Dynamics and local structure of colossal magnetoresistance manganites

We report Extended X-ray Absorption Fine Structure and anelastic spectroscopy measurements on on hole doped manganese oxides La1-xCaxMnO3 which present the colossal magnetoresistance effect. EXAFS measurements were realized both in the absence and presence of an applied magnetic field of 1.1 Tesla, in a wide temperature range (between 330 and 77 K) and at various dopings (x = 0.25 and x = 0.33). The magnetic field orders the magnetic moments so favouring the electron mobility and the reduction of Mn-O octahedra distortions. We observe the presence of four short and two long Mn-O distances (1.93 and 2.05 Angstrom respectively) above and also below the metal-insulator phase transition. The overall distortion decreases but does not completely disappear in the metallic phase suggesting the possible coexistence of metallic and insulating regions at low temperatures. The magnetic field reduces the lattice distortions showing evidence of a microscopic counterpart of the macroscopic colossal magnetoresistance. We also present preliminary anelastic relaxation spectra in a wide temperature range from 900 K to 1 K on a sample with x = 0.40, in order to study the structural phase transitions and the lattice dynamics. A double peak has been observed at the metal-insulator transition in the imaginary part of Young's modulus. This double peak indicates that the metal-insulator transition could be a more complex phenomenon than a simple second order phase transition. In particular the peak at lower temperatures can be connected with the possible presence of inhomogeneous phase structures. Another intense dissipation peak has been observed corresponding to the structural orthorhombic-trigonal transition around 750 K.

Evolution of polyandry by reduction in progeny number variance in structured populations

When there is a variation in the quality of males in a population, multiple mating can lead to an increase in the genetic fitness of a female by reducing the variance of the progeny number. The extent of selective advantage obtainable by this process is investigated for a population subdivided into structured demes. It is seen that for a wide range of model parameters (deme size, distribution of male quality, local resource level), multiple mating leads to a considerable increase in the fitness. Frequency-dependent selection or a stable coexistence between polyandry and monandry can also result when the possible costs involved in multiple mating are taken into account.

An assessment of the reduction potential of hydrogen plasma

Hydrogen plasma can be used for deoxidation of functional materials containing reactive metals in both bulk and thin film forms. Since the different species in the plasma are not in thermodynamic equilibrium, application of classical thermodynamics to the analysis of such a system is associated with some difficulties. While global equilibrium approaches have been tried, with and without additional approximations or constraints, there is some ambiguity in the results obtained. Presented in this article is the application of a local equilibrium concept to assess the thermodynamic limit of the reaction of each species present in the gas with oxides or oxygen dissolved in metals. Each reaction results in a different pal tial pressure of H2O. Because of the higher reactivity of the dissociated and ionized species and the larger thermodynamic driving force for reactions involving these species, they act as powerful reducing agents. It is necessary to remove the products of reaction from the plasma to prevent back reaction and gradual approach to global equilibrium. A quantitative description using the framework of the Ellingham-Richardson-Jeffes diagrams is presented.

Statistical thermodynamics of lattice models in zeolites: Implications of local versus global mean field interactions

The statistical thermodynamics of adsorption in caged zeolites is developed by treating the zeolite as an ensemble of M identical cages or subsystems. Within each cage adsorption is assumed to occur onto a lattice of n identical sites. Expressions for the average occupancy per cage are obtained by minimizing the Helmholtz free energy in the canonical ensemble subject to the constraints of constant M and constant number of adsorbates N. Adsorbate-adsorbate interactions in the Brag-Williams or mean field approximation are treated in two ways. The local mean field approximation (LMFA) is based on the local cage occupancy and the global mean field approximation (GMFA) is based on the average coverage of the ensemble. The GMFA is shown to be equivalent in formulation to treating the zeolite as a collection of interacting single site subsystems. In contrast, the treatment in the LMFA retains the description of the zeolite as an ensemble of identical cages, whose thermodynamic properties are conveniently derived in the grand canonical ensemble. For a z coordinated lattice within the zeolite cage, with epsilon(aa) as the adsorbate-adsorbate interaction parameter, the comparisons for different values of epsilon(aa)(*)=epsilon(aa)z/2kT, and number of sites per cage, n, illustrate that for -1 0. We compare the isotherms predicted with the LMFA with previous GMFA predictions [K. G. Ayappa, C. R. Kamala, and T. A. Abinandanan, J. Chem. Phys. 110, 8714 (1999)] (which incorporates both the site volume reduction and a coverage-dependent epsilon(aa)) for xenon and methane in zeolite NaA. In all cases the predicted isotherms are very similar, with the exception of a small steplike feature present in the LMFA for xenon at higher coverages. (C) 1999 American Institute of Physics. [S0021-9606(99)70333-8].

