Magnetic susceptibility studies of lead oxyhalide glasses containing transition metal oxides

Magnetic susceptibility studies of lead oxyhalide glasses containing high concentrations of transition metal oxides such as MnO and Fe2O3 have been performed. While they exhibit predominantly antiferromagnetic interactions, the low temperature (<100K) region is dominated by paramagnetic contributions. The behaviour in these glasses is found to be similar to that of covalent oxide glasses and is different from that of purely ionic sulphate glasses.

Electron spin resonance studies of d5 ions (Fe3+ and Mn2+) in lead oxide-lead halide glasses

Electron spin resonance (ESR) of d5 ions (Fe3+ and Mn2+) has been investigated in PbO---PbF2 and PbO---PbCl2 glasses in wide ranges of composition. ESR spectra of d5 ions in these glasses exhibit significant differences which we have attributed to at least three important causes: (i) The ionic potentials of Fe3+ and Mn2+ are different. Hence Fe3+ ions tend to acquire their own environment while Mn2+ ions take up substitutional (Pb2+ ion) positions. (ii) The sizes and nephelauxetic behaviours of O2- and F- ions are similar. Thus even when there is a mixed anionic coordination, the environment of Mn2+ ions is highly symmetrical in oxyfluoride glasses. The Mn2+ spectra in oxychloride glasses are considerably different. (iii) Increase in halide ion concentration increases the ionicity of lead-ligand bonding and favours a more symmetrical environment around dopant ions in halide-rich glasses. The features in ESR spectra have been interpreted in the light of known behaviour of d5 ions in glasses and also in the context of known structural features of PbO---PbX2 glasses. Dopant ions appear to cluster at high concentrations although isolated low-symmetry sites are still observed. Effects of crystallization and annealing upon ESR spectra have also been investigated.

Large scale surveys suggest limited mercury availability in tropical north Queensland (Australia)

Little is known about the threat of mercury (Hg) to consumers in food webs of Australia's wet-dry tropics. This is despite high concentrations in similar biomes elsewhere and a recent history of gold mining that could lead to a high degree of exposure for biota. We analysed Hg in water, sediments, invertebrates and fishes in rivers and estuaries of north Queensland, Australia to determine its availability and biomagnification in food webs. Concentrations in water and sediments were low relative to other regions of Hg concern, with only four of 138 water samples and five of 60 sediment samples above detection limits of 0.1 mu g L-1 and 01 mu g g(-1), respectively. Concentrations of Hg in fishes and invertebrates from riverine and wetland food webs were well below international consumption guidelines, including those in piscivorous fishes, likely due to low baseline concentrations and limited rates of biomagnification (average slope of log Hg vs. delta N-15 = 0.08). A large fish species of recreational, commercial, and cultural importance (the barramundi, Lates calcarifer), had low concentrations that were below consumption guidelines. Observed variation in Hg concentrations in this species was primarily explained by age and foraging location (floodplain vs. coastal), with floodplain feeders having higher Hg concentrations than those foraging at sea. These analyses suggest that there is a limited threat of Hg exposure for fish-eating consumers in this region. (C) 2011 Published by Elsevier B.V.

Ionic conductivity and dielectric measurements in single crystal β---AgI

Ionic conductivity measurements have been made on pure, copper-doped and cadmium-doped single crystals. Dielectric measurements in the frequency range 30Hz–100Hz showed that there was no anomalously to be (0.64 ± 0.02) eV and migration energies for silver ion intersitials and vacancies in the c direction to be (0.41 ± 0.02) eV and (0.50 ± 0.02) eV respectively. ESR measurements have shown that copper exists as Cu+ in these crystals. Dielectric measurements in the frequency range (OHz–100KHz showed that there was no anomalously high value for ε as reported earlier.

