Catalyzed Crystallization of Glass-Forming Melts
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The crystallization separation theory and simulation optimization in solution crystallization are outlined.The crystallization processes such as direct cooling crystallization,reaction crystallization,distillation crystallization coupling,redox crystallization liquid membrane,extraction crystallization,magnetization crystallization and so on are summarized.Reasonable designing of crystallizer and crystallization technology is reliable guarantee for industrialization of crystallization processes.The falling film crystallizer,Bremband crystallization technology and the plate type crystallizer are evaluated.It is pointed out that the new crystallization separation unit and technology,technology industrialization,the mechanism of heat and mass transfer of crystallization process need to be further studied.
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Nucleation of barite (BaSO4) has broad implications in geological, environmental, and materials sciences. While impurity metals are common, our understanding of how they impact nucleation remains dim. Here, we used classical optical microscopy compared to fast X-ray nanotomography (XnT) to investigate heterogeneous nucleation of barite on silica in situ with Sr2+ as an impurity ion. The observed barite nucleation rates were consistent with classical nucleation theory (CNT), where barite crystals displayed a nonuniform size distribution, exhibiting distinct morphologies and incubation periods in Sr-free solutions. While undetectable with optical microscopy, nanotomography revealed that addition of Sr2+ enhances nucleation rates driven by the pre-factor in CNT, likely because both adsorbed Ba2+ and Sr2+ act as precursor sites on which nucleation occurs. Sr2+ simultaneously inhibits growth, however, leading to a homogeneous distribution of smaller crystals. This finding will enable an improved predictive understanding of nucleation in natural and synthetic environments.
Classical nucleation theory
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An experimental investigation to explore the interaction between bubbles forming at adjacent nucleation sites is presented. The results obtained are consistent with the results of Calka’s and Knowles’ experimental investigations and confirm that nucleation site activation/deactivation, whereby a bubble growing at a nucleation site is able to promote/hinder the formation of a bubble at an adjacent nucleation site by depositing/displacing a vapor nucleus in the nucleation cavity, is instrumental in determining how a bubble forming at a nucleation site influences the nucleation of the subsequent bubble at an adjacent nucleation site.
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The nucleation and growth kinetics for the synthesis of ZnO nanoparticles from ZnCl2 and NaOH in ethanol were determined as a function of the reactant concentrations and the concentration of added water. It was found that the presence of water is essential for the controlled nucleation of ZnO. The nucleation rate increases with increasing reactant concentrations, which is in agreement with classical nucleation theory.
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The induction times for electrodeposition of individual Ag nanoparticles on Pt nanodisk electrodes in acetonitrile were used to determine the critical nucleus size and activation energy barrier associated with the formation of Ag nuclei. Induction times for the nucleation and growth of a single Ag nanoparticle were determined following the application of a potential step to reduce Ag+ at overpotentials, η, ranging from −130 to −70 mV. Sufficiently small Pt electrodes (5.1 × 10–10–2.6 × 10–11 cm2) were used to ensure that the detection of a single Ag nucleation event occurred during the experimental observation time (150 ms–1000 s). Multiple measurements of Ag nucleation induction times were recorded to determine nucleation rates as a function of η using cumulative probability theory. Both classical nucleation theory (CNT) and the atomistic theory of electrochemical nucleation were employed to analyze experimental nucleation rates, without a requisite knowledge of the nucleus geometry or surface free energy. Using the CNT, the number of atoms comprising the critical size nucleus, Nc, was estimated to be 1–9 atoms for η ranging from −130 to −70 mV, in good agreement with 1–5 atoms obtained using atomistic theory. The experimental nucleation rates were also used to determine the activation energy barriers for nucleation from the CNT, which varied from 3.31 ± 0.05 to 13 ± 1 kT over the same range of η.
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We report a case in which two different crystallization mechanisms occurring in the same crystallization experiment are found to yield different polymorphic outcomes. In particular, we focus on crystallization of glycine from neutral aqueous solution. Crystallization in the bulk solution gives only the metastable alpha-polymorph, as observed in previous studies, whereas crystallization by evaporation of a thin film of the solution on the walls of the crystallization vessel is found to give rise to the thermodynamically stable gamma-polymorph, and furthermore produces an uncharacteristic crystal morphology for this polymorph. A detailed set of control experiments are described that elucidate mechanistic details relating to the latter crystallization process. The fact that crystallization on the walls of a crystallization vessel can yield a different polymorphic outcome from crystallization in the bulk solution in the same experiment has potentially much wider significance with regard to other polymorphic systems.
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