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At least 487 records · Page 27

Polymorphic Metastability in Colloidal Semiconductor Nanocrystals

Metastable polymorphs of inorganic solids often possess material properties not present in the corresponding thermodynamic polymorphs, making them targets for the development of new functional materials. In contrast with isolating metastable bulk materials, syntheses of metastable polymorphs on the nanoscale are aided by fast non-equilibrium reaction kinetics and the favorable thermodynamic influence of surface energies, giving rise to greater ease of access to metastable high-temperature polymorphs and, in some cases, new polymorphs that do not exist in the bulk. The syntheses of metastable semiconductor nanocrystals are of interest for their potentially unique optoelectronic and physicochemical properties. However, in many material systems, synthesizing nanocrystalline products away from thermodynamic equilibrium in a predictable manner remains an outstanding challenge. This review outlines direct synthetic methodologies that have been developed to enable control over the nucleation and growth of metastable polymorphs of semiconductor nanocrystals by tailoring reaction conditions, precursor kinetics, ligand and surface effects, and other synthetic levers. The case studies reviewed herein expound on the direct syntheses of metastable ZnSe, Cu 2 SnSe 3 , CuInSe 2 , Ag 2 Se, and AgInSe 2 nanocrystals, and although there remain numerous examples of metastable nanocrystal syntheses outside of these metal chalcogenide systems, the concepts discussed are of general utility to the field of metastable nanocrystal syntheses as a whole. Explicit examples in which new functional properties are afforded by metastable polymorphs of the aforementioned material systems are presented within the context of applications for solar cells, photonics, and optical sensing. Finally, the factors that affect the kinetic persistence of metastable nanocrystalline polymorphs are discussed at length for these material systems.

36 MATERIALS SCIENCE↗

High-gradient magnetic filtration of UO 2 colloids from aqueous suspensions

Environmental samples often contain innocuous components that make trace actinide analysis difficult and expensive. Therefore, it is expedient to separate these materials from actinide particles. One characteristic of many actinides is that they are paramagnetic. High-gradient magnetic filtration (HGMF) is a non-destructive technique that selectively captures magnetic constituents from a matrix containing non-magnetic species. Here, in this work, a novel HGMF device made of a permanent magnet array was used to effectively separate UO 2 particles from undesirable soil species. Up to 88% of the UO 2 particles present in suspensions were effectively captured by HGMF, resulting in their enrichment and a substantial reduction in the concentrations of other constituents.

Actinide separations↗

Effect of particle size on the capture of uranium oxide colloidal particles from aqueous suspensions via high-gradient magnetic filtration

The effectiveness of High Gradient Magnetic Filtration (HGMF) in capturing uranium oxide particles from suspensions was investigated in this study. Two sets of experiments were performed to evaluate the importance of size on the capture of uranium oxide particles. The first considered two batches sieved into size bins of< 5, 5–10, 10–15, and 15–20 µm, while the second was performed using two suspensions with diameters smaller than 1.0 µm and between 1.0 and 1.5 µm. Iron oxide experiments, with particles between 0.3 and 0.8 µm, were performed for calibration purposes. In all experiments, a surfactant (Triton-X100 or sodium dodecyl sulfate) was used to prevent particle aggregation and limit the influence of non-magnetic capture mechanisms. A magnetic field of approximately 1.1 Tesla was generated using a water cooled electromagnet. HGMF was performed using tubular filters packed with ferromagnetic stainless-steel wool. Of the initial four uranium oxide particle sizes, magnetic capture was only observed for particles with a diameter of less than 5 µm, while larger particles experienced no magnetic and minimal total capture. For particles with diameters smaller than 1.0 µm and between 1.0 and 1.5 µm, capture efficiencies increased by 39 ± 9% and 34 ± 6% respectively, solely due to the magnetic field. Although the magnetic force is proportional to particle diameter, the capture efficiency decreased as diameter increased. So these results suggest that Brownian diffusion, which is influential for micron sized particles and increases with decreasing particle size, is acting in conjunction with the magnetic force to influence the efficacy of HGMF for uranium oxide. This important finding underscores the effectiveness of Brownian diffusion in increasing the rate of collision between particles and collector fibers. A stochastic trajectory model was developed to incorporate the influence of Brownian motion on particle behavior and filter removal efficiency. Modeling results are discussed and compared for uranium and iron oxide particles.

42 ENGINEERING↗

In-situ imaging of nucleation and growth of superlattices from nanoscale colloidal nanoparticles

Nanoparticle-based superlattices have attracted extensive research efforts due to their versatile composition and packing-dependent optical, magnetic, electronic, catalytic, mechanical properties. Yet the experimental understanding of the thermodynamics and pathways of the crystallization processes for these systems, which govern their ultimate morphology, size, and packing structure, has for long remained underexplored. Here, this minireview highlights recent integration of liquid-phase transmission electron microscopy, which allows for real-space, real-time direct imaging of the crystallization processes at the single-particle level, with simulation and the conceptual framework established by pioneers such as Dr. A. A. Chernov. Different aspects of superlattice formation were revealed by direct imaging for the first time, such as the existence of prenucleation precursor in nonclassical crystallization, surface energy-dependent growth, and coalescence, allowing for the charting of phase coordinates and thermodynamic quantities at the nanoscale. We discuss the similarities and differences of crystal growth behaviors in atomic and nanoparticle systems, as well as engineering opportunities to fashion, shape, and achieve quality control in superlattice formation from nanoparticles, for next-generation optical and mechanical metamaterials.

36 MATERIALS SCIENCE↗

Selective capture and recovery of uranium oxide colloids from aqueous soil suspensions using high gradient magnetic filtration

High Gradient Magnetic Filtration (HGMF) is a promising method for the selective capture and recovery of uranium oxide from surface soils. To date, however, magnetic filtration of uranium oxide has only been demonstrated at a proof-of-principle scale using relatively small filters (<5 cm 3 ) at low flowrates (<60 mL/min). Here, to explore the efficacy of magnetic filtration of uranium oxide at a larger scale, a newly designed HGMF apparatus that is more than an order of magnitude larger than our earlier filters (106 cm 3 ) was designed, fabricated, and tested at relatively high flowrates. Filtration experiments were performed using aqueous uranium oxide particle suspensions with Arizona Road Dust (ARD) as a soil simulant. At a flowrate of 125 mL/min, the apparatus’ uranium capture rate was exceptionally high (96 %), but selectivity was poor due to the high rate of capture for diamagnetic soil constituents (e.g., 77 % for silicon). All particles were captured at a lower rate when the flowrate was increased to 250 mL/min, but uranium selectivity was significantly increased due to the more substantial reduction in diamagnetic particle capture (i.e., capture rate of 77 % and 15 % for uranium and silicon, respectively). When backwashing the apparatus at the same flowrates used during filtration experiments, the rate of uranium recovery tended to be fairly low. Nevertheless, higher flowrates (1 L/min) and sonication were both shown to be highly effective methods of increasing uranium recovery. Magnetic field simulations were also performed to investigate potential optimizations to the design of the apparatus. These simulations showed that the intensity of the applied magnetic field could be increased by increasing the thickness of the steel magnetic housing. Additionally, stochastic trajectory simulations were performed to investigate the potential mechanisms of particle capture.

HGMF↗