A multifold reduction in the transition Reynolds number, and ultra-fast mixing, in a micro-channel due to a dynamical instability induced by a soft wall

A dynamical instability is observed in experimental studies on micro-channels of rectangular cross-section with smallest dimension 100 and 160 mu m in which one of the walls is made of soft gel. There is a spontaneous transition from an ordered, laminar flow to a chaotic and highly mixed flow state when the Reynolds number increases beyond a critical value. The critical Reynolds number, which decreases as the elasticity modulus of the soft wall is reduced, is as low as 200 for the softest wall used here (in contrast to 1200 for a rigid-walled channel) The instability onset is observed by the breakup of a dye-stream introduced in the centre of the micro-channel, as well as the onset of wall oscillations due to laser scattering from fluorescent beads embedded in the wall of the channel. The mixing time across a channel of width 1.5 mm, measured by dye-stream and outlet conductance experiments, is smaller by a factor of 10(5) than that for a laminar flow. The increased mixing rate comes at very little cost, because the pressure drop (energy requirement to drive the flow) increases continuously and modestly at transition. The deformed shape is reconstructed numerically, and computational fluid dynamics (CFD) simulations are carried out to obtain the pressure gradient and the velocity fields for different flow rates. The pressure difference across the channel predicted by simulations is in agreement with the experiments (within experimental errors) for flow rates where the dye stream is laminar, but the experimental pressure difference is higher than the simulation prediction after dye-stream breakup. A linear stability analysis is carried out using the parallel-flow approximation, in which the wall is modelled as a neo-Hookean elastic solid, and the simulation results for the mean velocity and pressure gradient from the CFD simulations are used as inputs. The stability analysis accurately predicts the Reynolds number (based on flow rate) at which an instability is observed in the dye stream, and it also predicts that the instability first takes place at the downstream converging section of the channel, and not at the upstream diverging section. The stability analysis also indicates that the destabilization is due to the modification of the flow and the local pressure gradient due to the wall deformation; if we assume a parabolic velocity profile with the pressure gradient given by the plane Poiseuille law, the flow is always found to be stable.

Controlling air solubility to maintain `'Cassie'' state for sustained drag reduction

`'Cassie'' state of wetting can be established by trapping air pockets on the crevices of textured hydrophobic surfaces, leading to significant drag reduction. However, this drag reduction cannot be sustained due to gradual dissolution of trapped air into water. In this paper, we explore the possibility of sustaining the underwater Cassie state of wetting in a microchannel by controlling the solubility of air in water; the solubility being changed by controlling the local absolute pressure near the surface. We show that using this method, we can in fact make the water locally supersaturated with air thus encouraging the growth of trapped air pockets on the surface. In this case, the water acts as a pumping medium, delivering air to the crevices of the hydrophobic surface in the microchannel, where the presence of air pockets is most beneficial from the drag reduction perspective. In our experiments, the air trapped on a textured surface is visualized using total internal reflection based technique, at different local absolute pressures with the pressure drop (or drag) also being simultaneously measured. We find that, by controlling the pressure and hence the solubility close to the surface, we can either shrink or grow the trapped air bubbles, uniformly over a large surface area. The experiments show that, by precisely controlling the pressure and hence the solubility we can sustain the `'Cassie state'' over extended periods of time. This method thus provides a means of getting sustained drag reduction from a textured hydrophobic surface in channel flows. (C) 2014 Elsevier B.V. All rights reserved.

