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At least 613 records · Page 34

Separations of U/Pu and Np/Pu using fluoride volatility

Here the importance of uranium/plutonium and neptunium/plutonium separations at large scale or at environmental levels is such that the reactivity of nitrogen trifluoride (NF 3 ) with respect to other fluorinating reagents warranted investigation. We show that NF 3 does not convert PuO 2 or PuF 4 to PuF 6 , during separations of U/Pu and Np/Pu, even under forcing conditions. Herein, this is analytically demonstrated to trace level. This rather exclusive behavior has been reported for only one other reagent: BrF 3 . Confidence in this result now allows for rapid and selective separations of volatile UF 6 and NpF 6 from plutonium. Preliminary data concerning the separation of 233 Pa from 237 Np is also described.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pulsed laser deposition of transparent fluoride glass

Here, the presence of reduced zirconium in fluorozirconate (FZ) glasses is highly unfavorable due to its detrimental effect on glass quality. Previous researchers have relied upon the use of a fluorine-containing processing gas to prevent the reduction of zirconium in FZ glasses deposited as thin films by pulsed laser deposition (PLD). However, the use of a fluorine-containing processing gas as an oxidizing agent is disadvantageous, due to its toxicity. Eliminating the need for the processing gas would lead to a significantly safer and simpler process. Our approach is to incorporate indium, which is multivalent, into the PLD ablation target in order to stabilize the zirconium and remove the need for a processing gas. A ZLANI glass, based on the composition 60.24ZrF 4 -4.13LaF 3 -3.54AlF 3 -31.49NaF-0.59InF 3 (values are in mol%), was synthesized for use as an ablation target. Using the ZLANI target, FZ glass films were successfully deposited on fused silica substrates by PLD, without the need for any processing gas. Multiple depositions were performed to observe the effects of deposition duration on growth rate and on film roughness. The deposited films are transparent with a brownish coloration. The source of this coloration is postulated to be color centers that are created during synthesis. Thermal annealing increases light transmission through the films up to 400%, depending upon wavelength, in the UV and visible spectrum (350–600 nm), after a series of heat treatments culminating at 300 °C. The fact that the transparency of the films can be correlated to annealing temperature suggests that the films may be of use as passive temperature sensors.

36 MATERIALS SCIENCE↗

Thermal properties and phase transition in the fluoride, (NH{sub 4}){sub 3}SnF{sub 7}

Calorimetric, dilatometric and differential thermal analysis studies were performed on (NH{sub 4}){sub 3}SnF{sub 7} for a wide range of temperatures and pressures. Large entropy (δS{sub 0}=22 J/mol K) and elastic deformation (δ(ΔV/V){sub 0}=0.89%) jumps have proven that the Pa-3↔Pm-3m phase transition is a strong first order structural transformation. A total entropy change of ΔS{sub 0}=32.5 J/mol K is characteristic for the order–disorder phase transition, and is equal to the sum of entropy changes in the related material, (NH{sub 4}){sub 3}TiF{sub 7}, undergoing transformation between the two cubic phases through the intermediate phases. Hydrostatic pressure decreases the stability of the high temperature Pm-3m phase in (NH{sub 4}){sub 3}SnF{sub 7}, contrary to (NH{sub 4}){sub 3}TiF{sub 7}, characterised by a negative baric coefficient. The effect of experimental conditions on the chemical stability of (NH{sub 4}){sub 3}SnF{sub 7} was observed. - Graphical abstract: Strong first order structural transformation Pa-3↔Pm-3m in (NH{sub 4}){sub 3}SnF{sub 7} is associated with very large total entropy change of ΔS{sub 0}=32.5 J/mol K characteristic for the ordering processes and equal to the sum of entropy changes in the related (NH{sub 4}){sub 3}TiF{sub 7} undergoing transformation between the same two cubic phases through the intermediate phases. - Highlights: • (NH{sub 4}){sub 3}SnF{sub 7} undergoes strong first order Pa-3↔Pm-3m phase transition. • Anomalous behaviour of ΔC{sub p} and ΔV/V exists far below phase transition temperature. • Structural distortions are accompanied by huge total entropy change ΔS≈Rln50. • High pressure strongly increases the stability of Pa-3 phase in (NH{sub 4}){sub 3}SnF{sub 7}. • Entropy of the Pa-3↔Pm-3m phase transition does not depend on pressure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of anodization parameters on the structural morphology of titanium in fluoride containing electrolytes