Enhanced ionic conductivity in nano-composite solid polymer electrolyte: (PEG) (x) LiBr: y(SiO2)

In this paper, we report an enhancement in ionic conductivity in a new nano-composite solid polymer electrolyte namely, (PEG) (x) LiBr: y(SiO2). The samples were prepared, characterized, and investigated by XRD, IR, NMR, and impedance spectroscopy. Conductivity as a function of salt concentration shows a double peak. Five weight percent addition of silica nanoparticles increases the ionic conductivity by two orders of magnitude. Conductivity exhibits an Arrhenius type dependence on temperature. IR study has shown that the existence of nanoparticles in the vicinity of terminal OaEuro center dot H group results in a shift in IR absorption frequency and increase in amplitude of vibration of the terminal OaEuro center dot H group. This might lead to an enhancement in conductivity due to increased segmental motion of the polymer. Li-7 NMR spectroscopic studies also seem to support this. Thus addition of nanoparticle inert fillers still seems to be a promising technique to enhance the ionic conductivity in solid polymer electrolytes.

Self-consistent microscopic treatment of the effects of self-motion of the probe on ionic and dipolar solvation dynamics

A simple but self-consistent microscopic theory for the time dependent solvation energy of both ions and dipoles is presented which includes, for the first time, the details of the self-motion of the probe on its own solvation dynamics. The theory leads to several interesting predictions. The most important of them is that, for dipolar solvation, both the rotational and the translational motions of the dipolar solute probe can significantly accelerate the rate of solvation. In addition, the rotational self-motion of the solute can also give rise to an additional mechanism of nonexponentiality in solvation time correlation functions in otherwise slow liquids. A comparison between the present theoretical predictions and the recent experimental studies of Maroncelli et al. on solvation dynamics of aniline in l-propanol seems to indicate that the said experiments have missed the initial solvent response up to about 45 ps. After mapping the experimental results on the redefined time scale, the theoretical results can explain the experimental results for solvation of aniline in 1-propanol very well. For ionic solvation, the translational motion is significant for light solutes only. For example, for Li+ in water, translational motion speeds up the solvation by about 20%. The present theory demonstrates that in dipolar solvation the partial quenching of the self-motion due to the presence of specific solute-solvent interactions (such as H-bonding) may lead to a much slower solvation than that when the self-motion is present. This point has been discussed. In addition, we present the theoretical results for solvation of aniline in propylene carbonate, Here, the solvation is predicted to be complete within 15-20 ps.

Noise and outlier removal from jet engine health signals using weighted FIR median hybrid filters

The removal of noise and outliers from measurement signals is a major problem in jet engine health monitoring. Topical measurement signals found in most jet engines include low rotor speed, high rotor speed. fuel flow and exhaust gas temperature. Deviations in these measurements from a baseline 'good' engine are often called measurement deltas and the health signals used for fault detection, isolation, trending and data mining. Linear filters such as the FIR moving average filter and IIR exponential average filter are used in the industry to remove noise and outliers from the jet engine measurement deltas. However, the use of linear filters can lead to loss of critical features in the signal that can contain information about maintenance and repair events that could be used by fault isolation algorithms to determine engine condition or by data mining algorithms to learn valuable patterns in the data, Non-linear filters such as the median and weighted median hybrid filters offer the opportunity to remove noise and gross outliers from signals while preserving features. In this study. a comparison of traditional linear filters popular in the jet engine industry is made with the median filter and the subfilter weighted FIR median hybrid (SWFMH) filter. Results using simulated data with implanted faults shows that the SWFMH filter results in a noise reduction of over 60 per cent compared to only 20 per cent for FIR filters and 30 per cent for IIR filters. Preprocessing jet engine health signals using the SWFMH filter would greatly improve the accuracy of diagnostic systems. (C) 2002 Published by Elsevier Science Ltd.

