Photoelectron spectroscopic study of CdS nanocrystallites

Nanocrystallites of semiconductors, especially those belonging to II-VI and III-V groups, show size-dependent optical and electrical properties. In this paper we report on x-ray photoemission results of CdS nanocrystallites of two different sizes and compare these results with bulk CdS. The S 2p and 2s core levels of the nanocrystallites reveal three different types of sulfur, unlike bulk CdS, which shows only one kind of sulfur species. Details of the spectroscopic results provide estimates of the size of the nanocrystallites, while also indicating the origin of the stability of such small clusters. [S0163-1829(99)03811-4].

A double U-slot patch antenna with dual wideband characteristics

Microstrip patch antennas are strong candidates for use in many wireless communications applications. This paper proposes the use of a patch antenna with two U-shaped slots to achieve dual band operation. A thick substrate helps broaden the individual bandwidths. The antenna is designed based on extensive IE3D simulation studies. A prototype antenna is fabricated and experimentally verified for the required performance.

AC breakdown characteristics of epoxy alumina nanocomposites

Experiments were conducted to measure the ac breakdown strength of 0.5 mm, thick epoxy alumina nanocomposites with different filler concentrations of 0.1, 1 and 5wt%. The experiments were performed as per the ASTM D 149 standard. It was observed that the ac breakdown strength was marginally lower up to 1wt% filler concentration and then increased at 5wt% filler concentration as compared to the unfilled epoxy. The Weibull shape parameter (β) increased with the addition of nanoparticles to epoxy. The dependence of thickness on the ac breakdown strength was also analyzed by conducting experiments on 1mm and 3mm thick unfilled epoxy and epoxy alumina nanocomposites of 1wt% and 5wt% filler concentrations. The DSC analysis was done to understand the material properties at the filler resin interface in order to study the effect of the filler concentration and thereby the influence of the interface on the ac breakdown strength of epoxy nanocomposites.

Insights into the Regulatory Characteristics of the Mycobacterial Dephosphocoenzyme A Kinase: Implications for the Universal CoA Biosynthesis Pathway

Being vastly different from the human counterpart, we suggest that the last enzyme of the Mycobacterium tuberculosis Coenzyme A biosynthetic pathway, dephosphocoenzyme A kinase (CoaE) could be a good anti-tubercular target. Here we describe detailed investigations into the regulatory features of the enzyme, affected via two mechanisms. Enzymatic activity is regulated by CTP which strongly binds the enzyme at a site overlapping that of the leading substrate, dephosphocoenzyme A (DCoA), thereby obscuring the binding site and limiting catalysis. The organism has evolved a second layer of regulation by employing a dynamic equilibrium between the trimeric and monomeric forms of CoaE as a means of regulating the effective concentration of active enzyme. We show that the monomer is the active form of the enzyme and the interplay between the regulator, CTP and the substrate, DCoA, affects enzymatic activity. Detailed kinetic data have been corroborated by size exclusion chromatography, dynamic light scattering, glutaraldehyde crosslinking, limited proteolysis and fluorescence investigations on the enzyme all of which corroborate the effects of the ligands on the enzyme oligomeric status and activity. Cysteine mutagenesis and the effects of reducing agents on mycobacterial CoaE oligomerization further validate that the latter is not cysteine-mediated or reduction-sensitive. These studies thus shed light on the novel regulatory features employed to regulate metabolite flow through the last step of a critical biosynthetic pathway by keeping the latter catalytically dormant till the need arises, the transition to the active form affected by a delicate crosstalk between an essential cellular metabolite (CTP) and the precursor to the pathway end-product (DCoA).

Electrochemical studies of polyaniline in a gel polymer electrolyte - High energy and high power characteristics of a solid-state redox supercapacitor

Studies on redox supercapacitors employing electronically conducting polymers are of great importance for hybrid power sources and pulse power applications. In the present study, polyaniline (PANI) has been potentiodynamically deposited on stainless steel substrate and characterized in a gel polymer electrolyte (GPE). Use of the GPE facilitates a voltage limit of the capacitor to 1 V, instead of 0.75 V in aqueous electrolytes. From charge-discharge studies of the solid-state PANI capacitors, a specific capacitance of 250 F g(-1) has been obtained at a specific power of 7.5 kW kg(-1) of PANI. The values of specific capacitance and specific power are considerably higher than those reported in the literature. High energy and high power characteristics of the PANI are presented. (C) 2002 The Electrochemical Society.

