Electrochemical detection and removal of lead in water using poly(propylene imine) modified re-compressed exfoliated graphite electrodes

Modification of exfoliated graphite (EG) electrode with generation 2 poly(propylene imine) dendrimer by electrodeposition resulted in an electrochemical sensor which was used to detect lead ions in water to a limit of 1 ppb and a linear response between 2.5 and 40 ppb using square wave anodic stripping voltammetry (SW-ASV). Pb(II) was also removed from spiked water sample using a 40-mm diameter unmodified EG electrode with an applied potential of -1,000 mV for 180 min. A removal efficiency of 99% was calculated from a 150 mL sample. The results obtained in both cases using SW-ASV, correlated with atomic absorption spectroscopy.

Combined Raman and infrared investigation of the insulator-to-metal transition in NiS(2-x)Se(x) compounds

Ambient-condition Raman spectra were collected in the strongly correlated NiS(1-x)Se(x) pyrite (0 <= x <= 1.2). Two samples (x = 0 and x = 0.55) were studied as a function of pressure up to 10 GPa, and for the x = 0.55 sample the pressure dependence of the infrared reflectivity was also measured (0-10 GPa). This gave a complete picture of the optical response of that system on approaching the metallic state both by application of pressure and/or by Se alloying, which corresponds to a volume expansion. A peculiar nonmonotonic (V-shaped) volume dependence was found for the quasiparticle spectral weight of both pure and Se-doped compounds. In the x = 0.55 sample the vibrational frequencies of the chalcogen dimer show an anomalous volume dependence on entering the metallic phase. The abrupt softening observed, particularly significant for the Se-Se pair, indicates the relevant role of the softness of the Se-Se bond as previously suggested by theoretical calculations.

Electronic structure of early transition metal oxides, Ca1−xSrxVO3 and La1−xCaxVO3: What can we learn from photoelectron spectroscopy

Photoemission spectroscopy offers the unique possibility of mapping out the electronic structure of the occupied electron states. However, the extreme surface sensitivity of this technique ensures that only the surface and the near-surface regions of any sample are probed. An important question arises in this context—Is the electronic structure of the surface region the same as that of the bulk? We address this issue using two different series of vanadium oxides, Ca1−xSrxVO3 and La1−xCaxVO3. Our results clearly establish that the electronic structure of the surface region is drastically different from that of the bulk in both these cases. We provide a method to separate the two contributions: one arising from the near-surface region and the other representative of the bulk. This separation allows us to deduce some very unusual behaviors of the electronic structures in these systems.

(Dimethylamino)borylene and Related Complexes of Electron-Rich Metal Fragments: Generation of Nucleophile-Resistant Cations by Spontaneous Halide Ejection

Spontaneous halide ejection from a three-coordinate Lewis acid has been shown to offer a remarkable new route to cationic metal complexes featuring a linear, multiply bonded boron-donor Ligand. The exploitation of electron-rich [CpM(PR3)(2)] fragments within boryl systems of the type LnMB(hal)NR2 leads to the spontaneous formation in polar solvents of chemically robust borylene complexes, [LnM(BNR2)](+), with exceptionally low electrophilicity and short M-B bonds. This is reflected by M-B distances (ca. 1.80 angstrom for FeB systems) which are more akin to alkyl-/aryl-substituted borylene complexes and, perhaps most strikingly, by the very low exothermicity associated with the binding of pyridine to the two-coordinate boron center (Delta H = -7.4 kcal mol(-1), cf. -40.7 kcal mol(-1) for BCl3). Despite the strong pi electron release from the metal fragment implied by this suppressed reactivity and by such short M-B bonds, the barrier to rotation about the Fe=B bond in the unsymmetrical variant [CpFe(dmpe)(BN{C6H4OMe-4}Me)](+) is found to be very small (ca. 2.9 kcal mol(-1)). This apparent contradiction is rationalized by the orthogonal orientations of the HOMO and HOMO-2 orbitals of the [CpML2](+) fragment, which mean that the M-B pi interaction does not fall to zero even in the highest energy conformation.