Manipulation of the Hydration Levels in Minerals of Sodium Cadmium Bisulfate toward the Design of Functional Materials

Several variants of hydrated sodium cadmium bisulfate, Na(2)Cd(2)(SO(4))(3) center dot 3H(2)O, Na(2)Cd(SO(4))(2) center dot 2H(2)O, and Na(2)Cd(SO(4))(2) center dot 4H(2)O have been synthesized, and their thermal properties followed by phase transitions have been invesigated. The formation of these phases depends on the stochiometry and the time taken for crystallization from water. Na(2)Cd(2)(SO(4))(3)center dot 3H(2)O, which crystallizes in the trigonal system, space group P3c, is grown from the aqueous solution in about four weeks. The krohnkite type mineral Na(2)Cd(SO(4))(2) center dot 2H(2)O and the mineral astrakhanite, also known as blodite, Na(2)Cd (SO(4))(2)center dot 4H(2)O, crystallize concomittantly in about 24 weeks. Both these minerals belong to the monoclinic system(space group P2(1)/c). Na(2)Cd(2)(SO(4))(3)center dot 3H(2)O loses water completely when heated to 250 degrees C and transforms to a dehydrated phase (cubic system, space group I (4) over bar 3d) whose structure has been established using ab initio powder diffration techniques. Na(2)Cd(SO(4))(2)center dot 2H(2)O transforms to alpha-Na(2)Cd(SO(4))(2) (space group C2/c) on heating to 150 degrees C which is a known high ionic conductor and remains intact over prolonged periods of exposure to moisture (over six months). However, when alpha-Na(2)Cd(SO(4))(2) is heated to 570 degrees C followed by sudden quenching in liquid nitrogen beta-Na(2)Cd(SO(4))(2) (P2(1)/c) is formed. beta-Na(2)Cd(SO(4))(2) takes up water from the atmosphere and gets converted completely to the krohnkite type mineral in about four weeks. Further, beta-Na(2)Cd(SO(4))(2) has a conductivity behavior comparable to the a-form up to 280 degrees C, the temperature required for the transformation of the beta- to alpha-form. These experiments demonstrate the possibility of utilizing the abundantly available mineral sources as precursors to design materials with special properties.

NO Reduction Over Noble Metal Ionic Catalysts

In last 40 years, catalysis for NO (x) removal from exhaust gas has received much attention to achieve pollution free environment. CeO(2) has been found to play a major role in the area of exhaust catalysis due to its unique redox properties. In last several years, we have been exploring an entirely new approach of dispersing noble metal ions in CeO(2) and TiO(2) for redox catalysis. We have extensively studied Ce(1-x) M (x) O(2-delta) (M = Pd, Pt, Rh), Ce(1-x-y) A (x) M (y) O(2-delta) (A = Ti, Zr, Sn, Fe; M = Pd, Pt) and Ti(1-x) M (x) O(2-delta) (M = Pd, Pt, Rh, Ru) catalysts for exhaust catalysis especially NO reduction and CO oxidation, structure-property relation and mechanism of catalytic reactions. In these catalysts, lower valent noble metal ion substitution in CeO(2) and TiO(2) creates noble metal ionic sites and oxide ion vacancy. NO gets molecularly adsorbed on noble metal ion site and dissociatively adsorbed on oxide ion vacancy site. Dissociative chemisorption of NO on oxide ion vacancy leads to preferential conversion of NO to N(2) instead of N(2)O over these catalysts. It has been demonstrated that these new generation noble metal ionic catalysts (NMIC) are much more catalytically active than conventional nano crystalline noble metal catalysts especially for NO reduction.

