Bandgap modification of TiO<Subscript>2</Subscript> sol–gel films by Fe and Ni doping

Nickle and iron doped TiO₂ thin films were prepared on glass substrates by sol–gel dip coating process. Indirect and direct optical energy gaps were calculated with the incorporation of different concentrations of both the ions. Indirect bandgap was found to be a strong function of the dopant concentration, whereas direct energy gap has negligible dependence on the nature of dopant and its concentration. Direct energy gap has always been found to retain a value higher than the indirect energy gap. Variation of observed energy gap properties shows a trend similar to that reported on the basis of numerical calculations or the samples obtained by other techniques. Increase in refractive index and corresponding density of the film sample does not support the change in turn over frequency. The influence of crystalline phase change is also ruled out by XRD investigations. It is concluded that red shift of band edge absorption takes place by incorporation of dopant and sol–gel dip coating technique offers an effective low cost route to the production of these coatings.     

Mechanism of Charge Transfer Initiation by the Dimethyl Phenyl Phosphine/Fe(III) Catalyst System

The dimethyl phenyl phosphine (DMPP) initiated polymerization of methyl methacrylate (MMA) in dimethylsulfoxide was studied. Polymerization of MMA in this system required the presence of transition metal ions like Fe³⁺ or Cu²⁺. Kinetic studies showed that the propagation was free radical in nature. An interaction between DMPP and MMA was detected spectrophotometrically. A proposed mechanism involves a transition metal ion-activated dipole interaction between the carbonyl oxygen and the phosphorus atom with the ultimate formation of a methyl methacrylate type of free radical.     

Molecular motion in zinc hydrazone grid complexes

Four new grid forming hydrazone ligands substituted with methoxy and dimethylamino groups were synthesised. Combination of these ligands with zinc triflate in acetonitrile resulted in self-assembly to form grids as indicated by ¹H NMR and ES-MS. ¹H NMR also showed thermally induced rotation of the intercalated phenyl ring in both the new grids, and in three previously reported grid compounds. Of these seven, five were amenable to study by variable temperature ¹H NMR. Though the observed rates varied by more than an order of magnitude depending upon ligand structure and level of deprotonation, activation energies were similar (～60 kJ/mol) for all complexes studied. This suggests a model in which dissociation of the central pyrimidine ligand precedes phenyl group rotation with an enthalpy of dissociation near zero. The rate of rotation of the phenyl ring increases with an introduction of electron-donating substituents on the phenyl ring, possibly due to an increased repulsion between π systems.     

Rigidity of conformally compact manifolds with the round sphere as the conformal infinity

In this paper, we prove that under a lower bound on the Ricci curvature and an assumption on the asymptotic behavior of the scalar curvature, a complete conformally compact manifold whose conformal boundary is the round sphere has to be the hyperbolic space. It generalizes similar previous results where stronger conditions on the Ricci curvature or restrictions on dimension are imposed.     

Astroparticle physics: Working group report

The astroparticle physics working group witnessed intense discussion and activity covering a broad range of topics ranging from supergravity and baryogenesis to compact stars and the large scale structure of the Universe. A summary of some of the subject areas in which collaborations were initiated during WHEPP-5 is presented below.     

Mechanism and kinetics of the isothermal thermodegradation of ethylene-propylene-diene (EPDM) elastomers

The thermal degradation behavior of a range of ethylene-propylene-diene (EPDM) elastomers, covering the whole range of composition, has been examined under isothermal conditions between 410 and 440 °C using thermogravimetric analysis. The kinetic parameters of degradation for the polymers have been evaluated using different mathematical models based on different proposed mechanisms of degradation. The experimental data were fitted to the models using non-linear regression analysis technique based on Marquardt-Levenberg algorithm. It appears that the degradation of EPDMs follows the Avrami-Erofeev two-dimensional nucleation model or a random chain-scission mechanism. No observable trend was found between the ethylene content of EPDM and the activation energy of degradation.     

Microstructure characterization and phase transformation kinetic study of ball-milled m-ZrO2–30 mol% a-TiO2 mixture by Rietveld method

High-energy ball milling of monoclinic ZrO₂–30 mol% anatase TiO₂ mixture at different durations results in the formation of m-ZrO₂–a-TiO₂ solid solution from which the nucleation of nanocrystalline cubic (c) ZrO₂ polymorphic phase sets in. Post-annealing of 12 h ball-milled sample at different elevated temperatures for 1 h results in almost complete formation of c-ZrO₂ phase. Microstructure of the unmilled, all the ball milled and annealed samples has been characterized by Rietveld's X-ray powder structure refinement method. Particle size, rms lattice strain, change in lattice parameters and phase content of individual phases have been estimated from Rietveld analysis, and are utilized to interpret the results. In course of milling, (1 1 1) of cubic lattice became parallel to () plane of monoclinic lattice due to the orientation effect and cubic phase may have been formed on the (0 0 1) of the m-ZrO₂–a-TiO₂ solid solution lattice. A comparative study of microstructure and phase transformation kinetics of ZrO₂–10, 20 and 30 mol% a-TiO₂ ball-milled and post-annealed samples reveals that rate of phase transformation m→c-ZrO₂ increases with increasing a-TiO₂ concentration and 30 mol% of nanocrystalline c-ZrO₂ phase can be obtained within 4 h of milling time in the presence of 30 mol% of a-TiO₂. The post-annealing treatment at 773, 873 and 973 K for 1 h duration each reveals that rate of c-ZrO₂ formation with increasing temperature is retarded with increasing a-TiO₂ concentration but the amount of c-ZrO₂ becomes almost equal (95 mol%) at 973 K. It suggests that almost fully stabilized nanocrystalline c-ZrO₂ can be formed by adding a tetravalent solute to m-ZrO_2.     

Photocatalytic properties and luminescent sensing of a new 2D layer coordination polymer

A 2D coordination polymer [Zn2(betc)(bip)2]·3H2O (1) has been synthesised by deploying mixed ligand strategy . The photoluminescence properties of 1 in different solvents have been investigated and its sensing properties to detect nitroaromatic compounds (NACs) have been explored. 1 displayed selective sensing for 4- nitrotoluene (4-NT) with lower limit of detection (LOD) 0.62 ppm. The probable mechanism for sensing of NACs by 1 ha s been addressed using quantum chemical calculations. Also photocatalytic properties of 1 to photo-decompose model aromatic dyes viz. methyl violet (MV) and 20 rhodamine B (Rh B) have been evaluated. The experiments indicated that 1 displayed better photocatalytic performance in photo-degrading MV than Rh B. The plausible mechanism through which 1 displayed photocatalytic degradation of aromatic dyes had been revealed using density of states (DOS) and partial DOS calculations.

The probable mechanism for the photocatalytic property and emission quenching of 1 has been proposed with the aid of density of states and partial density of states calculations.