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Mechanism of YF3 Nanoparticle Formation in Reverse Micelles

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journal contribution
posted on 04.10.2011, 00:00 by Jean-Luc Lemyre, Sébastien Lamarre, Ariane Beaupré, Anna M. Ritcey
This article reports an investigation of the mechanism of YF3 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 Y3+ dispersed in nonionic reverse micelles. The two methods yield amorphous and single-crystal nanoparticles, respectively. The kinetics of reagent mixing are studied by 19F 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 Y3+ 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 Y3+-containing micelles with microdroplets of aqueous F. These conditions lead to the formation of crystalline particles and a wider size distribution of unstable nuclei.