Studies on age-hardening characteristics of ceramic particle/matrix interfaces in Al-Cu-SiCp composites using ultra low-load-dynamic microhardness measurements

Ultra low-load-dynamic microhardness testing facilitates the hardness measurements in a very low volume of the material and thus is suited for characterization of the interfaces in MMC's. This paper details the studies on age-hardening behavior of the interfaces in Al-Cu-5SiC(p) composites characterized using this technique. Results of hardness studies have been further substantiated by TEM observations. In the solution-treated condition, hardness is maximum at the particle/matrix interface and decreases with increasing distance from the interface. This could be attributed to the presence of maximum dislocation density at the interface which decreases with increasing distance from the interface. In the case of composites subjected to high temperature aging, hardening at the interface is found to be faster than the bulk matrix and the aging kinetics becomes progressively slower with increasing distance from the interface. This is attributed to the dislocation density gradient at the interface, leading to enhanced nucleation and growth of precipitates at the interface compared to the bulk matrix. TEM observations reveal that the sizes of the precipitates decrease with increasing distance from the interface and thus confirms the retardation in aging kinetics with increasing distance from the interface.

Sulfur transfer reactions of tetrathiomolybdate in water: Synthesis of alkyl disulfides from alkyl halides

Reaction of a number of alkyl halides with tetrathiomolybdate in water as the solvent affords the corresponding disulfides in good yields.

Synthesis of thiolactones using benzyltriethylammonium tetrathiomolybdate as sulfur transfer reagent

An interesting sulfur transfer reaction mediated by benzyltriethylammonium tetrathiomolybdate [(PhCH2NEt3)(2)MoS4] converts omega-halo acid chlorides to the corresponding thiolactones in moderate to good yields in one step. (C) 1997 Elsevier Science Ltd.

A perspective of biological supramolecular electron transfer

Electron transfer is an essential activity in biological systems. The migrating electron originates from water-oxygen in photosynthesis and reverts to dioxygen in respiration. In this cycle two metal porphyrin complexes possessing circular conjugated system and macrocyclic pi-clouds, chlorophyll and hems, play a decisive role in mobilising electrons for travel over biological structures as extraneous electrons. Transport of electrons within proteins (as in cytochromes) and within DNA (during oxidative damage and repair) is known to occur. Initial evaluations did not favour formation of semiconducting pathways of delocalized electrons of the peptide bonds in proteins and of the bases in nucleic acids. Direct measurement of conductivity of bulk material and quantum chemical calculations of their polymeric structures also did not support electron transfer in both proteins and nucleic acids. New experimental approaches have revived interest in the process of charge transfer through DNA duplex. The fluorescence on photoexcitation of Ru-complex was found to be quenched by Rh-complex, when both were tethered to DNA and intercalated in the base stack. Similar experiments showed that damage to G-bases and repair of T-T dimers in DNA can occur by possible long range electron transfer through the base stack. The novelty of this phenomenon prompted the apt name, chemistry at a distance. Based on experiments with ruthenium modified proteins, intramolecular electron transfer in proteins is now proposed to use pathways that include C-C sigma-bonds and surprisingly hydrogen bonds which remained out of favour for a long time. In support of this, some experimental evidence is now available showing that hydrogen bond-bridges facilitate transfer of electrons between metal-porphyrin complexes. By molecular orbital calculations over 20 years ago. we found that "delocalization of an extraneous electron is pronounced when it enters low-lying virtual orbitals of the electronic structures of peptide units linked by hydrogen bonds". This review focuses on supramolecular electron transfer pathways that can emerge on interlinking by hydrogen bonds and metal coordination of some unnoticed structures with pi-clouds in proteins and nucleic acids, potentially useful in catalysis and energy missions.

Modelling electricity demand with representative load curves

Models for electricity planning require inclusion of demand. Depending on the type of planning, the demand is usually represented as an annual demand for electricity (GWh), a peak demand (MW) or in the form of annual load-duration curves. The demand for electricity varies with the seasons, economic activities, etc. Existing schemes do not capture the dynamics of demand variations that are important for planning. For this purpose, we introduce the concept of representative load curves (RLCs). Advantages of RLCs are demonstrated in a case study for the state of Karnataka in India. Multiple discriminant analysis is used to cluster the 365 daily load curves for 1993-94 into nine RLCs. Further analyses of these RLCs help to identify important factors, namely, seasonal, industrial, agricultural, and residential (water heating and air-cooling) demand variations besides rationing by the utility. (C) 1999 Elsevier Science Ltd. All rights reserved.

