Are Metallocene-Acetylene (M = Ti, Zr, Hf) Complexes Aromatic Metallacyclopropenes?

The bonding nature of metallocene acetylene complexes Cp2M(eta(2)-H3SiC2SiH3) 1M and CP2M (eta(2)- HC2H) 1M' (M = Ti, Zr, Hf) wits studied by density functional theory method. It is found that this acetylene complex has indeed it metallacyclopropene moiety with two in-plane M-C sigma-bonds and one out-of-plane pi-bond interacting with the metal center, resulting in the formation of it delocalized three-center and two-electron (3c-2e) system. Along with its delocalized out-of-plane bonding, this complex has been characterized its aromatic on the basis of the computed stabilizing energy and negative nucleus-independent chemical shifts (NICS). The aromatic stabilization increases from Ti to Zr and Hf, and this is because of the increased charge separation between the CP2M fragment and the H3SiC2SiH3 (also HC2H) unit. The decrease of the M-C bond length from Zr to Hf is ttributed to the increased s character of both M and C hybridization of the M-C a-bonds.

Ab initio electronic structures of rhombohedral and cubic HgXO3 (X = Ti, Pb)

First-principles calculations were performed for orthorhombic HgO, rhombohedral and cubic phases of HgTiO3 (HTO) and HgPbO3 (HPO). The calculations show that in the rhombohedral phase HTO is a direct gap insulator with a gap of ~1.6 eV. The rhombohedral phase of HPO, on the other hand, shows a weak metallic character. The results provide an explanation for the electrical properties of these compounds. The cubic phases of HTO and HPO are invariably metallic in nature, thereby suggesting that for HTO the rhombohedral–cubic transition must also be accompanied by a change in the electrical state. Examination of the electronic density of states of these systems revealed no significant on-site mixing of Hg 5d and Hg 6s states in any of these materials.

Rational design of 3D dendritic TiO2 nanostructures with favorable architectures

Controlling the morphology and size of titanium dioxide (TiO2) nanostructures is crucial to obtain superior photocatalytic, photovoltaic, and electrochemical properties. However, the synthetic techniques for preparing such structures, especially those with complex configurations, still remain a challenge because of the rapid hydrolysis of Ti-containing polymer precursors in aqueous solution. Herein, we report a completely novel approach-three- dimensional (3D) TiO2 nanostructures with favorable dendritic architectures-through a simple hydrothermal synthesis. The size of the 3D TiO2 dendrites and the morphology of the constituent nano-units, in the form of nanorods, nanoribbons, and nanowires, are controlled by adjusting the precursor hydrolysis rate and the surfactant aggregation. These novel configurations of TiO2 nanostructures possess higher surface area and superior electrochemical properties compared to nanoparticles with smooth surfaces. Our findings provide an effective solution for the synthesis of complex TiO2 nano-architectures, which can pave the way to further improve the energy storage and energy conversion efficiency of TiO 2-based devices.

Preparation of reticulated MAX-phase support with morphology-controllable nanostructured ceria coating for gas exhaust catalyst devices

Reticulated porous Ti3AlC2 ceramic, a member of the MAX-phase family (Mn+1AXn phases, where M is an early transition metal, A is an A-group element, and X is carbon and/or nitrogen), was prepared from the highly dispersed aqueous suspension by a replica template method. Through a cathodic electrogeneration method, nanocrystalline catalytic CeO2 coatings were deposited on the conductive porous Ti 3AlC2 supports. By adjusting the pH value and cathodic deposition current, coatings exhibiting nanocellar, nanosheets-like, or bubble-free morphologies can be obtained. This work expects to introduce a novel practically feasible material system and a catalytic coating preparation technique for gas exhaust catalyst devices.

Surface chemistry, dispersion behavior, and slip casting of Ti 3AlC2 suspensions

The surface chemistry and dispersion properties of aqueous Ti 3AlC2 suspension were studied in terms of hydrolysis, adsorption, electrokinetic, and rheological measurements. The Ti 3AlC2 particle had complex surface hydroxyl groups, such as ≡Ti-OH,=Al-OH, and -OTi-(OH)2, etc. The surface charging of the Ti3AlC2 particle and the ion environment of suspensions were governed by these surface groups, which thus strongly influenced the stability of Ti3AlC2 suspensions. PAA dispersant was added into the Ti3AlC2 suspension to depress the hydrolysis of the surface groups by the adsorption protection mechanism and to increase the stability of the suspension by the steric effect. Ti3AlC2 suspensions with 2.0 dwb% PAA had an excellent stability at pH=∼5 and presented the characteristics of Newtonian fluid. Based on the well-dispersed suspension, dense Ti3AlC2 materials were obtained by slip casting and after pressureless sintering. This work provides a feasible forming method for the engineering applications of MAX-phase ceramics, wherein complex shapes, large dimensions, or controlled microstructures are needed.

