Relation between effective atomic charge and chemical shifts in X-ray absorption spectra of transition-metal compounds

Chemical shifts of K absorption discontinuities, Delta E, of several manganese, iron and cobalt oxides with the metal in the formal oxidation states between +2 and +4, have been measured. These data, together with data in the literature on other compounds of these metals, can be fitted into the expression Delta E=aq+bq2, where q is the effective atomic charge on the metal. Theoretical considerations also support this functional relationship between Delta E and q.

Phase Transformation Introduced by Mechanical and Chemical Surface Preparations of Tetragonal Zirconia Polycrystals

Cutting of Y2O3-doped TZP rods by a low-speed diamond saw introduces an unidentified, metastable phase X (x-ZrO2) coexisting with the tetragonal (t-ZrO2) and the monoclinic (m-ZrO2) phases initially present in the sample. Further mechanical deformation of the cut surface by indentation or polishing sustains the x-ZrO2. Chemical etching removes the x-ZrO2 and increases the m-ZrO2content.

Potassium titanyl phosphate and its isomorphs: Growth, properties, and applications

Potassium titanyl phosphate (KTP) and its isomorphs have received enormous attention in the last 2 decades. In particular, KTP assumes importance due to its large nonlinear optic and electrooptic coefficients together with the broad thermal and angular acceptance for second harmonic generation. This article provides an overview of the material aspects, structural, physical, and chemical properties and device feasibility of the KTP family of crystals. Some of the current areas of research and development along with their significance in understanding the physical properties as well as device applications are addressed. Optical waveguide fabrication processes and characteristics with their relevance to the present-day technology are highlighted. Studies performed so far have enabled us to understand the fundamental aspects of these materials and what needs to be pursued vigorously is the exploitation of their device applications to the maximum extent.

Autonomous and non-autonomous traits mediate social cooperation in Dictyostelium discoideum

In the trishanku (triA(-)) mutant of the social amoeba Dictyostelium discoideum, aggregates are smaller than usual and the spore mass is located mid-way up the stalk, not at the apex. We have monitored aggregate territory size, spore allocation and fruiting body morphology in chimaeric groups of (quasi-wild-type) Ax2 and triA(-) cells. Developmental canalisation breaks down in chimaeras and leads to an increase in phenotypic variation. A minority of triA(-) cells causes largely Ax2 aggregation streams to break up; the effect is not due to the counting factor. Most chimaeric fruiting bodies resemble those of Ax2 or triA(-). Others are double-deckers with a single stalk and two spore masses, one each at the terminus and midway along the stalk. The relative number of spores belonging to the two genotypes depends both on the mixing ratio and on the fruiting body morphology. In double-deckers formed from 1:1 chimaeras, the upper spore mass has more Ax2 spores, and the lower spore mass more triA(-) spores, than expected. Thus, the traits under study depend partly on the cells' own genotype and partly on the phenotypes, and so genotypes, of other cells: they are both autonomous and non-autonomous. These findings strengthen the parallels between multicellular development and behaviour in social groups. Besides that, they reinforce the point that a trait can be associated with a genotype only in a specified context.

Kinetics and chemical analysis of photoinduced interdiffusion in nanolayered Se/As2S3 films

We have studied the kinetics of photoinduced effects in nanolayered Se/As2S3 film by in situ optical absorption measurements, which reveal that photodarkening in these films is followed by photoinduced diffusion. An increase in disorder during photodarkening and its subsequent decrease during photoinduced diffusion were also observed. The observation of photodarkening of Se at room temperature when confined between As2S3 layers suggests that the glass transition temperature of Se shifts to higher energy. The analysis shows that the atoms which take part in photodarkening play a vital role in photoinduced diffusion. The x-ray photoelectron spectroscopy measurements show the atomic movements during photoinduced diffusion. It also shows that some of the As–S bonds are converted into As–Se bonds. Since it is energetically difficult to break an As–S bond to form an As–Se bond, we assume that the new bond formations are taking place by the bond rearrangement mechanism.

