Sodium-ion battery cathodes Na2FeP2O7 and Na2MnP2O7: diffusion behaviour for high rate performance

Na-ion batteries are currently the focus of significant research activity due to the relative abundance of sodium and its consequent cost advantages. Recently, the pyrophosphate family of cathodes has attracted considerable attention, particularly Li2FeP2O7 related to its high operating voltage and enhanced safety properties; in addition the sodium-based pyrophosphates Na2FeP2O7 and Na2MnP2O7 are also generating interest. Herein, we present defect chemistry and ion migration results, determined via atomistic simulation techniques, for Na2MP2O7 (where M = Fe, Mn) as well as findings for Li2FeP2O7 for direct comparison. Within the pyrophosphate framework the most favourable intrinsic defect type is found to be the antisite defect, in which alkali-cations (Na/Li) and M ions exchange positions. Low activation energies are found for long-range diffusion in all crystallographic directions in Na2MP2O7 suggesting three-dimensional (3D) Na-ion diffusion. In contrast Li2FeP2O7 supports 2D Li-ion diffusion. The 2D or 3D nature of the alkali-ion migration pathways within these pyrophosphate materials means that antisite defects are much less likely to impede their transport properties, and hence important for high rate performance.

Super-Resolution Reconstruction in Frequency-Domain Optical-Coherence Tomography Using the Finite-Rate-of-Innovation Principle

The standard approach to signal reconstruction in frequency-domain optical-coherence tomography (FDOCT) is to apply the inverse Fourier transform to the measurements. This technique offers limited resolution (due to Heisenberg's uncertainty principle). We propose a new super-resolution reconstruction method based on a parametric representation. We consider multilayer specimens, wherein each layer has a constant refractive index and show that the backscattered signal from such a specimen fits accurately in to the framework of finite-rate-of-innovation (FRI) signal model and is represented by a finite number of free parameters. We deploy the high-resolution Prony method and show that high-quality, super-resolved reconstruction is possible with fewer measurements (about one-fourth of the number required for the standard Fourier technique). To further improve robustness to noise in practical scenarios, we take advantage of an iterated singular-value decomposition algorithm (Cadzow denoiser). We present results of Monte Carlo analyses, and assess statistical efficiency of the reconstruction techniques by comparing their performance against the Cramer-Rao bound. Reconstruction results on experimental data obtained from technical as well as biological specimens show a distinct improvement in resolution and signal-to-reconstruction noise offered by the proposed method in comparison with the standard approach.

An experimental study on loading rate effect on acoustic emission based b-values related to reinforced concrete fracture

This article reports on analysis of fracture processes in reinforced concrete (RC) beams with acoustic emission (AE) technique. An emphasis was given to study the effect of loading rate on variation in AE based b-values with the development of cracks in RC structures. RC beams of length 3.2 m were tested under load control at a rate of 4 kN/s, 5 kN/s and 6 kN/s and the b-value analysis available in seismology was used to study the fracture process in RC structures. Moreover, the b-value is related to the strain in steel to assess the damage state. It is observed that when the loading rate is higher, quick cracking development lead to rapid fluctuations and drops in the b-values. Also it is observed that concrete behaves relatively more brittle at higher loading rates (or at higher strain rates). The average b-values are lower as a few but larger amplitudes of AE events occur in contrast to more number of low amplitude AE events occur at low loading rates (or at low strain rates). (C) 2014 Elsevier Ltd. All rights reserved.