Anodic deposition of porous RuO2 on stainless steel for supercapacitor studies at high current densities

Ruthenium dioxide is deposited on stainless steel (SS) substrate by galvanostatic oxidation of Ru3+. At high current densities employed for this purpose, there is oxidation of water to oxygen, which occurs in parallel with Ru3+ oxidation. The oxygen evolution consumes a major portion of the charge. The oxygen evolution generates a high porosity to RuO2 films, which is evident from scanning electron microscopy studies. RuO2 is identified by X-ray photoelectron spectroscopy. Cyclic voltammetry and galvanostatic charge–discharge cycling studies indicate that RuO2/SS electrodes possess good capacitance properties. Specific capacitance of 276 F g−1 is obtained at current densities as high as 20 mA cm−2 (13.33 A g−1). Porous nature of RuO2 facilitates passing of high currents during charge–discharge cycling. RuO2/SS electrodes are thus useful for high power supercapacitor applications.

Multiphase porous media model for Intermittent Microwave Convective Drying (IMCD) of food

Intermittent microwave convective (IMCD) drying is an advanced drying technology that improves both energy efficiency and food quality during the drying of food materials. Despite numerous experimental studies available for IMCD, there is no complete multiphase porous media model available to describe the process. A multiphase porous media model considering liquid water, gases and the solid matrix inside the food during drying can provide in depth understanding of IMCD. In this article, firstly a multiphase porous media model was developed for IMCD. Then the model is validated against experimental data by comparing moisture content and temperature distributions after each heating and tempering periods. The profile of vapour pressures and evaporation during IMCD are presented and discussed. The relative contribution of water and vapour fluxes due to gas pressure and diffusion demonstrated that the fluxes due are relatively higher in IMCD compared to convection drying and this makes the IMCD faster.

Enhanced dielectric response of ZrO2 upon Ti doping and introduction of O vacancies

We determine the electronic properties and dielectric response of zirconia (ZrO2) with oxygen vacancies (O vacancies) and Ti doping using first-principles density functional theory calculations based on pseudopotentials and a plane wave basis. We find significantly enhanced static dielectric response in zirconia with Ti doping and introduction of oxygen vacancies. Softening of phonon modes are responsible for the enhanced dielectric response of doped samples compared to pure zirconia.

Reactive Pulsed Laser Deposition of titanium nitride thin film: Optimization of process parameters using Secondary Ion Mass Spectrometry

Reactive Pulsed Laser Deposition is a single step process wherein the ablated elemental metal reacts with a low pressure ambient gas to form a compound. We report here a Secondary Ion Mass Spectrometry based analytical methodology to conduct minimum number of experiments to arrive at optimal process parameters to obtain high quality TiN thin film. Quality of these films was confirmed by electron microscopic analysis. This methodology can be extended for optimization of other process parameters and materials. (C) 2009 Elsevier B.V. All rights reserved.

Kinetics of Pressureless Infiltration of Al-Mg Melts into Porous Alumina Preforms

Effective “hydrodynamic” radii governing infiltration kinetics of reactive Al-Mg melts into alumina preforms were found to be three orders of magnitude smaller than the average pore size of the packed bed and also smaller compared with the kinetics for a nonreactive system. A sinusoidal capillary model was developed to predict flow kinetics within the packed bed. For the reactive system, two factors were ascribed for additional melt retardation: (1) different intrinsic wettabilities of the two liquids on alumina, thereby leading to significantly different “effective” local contact angles; and (2) local solute depletion from the meniscus, which was incorporated as a time-dependent contact angle.

