Study on the Agglomeration Kinetics of Uranium Peroxide

Considering the previous study dealing with thermodynamic and kinetic phenomena (nucleation and crystal growth) during the uranium peroxide precipitation, this work focuses on the agglomeration mechanism. It provides the results obtained from the experiments carried out in a MSMPR reactor operating at steady state. The influence of the operating parameters on the uranium peroxide agglomerates was studied in order to identify the agglomeration kernel. The method is based on the resolution of the population balance equation using the method of moments and the experimental particle size distributions. The results lead to a size-independent kernel directly proportional to the crystal growth rate. Under the stirring conditions studied, the agglomeration appears to be significantly reduced by mixing which results in a kernel inversely proportional to the average shear rate. The agglomeration kinetic law obtained in this study will be used for the process modelling in a further study.     

On the evolution of particle size average and size distribution in suspension polymerization processes

The dispersion of methyl methacrylate (MMA) and its suspension polymerization were used as models to elaborate the evolution of particle size average and size distribution in the course of suspension polymerization. The underlying mechanisms for the occurrence of the dynamic and static steady states in the population of drops were defined and their effects on the evolution of drop/particle size average and size distributions were examined. The characteristic intervals of suspension polymerizations (transition, steady-state, growth, and identification) were elaborated. The formation of satellite droplets and their evolution in the course of polymerization were also discussed.     

Thermodynamics and kinetics of evaporative crystallization of sodium gluconate

Thermodynamic properties of sodium gluconate (SG) aqueous solution have been measured over the 303.15–343.15 K temperature range including solubility, density, and viscosity. For proper crystallization of SG, the kinetics of evaporative crystallization with spontaneous nucleation was subsequently investigated in a semi-batch mode. The crystals present a size-dependent growth rate, and the number particle size distribution (PSD) data were well fitted with the MJ2 model. The effects of supersaturation, suspension density, and agitation intensity were carefully analyzed to contribute to a better understanding for the control of crystal size of SG.     

Nucleation of NaCl nanoparticles in supercritical water: molecular dynamics simulations

Formation of NaCl nanoparticles in supercritical water is studied using molecular dynamics simulation method. We have simulated particle nucleation and growth in NaCl-H2O fluids, with salt concentration of 5.1 wt %, in the temperature and density range of 673-1073 K and 0.17-0.34 g/cm(3), respectively. The cluster size distributions, the size of critical nuclei and cluster lifetimes are reported. The size distribution of emerging clusters shows a very strong dependence on the system's density, with larger clusters forming at lower densities. Clusters consisting of approximately 14-24 ions appear critical for the thermodynamic states examined. The local structures of critical clusters are found to be amorphous. The lifetime values for clusters containing more than 20 ions are in the range of 10-50 ps. We have calculated the NaCl nucleation rates, which appear to be on the order of 10(28) cm(-3) s(-1).     

A kinetic modeling of particle formation by gas antisolvent process: Precipitation of aspirin

Population balance equations (PBEs) are often integro-partial differential in nature due to complexities involved in nonconventional crystallization processes, especially gas antisolvent (GAS). The reason is that they include phenomena such as primary nucleation, secondary nucleation, crystal growth, agglomeration, and/or breakage of crystals. Therefore, the solution to such models has become rather difficult. Considering these difficulties, a powerful numerical algorithm was adopted in this paper to treat the population balance model for the precipitation of aspirin by the GAS process. This method was the combination of Lax–Wendroff and Crank–Nicholson numerical methods. It was used to investigate the effect of significant operating parameters, that is, antisolvent addition rate, process temperature, and solute concentration, on the final product properties for two solvents. The antisolvent addition rate was varied between 8 and 40 bar/min, the process temperature was kept constant at levels 37°C and 42°C, the solute concentration was manipulated at two levels, namely, 0.2 and 0.27 g solute/g solution, and methanol and acetone were used as the organic solvents. The results indicated the successful performance of the applied method in treating PBE, since smooth particle size distributions were produced, which were in an acceptable agreement with the experimental data of the investigated system.     

