EPR and Optical Studies of Mo5+ Ions in Lithium Molybdoborate Glasses

Electron paramagnetic resonance (EPR) and optical absorption studies of Li2O–MoO3–B2O3 with varying concentrations of Li2O, MoO3 and B2O3 have been carried out at room temperature. Two series of glasses, one with constant MoO3 (CM) and another with constant borate (CB), have been investigated. Characteristic EPR spectra of Mo5+ have been observed centered around g ≅ 2.00, which are attributed to Mo5+ ion in an octahedral coordination sphere with an axial distortion. The spectra also show strong dependence on the concentration of Li2O and B2O3. Spin concentrations (N) and magnetic susceptibilities (χ) have been calculated. In the CM series, the N values decrease with increasing Li2O content up to 30 mol%, while in the CB series variation of N is found to increase initially up to 20 mol%, and with further increase in the Li2O content the N values tend to decrease. The variation of magnetic susceptibilities is almost similar to that observed with the variation of N. From the optical absorption spectra, an absorption edge (α) has been evaluated. In the CM series, the values of α show a blueshift. On the other hand, in the CB series a redshift is observed. The observed variations in spectral parameters are explained by considering the molybdoborate network. Addition of Li2O to the CM and CB series results in modification of [MoO6/2]0 → [MoOO5/2]− and [BO3/2]0 → [BO4/2]− → [BOO2/2]− groups, respectively, leading to creation of nonbridging oxygens. The optical basicity of the glasses has been evaluated in both the CM and the CB glasses. The optical basicity can be used to classify the covalent-to-ionic ratios of the glass, since an increasing optical basicity indicates decreasing covalency. It is observed that the covalency between Mo5+ ions and oxygen ligands increases in the CB series, whereas in the CM series the covalency between Mo5+ ions and oxygen ligands decreases

EPR and optical absorption studies of Fe3 ions in sodium borophosphate glasses

Electron paramagnetic resonance (EPR) and optical absorption spectral investigations have been carried out on Fe3 ions doped sodium borophosphate glasses (NaH2PO4B2O 3Fe2O3). The EPR spectra exhibit resonance signals with effective g values at g=2.02, g=4.2 and g=6.4. The resonance signal at g=4.2 is due to isolated Fe3 ions in site with rhombic symmetry whereas the g=2.02 resonance is due to Fe3 ions coupled by exchange interaction in a distorted octahedral environment. The EPR spectra at different temperatures (123295 K) have also been studied. The intensity of the resonance signals decreases with increase in temperature whereas linewidth is found to be independent of temperature. The paramagnetic susceptibility (Ï) was calculated from the EPR data at various temperatures and the Curie constant (C) and paramagnetic Curie temperature (θp) have been evaluated from the 1/Ï versus T graph. The optical absorption spectrum exhibits bands characteristic of Fe3 ions in octahedral symmetry. The crystal field parameter (Dq) and the Racah interelectronic repulsion parameters (B and C) have also been evaluated and discussed. © 2010 Elsevier Ltd

EPR Study of Fe 3+ - and Ni 2+ -Doped Macroporous CaSiO 3 Ceramics

Thermally stable macroporous CaSiO 3 , Fe 3+ - and Ni 2+ -doped (0.5 to 5 mol%) ceramics have been prepared by solution combustion process by mixing respective metal nitrates (oxidizers), fumed silica. Diformol hydrazine is used as a fuel. The combustion products were identified by their X-ray diffraction and thermal gravimetry/differential thermal analysis. Single phases of β-CaSiO 3 and α-CaSiO 3 were observed at 950 and 1200 °C, respectively. The phase transition temperatures of combustion-derived CaSiO 3 were found to be lower compared to those obtained via solid-state reaction method. It is interesting to note that with an increase in the calcination temperature the samples become more porous with an increase in the pore diameter from 0.2 to 8 µm. The electron paramagnetic resonance (EPR) spectrum of Fe 3+ ions in CaSiO 3 exhibits a weak signal at g = 4.20 ± 0.1 followed by an intense signal at g = 2.0 ± 0.1. The signal at g = 4.20 is ascribed to isolated Fe 3+ ions at rhombic site. The signal at g = 2.0 is due to Fe 3+ coupled together with dipolar interaction. In Ni 2+ -doped CaSiO 3 ceramics the EPR spectrum exhibits a symmetric absorption at g = 2.23 ± 0.1. This deviation from the free electron g -value is ascribed to octahedrally coordinated Ni 2+ ions with moderately high spin–orbit coupling. The number of spins participating in resonance and the paramagnetic susceptibilities have been evaluated from EPR data as a function of Fe 3+ as well as Ni 2+ content. The effect of alkali ions (Li, Na and K) on the EPR spectra of these ceramics has also been studied

