Optimization of preparative chromatographic separation of multiple rare earth elements

This work presents a method to optimize multi-product chromatographic systems with multiple objective functions. The system studied is a neodymium, samarium, europium, gadolinium mixture separated in an ion exchange chromatography step. A homogeneous Langmuir Mobile Phase Modified model is calibrated to fit the experiments, and then used to perform the optimization task. For the optimization a multi-objective Differential Evolution algorithm was used, with weighting based on relative value of the components to find optimal operation points along the Pareto front. The objectives of the Pareto front are weighted productivity and weighted yield with purity as an equality constraint. A prioritizing scheme based on relative values is applied for determining the pooling order. A simple rule of thumb for pooling strategy selection is presented. The multi-objective optimization gives a Pareto front which shows the rule of thumb, as a gap in one of the objective functions.     

Temperature-dependence of the structural and afterglow luminance properties of polymer/SrAlxOy:Eu,Dy composites

Although aluminate phosphors have attracted great interest for applications in lamps, cathode ray tubes and plasma display panels, there still remain issues affecting operational parameters such as luminescence efficiency, stability against temperature, high color purity and perfect decay time. In addition, issues involving important aspects of the monoclinic↔hexagonal phase transition temperature still exist. In this work, SrAl_xO_y:Eu²⁺,Dy³⁺ phosphor powders were prepared by the sol–gel method. X-ray diffraction (XRD) has shown that both crystallinity and crystallite sizes increased as the temperature increased. Both SrAl₂O₄ and Sr₂Al₃O₆ phases were observed. Photoluminescence (PL) characterization shows temperature-dependence, which indicates emission at low and high annealing temperatures originating from Eu²⁺ and Eu³⁺ ions. Thermoluminescence glow and decay measurements provided useful insight on the influence of traps on luminescence behavior. Differential scanning calorimetry (DSC) and thermogravimetric studies (TGA) on composites of the phosphor in low density polyethylene (LDPE) demonstrated the varied influence of annealing temperature on some luminescence and thermal properties.     

The effect of oxygen pressure on the structure, morphology and photoluminescence intensity of pulsed laser deposited Gd2O2S:Tb3+ thin film phosphor

Luminescent Gd₂O₂S:Tb³⁺ phosphor thin films were grown on Si (100) substrates, using the pulsed laser deposition technique. The films were grown in 100 to 300 mTorr oxygen gas (O₂) atmospheres when the substrate temperature was kept constant at 400 or 600°C. The effect of the O₂ ambient on the structure and morphological properties of the films were analyzed using x-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM), respectively. Spherical nanoparticles deposited on the Si (100) substrates were shown to crystallize in the hexagonal structure of Gd₂O₂S. The photoluminescence (PL) spectra of all the films were characterized by a stable green emission peak with a maximum at 545 nm. Improved PL intensity was observed from the films deposited at higher oxygen pressures and higher substrate temperatures. Particles sizes of the nanoparticles deposited under the different conditions varied between 19 and 36 nm for the different samples. Smaller and more densely packet particles were produces at the higher O₂ pressures and the higher temperature.     

Synthesis and characterization of structural and luminescence properties of blue — green BaAlxOy:Eu2+ phosphor by solution — combustion method

Europium-doped barium aluminate (BaAl _x O _y :Eu²⁺) phosphors were obtained at low temperatures (500°C) using the solution — combustion of corresponding metal nitrate-urea solution mixtures. The particle size and morphology and the structural and luminescent properties of the synthesized phosphors were examined by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), Electron diffraction spectroscopy (EDS) and photoluminescence (PL). It was found that the change in Ba: Al molar ratios showed greatly influence not only on the particle size and morphology, but also on their PL spectra and crystalline structure. The structure of BaAl _x O _y nanophosphors changes from a hexagonal Ba₂Al₁₀O₁₇ phase for samples with 6:100 molar ratios to a hexagonal BaAl₂O₄ one with an increase in Ba content. The peak of the emission band occurs at a longer wavelength (around 615 nm) with a decrease in Ba concentration but displays a broad blue-green emission band composed from two emissions with the maximum at 495 and 530nm coming from Eu²⁺ in two sites for increasing Ba content. The blue-green emission is probably due to the influence of 5d electron states of Eu²⁺ in the crystal field because of atomic size variation causing crystal defects while the red emission is due to f - f transitions. These findings clearly demonstrate the possibility of fine tuning the colour emission.     