Rheology and crystallization behavior of asymmetric PLLA/PDLA blends based on linear PLLA and PDLA with different structures

In this study, several asymmetric poly(L‐lactide)/poly(D‐lactide) (PLLA/PDLA) blends were prepared by adding small amounts of PDLA with different structures into linear PLLA matrix. The effect of PDLA on rheological behavior, crystallization behavior, nucleation efficiency and spherulite growth of PLLA was investigated. Rheological results indicated that PLLA/PDLA blends showed solid‐like viscoelastic behavior at low temperature (<200°C), and the cross‐linking density of PLLA/PDLA melt at 180°C followed the order: PLLA/6PDLA > PLLA/L‐PDLA > PLLA/3PDLA > PLLA/4PDLA. No‐isotherm and isotherm crystallization results indicated that the crystallization capacity of PLLA/PDLA blends was strongly related to the PDLA structure, crystallization temperature and thermal treatment temperature. Furthermore, the dimension of crystal growth during isotherm crystallization presented the obvious dependent on the PDLA structure. The nucleation efficiency of sc‐crystallites in the blends and spherulite density during isothermal crystallization were also studied. Nucleation efficiency of sc‐crystallites in the PLLA/S‐PDLA blends showed the obvious dependent on thermal treatment temperature with respect to PLLA/L‐PDLA, and nucleation efficiency sc‐crystallites in the PLLA/S‐PDLA blends first decreased and then increased as the thermal treatment temperature increased. Spherulite density of PLLA/PDLA blends was also related to thermal treatment temperature and the PDLA structure. This study has discussed the temperature dependence of the stereocomplex networks between PLLA and PDLA with different structure, and then its consequential influence on rheology and crystallization capacity of PLLA, which would provide the theoretical direction for PLA processing. Copyright © 2016 John Wiley & Sons, Ltd.     

Drug nanoparticles by antisolvent precipitation: mixing energy versus surfactant stabilization

Organic itraconazole (ITZ) solutions were mixed with aqueous solutions to precipitate sub-300 nm particles over a wide range of energy dissipation rates, even for drug loadings as high as 86% (ITZ weight/total weight). The small particle sizes were produced with the stabilizer poloxamer 407, which lowered the interfacial tension, increasing the nucleation rate while inhibiting growth by coagulation and condensation. The highest nucleation rates and slowest growth rates were found at temperatures below 20 degrees C and increased with surfactant concentration and Reynolds number (Re). This increase in the time scale for growth reduced the Damkohler number (Da) (mixing time/precipitation time) to low values even for modest mixing energies. As the stabilizer concentration increased, the average particle size decreased and reached a threshold where Da may be considered to be unity. Da was maintained at a low value by compensating for a change in one variable away from optimum conditions (for small particles) by manipulating another variable. This tradeoff in compensation variables was demonstrated for organic flow rate vs Re, Re vs stabilizer concentration, stabilizer feed location (organic phase vs aqueous phase) vs stabilizer concentration, and stabilizer feed location vs Re. A decrease in the nucleation rate with particle density in the aqueous suspension indicated that secondary nucleation was minimal. A fundamental understanding of particle size control in antisolvent precipitation is beneficial for designing mixing systems and surfactant stabilizers for forming nanoparticles of poorly water soluble drugs with the potential for high dissolution rates.     

Homogeneous nucleation of metals in a plasma-quench reactor

We present a new and general application of the method of moments for modeling the nucleation of condensates in a steady-state supersonic nozzle flora generated in a plasma-quench reactor. A closed set of growth/evaporation rate equations has been employed to propagate the moments of the particle size distribution without invoking the usual coarse-graining or truncation approximations of conventional binning approaches. The method has been employed to calculate the nucleation rates, particle number density, and the particle-size distribution for 11 elemental metals (Ag, Al, Be, Ce, Cr, Fe, Gd, Ti, Th, U, and Zr) condensing in a model argon nozzle flow. We have identified the regions in the nozzle of maximum nucleation rate, and have shown how different particle-size distributions can develop in different regions.     