STM verification of the reduction of the Young's modulus of CdS nanoparticles at smaller sizes

We demonstrate the first STM evaluation of the Young's modulus (E) of nanoparticles (NPs) of different sizes. The sample deformation induced by tip-sample interaction has been determined using current-distance (I-Z) spectroscopy. As a result of tip-sample interaction, and the induced surface deformations, the I-z curves deviates from pure exponential dependence. Normally, in order to analyze the deformation quantitatively, the tip radius must be known. We show, that this necessity is eliminated by measuring the deformation on a substrate with a known Young's modulus (Au(111)) and estimating the tip radius, and afterwards, using the same tip (with a known radius) to measure the (unknown) Young's modulus of another sample (nanoparticles of CdS). The Young's modulus values found for 3 NP's samples of average diameters of 3.7, 6 and 7.5 nm, were E similar to 73%, 78% and 88% of the bulk value, respectively. These results are in a good agreement with the theoretically predicted reduction of the Young's modulus due to the changes in hydrostatic stresses which resulted from surface tension in nanoparticles with different sizes. Our calculation using third order elastic constants gives a reduction of E which scales linearly with 1/r (r is the NP's radius). This demonstrates the applicability of scanning tunneling spectroscopy for local mechanical characterization of nanoobjects. The method does not include a direct measurement of the tip-sample force but is rather based on the study of the relative elastic response. (C) 2014 Elsevier B.V. All rights reserved.

Field and potential around local scatterers in thin metal films studied by scanning tunneling potentiometry

We report the direct observation of electrochemical potential and local transport field variations near scatterers like grain boundaries, triple points, and voids in thin platinum films studied by scanning tunneling potentiometry. The field is highest at a void, followed by a triple point and a grain boundary. The local transport field near a void can even be four orders of magnitude higher than the macroscopic field, indicating that the void is the most likely place for an electromigration induced failure. The field build up for a particular type of scatterer depends on the grain connectivity. We estimate an average grain boundary reflection coefficient for the film from the temperature dependence of its resistivity.

Non-linear regression model for spatial variation in precipitation chemistry for South India

Chemical composition of rainwater changes from sea to inland under the influence of several major factors - topographic location of area, its distance from sea, annual rainfall. A model is developed here to quantify the variation in precipitation chemistry under the influence of inland distance and rainfall amount. Various sites in India categorized as 'urban', 'suburban' and 'rural' have been considered for model development. pH, HCO3, NO3 and Mg do not change much from coast to inland while, SO4 and Ca change is subjected to local emissions. Cl and Na originate solely from sea salinity and are the chemistry parameters in the model. Non-linear multiple regressions performed for the various categories revealed that both rainfall amount and precipitation chemistry obeyed a power law reduction with distance from sea. Cl and Na decrease rapidly for the first 100 km distance from sea, then decrease marginally for the next 100 km, and later stabilize. Regression parameters estimated for different cases were found to be consistent (R-2 similar to 0.8). Variation in one of the parameters accounted for urbanization. Model was validated using data points from the southern peninsular region of the country. Estimates are found to be within 99.9% confidence interval. Finally, this relationship between the three parameters - rainfall amount, coastline distance, and concentration (in terms of Cl and Na) was validated with experiments conducted in a small experimental watershed in the south-west India. Chemistry estimated using the model was in good correlation with observed values with a relative error of similar to 5%. Monthly variation in the chemistry is predicted from a downscaling model and then compared with the observed data. Hence, the model developed for rain chemistry is useful in estimating the concentrations at different spatio-temporal scales and is especially applicable for south-west region of India. (C) 2008 Elsevier Ltd. All rights reserved.

