Kaushik Sanyal

Photoluminescence and EPR studies on Fe3+ doped ZnAl2O4: an evidence for local site swapping of Fe3+ and formation of inverse and normal phase

Considering that ZnAl2O4 spinel has two different sites (octahedral and tetrahedral) and its properties change with dopant ion distribution among these two sites; ZnAl2O4 doped with varied concentrations of Fe(3+) was synthesized by a low temperature sol-gel combustion method. Phase purity and structural investigations were carried out using Rietveld refined X-ray diffraction which shows a decrease in the value of cell parameters at higher doping levels. Photoluminescence (PL) and electron paramagnetic resonance (EPR) studies have shown that on doping, Fe(3+) ions were distributed in both tetrahedral and octahedral sites. At octahedral sites, Fe(3+) exhibited a broad red emission around 745 nm while at tetrahedral sites it exhibited well-defined vibronic sidebands at 665, 674, 684 and 693 nm along with a broad blue band with a maxima at 445 nm at room temperature. EPR studies have shown a broad spectrum at g ≈ 2.2 which corresponds to the Fe(3+) in octahedral sites, while the broad signal at g ≈ 4.2 belongs to Fe(3+) in tetrahedral sites. It was also inferred from these studies that Fe(3+) prefers to occupy octahedral sites at higher concentrations and at higher annealing temperatures. The PL decay behavior of Fe(3+) in ZnAl2O4 has also shown that two different types of Fe(3+) ions were present in this matrix. The first type was a long lived species (τ ≈ 170 μs) present at octahedral sites and the other was a short lived species (τ ≈ 40 μs) present at the tetrahedral sites; the fraction of the long lived species predominate at higher concentrations. Thus the present work is mainly focused on understanding the tuning of local site occupancy of the dopant ion among those sites with varying concentration and annealing temperature, using the dopant ion itself as a spectroscopic probe, which further helps in understanding the phase (inverse and normal) of the spinel.

Luminescence of undoped and Eu3+ doped nanocrystalline SrWO4 scheelite: time resolved fluorescence complimented by DFT and positron annihilation spectroscopic studies

SrWO4 (SWO) and Eu3+ doped SrWO4 (SEWO) scheelite samples were synthesized using a polyol method. Crystallite sizes of the as prepared samples annealed at 300 and 500 °C are in a similar range (<20 nm) whereas those annealed at 700 and 900 °C are about ∼40–50 nm and 80–100 nm, respectively. Photoluminescence (PL) spectra of SWO samples show a broad peak corresponding to the oxygen to tungsten charge transfer transition. Along with the enhancement in emission intensity in the samples annealed at 700 and 900 °C, there is a blue shift in peak maxima. Our first principles quantum mechanical calculations showed that the break in symmetry of the unit cell of SrWO4 creates inherent defects in the lattice which are responsible for the reduction of the electronic band gap in the SrWO4 sample with decrease in size. On europium doping; energy transfer from the O2− → W6+ charge transfer band to Eu3+ takes place and the reason behind this is explained using density functional theory (DFT) calculations. Based on time resolved PL measurements, it is suggested that Eu3+ ions occupy two sites in SWO; a regular symmetric Sr2+ site and an asymmetric site (closer to charge compensating defects). With increase in annealing temperature, emission intensity as well as asymmetry around europium increased. The changes in asymmetry around europium and defect densities as determined from positron annihilation lifetime spectroscopy (PALS) suggest that though the overall vacancy concentration is reduced with an increase in annealing temperature, it is likely that vacancies closer to europium are slowly annealed out than the others.

Direct Determination of Oxidation States of Uranium in Mixed-Valent Uranium Oxides Using Total Reflection X-ray Fluorescence X-ray Absorption Near-Edge Spectroscopy

Total reflection X-ray fluorescence (TXRF)-based X-ray absorption near-edge spectroscopy has been used to determine the oxidation state of uranium in mixed-valent U3O8 and U3O7 uranium oxides. The TXRF spectra of the compounds were measured using variable X-ray energies in the vicinity of the U L3 edge in the TXRF excitation mode at the microfocus beamline of the Indus-2 synchrotron facility. The TXRF-based X-ray absorption near-edge spectroscopy (TXRF-XANES) spectra were deduced from the emission spectra measured using the energies below and above the U L3 edge in the XANES region. The data processing using TXRF-XANES spectra of U(IV), U(V), and U(VI) standard compounds revealed that U present in U3O8 is a mixture of U(V) and U(VI), whereas U in U3O7 is mixture of U(IV) and U(VI). The results obtained in this study are similar to that reported in literature using the U M edge. The present study has demonstrated the possibility of application of TXRF for the oxidation state determination and elemental speciation of radioactive substances in a nondestructive manner with very small amount of sample requirement.