In the present work, formation of titania nanopores on titanium substrate was investigated in aqueous (sulphuric acid) and neutral organic (glycerol) electrolytes containing different concentrations of HF (0.1-0.2 M). The surface morphology, topography and phase structures were analyzed using scanning electron microscopy, atomic force microscopy and X-ray diffraction techniques, respectively. Under optimized electrolyte conditions, titania nanopore is obtained with the average pore diameter of 64 nm and 84 nm for aqueous and organic electrolytes, respectively. Atomic force microscope investigation shows that the porous layer forms under a competition of titania formation and oxide dissolution up to a limiting thickness of {approx} 75 nm and 100 nm respectively for aqueous and organic electrolytes. The porous structure was observed at 0.15 M HF concentration. It was found that depending on the electrolytes the pore diameter alters and also its concentration effected the porous structures formation. Compared to aqueous electrolytes, organic electrolytes showed larger diameter pores. From the X-ray diffraction measurement it is evident that the as prepared titania nanopores are amorphous in nature, whereas the anodized heat treated titania nanopores are in anatase phase. - Highlights: Black-Right-Pointing-Pointer Aqueous and organic electrolytes were used to synthesize nanoporous titania. Black-Right-Pointing-Pointer The surface morphology varies with various concentrations of HF. Black-Right-Pointing-Pointer Nanopores were formed at optimum HF concentration of 0.15 M. Black-Right-Pointing-Pointer Nanopore diameter was found to be affected by the electrolyte used.

36 MATERIALS SCIENCE↗

Microwave-assisted synthesis and characterization of hierarchically structured calcium fluoride

Graphical abstract: CaF{sub 2} with different morphologies and hierarchical structure such as dendrites, spherical and cube was prepared under microwave-assisted condition by a simple solvothermal synthesis route using CaCl{sub 2} and [BMIM]BF{sub 4} as initial reagents, respectively. It was found that the species of precursor was of vital importance for the formation of CaF{sub 2} crystals. That is, precursors itself also acted as structure directing agent. The outstanding features of the approach to obtain hierarchical structure CaF{sub 2} were its simplicity, effectiveness and ease of assembly. On the basis of the experimental results, a possible growth mechanism of the CaF{sub 2} crystals was proposed. Display Omitted Highlights: ► CaF{sub 2} with hierarchical structure was synthesized under microwave-assisted conditions. ► Characteristic morphologies with cube, dendrite, hierarchical sphere, etc. were observed. ► Thin cubes assembled into a spherical structure. ► Ionic liquid of [BMIM]BF{sub 4} was fluorine source. ► Possible growth mechanisms of CaF{sub 2} crystals were discussed. -- Abstract: CaF{sub 2} with different morphologies and hierarchical structures was prepared under microwave-assisted condition by a simple hydrothermal route using CaCl{sub 2} and ionic liquid [BMIM]BF{sub 4} as initial reagents, respectively. It was found that both the precursor and pH values played an important role in the formation of CaF{sub 2} crystals with different morphologies. The results suggested that the CaF{sub 2} with cube and spherical structures was obtained at different pH values (4, 8, 11), while the CaF{sub 2} with dendrite shape was formed through an oriented self-assembly growth using (NH{sub 4}){sub 2}HPO{sub 4} as a structure directing agent. Scanning electron microscope observation showed that the as-prepared CaF{sub 2} was of three-dimensional eight-horn-shaped dendritic structure. The influence of the pH values for the reaction solution and precursors has been discussed in detail. On the basis of the experimental results, possible growth mechanisms of the CaF{sub 2} microcrystals were proposed.

36 MATERIALS SCIENCE↗

Optical properties of differing nanolayered structures of divalent europium doped barium fluoride thin films synthesized by pulsed laser deposition

Optically-active thin films are employed in a variety of applications, such as LEDs and photovoltaics, due to their ability to act as up- or down-photon energy converters. Their performance depends critically on their composition and structure; thus, the use of novel synthesis techniques that allow for their control at the nanoscale level can result in improved efficiency and practicality. Here, layered thin films consisting of Eu 2+ - doped BaF 2 nanocrystalline layers separated by amorphous Al 2 O 3 were synthesized via sequential pulsed laser deposition using three separate targets for the different components; this synthesis technique provides precise control of layer thickness at the nanoscale along with dopant distribution within the film. Cross-sectional transmission electron microscopy analysis verified the desired nano-layering. Post-deposition heat treatments in a nitrogen atmosphere resulted in samples exhibiting steady emission with a broad peak ranging from 400 to 600 nm and a shoulder at 410 nm. The CIE 1931 chromaticity coordinates are x = 0.26-0.29 and y = 0.32-0.35 and vary as a function of the sample configuration. Because the chromaticity coordinates are close to those of a pure white light (x = 0.33, y = 0.33), these films demonstrate advantageous properties for applications with UV-pumped white light LEDs.

36 MATERIALS SCIENCE↗

Optical properties of Eu{sup 2+} doped antipervoskite fluoride single crystals

Single crystals of pure and Eu{sup 2+} doped LiBaF{sub 3} have been grown from melt by using a vertical Bridgman-Stockbarger method. Absorption and luminescence spectra for pure and rare-earth-doped LiBaF{sub 3} were studied. At ambient conditions the photoluminescence spectra consisted of sharp lines peaked at {approx}359 nm attributed to the {sup 6}P7/2{yields}{sup 8}S7/2 transitions in the 4f{sub 7} electronic configuration of Eu{sup 2+} and a broad band extending between 370 and 450 nm attributed to Eu{sup 2+} trapped exciton recombination. The effect of {sup 60}Co gamma irradiation has also been investigated.