High Oxygen Storage Capacity and High Rates of CO Oxidation and NO Reduction Catalytic Properties of Ce1-xSnxO2 and Ce0.78Sn0.2Pd0.02O2-delta

Ce1-xSnxO2 (x = 0.1-0.5) solid solution and its Pd substituted analogue have been prepared by a single step solution combustion method using tin oxalate precursor. The compounds were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and H-2/temperature programmed redution (TPR) studies. The cubic fluorite structure remained intact up to 50% of Sri substitution in CeO2, and the compounds were stable up to 700 C. Oxygen storage capacity of Ce1-xSnxO2 was found to be much higher than that of Ce1-xZrxO2 due to accessible Ce4+/Ce3+ and Sn4+/Sn2+ redox couples at temperatures between 200 and 400 C. Pd 21 ions in Ce0.78Sn0.2Pd0.02O2-delta are highly ionic, and the lattice oxygen of this catalyst is highly labile, leading to low temperature CO to CO2 conversion. The rate of CO oxidation was 2 mu mol g(-1) s(-1) at 50 degrees C. NO reduction by CO with 70% N-2 selectivity was observed at similar to 200 degrees C and 100% N-2 selectivity below 260 degrees C with 1000-5000 ppm NO. Thus, Pd2+ ion substituted Ce1-xSnxO2 is a superior catalyst compared to Pd2+ ions in CeO2, Ce1-xZrxO2, and Ce1-xTixO2 for low temperature exhaust applications due to the involvement of the Sn2+/Sn4+ redox couple along with Pd2+/Pd-0 and Ce4+/Ce3+ couples.

Extended Kalman filters using explicit and derivative-free local linearizations

We propose three variants of the extended Kalman filter (EKF) especially suited for parameter estimations in mechanical oscillators under Gaussian white noises. These filters are based on three versions of explicit and derivative-free local linearizations (DLL) of the non-linear drift terms in the governing stochastic differential equations (SDE-s). Besides a basic linearization of the non-linear drift functions via one-term replacements, linearizations using replacements through explicit Euler and Newmark expansions are also attempted in order to ensure higher closeness of true solutions with the linearized ones. Thus, unlike the conventional EKF, the proposed filters do not need computing derivatives (tangent matrices) at any stage. The measurements are synthetically generated by corrupting with noise the numerical solutions of the SDE-s through implicit versions of these linearizations. In order to demonstrate the effectiveness and accuracy of the proposed methods vis-à-vis the conventional EKF, numerical illustrations are provided for a few single degree-of-freedom (DOF) oscillators and a three-DOF shear frame with constant parameters.

A Classification of Homogeneous Operators in the Cowen-Douglas Class

A complete list of homogeneous operators in the Cowen-Douglas class B-n(D) is given. This classification is obtained from an explicit realization of all the homogeneous Hermitian holomorphic vector bundles on the unit disc under the action of the universal covering group of the bi-holomorphic automorphism group of the unit disc.

Local structure of Sr2FeMoxW1-xO6 double perovskites across the composition-driven metal to insulator transition

Sr2FeMoO6 oxides exhibit a half-metallic ferromagnetic (HM-FM) ground state and peculiar magnetic and magnetotransport properties, which are interesting for applications in the emerging field of spintronics and attractive for fundamental research in the field of heavily correlated electron systems. Sr2FeWO6 is an insulator with an antiferromagnetic (I-AFM) ground state. The solid solutions Sr2FeMoxW1-xO6 also have peculiar properties-W doping enhances chemical order which allows stabilization of the HM-FM state; as the W content exceeds a certain value a metal to insulator transition (MIT) occurs. The role of W in determining the physical properties of Sr2FeMoxW1-xO6 systems has been a matter of intense investigation. This work deals with the problem of the structural and electronic changes related to the MIT from a local perspective by means of x-ray absorption spectroscopy (XAS). This technique allows one to probe in detail the local structure and electronic modifications around selected absorber ions (W, Mo, Fe and Sr in our case). The results of XAS analysis in the whole composition range (0 <= x <= 1), in the near edge (XANES) and extended (EXAFS) regions, demonstrate an abrupt change of the local structure around the Fe and Mo sites at the critical composition, x(c). This change represents the microstructural counterpart associated with the MIT. Conversely, the local structure and electronic configuration of W ions remain unaltered in the whole composition range, suggesting indirect participation of W in the MIT.

Studies in metal-ammonia reduction-5: Reduction and reductive methylation of some naphthoic acids

Birch reductio and reductive methylations of some substituted naphtholic acids have been examined. The factors influencing the mechanism of reduction process have been discussed. Some of the reduced naphthoic acids are useful synthons for synthesis.