Porous lithium rich Li1.2Mn0.54Ni0.22Fe0.04O2 prepared by microemulsion route as a high capacity and high rate capability positive electrode material

A porous layered composite of Li2MnO3 and LiMn0.35Ni0.55Fe0.1O2 (composition:Li1.2Mn0.54Ni0.22Fe0.04O2) is prepared by inverse microemulsion method and studied as a positive electrode material. The precursor is heated at several temperatures between 500 and 900 degrees C. The X-ray diffraction, scanning electron microscopy, and transmission electron microscopy studies suggested that well crystalline submicronsized particles are obtained. The product samples possess mesoporosity with broadly distributed pores around 10 similar to 50 nm diameter. Pore volume and surface area decrease by increasing the temperature of preparation. However, the electrochemical activity of the composite samples increases with an increase in temperature. The discharge capacity values of the samples prepared at 900 degrees C are about 186 mAh g(-1) at a specific current of 25 mA g(-1) with an excellent cycling stability. The composite sample also possesses high rate capability. The high rate capability is attributed to the porous nature of the material. (C) 2014 Elsevier Ltd. All rights reserved.

ELLIPSE FITTING USING FINITE RATE OF INNOVATION PRINCIPLES

We address the problem of parameter estimation of an ellipse from a limited number of samples. We develop a new approach for solving the ellipse fitting problem by showing that the x and y coordinate functions of an ellipse are finite-rate-of-innovation (FRI) signals. Uniform samples of x and y coordinate functions of the ellipse are modeled as a sum of weighted complex exponentials, for which we propose an efficient annihilating filter technique to estimate the ellipse parameters from the samples. The FRI framework allows for estimating the ellipse parameters reliably from partial or incomplete measurements even in the presence of noise. The efficiency and robustness of the proposed method is compared with state-of-art direct method. The experimental results show that the estimated parameters have lesser bias compared with the direct method and the estimation error is reduced by 5-10 dB relative to the direct method.

Off-site impacts of agricultural composting: role of terrestrially derived organic matter in structuring aquatic microbial communities and their metabolic potential

While considered as sustainable and low-cost agricultural amendments, the impacts of organic fertilizers on downstream aquatic microbial communities remain poorly documented. We investigated the quantity and quality of the dissolved organic matter leaching from agricultural soil amended with compost, vermicompost or biochar and assessed their effects on lake microbial communities, in terms of viral and bacterial abundances, community structure and metabolic potential. The addition of compost and vermicompost significantly increased the amount of dissolved organic carbon in the leachate compared with soil alone. Leachates from these additions, either with or without biochar, were highly bioavailable to aquatic microbial communities, although reducing the metabolic potential of the community and harbouring more specific communities. Although not affecting bacterial richness or taxonomic distributions, the specific addition of biochar affected the original lake bacterial communities, resulting in a strongly different community. This could be partly explained by viral burst and converging bacterial abundances throughout the samples. These results underline the necessity to include off-site impacts of agricultural amendments when considering their cascading effect on downstream aquatic ecosystems.

One-Carbon Metabolic Pathway Rewiring in Escherichia coli Reveals an Evolutionary Advantage of 10-Formyltetrahydrofolate Synthetase (Fhs) in Survival under Hypoxia

In cells, N-10-formyltetrahydrofolate (N-10-fTHF) is required for formylation of eubacterial/organellar initiator tRNA and purine nucleotide biosynthesis. Biosynthesis of N-10-fTHF is catalyzed by 5,10-methylene-tetrahydrofolate dehydrogenase/cyclohydrolase (FolD) and/or 10-formyltetrahydrofolate synthetase (Fhs). All eubacteria possess FolD, but some possess both FolD and Fhs. However, the reasons for possessing Fhs in addition to FolD have remained unclear. We used Escherichia coli, which naturally lacks fhs, as our model. We show that in E. coli, the essential function of folD could be replaced by Clostridium perfringens fhs when it was provided on a medium-copy-number plasmid or integrated as a single-copy gene in the chromosome. The fhs-supported folD deletion (Delta folD) strains grow well in a complex medium. However, these strains require purines and glycine as supplements for growth in M9 minimal medium. The in vivo levels of N-10-fTHF in the Delta folD strain (supported by plasmid-borne fhs) were limiting despite the high capacity of the available Fhs to synthesize N-10-fTHF in vitro. Auxotrophy for purines could be alleviated by supplementing formate to the medium, and that for glycine was alleviated by engineering THF import into the cells. The Delta folD strain (harboring fhs on the chromosome) showed a high NADP(+)-to-NADPH ratio and hypersensitivity to trimethoprim. The presence of fhs in E. coli was disadvantageous for its aerobic growth. However, under hypoxia, E. coli strains harboring fhs outcompeted those lacking it. The computational analysis revealed a predominant natural occurrence of fhs in anaerobic and facultative anaerobic bacteria.