Manifestation of geometric frustration on magnetic and thermodynamic properties of the pyrochlores Sm2X2O7 (X=Ti,Zr)

We present here magnetization, specific heat, and Raman studies on single-crystalline specimens of the first pyrochlore member Sm2Ti2O7 of the rare-earth titanate series. Its analogous compound Sm2Zr2O7 in the rare-earth zirconate series is also investigated in the polycrystalline form. The Sm spins in Sm2Ti2O7 remain unordered down to at least T=0.5 K. The absence of magnetic ordering is attributed to very small values of exchange (θcw∼−0.26 K) and dipolar interaction (μeff∼0.15 μB) between the Sm3+ spins in this pyrochlore. In contrast, the pyrochlore Sm2Zr2O7 is characterized by a relatively large value of Sm-Sm spin exchange (θcw∼−10 K); however, long-range ordering of the Sm3+ spins is not established at least down to T=0.67 K due to frustration of the Sm3+ spins on the pyrochlore lattice. The ground state of Sm3+ ions in both pyrochlores is a well-isolated Kramers doublet. The higher-lying crystal field excitations are observed in the low-frequency region of the Raman spectra of the two compounds recorded at T=10 K. At higher temperatures, the magnetic susceptibility of Sm2Ti2O7 shows a broad maximum at T=140 K, while that of Sm2Zr2O7 changes monotonically. Whereas Sm2Ti2O7 is a promising candidate for investigating spin fluctuations on a frustrated lattice, as indicated by our data, the properties of Sm2Zr2O7 seem to conform to a conventional scenario where geometrical frustration of the spin excludes their long-range ordering.

Modelling of solute transport in a mild heterogeneous porous medium using stochastic finite element method: Effects of random source conditions

Randomness in the source condition other than the heterogeneity in the system parameters can also be a major source of uncertainty in the concentration field. Hence, a more general form of the problem formulation is necessary to consider randomness in both source condition and system parameters. When the source varies with time, the unsteady problem, can be solved using the unit response function. In the case of random system parameters, the response function becomes a random function and depends on the randomness in the system parameters. In the present study, the source is modelled as a random discrete process with either a fixed interval or a random interval (the Poisson process). In this study, an attempt is made to assess the relative effects of various types of source uncertainties on the probabilistic behaviour of the concentration in a porous medium while the system parameters are also modelled as random fields. Analytical expressions of mean and covariance of concentration due to random discrete source are derived in terms of mean and covariance of unit response function. The probabilistic behaviour of the random response function is obtained by using a perturbation-based stochastic finite element method (SFEM), which performs well for mild heterogeneity. The proposed method is applied for analysing both the 1-D as well as the 3-D solute transport problems. The results obtained with SFEM are compared with the Monte Carlo simulation for 1-D problems.

Unsteady natural convection from a horizontal annulus filled with a porous medium

The unsteady natural convection flow from a horizontal cylindrical annulus filled with a non-Darcy porous medium has been studied. The unsteadiness in the problem arises due to the impulsive change in the wall temperature of the outer cylinder. The Navier–Stokes equations along with the energy equation governing the unsteady natural convection flow have been solved by the finite-volume method. The effect of time variation on the heat transfer is more pronounced only in a small time interval immediately after the start of the impulsive motion and the steady state is reached after certain time. The results show that the annulus completely filled with a porous medium has the best insulating effectiveness. Convection in the horizontal annulus is confined mostly at top and bottom regions. Hence, only these regions should be insulated. In case of annulus partially filled with a porous material, insulating the region near the outer cylinder is more effective than insulating the region near the inner cylinder. The effect of Darcy number on the heat transfer is more pronounced than that of the Grashof number.

Study of (Ba3MMWO9)-M-II-W-IV (M-II = Ca, Zn; M-IV = Ti, Zr) perovskite oxides: Competition between 3C and 6H perovskite structures

We describe an investigation of (Ba3MMWO9)-M-II-W-IV oxides for M-II = Ca, Zn, and other divalent metals and M-IV = Ti, Zr. In general, a 1:2-ordered 6H (hexagonal, P6(3)/mmc) perovskite structure is stabilized at high temperatures (1300 degrees C) for all of the (Ba3MTiWO9)-Ti-II oxides investigated. An intermediate phase possessing a partially ordered 1:1 double perovskite (3C) structure with the cation distribution, Ba-2(Zn2/3Ti1/3)(W2/3Ti1/3)O-6, is obtained at 1200 degrees C for Ba3ZnTiWO9. Sr substitution for Ba in the latter stabilizes the cubic 3C structure instead of the 6H structure. A metastable Ba3CaZrWO9 that adopts the 3C (cubic, Fm (3) over barm) structure has also been synthesized by a low-temperature metathesis route. Besides yielding several new perovskite oxides that may be useful as dielectric ceramics, the present investigation provides new insights into the complex interplay of crystal chemistry (tolerance factor) and chemical bonding (anion polarization and d(0)-induced distortion of metal-oxygen octahedra) in the stabilization of 6H versus 3C perovskite structures for the (Ba3MMWO9)-M-II-W-IV series.