Gibbs energy formation of lead titanate

The Gibbs energy of formation of titania-saturated lead titanate has been determined by e.m.f. measurements on the solid state cell;Pt,Ir,Pb + Pb1−xTiO3−x + TiO2(rutile)/CaO-ZrO2/Ni + NiO,Pt in the temperature range 1075–1350 K. The results obtained are significantly different from those reported in the literature based upon vapour pressure measurements, employing Knudsen effusion and transportation techniques, and assuming that the vapor phase consisted entirely of monomeric PbO molecules. A reanalysis of the data obtained in the earlier vapor pressure studies using mass spectrometric measurements on polymeric PbO species in the gas phase, gives Gibbs energies of formation of lead titanate which are in better agreement with those obtained in this study. Earlier electrochemical measurements by Mehrotra et al. and more recent electrochemical measurements by Schmahl et al. both employing CaO-ZrO2 solid electrolytes are in good agreement with the present study. The electro-chemical measurements by Schmahl et al. using PbF 2 solid electrolyte give a slightly more positive Gibbs energy of formation. There was no evidence supporting the formation of compounds other than Pb1−xTiO3−x from yellow PbO and rutile form of TiO2 in the temperature range covered in this study.Résumé L'enthalpie libre de formation du titanate de plomb saturé en oxyde de titane a été déterminée par des mesures de FEM de la pile: Pt,Ir,Pb + Pb1−xTiO3−x + TiO2(rutile)/CaO-ZrO2/Ni + NiO,Pt dans le domaine de températures 1075–1350 K. Les résultats obtenus, different appréciablement de ceux publiés, déterminés par mesures de tensions de vapeur (techniques de transport et d'effusion de Knudsen) en supposant que la phase gazeuse etait uniquement constituée de molécules monomériques de PbO. Une réanalyse des résultats de la littérature, à partir de mesures par spectrométrie de masse sur les polymères de PbO gazeux, donne des enthalpies libres de formation du titanate de plomb se rapprochant de celles obtenues dans cette étude. Les mesures de Mehrotra et al. et plus récemment de Schmahl et al. utilisant toutes deux l'électrolyte CaO-ZrO2 concordent bien avec celles de la présente étude. Les mesures de Schmahl et al., à l'aide de l' électrolyte solide PbF2, donnent une enthalpie de formation légèrement plus positive. Pour la gammede températures étudiée, rien ne permet de supposer que des composés autres que Pb1−x TiO3−x puissent se former à partir du PbO Gaune) et du rutile (TiO2).

Electromechanical dynamics and optimization of pectoral fin-based ionic polymer-metal composite underwater propulsor

Ionic polymer-metal composites are soft artificial muscle-like bending actuators, which can work efficiently in wet environments such as water. Therefore, there is significant motivation for research on the development and design analysis of ionic polymer-metal composite based biomimetic underwater propulsion systems. Among aquatic animals, fishes are efficient swimmers with advantages such as high maneuverability, high cruising speed, noiseless propulsion, and efficient stabilization. Fish swimming mechanisms provide biomimetic inspiration for underwater propulsor design. Fish locomotion can be broadly classified into body and/or caudal fin propulsion and median and/or paired pectoral fin propulsion. In this article, the paired pectoral fin-based oscillatory propulsion using ionic polymer-metal composite for aquatic propulsor applications is studied. Beam theory and the concept of hydrodynamic function are used to describe the interaction between the beam and water. Furthermore, a quasi-steady blade element model that accounts for unsteady phenomena such as added mass effects, dynamic stall, and the cumulative Wagner effect is used to obtain hydrodynamic performance of the ionic polymer-metal composite propulsor. Dynamic characteristics of ionic polymer-metal composite fin are analyzed using numerical simulations. It is shown that the use of optimization methods can lead to significant improvement in performance of the ionic polymer-metal composite fin.

Lead Retention by Soils at Field Moisture Contents

The majority of studies pertaining to lead retention by clays and soils have examined the mechanisms, kinetics, and adsorption isotherms using the batch experiment technique that employs solid: water extracts of 1:10 and 1:20. Field soil deposits generally have much lower gravimetric water content ranging between 9 and 45%. Given the wide disparity in the solids: water ratio employed in the batch experiment technique and that prevailing in field deposits, this paper examines the lead retention characteristics of soils at field moisture contents (6%, 13%, and 25%) using artificially lead-contaminated soil specimens. A residually derived (i.e., formed by in-situ weathering of parent rock) red soil was used to prepare the artificially contaminated soil specimens. The impact of variations in clay content on lead retention was examined by diluting the residual soil with various amounts (0 to 60%) of river sand. Soil specimens remolded at 6 and 13% moisture contents produced very stiff to hard soils on compaction, while specimens remolded at 25% moisture content existed in the slurry state. The soil specimens were contaminated with low (30mg/kg) to high (2500mg/kg) concentrations of lead ions by remolding them with 160ppm to 10,000ppm ionic lead solutions. Lead retention by soils at field moisture contents was determined by extracting the lead from the soil using a water leach test. Experimental results showed that the bulk (71 to 99%) of the added lead was retained by the soil in insoluble form at the field moisture content. Correlations between the amount of lead retained and soil/solution parameters indicated that the amounts of Pb retained at field moisture content is a function of the initial Pb addition, total sand content, effective clay porosity, and soil pH.

