Crystallization and Drying in Thin Sucrose Films During Panning

Sucrose crystallization in thin films (50–55 μm) was studied, using a videomicroscopy technique, at conditions encountered during hard panning processes. No nucleation occurred in unseeded films, while a linear increase in seeded crystals occurred during drying. Crystal growth rate increased with temperature (25–30°C) and with air velocity (2.4–12.5 m/sec), but did not change with varying sucrose concentrations (70–76% w/w) and relative humidities (0–66% at 30°C). FD & C Yellow No. 5 food coloring in the dye form (0.05–0.5 g/100 mL) showed no effects while similar concentrations in the lake form inhibited crystal growth rate.     

Analysis of supersaturation and nucleation in a moving solution droplet with flowing supercritical carbon dioxide

A supercritical antisolvent (SAS) process is employed for production of solid nanoparticles from atomized droplets of dilute solution in a flowing supercritical carbon dioxide (SC CO₂) stream by attaining extremely high, very rapid, and uniform supersaturation. This is facilitated by a two‐way mass transfer of CO₂ and solvent, to and from the droplet respectively, rendering rapid reduction in equilibrium solubility of the solid solute in the ternary solution. The present work analyses the degree of supersaturation and nucleation kinetics in a single droplet of cholesterol solution in acetone during its flight in a flowing SC CO₂ stream. Both temperature and composition are assumed to be uniform within the droplet, and their variations with time are calculated by balancing the heat and mass transfer fluxes to and from the droplet. The equilibrium solubility of cholesterol with CO₂ dissolution has been predicted as being directly proportional to the Partial Molar Volume Fraction (PMVF) of acetone in the binary (CO₂–acetone) system. The degree of supersaturation has been simulated up to the time required to attain almost zero cholesterol solubility in the droplet for evaluating the rate of nucleation and the size of the stable critical nuclei formed. The effects of process parameters have been analysed in the pressure range of 7.1–35.0 MPa, temperature range of 313–333 K, SC CO₂ flow rate of 0.1136–1.136 mol s^?1, the ratio of the volumetric flow rates of CO₂‐to‐solution in the range of 100–1000, and the initial mole fraction of cholesterol in acetone solution in the range of 0.0025–0.010. The results confirm an extremely high and rapid increase in degree of supersaturation, very high nucleation rates and stable critical nucleus diameter of the order of a nanometre. Copyright © 2005 Society of Chemical Industry     

Heterogeneous Plantinum Nucleation and Crystallization of a Heavy-Metal Fluoride Glass

The effect of controlled heterogeneous nucleation by platinum on the crystallization of a ZrF₄-BaF₂-LaF₃-AlF₃-NaF (ZBLAN) glass was studied. Various levels of platinum were incorporated into this glass by a combination of PtCl₂-doping and melting-atmosphere variation. The effect of doping levels and melting conditions on the incorporation of platinum and the subsequent nucleation of crystals was studied by optical microscopy, scanning electron microscopy, differential scanning calorimetry (DSC), and X-ray diffraction. Increased platinum in the glass resulted in an increased number of nucleation sites for the growth of β-ZrF₄-BaF₂ crystals. Analysis of isothermal and ramp-rate DSC measurements indicated that the crystallization of this glass changed from surface controlled to bulk controlled with an increased number of nuclei. This was confirmed by optical microscopy. In addition, Avrami analysis of the isothermal crystallization data gave an accurate approximation of the number of nuclei in the glass.     

Prediction of foam growth and its nucleation in free and limited expansion

The influence volume approach (IVA) is often utilized for modeling the mass transfer process dictating bubble growth dynamics in physical foaming. However, the assumed concentration profile in the IVA method is only valid when the changes in dissolved gas concentration are small (less than 5%). In addition, the validity of the IVA method is difficult to justify in chemical foaming applications because of the difficulties involved in defining the dissolved gas concentration profile.In the present work, we define two distinct stages of bubble growth for physical foaming. These two stages are termed as free and limited expansion and are controlled by the bubble nucleation rate. Bubble nucleation is assumed to occur only in the free expansion stage. In this stage, the bubble pressure drops substantially from an initially high pressure in the supersaturated state while the dissolved gas concentration changes very little. The second stage of our two-stage mass transfer model is termed the limited expansion stage and accounts for bubble growth in the late stages of foam evolution, when the pressure changes become small. However, in the limited stage of bubble growth the dissolved gas concentration drops significantly, as the available dissolved gas is depleted. To summarize our two-stage mass transfer model of foam expansion, the pressure difference between the bubble phase and the liquid phase is the primary mechanism for driving mass transfer in the early (free) stages of foam growth and the concentration difference is the driver for bubble growth in the late (limited) stages of growth. The first stage can be regarded as the nucleation stage and it is relatively short; while the second stage can be regarded as the bubble growth stage and is much longer. Most of the bubble volume expansion takes place in the second stage.The concentration gradient at the bubble edge, which is often ignored in other models, is analyzed in detail in this paper. The details of our novel mass transfer model are also presented.     