Some mechanisms of tribofilm formation in metal/metal and ceramic/metal sliding interactions

Tribological interaction often generates new structures and materials which form the interface between the sliding pair. The new material designated tribofilm here may be protective or tribologically deleterious. The tribofilm plays a major role in determining the friction and wear of the interaction. Here, we give three examples: mechanically mixed, chemically generated and thermally activated, of tribofilms formed in three different tribological systems and speculate on the mechanism of their formation.

Structure and properties of zinc alloy based metal matrix composites

Zinc-aluminium cast alloys (ZA alloys) exhibit good castability and mechanical properties but these alloys lack creep resistance and high temperature stability. One solution to improve these properties is to reinforce with ceramic particles or fibres, to result in MMCs. MMCs can be produced using casting technique involving infiltration. A systematic investigation was taken and this paper discusses the salient findings of the study on the ZA-27 alloy based MMCs produced through squeeze casting. (Reinforcing fibers: SAFFIL (chopped alumina) or mullite.)

A k-epsilon model for turbulent weld pool convection in gas metal arc welding process

In this paper, we present a modified k - epsilon model capable of addressing turbulent weld-pool convection in a GMAW process, taking into account the morphology of the phase change interface during a Gas Metal Arc Welding (GMAW) process. A three-dimensional turbulence mathematical model has been developed to study the heat transfer and fluid flow within the weld pool by considering the combined effect of three driving forces, viz., buoyancy, Lorentz force and surface tension (Marangoni convection). Mass and energy transports by the droplets are considered through the thermal analysis of the electrode. The falling droplet's heat addition to the molten pool is considered to be a volumetric heat source distributed in an imaginary cylindrical cavity ("cavity model") within the weld pool. This nature of heat source distribution takes into account the momentum and the thermal, energy of the falling droplets. The numerically predicted weld pool dimensions both from turbulence and laminar models are then compared with the experimental post-weld results sectioned across the weld axis. The above comparison enables us to analyze the overall effects of turbulent convection on the nature of heat and fluid flow and hence on the weld pool shape/size during the arc welding processes.

Enhanced photoluminescence of Gd2O3:Eu3+ nanophosphors with alkali (M = Li+, Na+, K+) metal ion co-doping

Gd1.95Eu0.4M0.01O3 (M = Li+ Na+ K+) nanophosphors have been synthesized by a low temperature solution combustion (LSC) method. Powder X-ray diffraction pattern (PXRD), scanning electron microscopy (SEM), UV-vis and photoluminescence (PL) measurements were carried out to characterize their structural and luminescent properties. The excitation and emission spectra indicated that the phosphor could be well excited by UV light (243 nm) and emit red light about 612 nm. The effect of alkali co-dopant on PL properties has been examined. The results showed that incorporation of Li+, Na+ and K+ in to Gd2O3:Eu3+ phosphor would lead to a remarkable increase of photoluminescence. The PL intensity of Gd2O3:Eu3+ phosphor was improved evidently by co-doping with Li+ ions whose radius is less than that of Gd3+ and hardly with Na+, K+ whose radius is larger than that of Gd3+. The effect of co-dopants on enhanced luminescence was mainly regarded as the result of a suitable local distortion of crystal field surrounding the Eu3+ activator. These results will play an important role in seeking some more effective co-dopants. (C) 2011 Published by Elsevier B.V.

Durable Transition-Metal-Carbide-Supported Pt-Ru Anodes for Direct Methanol Fuel Cells

Molybdenum carbide (MoC) and tungsten carbide (WC) are synthesized by direct carbonization method. PtRu catalysts supported on MoC, WC, and Vulcan XC-72R are prepared, and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy in conjunction with electrochemistry. Electrochemical activities for the catalysts towards methanol electro-oxidation are studied by cyclic voltammetry. All the electro-catalysts are subjected to accelerated durability test (ADT). The electrochemical activity of carbide-supported electro-catalysts towards methanol electro-oxidation is found to be higher than carbon-supported catalysts before and after ADT. The study suggests that PtRu/MoC and PtRu/WC catalysts are more durable than PtRu/C. Direct methanol fuel cells (DMFCs) with PtRu/MoC and PtRu/WC anodes also exhibit higher performance than the DMFC with PtRu/C anode.