On the strain rate sensitivity of plastic flow in metallic glasses

The nanoindentation technique was employed to examine the strain rate sensitivity, m, and its dependence on the structural state of a Zr-based bulk metallic glass (BMG). The free volume content in the BMG was varied by examining samples in the as-cast (AC), shot-peened (SP), and structurally relaxed (SR) states. Hardness values measured at different loading rates and over a temperature range of 300-423 K as well as the strain-rate jump tests conducted in the quasi-static regime at room temperature, show that m is always negative. All the load-displacement (P-h) curves in this temperature regime exhibit serrated load-displacement responses, indicating that the shear band mediated inhomogeneous plastic flow governs deformation. Such localization of flow and associated softening is the raison d'etre for the negative m. Significant levels of pile-up around the indents were also noted. The order in the average values of hardness, pile-up heights, and the displacement bursts on the P-h curves was always such that SR > AC > SP, which is also the order of increasing free volume content. These observations were utilized to discuss the reasons for the negative strain rate sensitivity, and its dependence on the structural state of metallic glasses. It is suggested that the positive values of m reported in the literature for them are possibly experimental artefacts that arise due to large pile ups around the indents which lead to erroneous estimation in hardness values. (C) 2014 Elsevier B.V. All rights reserved.

Characterizing the Impact of Feedback Delays on Wideband Rate Adaptation

In contemporary orthogonal frequency division multiplexing (OFDM) systems, such as Long Term Evolution (LTE), LTE-Advanced, and WiMAX, a codeword is transmitted over a group of subcarriers. Since different subcarriers see different channel gains in frequency-selective channels, the modulation and coding scheme (MCS) of the codeword must be selected based on the vector of signal-to-noise-ratios (SNRs) of these subcarriers. Exponential effective SNR mapping (EESM) maps the vector of SNRs into an equivalent flat-fading SNR, and is widely used to simplify this problem. We develop a new analytical framework to characterize the throughput of EESM-based rate adaptation in such wideband channels in the presence of feedback delays. We derive a novel accurate approximation for the throughput as a function of feedback delay. We also propose a novel bivariate gamma distribution to model the time evolution of EESM between the times of estimation and data transmission, which facilitates the analysis. These are then generalized to a multi-cell, multi-user scenario with various frequency-domain schedulers. Unlike prior work, most of which is simulation-based, our framework encompasses both correlated and independent subcarriers and various multiple antenna diversity modes; it is accurate over a wide range of delays.

Discrete-Rate Adaptation and Selection in Energy Harvesting Wireless Systems

In a system with energy harvesting (EH) nodes, the design focus shifts from minimizing energy consumption by infrequently transmitting less information to making the best use of available energy to efficiently deliver data while adhering to the fundamental energy neutrality constraint. We address the problem of maximizing the throughput of a system consisting of rate-adaptive EH nodes that transmit to a destination. Unlike related literature, we focus on the practically important discrete-rate adaptation model. First, for a single EH node, we propose a discrete-rate adaptation rule and prove its optimality for a general class of stationary and ergodic EH and fading processes. We then study a general system with multiple EH nodes in which one is opportunistically selected to transmit. We first derive a novel and throughput-optimal joint selection and rate adaptation rule (TOJSRA) when the nodes are subject to a weaker average power constraint. We then propose a novel rule for a multi-EH node system that is based on TOJSRA, and we prove its optimality for stationary and ergodic EH and fading processes. We also model the various energy overheads of the EH nodes and characterize their effect on the adaptation policy and the system throughput.