Solution combustion derived nanocrystalline Zn2SiO4 : Mn phosphors: A spectroscopic view

Manganese doped nanocrystalline willemite powder phosphors Zn2-xMnxSiO4 (0.1less than or equal toxless than or equal to0.5) have been synthesized by a low-temperature initiated, self-propagating, gas producing solution combustion process. The phosphors have been characterized by using x-ray diffraction (XRD), energy dispersive spectroscopy, scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR), electron paramagnetic resonance (EPR), and photo luminescence (PL) spectroscopic techniques. The lattice parameters calculated from XRD confirm that Zn2-xMnxSiO4 has a rhombohedral space group R (3) over barH. The XRD patterns confirm that Zn2-xMnxSiO4 phosphor samples undergo a phase transformation from beta-willemite to alpha-willemite phase at 950 degreesC. The EPR spectra of Mn2+ ions exhibit resonance signals at gcongruent to3.24 and gcongruent to2.02, with a sextet hyperfine structure centered around gcongruent to2.02. The EPR signals of Mn2+ give a clear indication of the presence of two different Mn2+ sites. The magnitude of the hyperfine splitting (A) indicates that the Mn2+ is in an ionic environment. The number of spins participating in resonance (N), the paramagnetic susceptibility (chi), and the zero-field splitting parameter (D) have been evaluated as function of x. It is interesting to observe that the variation of N with temperature obeys Boltzmann. The paramagnetic susceptibility is calculated from the EPR data at various temperatures and the Curie constant and Curie paramagnetic temperature was evaluated from the 1/chi versus T graph. The luminescence of Mn2+ ion in Zn2SiO4 shows a strong green emission peak around 520 nm from the synthesized phosphor particles under UV excitation (251 nm). The luminescence is assigned to a transition from the upper T-4(1)-->(6)A(1) ground state. The mechanism involved in the generation of a green emission has been explained in detail. The effect of Mn content on luminescence has also been studied. (C) 2004 American Institute of Physics

Synthesis, characterization and TL studies of porous CaSiO3 ceramic powders

Nanocryst. porous CaSiO3 ceramic powders have been synthesized by a novel low temp. initiated self-​propagating, gas producing soln. combustion process and characterized by XRD, SEM, EDS (energy dispersive spectroscopy)​, porosity, surface area and thermoluminescence (TL) studies. The effect of temp. on cryst. phase formation, amt. of porogens and particle size of porous CaSiO3 have been investigated. Single phase β-​CaSiO3 and α-​CaSiO3 were formed at 950° and 1200°C resp. The phase transformation temps. of combustion derived CaSiO3 were found to be low compared to the powders obtained via solid state reaction method. The microstructure and morphol. were studied by SEM and it was noted that with increase in calcination temp., the samples became more porous and the pore diam. increased from 0.25 to 8 μm. The samples calcined at 950°C for 3 h had 17.5​% porosity, however, the porosity increased to 31.6​% on calcination at 1200°C for 3 h. The surface areas of the as-​formed and calcined (at 950° and 1200°C) CaSiO3 samples were found to be 31.93, 0.585 and 3.48 m2·g-​1 resp. The TL intensity in powder sample was more intense when compared to the pelletized CaSiO3 and it was further obsd. that there was a shift in glow peak temps. in pelletized sample. This is attributed to the interparticle spacing and pressure-​induced defects

Combustion synthesis, characterization and Raman studies of ZnO nanopowders

Spherical shaped ZnO nanopowders (14-50 nm) were synthesized by a low temperature solution combustion method in a short time <5 min. Rietveld analysis show that ZnO has hexagonal wurtzite structure with lattice constants a = 3.2511(1) , c = 5.2076(2) , unit cell volume (V) = 47.66(5) () 3 and belongs to space group P63mc. SEM micrographs reveal that the particles are spherical in shape and the powders contained several voids and pores. TEM results also confirm spherical shape, with average particle size of 14-50 nm. The values are consistent with the grain sizes measured from Scherrer's method and Williamson-Hall (W-H) plots. A broad UV-vis absorption spectrum was observed at �375 nm which is a characteristic band for the wurtzite hexagonal pure ZnO. The optical energy band gap of 3.24 eV was observed for nanopowder which is slightly lower than that of the bulk ZnO (3.37 eV). The observed Raman peaks at 438 and 588 cm -1 were attributed to the E 2 (high) and E 1 (LO) modes respectively. The broad band at 564 cm -1 is due to disorder-activated Raman scattering for the A 1 mode. These bands are associated with the first-order Raman active modes of the ZnO phase. The weak bands observed in the range 750-1000 cm -1 are due to small defects. © 2011 Elsevier B.V. All Rights Reserved