Selective micellar extraction of ultratrace levels of uranium in aqueous samples by task specific ionic liquid followed by its detection employing TXRF spectrometry

A task specific ionic liquid (TSIL) bearing phosphoramidate group, viz., N-propyl(diphenylphosphoramidate)trimethylammonium bis(trifluoromethanesulfonyl)imide, was synthesized and characterized by 1H NMR, 13C NMR, 31P NMR, and IR spectroscopies, elemental (C H N S) analysis, and electrospray ionization mass spectrometry (ESI-MS). Using this TSIL a cloud point extraction (CPE) or micelle mediated extraction procedure was developed for preconcentration of uranium (U) in environmental aqueous samples. Total reflection X-ray fluorescence spectrometry was utilized to determine the concentration of U in the preconcentrated samples. In order to understand the mechanism of the CPE procedure, complexation study of the TSIL with U was carried out by isothermal calorimetric titration, liquid-liquid extraction, 31P NMR and IR spectroscopies, and ESI-MS. The developed analytical technique resulted in quantitative extraction efficiency of 99.0 ± 0.5% and a preconcentration factor of 99 for U. The linear dynamic range and method detection limit of the procedure were found to be 0.1-1000 ng mL-1 and 0.02 ng mL-1, respectively. The CPE procedure was found to tolerate a higher concentration of commonly available interfering cations and anions, especially the lanthanides. The developed analytical method was validated by determining the concentration of U in a certified reference material, viz., NIST SRM 1640a natural water, which was found to be in good agreement at a 95% confidence limit with the certified value. The method was successfully applied to the U determination in three natural water samples with ≤4% relative standard deviation (1σ).

Direct determination of fluorine in high-purity water samples using vacuum sample chamber total reflection X-ray fluorescence spectrometry

A simple total reflection X-ray fluorescence (TXRF) method for the direct determination of trace F levels in water samples has been developed. This method involves the deposition of 5 μL aliquots of samples and calibration solutions on Si-wafer supports and measurement of their TXRF spectra using a vacuum chamber TXRF spectrometer with ultrathin window detector. The small size of the deposited sample fixed at the center of the Si-wafer support provided reproducible geometry that ensured the measured F Kα intensity was the same for different specimens containing the same amount of F and varied in proportion to the amount of F. This approach resulted in a calibration plot of F Kα intensity against the amount of F on TXRF specimens prepared using the same aliquot volumes containing different F concentrations. Fluorine in sample solutions was determined using this calibration plot. This approach avoided use of an internal standard and, thereby, F loss due to the acidic nature of internal standards while preparing the TXRF specimens by drying sample solutions on TXRF supports. This approach allowed determination of the F amount in synthetic samples and simulated water samples with an average deviation in the TXRF results of 4.1% from expected values and an RSD of 5.1% (1σ) for the F amount at ppm and sub-ppm levels. The use of Si-wafer supports helped to prepare small sample spots on TXRF supports with reproducible geometry and better detection limits. This also avoided interference from the O Kα peak of quartz supports with the F Kα peak.

Direct Multielemental Trace Determinations in Plutonium Samples by Total Reflection X-ray Fluorescence Spectrometry Using a Very Small Sample Amount

A simple, safe, and sensitive method for direct multielemental trace determinations in plutonium samples using total reflection X-ray fluorescence (TXRF) spectrometry has been developed. A very small volume (2 μL) of the sample solutions was deposited on TXRF supports after separation of the plutonium matrix from these solutions. Since the amount of the plutonium deposited on the supports was in the ng level only fixed on the supports and the specimen spots were not disturbed during the sample preparation, the samples could be analyzed directly without putting the instrument in a glovebox. This approach avoided a cumbersome operation of the instrument in a glovebox, which is normally utilized for Pu-based samples using other techniques. Similarly, the requirement of small amounts of the samples minimized the radiation dose to the operator as well as a cumbersome problem of management of radioactive analytical waste of plutonium samples. The samples were analyzed using the TXRF spectra of the specimens, concentration of the internal standard Se or Ga and predetermined sensitivity values. The elemental detection limits for the elements K-Sr varied from 1.06 to 0.09 ng. The elements K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Sr, Ba, Tl, and Pb were analyzed at μg/mL level. The analytical results of TXRF determinations showed average relative standard deviation (RSD) value of 4.5% (1σ, n = 3) and the TXRF determined results deviated from the expected values by 5.9% on average for samples prepared by adding multielements in plutonium solutions. Two real plutonium samples were also analyzed in similar manner. For the real plutonium sample solution the average RSD values of TXRF determinations were 10.6% (1σ, n = 3) for the elemental concentrations in the range of 0.2 to 61 μg/mL. These values are comparable with conventional trace element analytical techniques with added advantages mentioned above.