Thermo-physical and structural studies of sodium zinc borovanadate glasses in the region of high concentration of modifier oxides

This paper reports investigation of Na2O and ZnO modified borovanadate glasses in the highly modified regime of compositions. These glasses have been prepared by microwave route. Ultraviolet (UV) and visible, infrared (IR), Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) and Electron Paramagnetic Resonance (EPR) spectroscopies have been used to characterize the speciation in the glasses. Together with the variation of properties such as molar volume and glass transition temperatures, spectroscopic data indicate that at high levels of modification, ZnO tends to behave like network former. It is proposed that the observed variation of all the properties can be reasonably well understood with a structural model. The model considers that the modification and speciation in glasses are strongly determined by the hierarchy of group electronegativities. Further, it is proposed that the width of the transitions of glasses obtained under same condition reflects the fragility of the glasses. An empirical expression has been suggested to quantify fragility on the basis of width of the transition regions. (C) 2012 Elsevier Ltd. All rights reserved.

Gibbs Energy of Formation of Ca3Ti8Al12O37 and Phase Relations and Chemical Potentials in the System Al2O3-TiO2-CaO

The quaternary oxide in the system Al2O3-CaO-TiO2 is found to have the composition Ca3Ti8Al12O37 rather than CaTi3Al8O19 as reported in the literature. The standard Gibbs energy of formation of Ca3Ti8Al12O37 from component binary oxides is measured in the temperature range from 900 to 1250 K using a solid-state electrochemical cell incorporating single crystal CaF2 as the solid electrolyte. The results can be represented by the equation: delta G(f(0x))(0) (+/- 70)/J mol(-1) = -248474 - 15.706(T/K). Combining this information with thermodynamic data on calcium aluminates and titanates available in the literature, subsolidus phase relations in the pseudo-ternary system Al2O3-CaO-TiO2 are computed and presented as isothermal sections. The evolution of phase relations with temperature is highlighted. Chemical potential diagrams are computed at 1200 K, showing the stability domains of the various phases in the chemical potential-composition space. In each chemical potential diagram, chemical potential of one component is plotted against the cationic fraction of the other two components. The diagrams are valid at relatively high oxygen potentials where Ti is present in its four-valent state in all the oxide phases.

Thermodynamics of TmRhO3, Phase Equilibria, and Chemical Potentials in the System Tm-Rh-O

Phase equilibria in the system Tm-Rh-O at 1200 K is established by isothermal equilibration of selected compositions and phase identification after quenching to room temperature. Six intermetallic phases (Tm3Rh, Tm7Rh3, Tm5Rh3, Tm3Rh2, TmRh, TmRh2 +/-delta) and a ternary oxide TmRhO3 are identified. Based on experimentally determined phase relations, a solid-state electrochemical cell is devised to measure the standard free energy of formation of orthorhombic perovskite TmRhO3 from cubic Tm2O3 and beta-Rh2O3 in the temperature range from (900 to 1300) K. The results can be summarized as: Delta G(f,ox)(o) +/- 104/J.mol(-1) = -46474 + 3.925(T/K). Invoking the Neumann-Kopp rule, the standard enthalpy of formation of TmRhO3 from its constituent elements at 298.15 K is estimated as -1193.89 (+/- 2.86) kJ.mol(-1). The standard entropy of TmRhO3 at 298.15 K is evaluated as 103.8 (+/- 1.6) J.mol(-1).K-1. The oxygen potential-composition diagram and three-dimensional chemical potential diagram at 1200 K and temperature-composition diagrams at constant partial pressures of oxygen are computed from thermodynamic data. The compound TmRhO3 decomposes at 1688 (+/- 2) K in pure oxygen and at 1583 (+/- 2) K in air at standard pressure.

Electromagnetic jigsaw: metal-cutting by combining electromagnetic and mechanical Forces

The magnetic saw effect, induced by the Lorentz force generated due to the application of a series of electromagnetic ( EM) pulses, can be utilized to cut a metallic component containing a pre-existing cut or crack. By combining a mechanical force with the Lorentz force, the cut can be propagated along any arbitrary direction in a controlled fashion, thus producing an `electromagnetic jigsaw', yielding a novel tool-less, free-formed manufacturing process, particularly suitable for hard-to-cut metals. This paper presents validation of the above concept based on a simple analytical model, along with experiments on two materials - Pb foil and steel plate. (C) 2013 The Authors. Published by Elsevier B.V. Selection and/or peer-review under responsibility of Professor Bert Lauwers

The influence of termites on soil sheeting properties varies depending on the materials on which they feed

