Growth and characterization of model oxide catalysts

Oxide catalysts are frequently used to convert toxic species to environmentally benign molecules, and to prevent the formation of toxic species in the first place. In this paper, growth and characterization of model oxide systems employed in both approaches is discussed. An example of the former approach is the selective catalytic reduction (SCR) of NO emitted from power plants by NH₃, which employs tungsten and vanadium oxides supported on the anatase polymorph of TiO₂. To model SCR catalysts, epitaxial titanium, vanadium and tungsten oxide films were grown using molecular beam epitaxy and magnetron sputtering. Two different anatase orientations were grown on LaAlO₃ substrates and their interactions with vanadia were characterized. On LaAlO₃ (0 0 1), anatase exposed a (4 × 1) reconstructed (0 0 1) surface. Vanadia lifted the reconstruction and at 1 ML a (1 × 1) surface with mostly V⁵⁺ was observed. Continued V₂O₅ growth led to loss of order, but at high temperatures epitaxial VO₂ could be grown; vanadia behaved similarly on anatase films on LaAlO₃ (1 1 0). Results suggested that the monolayer is pseudomorphic with O adsorption oxidizing the surface V to 5+, since the anatase structure cannot accommodate more bulk oxygen, only a monolayer can be pseudomorphic and have only V⁵⁺. Thus the vanadia monolayer has unique structural and chemical properties that can help explain why vanadia monolayers on TiO₂ are much more active than bulk V₂O₅. For WO₃, a series of added row reconstructions were observed as the epitaxial films were reduced. The effect of these structures on surface chemistry was characterized by studying 1-propanol adsorption. The results indicated that the structure of the WO₃ surface did not alter its catalytic function but had a strong effect on reaction kinetics. As an example of a system where catalysts prevent the formation of toxic species, the reactivity of oxidized Pd surfaces used in CH₄ catalytic combustion were studied. An ordered PdO-like monolayer was found to be less reactive towards CO than adsorbed O on Pd. On the other hand, the PdO layer favored a lower activation energy C₃H₆ oxidation pathway. The results indicated that Pd oxidation reduces the sticking coefficient of reactive species but once molecules adsorb, the oxide surface can reduce the activation energy for subsequent reaction.     

Magnetic ordering of YBa2(Cu1−x Fe x )3O7

The Mössbauer spectra of YBa₂(Cu_1?x Fe _x )₃O₇ at room temperature show several doublets attributed to Fe in Cu(1) sites with different oxygen configurations. Here we present a systematic study performed at 4.2 K forx=0.005, 0.01, 0.03, 0.05, 0.10, 0.15. To obtain information about the magnetic ordered state two samples, withx=0.005 andx=0.15, have been studied at 4.2 K underB _ext=5 T. The Mössbauer spectra indicate that the iron moments are polarized forx=0.005, while in the ordered state (x=0.15) they have an antiferromagnetic or spin-glass-like arrangement with high anisotropy.     

Matching in a class of stationary axisymmetric perfect fluid solutions of Einstein's equations

The class of previously found stationary axisymmetric perfect fluid solutions of Einstein's equations is written inh-orthogonal coordinates,h being a space-like coordinate. Matching of a big number of solutions of the class with each other seems to be possible for a proper choice of some parameters. The exterior solutions of the class are matched explicitly with interior solutions. Also, interior solutions are matched explicitly with each other.     

Temperature dependence of hyperfine fields in intermediate valent140CeLa and140CeLu

The hyperfine fields for the systems¹⁴⁰CeLa and¹⁴⁰CeLu have been determined by time differential perturbed angular correlations (TDPAC) in the temperature range 4.2 K≤T≤330 K. Magnitude and temperature dependence of the paramagnetic enhancement factor β indicate that cerium in either system is of intermediate valence. This behaviour is discussed in terms of a theory proposed by Ramakrishnan et al. [1–3].     

Condensation film on an inclined rotating disk

The three dimensional problem of steady fluid deposition on an inclined rotating disk is solved by similarity transform. For a given spraying rate there may be one, two or no steady state solution. The inclination causes a downward draining flow and a lateral flow. Perturbation solutions compare well with exact similarity solutions when the fluid film is thin.     

Zn-doping effect on the energy barrier to magnetization reversal in superparamagnetic nickel ferrite nanoparticles

Measurements of ac-susceptibility and dc-magnetization were carried out on samples of Ni_1-xZn_xFe₂O₄ nanoparticles (x=0, 0.25, 0.5, 0.75) with average diameters 〈D〉≈7 nm. Values of the superparamagnetic blocking temperature T̄_B were obtained from the characteristic temperature behavior of the imaginary susceptibility χ_imag. An Arrhenius-type law, which accurately describes the relationship between the observation time τ_obs and the blocking temperature, was used to determine the effective energy barrier to magnetization reversal U_eff. A Zn-content dependence of the energy barrier is observed, where U_eff changes little for 0≤x≤0.25, it peaks at x=0.5, and decreases back upon further Zn-doping. The large increase of U_eff at x=0.5 is attributed to an enhanced magnetic anisotropy induced by the crossover between two spatial arrangements of spins in the A and B sub-lattices of the ferrimagnetic inverse spinel. PACS 75.50.Bb; 75.50.Gg; 75.30.Et     

Order conditions for linearly implicit fractional step Runge Kutta methods

^{In this paper, we study the consistency of a variant of fractionalstep Runge–Kutta methods. These methods are designed tointegrate efficiently semi-linear multidimensional parabolicproblems by means of linearly implicit time integration processes.Such time discretization procedures are also related to a splittingof the space differential operator (or the spatial discretizationof it) as a sum of ‘simpler’ linear differentialoperators and a nonlinear term.}     

A dynamic scorecard for monitoring baseline performance with application to tracking a mortgage portfolio

A principled technique for monitoring the performance of a consumer credit scorecard through time is derived from Kalman filtering. Standard approaches sporadically compare certain characteristics of the new applicants with those predicted from the scorecard. The new approach systematically updates the scorecard combining new applicant information with the previous best estimate. The dynamically updated scorecard is tracked through time and compared to limits calculated by sequential simulation from the baseline scorecard. The observation equation of the Kalman filter is tailored to take the results of fitting local scorecards by logistic regression to batches of new clients that arrive in the current time interval. The states in the Kalman filter represent the true or underlying score for each attribute in the card: the parameters of the logistic regression. Their progress in time is modelled by a random walk and the filter provides the best estimate of the scores using past and present information. We illustrate the technique using a commercial mortgage portfolio and the results indicate significant emerging deficiencies in the baseline scorecard.     

Einstein relation in chemically doped organic semiconductors

Based on the assumption of Gaussian energy distributions of the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO), analytical expressions of generalized Einstein relation in chemically doped organic semiconductor are developed, by approximation of Coulomb traps with a rectangle potential well. Numerical calculations show that traditional Einstein relations do not hold for chemically doped organic semiconductors. Similar to physical doping, the dependence of diffusion coefficient to mobility D/μ ratio on the carrier concentration has a maximum. An essential difference between chemical doping and physical doping is that, the D/μ ratio in chemically doped organic semiconductors depends not only on carrier concentration and doping concentration, but also on the applied electric field. PACS 71.20.Rv; 72.90.+y; 73.50.-h