Influence of plate length and plate cooling rate on solidification and microstructure of A356 alloy produced by oblique plate

A356 alloy melt solidifies partially when it flows down on an oblique plate cooled from bottom by counter flowing water. Columnar dendrites are continuously formed on the plate wall. Because of the forced convection, these dendrites are sheared off into equiaxed/fragmented grains and then washed away continuously by producing semisolid slurry at plate exit. Plate cooling rate provides required extent/amount of solidification whereas plate length enables necessary shear for producing semisolid slurry of desired quality. Slurry obtained is solidified in metal mould to produce semisolid-cast billets of desired microstructure. Furthermore, semisolid-cast billets are also heat-treated to improve surface quality. Microstructures of both semisolid-cast and heat-treated billets are compared. The effects of plate length and plate cooling rate on solidification and microstructure of billets produced by using oblique plate are illustrated. Three different plate lengths (200 mm, 250 mm, 300 mm) associated with three different heat transfer coefficients (1000, 2000 and 2500 W/(m(2).K)) are involved. Plate length of 250 mm with heat transfer coefficient of 2000 W/(m(2).K) gives fine and globular microstructures and is the optimum as there is absolutely no possibility of sticking of slurry to plate wall.

Electrospun SnSb Crystalline Nanoparticles inside Porous Carbon Fibers as a High Stability and Rate Capability Anode for Rechargeable Batteries

In an electrochemical alloying reaction, the electroactive particles become mechanically unstable owing to large volume changes occurring as a result of high amounts of lithium intake. This is detrimental for long-term battery performance. Herein, a novel synthesis approach to minimize such mechanical instabilities in tin particles is presented. An optimal one-dimensional assembly of crystalline single-phase tin-antimony (SnSb) alloy nanoparticles inside porous carbon fibers (abbreviated SnSb-C) is synthesized for the first time by using the electrospinning technique (employing non-oxide precursors) in combination with a sintering protocol. The ability of antimony to alloy independently with lithium is beneficial as it buffers the unfavorable volume changes occurring during successive alloying/dealloying cycles in Sn. The SnSb-C assembly provides nontortuous (tortuosity coefficient, =1) fast conducting pathways for both electrons and ions. The presence of carbon in SnSb-C completely nullifies the conventional requirement of other carbon forms during cell electrode assembly. The SnSb-C exhibited remarkably high electrochemical lithium stability and high specific capacities over a wide range of currents (0.2-5Ag(-1)). In addition to lithium-ion batteries, it is envisaged that SnSb-C also has potential as a noncarbonaceous anode for other battery chemistries, such as sodium-ion batteries.

Outer Bounds on the Secrecy Rate of the 2-User Symmetric Deterministic Interference Channel with Transmitter Cooperation

This paper derives outer bounds for the 2-user symmetric linear deterministic interference channel (SLDIC) with limited-rate transmitter cooperation and perfect secrecy constraints at the receivers. Five outer bounds are derived, under different assumptions of providing side information to receivers and partitioning the encoded message/output depending on the relative strength of the signal and the interference. The usefulness of these outer bounds is shown by comparing the bounds with the inner bound on the achievable secrecy rate derived by the authors in a previous work. Also, the outer bounds help to establish that sharing random bits through the cooperative link can achieve the optimal rate in the very high interference regime.

Correlation Between Decay Rate and Amplitude of Solar Cycles as Revealed from Observations and Dynamo Theory

Using different proxies of solar activity, we have studied the following features of the solar cycle: i) The linear correlation between the amplitude of cycle and its decay rate, ii) the linear correlation between the amplitude of cycle and the decay rate of cycle , and iii) the anti-correlation between the amplitude of cycle and the period of cycle . Features ii) and iii) are very useful because they provide precursors for future cycles. We have reproduced these features using a flux-transport dynamo model with stochastic fluctuations in the Babcock-Leighton effect and in the meridional circulation. Only when we introduce fluctuations in meridional circulation, are we able to reproduce different observed features of the solar cycle. We discuss the possible reasons for these correlations.