36 MATERIALS SCIENCE↗

Optical characterization of femtosecond laser induced active channel waveguides in lithium fluoride crystals

We successfully realized broad-band light-emitting color center waveguides buried in LiF crystals by using femtosecond laser pulses. The characterization of the waveguides was performed by optical microscopy, photoluminescence spectra, loss measurements and near-field profiling. The experimental results show that the direct-writing fabrication process induces low-index contrast active channel waveguides: their wavelength-dependent refractive index changes, estimated from 10{sup −3} to 10{sup −4} depending on the writing conditions, allow supporting few modes at visible and near-infrared wavelengths.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Investigation of sensitizer ions tunable-distribution in fluoride nanoparticles for efficient accretive three-center energy transfer

Cooperative upconversion luminescence of Yb³⁺-Yb³⁺ couples and three-center energy transfer mechanisms have been deeply investigated in Yb³⁺ doped and Yb³⁺-Tb³⁺ co-doped β-PbF₂ nanoparticles. As sensitizer ions, the distribution of Yb³⁺ ions, which is a key factor that affects the cooperative upconversion luminescence and three-center energy transfer processes, can be tuned by the structure of nanoparticles. Based on the three-center distributions in tetragonal PbYb{sub x}Tb{sub 1–x}F₅ nanoparticles, two different energy transfer models, Cooperative Energy Transfer (CET) and Accretive Energy Transfer (AET) mechanisms were established. Especially, AET model is observed and verified in this work for the first time. Experimental results obtained from photoluminescence spectroscopy study are in agreement with the theoretical calculations by applying rate equations in these models, strongly supporting the proposed three-center energy transfer mechanisms. The sensitization between Yb³⁺ ions only existing in AET process can greatly improve the energy transfer rates, further to enhance the quantum efficiency. The results that the calculated luminescence quantum efficiency in AET quantum cutting process is much higher than that in CET process (134% and 104%, respectively), can benefit for further increasing the conversion efficiency of c-Si solar cells.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Lithium fluoride injection layers can form quasi-Ohmic contacts for both holes and electrons

Thin LiF interlayers are typically used in organic light-emitting diodes to enhance the electron injection. Here, we show that the effective work function of a contact with a LiF interlayer can be either raised or lowered depending on the history of the applied bias. Formation of quasi-Ohmic contacts for both electrons and holes is demonstrated by electroluminescence from symmetric LiF/polymer/LiF diodes in both bias polarities. The origin of the dynamic switching is charging of electrically induced Frenkel defects. The current density–electroluminescence–voltage characteristics can qualitatively be explained. The interpretation is corroborated by unipolar memristive switching and by bias dependent reflection measurements.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Preparation and characterization of nanocomposite polymer electrolytes poly(vinylidone fluoride)/nanoclay

Polymer electrolytes are defined as semi solid electrolytes used as separator in lithium ion battery. Separator used as medium for transfer ions and to prevent electrical short circuits in battery cells. To obtain the optimal battery performance, separator with high porosity and electrolyte uptake is required. This can reduce the resistance in the transfer of ions between cathode and anode. The main objective of this work is to investigate the impact of different solvent (Dimethyl acetamide (DMAc), N-methyl-2-pyrrolidone (NMP) and dimethyl formamide (DMF)), pore forming agent poly(vinylpyrolidone) (PVP) and nanoclay as filler in addition of membrane using phase inversion method on the morphology, porosity, electrolyte uptake and degree of crystallinity. The membrane was prepared by the phase inversion method by adding PVP and Nanoclay using different solvents. The phase inversion method was prepared by dissolving Nanoclay and PVP in solvent for 1-2 hours, and then add the PVDF with stirring for 4 hours at 60°C. The membranes were characterized by porosity test, electrolyte uptake test, scanning electron microscope (SEM), and X-ray diffraction (XRD). The results showed that DMAc as solvent gives the highest value of porosity and electrolyte uptake. The addition of nanoclay and PVP enlarge the size of the pores and reduce the degree of crystallinity. So, the usage of DMAc as solvent is better than NMP or DMF.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrothermally synthesized barium fluoride nanocubes for thermoluminescence dosimetry

In this work, we report a hydrothermally synthesized Dy doped BaF{sub 2} (BaF{sub 2}:Dy) nanocubes and its Thermoluminescence studies. The synthesized BaF{sub 2}:Dy samples was found to posses FCC structure and having average size ~ 60-70 nm, as revealed through X-Ray Diffraction. Cubical morphology having size ~90 nm was observed from TEM analysis. The {sup 60}Co γ- ray irradiated BaF{sub 2}:Dy TL dosimetric experiments shows a pre-dominant single glow peak at 153 °C, indicating a single level trap present as a metastable state. Furthermore, BaF{sub 2}:Dy nanophosphor shows a sharp linear response from 10 Gy to 3 kGy, thus it can be applicable as a gamma dosimeter.

77 NANOSCIENCE AND NANOTECHNOLOGY↗