The mechanisms of latex particle formation and growth in the emulsion polymerization of styrene using the surfactant sodium dodecyl sulfate

A new method is presented that provides experimental information which is qualitatively and quantitatively sensitive to assumptions made as to the mechanisms of free radical entry and of latex particle formation in emulsion polymerization systems. The method consists of (1) obtaining (by electron microscopy) the full particle-size distributions (PSDs) at several different times soon after the cessation of latex particle nucleation, (2) using these PSDs to determine the volume dependences of the various rate coefficients governing particle growth by fitting the data to the appropriate evolution equations, and (3) employing these empirical rate coefficients to find that time dependence of the nucleation rate which fits the early-time PSD (again using the evolution equations). This method is quite sensitive to mechanistic assumptions: for example, one is able to determine whether or not the nucleation rate is an increasing or decreasing function of time. The technique is applied to a styrene nucleation system employing sodium dodecyl sulfate as surfactant at well above the critical micelle conventration. The data cannot be fitted even qualitatively by a simple one-step nucleation mechanis, whether it involes micellar entry or homogeneous nucleation. It is found, on the other hand, that the results can be accurately fitted by assuming that coagulation events between primary colloidal particles, perhaps formed by homogeneous nucleation, dominate both the nucleation process and the entry of free radicals into mature latex particles. In addition, the data indicate that the rate of free radical entry into the latex particles decreases with increasing particle size, at least for particles of unswollen radius less than ca. 40 nm.     

Preparation of PLLA/PLGA microparticles using solution enhanced dispersion by supercritical fluids (SEDS).

In this work, poly(L-lactic acid)/poly(lactide-co-glycolide) (PLLA/PLGA) microparticles were prepared using the technique of solution-enhanced dispersion by supercritical fluids (SEDS). For comparison, separate PLLA and PLGA microparticles were also produced by the same SEDS process. The produced microparticles were characterized by scanning electron microscopy, laser particle size analyzer, X-ray diffraction, differential scanning calorimetry, Fourier transform infrared spectroscopy, and gas chromatography. Results indicate that PLLA/PLGA microparticles possess sphere-like shapes with smooth surfaces. The mean particle size of PLLA/PLGA microparticles ranges from 1.76 to 2.15 microm, depending on the feeding ratio of PLLA to PLGA used in the SEDS process. The crystallinity of PLLA/PLGA microparticles decreases after the SEDS processing, so that the produced microparticles are in an amorphous state. Pure PLGA was hard to precipitate in small, fine microparticle form without the presence of PLLA. A model drug, paclitaxel, was encapsulated into PLLA/PLGA microparticles by the same SEDS process, and the in vitro release rate of paclitaxel from these PLLA/PLGA composites could be modulated by variation of the mixing ratio PLLA:PLGA. The prepared microparticles have negligible residual organic solvent. Drug-loaded PLLA/PLGA microparticles produced by SEDS have potential as an advanced colloidal suspension for pharmaceutical applications.     

Crystallization in charged two-component suspensions

We report on the crystallization of colloidal crystals comprising of charged particles with different size ratio dispersed in thoroughly deionized water. Single components were characterized carefully and their nucleation behavior was investigated before the preparation of mixtures. Mixtures investigated at constant particle number densities showed body centred cubic structure, conductivity, and shear moduli comply with the assumption of a randomly substituted crystal. Most importantly, for the first time we obtain the dependence of the nucleation rate densities in dependence on the composition and (for one fixed composition) the particle number density. The process of nucleation in random substitutional crystals is found to be similar to the one-component case.     

Growth dynamics of CdTe nanoparticles in liquid and crystalline phases

Normally the size dependence of the chemical potential is used to explain the growth dynamics of semiconductor nanoparticles. Instead we show that very small CdTe nanoparticles continue to grow at high dilution, the growth rate is virtually independent of monomer concentration, nucleation continues after the growth of larger particles has saturated, and the growth rate has a much greater nonlinear dependence on particle size than predicted by theory. We suggest that nanoparticle growth is fast in the liquid phase and then saturates as the particles change phase from liquid to crystal at a threshold size which depends on the growth temperature and not the monomer concentration. The photoluminescence quantum efficiency becomes high when tellurium is depleted in the reaction solution giving a cadmium enriched surface.     

Photo-oxidation of Isoprene with Organic Seed: Estimates of Aerosol Size Distributions Evolution and Formation Rates

ondary organic aerosol (SOA) formation from OH-initiated photo-oxidation of isoprene in the presence of organic seed aerosol. The dependence of the size distributions of SOA on both the level of pre-existing particles generated in situ from the photo-oxidation of trace hydrocarbons of indoor atmosphere and the concentration of precursor, has been investi-gated. It was shown that in the presence of high-level seed aerosol and low-level isoprene (typical urban atmospheric conditions), particle growth due to condensation of secondary organic products on pre-existing particles dominated; while in the presence of low-level seed aerosol and comparatively high-level isoprene (typical atmospheric conditions in rural re-gion), bimodal structures appeared in the size distributions of SOA, which corresponded to new particle formation resulting from homogeneous nucleation and particle growth due to condensation of secondary organic products on the per-existing particles respectively. The effects of concentrations of organic seed particles on SOA were also investigated. The particle size distributions evolutions as well as the corresponding formation rates of new particles indifferent conditions were also estimated.     