Nonisothermal melt-crystallization kinetics of isotactic polypropylene synthesized with a metallocene catalyst and compounded with different quantities of an α nucleator

The nonisothermal crystallization kinetics of a metallocene-made isotactic polypropylene (m-iPP) and its compounds with 0.1 wt % and 0.3 wt % of a sorbitol derivative [1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS); an α nucleator] were investigated by differential scanning calorimetry at different cooling rates from the melt. The nucleation efficiency was proved by a significant increase in the crystallization temperatures (accompanied by a slight augmentation of the degree of crystallinity and a decrease in the crystal sizes). This increase in the crystallization temperatures led to higher amounts of fractional content in the γ polymorph, even though DMDBS was supposed to be a nucleator for the α form. The Avrami and Ozawa methods effectively described only the early stage of crystallization, whereas a combined Avrami–Ozawa method was valid for the whole crystallization process. The values of the exponent for this method decreased for nucleated samples in the later stage of crystallization, especially in the case of m-iPP with 0.3 wt % DMDBS added (m-iPP03). The activation energy of the process and the surface free energy were also estimated. The production of considerable proportions of the γ polymorph in m-iPP03 corresponded to higher values of the activation energy and lower values of the surface free energy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of Ammonia on the Gas-Phase Hydration of the Common Atmospheric Ion HSO4?

Hydration directly affects the mobility, thermodynamic properties, lifetime and nucleation rates of atmospheric ions. In the present study, the role of ammonia on the formation of hydrogen bonded complexes of the common atmospheric hydrogensulfate (HSO₄⁻) ion with water has been investigated using the Density Functional Theory (DFT). Our findings rule out the stabilizing effect of ammonia on the formation of negatively charged cluster hydrates and show clearly that the conventional (classical) treatment of ionic clusters as presumably more stable compared to neutrals may not be applicable to pre-nucleation clusters. These considerations lead us to conclude that not only quantitative but also qualitative assessment of the relative thermodynamic stability of atmospheric clusters requires a quantum-chemical treatment.     

Importance of Low-Temperature Melt-Mixing on the Construction of Stereocomplex Crystallites with Superior Nucleation Efficiency in Asymmetric Poly(l-lactide)/Poly(d-lactide) Blends

The nucleation efficiency (NE) of stereocomplex crystallites (SCs) formed in asymmetric poly(L-lactide)/poly(D-lactide) (PLLA/PDLA) blends is generally unsatisfactory because the competition between stereocomplexation and chain mixing involved in the melt-mixing process can cause low formation efficiency and even severe aggregation of SCs. Herein, it is attempted to achieve high-efficient formation of finely dispersed SCs particles by designing a unique melt-mixing procedure, where the mixing of PLLA with 0.75 wt% PDLA is first performed at elevated temperatures (far above the melting temperature of SCs) to allow the homogeneous mixing of PLLA/PDLA chains and then at a low temperature (slightly above that of homocrystallites) to permit the full stereocomplexation of the premixed chains. It is found that the SCs formed in the blends exhibit unexpectedly low NEs (e.g., 54.5%), much inferior to that (73.6%) in the counterpart without undergoing premixing. This is because the introduction of premixing leads to a remarkable deterioration in the amount of SCs particles formed, despite decreased particle size, highlighting that the direct mixing at low temperatures of 170–180 °C (about 20–30 °C lower than that used in common melt-processing of PLA) is more effective for the construction of SCs with superior NE. The mechanisms for these striking findings are discussed.     

Numerical simulation of microstructure formation ofAZ91 using mCA method

A stochastic model for simulating the microstructure formation of Mg alloy AZ91 during solidification was developed based on the finite element method（FEM） for macroscopic model of heat transfer calculation and a modified Cellular Automaton （mCA） for microscopic modeling of nucleation, growth of crystal. In this model, the effect of solute redistribution, interface curvature and preferred orientation was considered. A numerical simulation was developed with C＋＋ program language. The computation was carded out to understand the effect of varying processing parameters, such as nucleation parameters and heat transfer coefficient, on the microstructure formation of AZ91. The result of simulation was displayed on screen.     

CALCULATION OF TRANSFORMATION VOLUME FRACTION TO HQ590 HOT ROLLED STRIP STEEL DURING CONTINUOUS COOLING

On the basis of phase transformation kinetics, the transformation of γ→α,P,B have been investigated through considering the effect of deformation. The calculation methods of volume fraction have also been given. Comparing with common method, the simulated results are in more agreement with experiment results.