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Unintended post-synthesis growth of noble metal colloids caused by excess amounts of reactants or highly reactive atom clusters represents a fundamental problem in colloidal chemistry, affecting product stability or purity. Hence, quantified kinetics could allow defining nanoparticle size determination in dependence of the time. Here, we investigate in situ the growth kinetics of ps pulsed laser-fragmented platinum nanoparticles in presence of naked atom clusters in water without any influence of reducing agents or surfactants. The nanoparticle growth is investigated for platinum covering a time scale of minutes to 50 days after nanoparticle generation, it is also supplemented by results obtained from gold and palladium. Since a minimum atom cluster concentration is exceeded, a significant growth is determined by time resolved UV/Vis spectroscopy, analytical disc centrifugation, zeta potential measurement and transmission electron microscopy. We suggest a decrease of atom cluster concentration over time, since nanoparticles grow at the expense of atom clusters. The growth mechanism during early phase (<1 day) of laser-synthesized colloid is kinetically modeled by rapid barrierless coalescence. The prolonged slow nanoparticle growth is kinetically modeled by a combination of coalescence and Lifshitz–Slyozov–Wagner kinetic for Ostwald ripening, validated experimentally by the temperature dependence of Pt nanoparticle size and growth quenching by Iodide anions. [ABSTRACT FROM AUTHOR]

Abstract: The shelf stability of nanoemulsions made by ultrasound, phase inversion composition, and the Ouzo effect was studied using a range of hydrocarbons, as the model oils, and surfactants. The cube of the average drop radius of the nanoemulsions displayed a linear increase with time. Both Ostwald ripening and coalescence can exhibit such behaviour. A new approach, based on the time evolution of drop size distribution, is proposed for unravelling the aging mechanism of nanoemulsions. Sequences of fall and rise in the average drop size of nanoemulsions were clearly observed. The decrease in the drop size could unambiguously be attributed to Ostwald ripening, but the increase could be due to either Ostwald ripening or coalescence/flocculation. Coalescence was identified as the dominant growth mechanism at low surfactant concentrations evidenced by drop size distribution broadening with time associated with the rise in the average drop size. Ostwald ripening was the dominant mechanism at higher surfactant concentrations where the drop size distributions broadened with time during the falls and narrowed with time during the rises of the average drop size. The nanoemulsions produced via the Ouzo process, displayed a coalescence-dependent transient stage and an Ostwald ripening dominated asymptotic regime in the absence of surfactant. The nanoemulsion produced via phase inversion was found to be the most stable one, however, still showed vulnerability to Ostwald ripening and flocculation in the long term. [Copyright &y& Elsevier]

Abstract: The influence of both the nature of the surfactant and surfactant concentration on the processes of droplet break-up and coalescence in the formation of decane-in-water nano-emulsions in a high-pressure homogenizer was investigated. Emulsions were produced using a Christison Scientific M110-S microfluidiser with an impinging jet high-shear chamber. For all six surfactants studied (Tween 20, Tween 80, Brij 96v, sucrose monolaurate, sucrose monomyristate and sucrose monopalmate), the droplet size decreased with increasing surfactant concentration reaching a limiting droplet size at a surfactant concentration of 15mM. The limiting droplet size for the different surfactants used were; Tween 20 (∼250±30nm), Tween 80 (∼320±40nm), Brij 96v (∼200±20nm) and the three sucrose monoesters had very similar sizes of ∼250±20nm. A hydrophobic fluorescent dye (1-undecylpyrene) was used to establish the extent of competition between droplet break-up and coalescence in the emulsification process. For all the emulsifiers studied, droplet coalescence in the process reduced as the amount of emulsifier increased, becoming zero at concentrations of about 15mM, i.e. the same concentration as that required to produce the limiting minimum droplet size. This shows that in the emulsification process droplet size is determined by both break-up and re-coalescence events, and at lower surfactant concentrations (<15mM) that the final droplet size is probably a consequence of multiple break-up events. Emulsion stability over 200h was investigated by measuring changes in the droplet size using dynamic light scattering. The increase in droplet volume was shown to be linear with respect to time, indicating an Ostwald ripening process. The observed ripening rate for the three sucrose monoesters (monopalmitate, monomyristate and monolaurate) was approximately 20nm3 s−1, which is the ripening rate calculated using the Lifshitz–Slesov–Wagner (LSW) theory. This ripening rate is the change in radius that results from movement of the oil through the continuous phase, taking into account the oil solubility in water and the diffusion coefficient of the decane-in-water. The ripening rate for Brij 96v was about three times larger than the calculated rate and there is an indication that the ripening rate increases slightly with increasing surfactant concentration, indicating that some enhancement due to the presence of micelles has occurred. With Tween 80 and 20 the ripening rates were 20 and 40 times, respectively, larger than those calculated using the solubility and diffusion coefficients. The increased rate has been shown to be first order with respect to the surfactant concentration indicating micelle mediated ripening. It is hypothesized that an optimum formulation for the sub-micron emulsion with these types of surfactant, will balance surfactant concentration to minimize droplet size during processing while aiming to minimize or prevent Ostwald ripening. [Copyright &y& Elsevier]

Abstract: The aging mechanisms of perfluorocarbon emulsions were investigated using image analysis. Oil-in-water emulsions of two perfluorocarbons, n-perfluorohexane and perfluorodecalin, were prepared with three emulsifiers, Lecithin, Span 20, and Pluronic F-68. The effect of the temperature and the replacement of water by an aqueous phase consisting of a microbial culture medium were also studied. The emulsions were prepared by sonication and their stability was followed through analysis of the evolution of mean droplet size. The results indicate that the stability of perfluorocarbon in water emulsions depends on all the parameters investigated and that two aging mechanisms, coalescence and molecular diffusion, may take place. Analysis of the evolution of the mean droplet size during long time periods indicate that coalescence is more common than previously reported for these systems and seems to be favored by a temperature increase. [Copyright &y& Elsevier]

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. [Copyright &y& Elsevier]