A new approach for understanding ion transport in glasses; example of complex alkali diborate glasses containing lead, bismuth and tellurium oxides

Mechanism of ion transport in glasses continues to be incompletely understood. Several of the theoretical models in vogue fail to rationalize conductivity behaviour when d.c. and a.c. measurements are considered together. While they seem to involve the presence of at least two components in d.c. activation energy, experiments fail to reveal that feature. Further, only minor importance is given to the influence of structure of the glass on the ionic conductivity behaviour. In this paper, we have examined several general aspects of ion transport taking the example of ionically conducting glasses in pseudo binary, yNa(2)B(4)O(7)center dot(1-y) M (a) O (b) (with y = 0 center dot 25-0 center dot 79 and M (a) O (b) = PbO, TeO2 and Bi2O3) system of glasses which have also been recently characterized. Ion transport in them has been studied in detail. We have proposed that non-bridging oxygen (NBO) participation is crucial to the understanding of the observed conductivity behaviour. NBO-BO switching is projected as the first important step in ion transport and alkali ion jump is a subsequent event with a characteristically lower barrier which is, therefore, not observed in any study. All important observations in d.c. and a.c. transport in glasses are found consistent with this model.

Real time monitoring of petroleum leakage detection using etched fiber Bragg grating

Detection of petroleum leakages in pipelines and storage tanks is a very important as it may lead to significant pollution of the environment, accidental hazards, and also it is a very important fuel resource. Petroleum leakage detection sensor based on fiber optics was fabricated by etching the fiber Bragg grating (FBG) to a region where the total internal reflection is affected. The experiment shows that the reflected Bragg's wavelength and intensity goes to zero when etched FBG is in air and recovers Bragg's wavelength and intensity when it is comes in contact with petroleum or any external fluid. This acts as high sensitive, fast response fluid optical switch in liquid level sensing, petroleum leakage detection etc. In this paper we present our results on using this technique in petroleum leakage detection.

ABOUT FORMS OF ELECTRONIC AND IONIC DEVICES WITH THERMIONIC CATHODES.

The miniaturization of electronic and ionic devices with thermionic cathodes and thc improvement of their vacuum properties are questions of very great interest to the electronic engineer. However there have bcen no proposals so far to analyse the problem of miniaturization of such devices In a fundamental way. The present work suggests a choice of the geometrical shape of the cathode, the anode and the envelope of the device, that may help towards such a fundamcnlal approach.It is shown that a design, in which the cathode and the envelope of the tube are made of thm prismatic shape and the anode coincides with the cnvclope, offers a slriknrg advantage over the conventional cylindrical design, in respect of over-all size. The use of the prismatic shape will lead to considerable economy in msterials and may facilitate simpler prodoct~ont echn~ques. I n respect of the miin criteria of vacuum, namely the grade of vacuum, the internal volume occupied by residual gases, the evolution of gases in the internal space and the diffusion of gases from outside into the devicc, it is shown that the prismatic form is at least as good as, if not somewhat superior lo, the cylindrical form.In the actual construction of thin prismatic tubes, manv practical problems will arise, the most important being the mechanical strength and stablity of the structure. But the changeover from the conventional cylindrical to the new prirmaiic form, with its basic advantages, is a development that merits close attention.