Oxygen vacancy and dopant concentration dependent magnetic properties of Mn doped TiO2 nanoparticle

Mn doped TiO₂ nanoparticles are synthesized by sol–gel method. Incorporation of Mn shifts the diffraction peak of TiO₂ to lower angle. The position and width of the Raman peak and photoluminescence intensity of the doped nanoparticles varies with oxygen vacancy and Mn doping level. The electron spin resonance spectra of the Mn doped TiO₂ show peaks at g = 1.99 and 4.39, characteristic of Mn²⁺ state. Reduction in the emission intensity, on Mn doping, is owing to the increase of nonradiative oxygen vacancy centers. Mn doped TiO₂, with 2% Mn, shows ferromagnetic ordering at low applied field. Paramagnetic contribution increases as Mn loading increases to 4% and 6%. Temperature dependent magnetic measurement shows a small kink in the ZFC curve at about 40 K, characteristic of Mn₃O₄. The ferromagnetic ordering is possibly due to the interaction of the neighboring Mn²⁺ ions via oxygen vacancy (F⁺ center). Increase in Mn concentration increases the fraction of Mn₃O₄ phase and thereby increases the paramagnetic ordering.     

Reduction of copper(II) complexes of tridentate ligands by nitric oxide and fluorescent detection of NO in methanol and water media

Two copper complexes, 1 and 2, with tridentate N-donor ligands, L(1) and L(2) [L(1)= (1-methyl-1H-imidazol-2-ylmethyl)-(2-pyridin-2-yl-ethyl)amine, L(2) = (2-pyridin-2-yl-ethyl)-pyridin-2 yl-methylamine] respectively, have been synthesized and characterized. On exposure to nitric oxide, the copper(II) centers in complexes 1 and 2 were found to undergo reduction in various solvents. In acetonitrile solvent the reduction was accompanied by a simultaneous N-nitrosation on the secondary amine center on the ligand frameworks. Complexes 3 and 4 were prepared with ligands L(3) and L(4), respectively. L(3) and L(4) [L(3) = 5-dimethylamino-naphthalene-1-sulfonic acid (1-methyl-1H-imidazol-2-ylmethyl)-(2-pyridin-2-yl-ethyl)-amide; L(4) = 5-dimethylamino-naphthalene-1-sulfonic acid(2-pyridin-2-yl-ethyl)-pyridin-2-ylmethyl-amide] are the dansyl derivatives of L(1) and L(2), respectively. Complex 4, due to paramagnetic quenching, does not display any fluorescence; however, on addition of nitric oxide to a methanol or water solution of complex 4, the fluorescence intensity of the fluorophore has been found to be restored. This is attributed to the reduction of the Cu(II) center by nitric oxide to diamagnetic Cu(I). The turn-on of quenched fluorescence intensity has been observed both in methanol and water media.     

Effect on thermoluminescence parameters of biotite mineral due to thermal quenching

The Thermally Stimulated Luminescence (TSL) at room temperature X-ray irradiated natural biotite in form of micro-grain powder was studied under various heating rates. TSL peaks showed at temperatures 393 K, 399.6 K, 403.5 K, 404.5 K, 406.9 K at their respective heating rates 2 K/s, 4 K/s, 6 K/s, 8 K/s and 10 K/s. The effect of thermal quenching on thermoluminescence parameters such as peak maximum temperature, peak area, FWHM, geometrical symmetry factor, the activation energy were investigated. From the symmetry factor it is clear that the TL glow curve follows the first order kinetics for the lowest heating rate, but as the heating rate increases it defers from the first order. The activation energies for each heating rates were calculated by using Chen peak shape methods for general order kinetics and found to be decreased for higher heating rates. When activation energy is calculated by variable heating rate method it is observed that the method overestimated the value of activation energy and pre-exponential frequency factor significantly due to thermal quenching.     

Luminescence characteristics of cobalt doped TiO2 nanoparticles

TiO₂ nanoparticles doped with two different concentrations of Cobalt, 0.02 and 0.04 mol, are prepared by sol–gel method. The crystalline phase of the doped and undoped nanoparticles and particle sizes are observed with X-ray diffraction and transmission electron microscope. FTIR confirms the bonding interaction of Co²⁺ in TiO₂ lattice framework. The UV absorption spectra of the doped material shows two absorption peaks in the visible region related to d–d electronic transitions of Co²⁺ in TiO₂ lattice. Compared to undoped TiO₂ nanoparticles, the cobalt doped samples show a red shift in the band gap. Steady state photoluminescence spectra give emission peaks related to oxygen defects. The decrease in the intensity ratio of UV/visible emission peaks confirms distortion of structural regularity and formation of defects after doping. The intensity ratio of different visible emission peaks is nearly same for undoped and 0.02 Co²⁺. However, this ratio decreases profoundly at 0.04 Co²⁺, due to concentration quenching effect. Photoluminescence excitation spectra, recorded at 598 nm emission wavelength, give different excitation peaks associated with oxygen vacancies and Co²⁺. Time resolved photoluminescence spectra give longer decay time for doped samples, indicating longer relaxation of conduction band electrons on the defect and on dopant sites.     

Synthesis of Vegetable Oil‐Based Polyurethane: A Study on Curing Kinetics Behavior

In the present study, biobased polyurethane (BPU) samples were synthesized from three different polyols along with polymeric hexamethylene diisocyanate. The three different polyols were synthesized by reacting castor oil with ethylene glycol, triethylene glycol, and triethanolamine. The synthesized polyols were confirmed using proton nuclear magnetic resonance (¹H NMR) spectra analysis. BPU samples were confirmed by the disappearance of isocyanate peak in the FTIR spectra. The cross‐linking densities of all BPU samples were determined using swelling studies. Curing kinetics behavior of all BPU samples were analyzed using differential scanning calorimetry at three different heating rates (5, 7.5, and 10°C/min). The curing kinetic parameters were studied using three nonisothermal methods such as Kissinger, Flynn–Wall–Ozawa, and Ozawa, respectively. The activation energies were found to increase with increasing degree of cure (α). Surface properties of all the synthesized BPU samples were evaluated by dynamic mechanical analysis and scanning electron microscopy.     

Regularity of a boundary point for quasilinear elliptic systems of the second order

There is considered a quasilinear elliptic system of the divergence type. There are obtained continuity conditions for a general solution and its gradient at a boundary point. These conditions depend on the geometry of the domain and also on the sparseness of eigenvalues of the coefficient matrix of the system.Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 43, No. 5, pp. 590–596, May, 1991.     

Application of radioisotope XRF for the determination of noble metals in aqueous solutions

Radiometric methods of determination of platium and palladium (0.1 to 5% of Pt and 0.1 to 2% of Pd), gold and indium (0.01 to 1% of Au and 1 to 4 g In/l) and of platinum and rhodium (0.1 to 9% of Pt and 0.05 to 1% of Rh) in aqueous solution has been worked out. A suitable measuring device has been designed and constructed. The methods are based on the measurement of characteristic radiation of the L_α line for gold and platinum and of the K-series for indium, palladium and rhodium, as well as on the measurement of scattered radiation from a²³⁸Pu source. The r.m.s. error of the determination varies from 0.01 to 0.10% of Pt, 0.002 to 0.01% of Au and 0.01 to 0.15% of Pd depending on the concentration. In the case of Rh and In the errors are 0.008% and 0.04 g In/l, respectively.