Fungus-growing termites are involved in many ecological processes and play a central role in influencing soil dynamics in the tropics. The physical and chemical properties of their nest structures have been largely described; however less information is available concerning the relatively temporary structures made above-ground to access food items and protect the foraging space (the soil `sheetings'). This study investigated whether the soil physical and chemical properties of these constructions are constant or if they vary depending on the type of food they cover. Soil samples and soil sheetings were collected in a forest in India, from leaves on the ground (LEAF), fallen branches (WOOD), and vertical soil sheetings covering the bark of trees (TREE). In this environment, termite diversity was dominated by Odontotermes species, and especially Odontotermes feae and Odontotermes obesus. However, there was no clear niche differentiation and, for example, O. feae termites were found on all the materials. Compared with the putative parent soil (control), TREE sheetings showed the greatest (and most significant) differences (higher clay content and smaller clay particle sizes, lower C and N content and smaller delta C-13 and delta N-15), while LEAF sheetings were the least modified, though still significantly different than the control soil. We suggest that the termite diversity is a less important driver of potential soil modification than sheeting diversity. Further, there is evidence that construction properties are adapted to their prospective life-span, with relatively long-lasting structures being most different from the parent soil. (C) 2015 Elsevier Masson SAS. All rights reserved.

Fly ash cenospheres as reinforcement in different polymer composites - a comparative study of physical and mechanical properties

The work reports the preparation of fly ash cenospheres bearing polymer composites, using various polymer matrix materials namely, low density polyethylene, high density polyethylene, polystyrene and polymethylmethacrylate followed by evaluation of properties. The composites are synthesized by including about 18% by weight fly ash cenospheres, into various polymer matrices using brabender facility in the temperature range 120-160 degrees C and at a mixing pressure of 50 MPa. Subsequently, they are cast into sheets through compression moulding. The test samples, made from the sheets, are characterized for physical as well as mechanical properties such as density, hardness, compression strength, impact response, wear and friction. The investigation reveals that the addition of fly ash cenospheres to various polymer matrices results in reduction of density. Further, improvements in the slide wear resistance and decrease in the co-efficient of friction values are noticed. As for interpreting the slide wear data, recourse to examination under scanning electron microscope is made in this paper. As regards the mechanical properties, hardness increases while the compression strength and impact energy decreases with inclusion of cenospheres in all the four types of samples investigated.

Review on Tin (II) Sulfide (SnS) Material: Synthesis, Properties, and Applications

Tin (II) sulphide (SnS), a direct band gap semiconductor compound, has recently received great attention due to its unique properties. Because of low cost, absence of toxicity, and good abundance in nature, it is becoming a candidate for future multifunctional devices particularly for light conversion applications. Although the current efficiencies are low, the cost-per-Watt is becoming competitive. At room temperature, SnS exhibits stable low-symmetric, double-layered orthorhombic crystal structure, having a = 0.4329, b = 1.1192, and c = 0.3984nm as lattice parameters. These layer-structured materials are of interest in various device applications due to the arrangement of structural lattice with cations and anions. The layers of cations are separated only by van der Waals forces that provide intrinsically chemically inert surface without dangling bonds and surface density of states. As a result, there is no Fermi level pinning at the surface of the semiconductor. This fact leads to considerably high chemical and environmental stability. Further, the electrical and optical properties of SnS can be easily tailored by modifying the growth conditions or doping with suitable dopants without disturbing its crystal structure.In the last few decades, SnS has been synthesized and studied in the form of single-crystals and thin-films. Most of the SnS single-crystals have been synthesized by Bridgeman technique, whereas thin films have been developed using different physical as well as chemical deposition techniques. The synthesis or development of SnS structures in different forms including single-crystals and thin films, and their unique properties are reviewed here. The observed physical and chemical properties of SnS emphasize that this material could has novel applications in optoelectronics including solar cell devices, sensors, batteries, and also in biomedical sciences. These aspects are also discussed.

Physical and numerical modeling of horizontal gas-hydrate wells

Methane hydrate, which is usually found under deep seabed or permafrost zones, is a potential energy resource for future years. Depressurization of horizontal wells bored in methane hydrate layer is considered as one possible method for hydrate dissociation and methane extraction from the hosting soil. Since hydrate is likely to behave as a bonding material to sandy soils, supported well construction is necessary to avoid well-collapse due to the loss of the apparent cohesion during depressurization. This paper describes both physical and numerical modeling of such horizontal support wells. The experimental part involves depressurization of small well models in a large pressure cell, while the numerical part simulates the corresponding problem. While the experiment models simulate only gas saturated initial conditions, the numerical analysis simulates both gas-saturated and more realistic water-saturated conditions based on effective stress coupled flow-deformation formulation of these three phases. © 2006 Taylor & Francis Group.