Mechanism of YF3 nanoparticle formation in reverse micelles

This article reports an investigation of the mechanism of YF(3) nanoparticle formation in two variants of the reverse microemulsion precipitation method. These two variants involve the addition of F(-), either as a microemulsion or directly as an aqueous solution, to Y(3+) dispersed in nonionic reverse micelles. The two methods yield amorphous and single-crystal nanoparticles, respectively. The kinetics of reagent mixing are studied by (19)F NMR and colorimetric model reactions, and the particle growth is monitored by TEM. Mixing and nucleation are shown to occur within seconds to minutes whereas particle growth continues for 4 to 48 h, depending on the particle type. Moreover, the growth rate remains constant during most of the growth period, indicating that Ostwald ripening is the most probable growth mechanism. The single-emulsion method also produces a minority amorphous population that exhibits significantly different growth kinetics, attributed to a coagulation mechanism. Secondary growth experiments, involving the addition of precursor ions to mature particles, have been conducted to evaluate the relative importance of nucleation and the competitive growth of existing particle populations. The key differences between the two methods reside in the nucleation step. In the case of the classical method, nucleation occurs upon intermicellar collisions and under conditions of comparable concentrations of Y(3+) and F(-). This method generates more numerous stable nuclei and smaller particles. In the single-microemulsion method, nucleation occurs in the presence of excess F(-) through the interaction of Y(3+)-containing micelles with microdroplets of aqueous F(-). These conditions lead to the formation of crystalline particles and a wider size distribution of unstable nuclei.     

Distribution kinetics of Ostwald ripening at large volume fraction and with coalescence

Condensation phase transitions from metastable fluids occur by nucleation with accompanying particle growth and eventual Ostwald ripening. During ripening the subcritical particles dissolve spontaneously while larger particles grow and possibly coalesce if their volume fraction is large enough. The classical diffusion-influenced rates are also affected by large particle concentrations and are here described by mass-dependent rates. We represent the kinetics of ripening through growth, dissolution, and biparticle coalescence by a new population dynamics equation for the particle size distribution (PSD). Numerical solutions of the scaled governing equations show that coalescence plays a major role in influencing the PSD when the scaled mass concentration (volume fraction) or number concentration is relatively large. The solution describes the time range from initial conditions to the final narrowing of polydispersity. We show that the time dependence of the average particle mass in the asymptotic period of ripening has a power-law increase dependent on rate expressions for particle growth and coalescence at large values of volume fraction.     

Microscopic investigations of homogeneous nucleation in charged sphere suspensions

We studied the homogeneous nucleation kinetics of an aqueous suspension of charged colloidal spheres under de-ionized conditions. Samples of equilibrium crystalline structure were shear molten and the metastable melt left to solidify after cessation of shear. At low particle number densities n, corresponding to low metastability of the melt, nucleation was monitored directly via video microscopy. We determined the nucleation rates gamma(t) by counting the number of newly appearing crystals in the observation volume per unit time. Using a suitable discrete adaptation of Avrami's [J. Chem. Phys. 7, 1003 (1939); ibid.8, 212 (1940); ibid.9, 177 (1941)] model for solidification via homogeneous nucleation and subsequent growth, we calculate the remaining free volume VF(t) to obtain the rate densities J(t) = gamma(t)/VF(t). We observe J(t) to rise steeply, display a plateau at a maximum rate density Jmax, and to decrease again. With increased n the plateau duration shrinks while Jmax increases. At low to moderate number densities fully solidified samples were analyzed by microscopy to obtain the grain-size distribution and the average crystallite size angle brackets(L). Under the assumption of stationarity, we obtained the nucleation rate density J(Avr), which increased strongly with increasing n. Interestingly, J(Avr) agrees quantitatively to Jmax and to J(Avr) as obtained previously from scattering data taken on the same sample at large n. Thus, by combination of different methods, reliable nucleation rate densities are now available over roughly one order of magnitude in n and eight orders of magnitude in J.     