Removal of Nitrogen Oxides in Diesel Engine Exhaust by Plasma Assisted Molecular Sieves

This paper reports the studies conducted on removal of oxides of nitrogen (NOx) from diesel engine exhaust using electrical discharge plasma combined with adsorbing materials such as molecular sieves. This study is being reported for the first time. The exhaust is taken from a diesel engine of 6 kW under no load conditions. The characteristic behavior of a pulse energized dielectric barrier discharge reactor in the diesel exhaust treatment is reported. The NOx removal was not significant (36%) when the reactor without any packing was used. However, when the reactor was packed with molecular sieves (MS -3A, -4A & -13X), the NOx removal efficiency was increased to 78% particularly at a temperature of 200 °C. The studies were conducted at different temperatures and the results were discussed.

Nonthermal-Plasma-Promoted Catalysis for the Removal of NOx From a Stationary Diesel-Engine Exhaust

A detailed study on the removal of oxides of nitrogen (NOx) from the exhaust of a stationary diesel engine was carried out using nonthermal-plasma (pulsed electrical-discharge plasma)-promoted catalytic process. In this paper, the filtered exhaust from the diesel engine is made to pass through a combination of nonthermal plasma reactor and a catalytic reactor connected in series. This combination is referred to as cascade. Two types of cascaded systems were studied. In one type, the plasma treating filtered exhaust was cascaded with a reduction catalyst V2O5/TiO2 using ammonia as reducing agent, and in the other type, the plasma treating filtered exhaust was cascaded with activated-alumina catalyst without any additive. Improved NOx-removal performance of both the cascaded processes and the role of nonthermal plasma in promoting catalysis are explained. Along with the NOx, total hydrocarbon and aldehydes were also removed. Furthermore, experiments were conducted at different temperatures and engine-loading conditions.

Application of Solar Powered High Voltage Discharge Plasma for NOX Removal in Diesel Engine Exhaust

This paper proposes a compact electric discharge plasma source for controlling NOX emission in diesel engine exhaust. Boost converter is used to boost to solar powered battery voltage to 24V, further an automobile ignition coil was used to generate the high voltage pulse using fly-back topology. This design is aimed at retrofitting the existing catalytic converters with pulse assisted cleaning technique. In this paper we bring out a relative comparison of discharge plasma and plasma-adsorbent process at different gas flow rates. Activated alumina was used as adsorbent. The main emphasis is laid on the development of a compact pulse source from 12V battery, which is powered by the solar, for the removal of NOX from the filtered diesel engine exhaust.

Synthesis, spectroscopic properties and biological evaluation of transition metal complexes of salicylhydrazone of anthranilhydrazide: X-ray crystal structure of copper complex

The transition metal complexes of salicylhydrazone of anthranilhydrazide (H2L) were synthesised. The structures of metal complexes were characterized by various spectroscopic [IR, NMR, UV-Vis, EPR], thermal and other physicochemical methods. The single-crystal X-ray diffraction study of [Cu(HL)Cl]center dot H2O reveal its orthorhombic system with space group P2(1)2(1)2 and Z=4. The copper center has a distorted square planar geometry with ONO and Cl as the donor atoms. The ligand and its metal chelates have been screened for their antimicrobial and anti-tubercular activities using serial dilution method. Metal complexes in general have exhibited better antibacterial and antifungal activity than the free ligand and in few cases better than the standard used. Among the bacterial strains used, the complexes are highly potent against Gram-positive strains compared to Gram-negative. Anti-tubercular activity exhibited by the Co(II) complex is comparable with the standard used. (C) 2011 Elsevier B. V. All rights reserved.