Infrared spectroscopic study of LiCoO2 thin films

Site disorder of Co3+ ions in sputtered films of lithium cobaltite has been examined using infrared spectroscopy. Both transmission and reflectance modes have been used to characterize the nature of IR absorption. It is found that Co3+ in the sputtered films occupy two types of octahedral sites that differ in the nature of second-neighbor environment. Li+ ions exhibit two bands, which may arise from tetrahedral and octahedral site occupancies or from the presence of disordered regions in the films. (C) 2002 Elsevier Science (USA).

Magnetically tunable nonlinear current-voltage characteristics in oxygen deficient manganite perovskites

(La0.667Ca0.333Mn1-xMO3-delta)-O-x (M = Mg, Li or Re) exhibit insulating behaviour and nonlinear current-voltage (J-E) relationship with voltage-limiting characteristics at temperatures below the ferromagnetic transition (T-c). The high current region is set in at field strengths <60 V/cm. Nonlinearity exponent, alpha in the relation J = kE(alpha) increases inversely with temperature. In presence of an external magnetic field, the J-E curves show higher current density at lower field strengths. Microstructural studies indicate that there is no segregation of secondary phases in the grain boundary regions. There is remarkable changes in p(T) as well as J-E curves with the grain size. Annealing studies in lower p(O2) atmospheres indicate that there is significant out-diffusion of oxygen ions through the grain boundary layer (GBL) regions creating oxygen vacancies in the GBL regions. The concentration of Mn4+ ions is lowered at the GBL due to oxygen vacancies, reducing the probability of hopping and resulting in insulating behaviour. Therefore an insulating barrier is introduced between two conducting grains and the carrier motion between the grains is inhibited. Thus below T-c, where sufficient increase in resistivity is observed the conduction may be arising as a result of spin dependent tunneling across the barrier. External electric field lowers the barrier height and establishes carrier transport across the barrier. Above certain field strength, barrier height diminishes significantly and thereby allowing large number of carriers for conduction, giving rise to highly nonlinear conductivity. (C) 2002 Elsevier Science B.V. All rights reserved.

Morphology and thermal characteristics of nano-sized Pb-Sn inclusions in Al

Nanoembedded aluminum alloys with bimetallic dispersoids of Sn and Pb of compositions Sn-82-Pb-18,Pb- Sn-64-Pb-36, and Sn-54-Pb-46 were synthesized by rapid solidification. The two phases, face-centered-cubic Pb and tetragonal Sn solid-solution, coexist in all the particles. The crystallographic relation between the two phases and the matrix depends upon the solidification pathways adopted by the particles. For Al-(Sn-82-Pb-18), we report a new orientation relation given by [011]Al//[010]Sn and (011)Al//(101)Sn. Pb exhibits a cube-on-cube orientation with Al in few particles, while in others no orientation relationship could be observed. In contrast, Pb in Sn-64-Pb-36 and Sn-54-Pb-46 particles always exhibits cube-on-cube orientation with the matrix. Sn does not show any orientation relationship with Al or Pb in these cases. Differential scanning calorimetry studies revealed melting at eutectic temperature for all compositions, although solidification pathways are different. Attempts were made to correlate these with the melting and heterogeneous nucleation. characteristics.

Role of in situ generated tribofilm on the tribological characteristics of monolith and TiB2 reinforced MoSi2 intermetallic

Wear experiments performed on steel disc with increasing load for monolithic MoSi2 of different densities and its composite with TiB2 showed three distinct wear regimes. The specimens exhibited severe wear rate below the lower and above the upper critical loads and mild wear in between the two critical loads. The increase in density of the monolith and the reinforcement of TiB2 were effective in reducing the coefficient of friction and the specific wear rate. The wear experiments have been performed in these three regimes (15, 50 and 75 N). The tribofilm formed on the pin surface was found to contain both pin and disc materials. The temperature of the pins during the sliding against EN-24 disc was calculated using one dimensional heat transfer equation at different loads for each composition. The composite experiences lower temperatures compared to the monoliths. (C) 2002 Elsevier Science B.V. All rights reserved.