Modeling nucleation and coagulation modes in the formation of particulate matter inside a turbulent exhaust plume of a diesel engine

This paper presents the results from a study that is aimed at predicting the nucleation, coagulation, and dynamics of particulate matter (PM) emissions from on-road heavy-duty diesel vehicles. The PM concentration is predicted from the composition of fuel, and operating and ambient conditions. A numerical algorithm for simultaneously solving the coagulation, condensation, and nucleation equations is developed. The effect of relative humidity on the nucleation rate and the nucleus size is also discussed. In addition, the effect of the ambient air dilution on PM size distribution is numerically predicted for a diesel-powered truck operating in a controlled environment at NASA Langley wind-tunnel facility. The particle size distribution and concentration are measured at four different locations in a turbulent plume from the diesel exhaust in the tunnel, and an excellent agreement between the measured and predicted PM concentration values at these locations inside the tunnel is observed.     

Mechanism of nanoparticle formation in self-assembled colloidal templates: population balance model and Monte Carlo simulation

Modeling the nanoparticle formation mechanism in water-in-oil microemulsion, a self-assembled colloidal template, has been addressed in this paper by two formalisms: the deterministic population balance equation (PBE) model and stochastic Monte Carlo (MC) simulation. These are based on time-scale analysis of elementary events consisting of reactant mass transport, solid solubilization, reaction, coalescence-exchange of drops, and finally nucleation and growth of nanoparticles. For the first time in such a PBE model, realistic binomial redistribution of molecules in the daughter drops (after coalescence-exchange of two drops) has been explicitly implemented. This has resulted in a very general model, applicable to processes with arbitrary relative rates of coalescence-exchange and nucleation. Both the deterministic and stochastic routes could account for the inherent randomness in the elementary events and successfully explained temporal evolution of mean and variance of nanoparticle size distribution. This has been illustrated by comparison with different yet broadly similar experiments, operating either under coalescence (lime carbonation to make CaCO(3) nanoparticles) or nucleation (hydride hydrolysis to make Ca(OH)(2) nanoparticles) dominant regimes. Our calculations are robust in being able to predict for very diverse process operation times: up to 26 min and 5 h for carbonation and hydrolysis experiments, respectively. Model predictions show that an increase in the external reactant addition rate to microemulsion solution is beneficial under certain general conditions, increasing the nanoparticle production rate significantly without any undesirable and perceptible change in particle size.     

Nanoparticle formation using a plasma expansion process

We describe a process in which nanosize particles with u narrow size distribution are generated by expanding a thermal plasma carrying vapor-phase precursors through a nozzle. The plasma temperature and velocity profiles are characterized by enthalpy probe measurements. by calorimetric energy balances. and by a model of the nozzle flow. Aerosol samples are extracted from the flow downstream of the nozzle by means of a capillary probe interfaced to a two-stage ejection diluter. The diluted aerosol is directed to a scanning electrical mobility spectrometer (SEMS) which provides on-line size distributions down to particle diameters of 4 nmt. We have generated silicon, carbon, and silicon carbide particles with number mean diameters of about 10 not or less, and we have obtained some correlations between the product and the operating conditions. Inspection of the size distributions obtained in the experiments, together with the modeling results, suggests that under our conditions silicon carbide formation is initiated by nucleation of extremely small silicon particles from supersaturated silicon vapor, followed by chemical reactions at the particle surfaces involving carbon-containing species from the gas phase.     

Temperature effects for isothermal polymer crystallization kinetics

We adopt the cluster size distribution model to investigate the effect of temperature on homogeneous nucleation and crystal growth for isothermal polymer crystallization. The model includes the temperature effects of interfacial energy, nucleation rate, growth and dissociation rate coefficients, and equilibrium solubility. The time dependencies of polymer concentration, number and size of crystals, and crystallinity (in Avrami plots) are presented for different temperatures. The denucleation (Ostwald ripening effect) is also investigated by comparing moment and numerical solutions of the population balance equations. Agreement between the model results and temperature-sensitive experimental measurements for different polymer systems required strong temperature dependence for the crystal-melt interfacial energy.