EPR and photoluminescence studies of ZnO:Mn nanophosphors prepared by solution combustion route

Nanocrystalline ZnO:Mn (0.1 mol%) phosphors have been successfully prepared by self propagating, gas producing solution combustion method. The powder X-ray diffraction of as-formed ZnO:Mn sample shows, hexagonal wurtzite phase with particle size of ∼40 nm. For Mn doped ZnO, the lattice parameters and volume of unit cell (a = 3.23065 Å, c = 5.27563 Å and V = 47.684 (Å)3) are found to be greater than that of undoped ZnO (a = 3.19993 Å, c = 5.22546 Å and V = 46.336 (Å)3). The SEM micrographs reveal that besides the spherical crystals, the powders also contained several voids and pores. The TEM photograph also shows the particles are approximately spherical in nature. The FTIR spectrum shows two peaks at ∼3428 and 1598 cm−1 which are attributed to O–H stretching and H–O–H bending vibration. The PL spectra of ZnO:Mn indicate a strong green emission peak at 526 nm and a weak red emission at 636 nm corresponding to 4T1 → 6A1 transition of Mn2+ ions. The EPR spectrum exhibits fine structure transition which will be split into six hyperfine components due to 55Mn hyperfine coupling giving rise to all 30 allowed transitions. From EPR spectra the spin-Hamiltonian parameters have been evaluated and discussed. The magnitude of the hyperfine splitting (A) constant indicates that there exists a moderately covalent bonding between the Mn2+ ions and the surrounding ligands. The number of spins participating in resonance (N), its paramagnetic susceptibility (χ) have been evaluated

EPR, thermo and photoluminescence properties of ZnO nanopowders

Nanocrystalline ZnO powders have been synthesized by a low temperature solution combustion method. The photoluminescence (PL) spectrum of as-formed and heat treated ZnO shows strong violet (402, 421, 437, 485 nm) and weak green (520 nm) emission peaks respectively. The PL intensities of defect related emission bands decrease with calcinations temperature indicating the decrease of Zn i and V o + caused by the chemisorptions of oxygen. The results are correlated with the electron paramagnetic resonance (EPR) studies. Thermoluminescence (TL) glow curves of gamma irradiated ZnO nanoparticles exhibit a single broad glow peak at �343 °C. This can be attributed to the recombination of charge carriers released from the surface states associated with oxygen defects, mainly interstitial oxygen ion centers. The trapping parameters of ZnO irradiated with various γ-doses are calculated using peak shape method. It is observed that the glow peak intensity increases with increase of gamma dose without changing glow curve shape. These two characteristic properties such as TL intensity increases with gamma dose and simple glow curve structure is an indication that the synthesized ZnO nanoparticles might be used as good TL dosimeter for high temperature application. © 2011 Elsevier B.V. All Rights Reserved

Nd2O3:Gd3+ nanocrystalline phosphor: gamma-Induced thermoluminescence, EPR and structural properties

Preparation of nanocrystalline Nd2O3:Gd3+ (2 mol%) phosphor was prepared by propellant combustion route at low temperature. Powder X-ray diffraction (PXRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) techniques were used to study the structural and morphological features. A and C type hexagonal phase of Nd2O3 was obtained in as-formed and calcined product at 900 degrees C for 3 h. SEM images show the product was highly porous, agglomerated and irregular shaped particles. The average crystallite size estimated from Scherrer's and W-H plots were found to be in the range similar to 20-50 nm. Combination of F-g and (F-g + E-g) modes were observed from Raman studies. A single TL glow peak at 409 K was recorded at a warming rate 5 degrees C s (1). TL response as a function of gamma-irradiation showed linear response up to 1.6 kGy and later it followed exponential growth. The phosphor show simple glow curve structure with less fading over a period of 30 days. Trap parameters were estimated from Chen's peak shape method. The activation energy (E) and frequency factor (s) was found to in the range 1.377-2.934 eV and 2.01 x 10(11)-8.70 x 10(22) Hz respectively. (C) 2013 Elsevier B.V. All rights reserved