Seismic passive earth pressure coefficients using the method of characteristics

The method of characteristics was used to generate passive earth pressure coefficients for an inclined wall retaining cohesionless backfill material in the presence of pseudostatic horizontal earthquake body forces. The variation of the passive earth pressure coefficients K-pq and K-pgamma with changes in horizontal earthquake acceleration coefficient due to the components of soil unit weight and surcharge pressure, respectively, has been obtained; a closed-form solution for K-pq is also provided. The passive earth resistance has been found to decrease sharply with an increase in the magnitude of horizontal earthquake acceleration. The computed passive earth pressure coefficients were found to be the lowest when compared to all of the previous solutions available in the literature.

Self-assembled molecular films of tetraamino metal (Co, Cu, Fe) phthalocyanines on gold and silver. Electrochemical and spectroscopic characterization

The formation of molecular films of 2,9,16,23-tetraamino metal phthalocyanines [TAM(II)Pc; M (II) = Co, Cu, and TAM(III)Pc; M = Fe] by spontaneous adsorption on gold and silver surfaces is described. The properties of these films have been investigated by cyclic voltammetry, impedance, and FT-Raman spectroscopy. The charge associated with Co(II) and Co(I) redox couple in voltammetric data leads to a coverage of (0.35+/-0.05) x 10(-10) mol cm(-2), suggesting that the tetraamino cobalt phthalocyanine is adsorbed as a monolayer with an almost complete coverage. The blocking behavior of the films toward oxygen and Fe(CN)(6)(3-/4-) redox couple have been followed by cyclic voltammetry and impedance measurements. This leads to an estimate of the coverage of about 85 % in the case of copper and the iron analogs. FT-Raman studies show characteristic bands around 236 cm(-1) revealing the interaction between the metal substrate and the nitrogen of the -NH2 group on the phthalocyanine molecules.

An infrared spectroscopic study of the low-spin to intermediate-spin state (1A1–3T1) transition in rare earth cobaltates, LnCoO3 (Ln=La, Pr and Nd)

Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO3 (Ln=La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoO3 and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition.

An XPS study on oxidation states of Pt and its alloys with Co and Cr and its relevance to electroreduction of oxygen

Cathodic reduction of oxygen in fuel cells is known to be enhanced on platinum alloys in relation to the platinum metal. The higher performance of the platinum alloys is as a result of the improved oxygen-reduction kinetics on the alloys but there is hardly any increase in the electrode platinum-surface-areas for the platinum alloys as compared to the platinum metal, and thus the higher performance is solely due to the enhanced electrocatalytic activity of the alloys as compared to the platinum metal. The present X-ray photoelectron spectroscopic (XPS) study on carbon-supported Pt, Pt–Co and Pt–Co–Cr electrocatalysts suggests the presence of a relatively lower Pt-oxide content on the alloys. The X-ray powder diffraction patterns for these electrocatalysts show that while the carbon-supported platinum electrocatalyst has a face-centered cubic (fcc) phase, carbon-supported Pt–Co and Pt–Co–Cr electrocatalysts exhibit a face-centered tetragonal (fct) phase. But, Pt electrocatalyst has a lower particle-size and, hence, a higher dispersion. Previous studies have shown higher activities on the Pt-alloys than on Pt, and have attributed it to changes in the electronic and structural characteristics of Pt. These changes can be correlated with the lower oxidation-state of Pt sites, as found in this study.

An infrared spectroscopic study of the low-spin to intermediate-spin state ((1)A(1)-T-3(1)) transition in rare earth cobaltates, LnCoO(3) (Ln = La, Pr and Nd)

Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO(3) (Ln = La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoo(3) and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition. (C) 2001 Published by Elsevier Science B.V.