Optical properties of ZnO nanoparticles synthesized by varying the sodium hydroxide to zinc acetate molar ratios using a Sol-Gel process

Material property dependence on the OH⁻/Zn²⁺ molar ratio of the precursor was investigated by varying the amount of NaOH during synthesis of ZnO. It was necessary to control the water content and temperature of the mixture to ensure the reproducibility. It was observed that the structural properties, particle size, photoluminescence intensity and wavelength of maximum intensity were influenced by the molar ratio of the precursor. The XRD spectra for ZnO nanoparticles show the entire peaks corresponding to the various planes of wurtzite ZnO, indicating a single phase. UV measurements show the absorption that comes from the ZnO nanoparticles in visible region. The absorption edge of these ZnO nanoparticles are shifted to higher energies and the determined band gap energies are blue shifted as the OH⁻/Zn² molar ration increases, due to the quantum confinement effects. The photoluminescence characterization of the ZnO nanostructures exhibited a broad emission band centred at green (600 nm) region for all molar ratios except for OH⁻/Zn²⁺ = 1.7 where a second blue emission around 468 nm was also observed. The photoluminescence properties of ZnO nanoparticles were largely determined by the size and surface properties of the nanoparticles.     

Effects of Pb2+ ions concentration on the structure and PL intensity of Pb-doped ZnAl2O4 nanocrystals synthesized using sol–gel process

Undoped and Pb²⁺-doped ultrafine cubic zinc aluminate (ZnAl₂O₄) hosts were successfully prepared at a relatively low temperature (~80 °C) using the sol–gel method. The concentration of Pb²⁺ was varied from 0 to 5 mol%. The TGA showed that the minimum annealing temperature required to obtain single phase ZnAl₂O₄ must be above 400 °C. The XRD data revealed that all the annealed samples were single phase crystalline structures and the estimated crystallites size were in the range of 21–30 nm in diameter. The FTIR results suggest that heat-treating can destroy some of the bonds. The surface morphology of the phosphors was influenced by the Pb²⁺ mol%. Undoped and Pb²⁺-doped ZnAl₂O₄ nanoparticles exhibit the violet emission at slightly different positions. The slight peak shifts suggests the possibilities that the luminescence centre can either be due to the defects level in the host or Pb²⁺ ions. The emission peaks at 390 and 399 nm are ascribed to the typical UV transitions ³P_0,1 → ¹S₀ in Pb²⁺ ion. At the higher Pb²⁺ mol%, the luminescence quenching behaviour occurs, which suggests that doping with Pb²⁺ ions is accompanied by the introduction of new defect sites that enhance non-radiative recombination of the excited electrons.     

Material and device properties of Cu(In,Ga)Se2 absorber films prepared by thermal reaction of InSe/Cu/GaSe alloys to elemental Se vapor

The aim of this work was to study the influence of selenization temperature on the morphological and structural properties of CuIn_1−xGa_xSe₂ (CIGS) polycrystalline thin films prepared by a two-step method. The compound and metallic precursors were deposited sequentially using GaSe, InSe and Cu sources by thermal evaporation. These identical InSe/Cu/GaSe precursors are then selenized with Se vapor in a vacuum system. All the CIGS films showed chalcopyrite structure and presence of secondary phases observed at low temperatures. High temperature treatment led to better crystalline and an increase in grain size. Solar cell devices are fabricated and J–V measurements performed under AM1.5 global solar spectra conditions at 25 °C are presented.     

The effect of argon gas pressure on structural,morphological and photoluminescence properties of pulsed laser deposited KY<Subscript>3</Subscript>F<Subscript>10</Subscript>:Ho<Superscript>3+</Superscript> thin films

KY₃F₁₀:Ho³⁺ thin films were deposited by a pulsed laser deposition technique with Nd–YAG laser radiation (λ = 266 nm) on (100) silicon substrate. The XRD and FE-SEM results show improved crystalline structure for the film deposited at a pressure of 1 Torr. The AFM results show that the RMS roughness of the films increases with rise in argon gas pressure. The EDS elemental mapping shows Y-excess for all the films deposited under all pressures, and this is attributed to its higher mass and low volatility as compared to K and F. XPS analysis further confirmed Y-excess in the deposited films. Green PL emission at 540 nm was investigated at three main excitation wavelengths, namely 362, 416 and 454 nm. The PL emission peaks increase with rise in background argon gas pressure for all excitation wavelengths. The highest PL intensity occurred at excitation of 454 nm for all the thin films. In addition, faint red (near infrared) emission was observed at 750 nm for all the excitations. The green emission at 540 nm is ascribed to the ⁵F₄–⁵I₈ and ⁵S₂–⁵I₈ transitions, and the faint red emission at 750 nm is due to the ⁵F₄–⁵I₇ and ⁵S₂–⁵I₇ transitions of Ho³⁺.