Modulation of lifetimes and diastereomeric discrimination in triplet-excited substituted butane-1,4-diones through intramolecular charge-transfer quenching

Triplet lifetimes have been determined for the diastereomers of a broad set of butane-l,4-dione derivatives (1-3). A remarkable dependence of lifetimes on conformational preferences is revealed in that the lifetimes are shorter for the meso diastereomers of 1-3 than those for the racemic ones. The intramolecular beta-phenyl quenching is promoted in the case of meso diastereomers by virtue of the gauche relationship between the excited carbonyl group and the beta-aryl ring, while a distal arrangement in the lowest energy conformation (H-anti) in racemic diastereomers prevents such a deactivation. The involvement of charge transfer in the intramolecular beta-phenyl quenching is suggested by the correlation of the triplet lifetimes of the meso diastereomers of compounds 2 with the nature of the substituent on the beta-phenyl rings. In the case of racemic diastereomers, beta-methoxy substitution on the beta-phenyl ring (2-OCH3, 3-OCH3) also led to a decrease of the triplet lifetimes when compared to those of the nonsubstituted compounds (2-H, 3-H). This shortening is accounted for by the deactivation of a small proportion of the excited molecules through beta-phenyl quenching. In addition to the above factors, the lifetimes in the case of meso diastereomers can further be controlled by increasing the energy spacing between the T-1 and T-2 states, since beta-phenyl quenching occurs from the latter for compounds 2 and 3. Through a rational conformational control, a surprisingly long triplet lifetime (300 ns) has been measured for the first time for a purely n,pi* triplet-excited beta-phenylpropiophenone dimer (1-rac).

Synthesis and characterization of novel charge transfer complexes formed by N,N%-bis(ferrocenylmethylidene)-p-phenylenediamine and N-(ferrocenylmethylidene)aniline

N,N'-Bis(ferrocenylmethylidene)-p-phenylenediamine 1 and N-(ferrocenylmethylidene) aniline 2 are readily synthesized by Schiff base condensation of appropriate units. Iodine (I-2), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetrachloro-1,4-benzoquinone (CA), tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) form charge transfer complexes with 1 and 2. IR spectroscopy suggests an increase in the amount of charge transferred from the ferrocenyl ring to the oxidant in the order, I-2 < CA < TCNQ < TCNE approximate to DDQ. EPR spectra of the oxidized binuclear complexes are indicative of localized species containing iron- and carbon-centered radicals. The Mossbauer spectrum of the iodine oxidized complex of 1 reveals the presence of both Fe(III) and Fe(II) centers. Variable temperature magnetic and Mossbauer studies show that the ratio of Fe(III)/Fe(II) centers varies as a function of temperature. The larger Fe(II)/Fe(III) ratio at lower temperatures is best explained by a retro charge transfer from the iodide to the iron(III) metal center. There is negligible solvent effect on the formation of the iodine oxidized charge transfer complex of 1. (C) 1999 Elsevier Science S.A. All rights reserved.

Unsteady flow and heat transfer on a semi-infinite flat plate with an aligned magnetic field

The unsteady laminar boundary layer flow of an electrically conducting fluid past a semi-infinite flat plate with an aligned magnetic field has been studied when at time t > 0 the plate is impulsively moved with a constant velocity which is in the same or opposite direction to that of free stream velocity. The effect of the induced magnetic field has been included in the analysis. The non-linear partial differential equations have been solved numerically using an implicit finite-difference method. The effect of the impulsive motion of the surface is found to be more pronounced on the skin friction but its effect on the x-component of the induced magnetic field and heat transfer is small. Velocity defect occurs near the surface when the plate is impulsively moved in the same direction as that of the free stream velocity. The surface shear stress, x-component of the induced magnetic field on the surface and the surface heat transfer decrease with an increasing magnetic field, but they increase with the reciprocal of the magnetic Prandtl number. However, the effect of the reciprocal of the magnetic Prandtl number is more pronounced on the x-component of the induced magnetic field. (C) 1999 Elsevier Science Ltd. All rights reserved.

Profile-Based Load Scheduling in Wireless Energy Harvesting Sensors for Data Rate Maximization

In this paper, power management algorithms for energy harvesting sensors (EHS) that operate purely based on energy harvested from the environment are proposed. To maintain energy neutrality, EHS nodes schedule their utilization of the harvested power so as to save/draw energy into/from an inefficient battery during peak/low energy harvesting periods, respectively. Under this constraint, one of the key system design goals is to transmit as much data as possible given the energy harvesting profile. For implementational simplicity, it is assumed that the EHS transmits at a constant data rate with power control, when the channel is sufficiently good. By converting the data rate maximization problem into a convex optimization problem, the optimal load scheduling (power management) algorithm that maximizes the average data rate subject to energy neutrality is derived. Also, the energy storage requirements on the battery for implementing the proposed algorithm are calculated. Further, robust schemes that account for the insufficiency of battery storage capacity, or errors in the prediction of the harvested power are proposed. The superior performance of the proposed algorithms over conventional scheduling schemes are demonstrated through computations using numerical data from solar energy harvesting databases.

