics of phase changes in clusters III: structures, properties, and crystal nucleation of iron nanoparticle Fe331

Molecular dynamics (MD) computer simulations have been carried out to study the structures, properties, and crystal nucleation of iron nanoparticles with 331 Fe atoms or with diameter around 2 nm. Structure information for the nanoparticles was analyzed from the MD simulations. Three crystalline phases and one amorphous phase were obtained by cooling the nanoparticles from their molten droplets at different cooling rates or with different lengths of cooling time periods. Molten droplets froze into three different solid phases and a solid-solid transition from a disordered body-centered cubic (BCC) phase to an ordered BCC phase were observed during the slow cooling and the quenching processes. Properties of nanoparticle Fe₃₃₁, such as melting point, freezing temperature, heat capacity, heat of fusion, heat of crystallization, molar volume, thermal expansion coefficient, and diffusion coefficient, have been estimated. Nucleation rates of crystallization to two solid phases for Fe₃₃₁ at temperatures of 750, 800, and 850 K are presented. Both classical nucleation theory and diffuse interface theory are used to interpret our observed nucleation results. The interfacial free energy and the diffuse interface thickness between the liquid phase and two different solid phases are estimated from these nucleation theories.     

Effect of cooling rate and Al content on solidification characteristics of AZ magnesium alloys using cooling curve thermal analysis

The solidification behavior of AZ Magnesium alloys in various cooling conditions was investigated using a computer-aided cooling curve thermal analysis method. In each case, the cooling curve and its first and second derivative curves have been plotted using accurate thermal analysis equipment and solidification characteristics were recognized from these curves. The cooling rates used in the present study range from 0.22 to 8.13 °C s^?1. The results of thermal analysis show that the solidification parameters of AZ alloys such as nucleation temperature (T _N,α), nucleation undercooling (?T _N,α), recalescence undercooling (?T _R,α), range of solidification temperature (?T _S) and total solidification time (t _f) are influenced by variation of cooling rate. Also, the effect of Al content on these parameters was studied. Microstructural evaluation was carried out to determine the correlation between the cooling rate and secondary dendrite arm spacing.     

Infrared Monitoring of Interlayer Water in Stacks of Purple Membranes†

The thermodynamic behavior of films of hydrated purple membranes from Halobacterium salinarum and the water confined in it was studied by Fourier transform infrared spectroscopy in the 180–280 K range. Unlike bulk water, water in the thin layers sandwiched between the biological membranes does not freeze at 273 K but will be supercooled to ～256 K. The melting point is unaffected, leading to hysteresis between 250 and 273 K. In its heating branch, a gradually increasing light‐scattering by ice is observed with rate‐limiting kinetics of tens of minutes. Infrared (IR) spectra decomposition provided extinction coefficients for the confined water vibrational bands and their changes upon freezing. Because of the hysteresis, at any given temperature in the 255–270 K range, the interbilayer water could be either liquid or frozen, depending on thermal history. We find that this difference affects the dynamics of the bacteriorhodopsin photocycle in the hysteresis range: the decay of the M and N states and the redistribution between them are different depending on whether or not the water was initially precooled to below the freezing point. However, freezing of interbilayer water does block the M to N transition. Unlike the water, the purple membrane lipids do not undergo any IR‐detectable phase transition in the 180–280 K range.