Relay Load Balancing in Queued Cooperative Wireless Networks with Rateless Codes

Relay selection combined with buffering of packets of relays can substantially increase the throughput of a cooperative network that uses rateless codes. However, buffering also increases the end-to-end delays due to the additional queuing delays at the relay nodes. In this paper we propose a novel method that exploits a unique property of rateless codes that enables a receiver to decode a packet from non-contiguous and unordered portions of the received signal. In it, each relay, depending on its queue length, ignores its received coded bits with a given probability. We show that this substantially reduces the end-to-end delays while retaining almost all of the throughput gain achieved by buffering. In effect, the method increases the odds that the packet is first decoded by a relay with a smaller queue. Thus, the queuing load is balanced across the relays and traded off with transmission times. We derive explicit necessary and sufficient conditions for the stability of this system when the various channels undergo fading. Despite encountering analytically intractable G/GI/1 queues in our system, we also gain insights about the method by analyzing a similar system with a simpler model for the relay-to-destination transmission times.

Evaluation and improvement of total transfer capability - A case study

With deregulation, the total transfer capability (TTC) calculation, which is the basis for evaluating available transfer capability (ATC), has become very significant. TTC is an important index in power markets with large volume of inter-area power exchanges and wheeling transactions taking place on an hourly basis. Its computation helps to achieve a viable technical and commercial transmission operation. The aim of the paper is to evaluate TTC in the interconnections and also to improve it using reactive optimization technique and UPFC devices. Computations are carried out for normal and contingency cases such as single line, tie line and generator outages. Base and optimized results are presented, and the results show how reactive optimization and unified power flow controller help to improve the system conditions. In this paper repeated power flow method is used to calculate TTC due to its ease of implementation. A case study is carried out on a 205 bus equivalent system, a part of Indian Southern grid. Parameters like voltage magnitude, L-index, minimum singular value and MW losses are computed to analyze the system performance.

Direct and sensitized (energy and electron transfer) geometric isomerization of stilbene within zeolites: a comparison between solution and zeolite as reaction media

The trans- and cis-stilbenes upon inclusion in NaY zeolite are thermally stable. Direct excitation and triplet sensitization results in geometric isomerization and the excited state behavior under these conditions are similar to that in solution. Upon direct excitation, a photostationary state consisting of 65% cis and 35% trans isomers is established. Triplet sensitization with 2-acetonaphthone gave a photostationary state consisting of 63% cis and 37% trans isomers. These numbers are similar to the ones obtained in solution. Thus, the presence of cations and the confined space within the zeolite have very little influence on the overall chemistry during direct and triplet sensitization. However, upon electron transfer sensitization with N-methylacridinium (NMA) as the sensitizer within NaY, isomerization from cis-stilbene radical cation to trans-stilbene occurs and the recombination of radical ions results in triplet stilbene. Prolonged irradiation gave a photostationary state (65% cis and 35% trans) similar to triplet sensitization. This behavior is unique to the zeolite and does not take place in solution. Steady state fluorescence measurements showed that the majority of stilbene molecules are close to the N-methylacridinium sensitizer. Diffuse reflectance flash photolysis studies established that independent of the isomer being sensitized only trans radical cation is formed. Triplet stilbene is believed to be generated via recombination of stilbene radical cation and sensitizer radical anion. One should be careful in using acidic HY zeolite as a medium for photoisomerization of stilbenes. In our hands, in these acidic zeolites isomerization dominated the photoisomerization. (C) 2002 Elsevier Science B.V. All rights reserved.

Energy transfer efficiency distributions in polymers in solution during folding and unfolding

Distribution of fluorescence resonance energy transfer (FRET) efficiency between the two ends of a Lennard-Jones polymer chain both at equilibrium and during folding and unfolding has been calculated, for the first time, by Brownian dynamics simulations. The distribution of FRET efficiency becomes bimodal during folding of the extended state subsequent to a temperature quench, with the width of the distribution for the extended state broader than that for the folded state. The reverse process of unfolding subsequent to a upward temperature jump shows different characteristics. The distributions show significant viscosity dependence which can be tested against experiments.

Numerical modeling of heat and mass transfer in laser surface alloying: Non-equilibrium solidification effects

A transient macroscopic model is developed for studying heat and mass transfer in a single-pass laser surface alloying process, with particular emphasis on non-equilibrium solidification considerations. The solution for species concentration distribution requires suitable treatment of non-equilibrium mass transfer conditions. In this context, microscopic features pertaining to non-equilibrium effects on account of solutal undercooling are incorporated through the formulation of a modified partition-coefficient. The effective partition-coefficient is numerically modeled by Means of a number of macroscopically observable parameters related to the solidifying domain. The numerical model is so developed that the modifications on account of non-equilibrium solidification considerations can be conveniently implemented in existing numerical codes based on equilibrium solidification considerations.