Simulation and experimental study on compositional evolution of Li-Co in LiCoO(2) thin films during sputter deposition

The compositional evolution in sputter deposited LiCoO(2) thin films is influenced by process parameters involved during deposition. The electrochemical performance of these films strongly depends on their microstructure, preferential orientation and stoichiometry. The transport process of sputtered Li and Co atoms from the LiCoO(2) target to the substrate, through Ar plasma in a planar magnetron configuration, was investigated based on the Monte Carlo technique. The effect of sputtering gas pressure and the substrate-target distance (d(st)) on Li/Co ratio, as well as, energy and angular distribution of sputtered atoms on the substrate were examined. Stable Li/Co ratios have been obtained at 5 Pa pressure and d(st) in the range 5 11 cm. The kinetic energy and incident angular distribution of Li and Co atoms reaching the substrate have been found to be dependent on sputtering pressure. Simulations were extended to predict compositional variations in films prepared at various process conditions. These results were compared with the composition of films determined experimentally using x-ray photoelectron spectroscopy (XPS). Li/Co ratio calculated using XPS was in moderate agreement with that of the simulated value. The measured film thickness followed the same trend as predicted by simulation. These studies are shown to be useful in understanding the complexities in multicomponent sputtering. (C) 2011 American Institute of Physics. doi:10.1063/1.3597829]

Experimental evidence for interplay of dynamic heterogeneity and finite-size effect in glassy polymers

Despite two decades of extensive research, direct experimental evidence of a dynamical length scale determining the glass transition of confined polymers has yet to emerge. Using a recently established experimental technique of interface micro-rheology we provide evidence of finite-size effect truncating the growth of a quantity proportional to a dynamical length scale in confined glassy polymers, on cooling towards the glass transition temperature. We show how the interplay of variation of polymer film thickness and this temperature-dependent growing dynamical length scale determines the glass transition temperature, which in our case of 2-3nm thick films, is reduced significantly as compared to their bulk values.

An Empirical Analysis of Heterogeneity in IEEE 802.11 MAC Protocol Implementations and its Implications

Wireless LAN (WLAN) market consists of IEEE 802.11 MAC standard conformant devices (e.g., access points (APs), client adapters) from multiple vendors. Certain third party certifications such as those specified by the Wi-Fi alliance have been widely used by vendors to ensure basic conformance to the 802.11 standard, thus leading to the expectation that the available devices exhibit identical MAC level behavior. In this paper, however, we present what we believe to be the first ever set of experimental results that highlight the fact that WLAN devices from different vendors in the market can have heterogeneous MAC level behavior. Specifically, we demonstrate with examples and data that in certain cases, devices may not be conformant with the 802.11 standard while in other cases, they may differ in significant details that are not a part of mandatory specifications of the standard. We argue that heterogeneous MAC implementations can adversely impact WLAN operations leading to unfair bandwidth allocation, potential break-down of related MAC functionality and difficulties in provisioning the capacity of a WLAN. However, on the positive side, MAC level heterogeneity can be useful in applications such as vendor/model level device fingerprinting.

Simulation and experimental study on compositional evolution of Li-Co in LiCoO2 thin films during sputter deposition

The compositional evolution in sputter deposited LiCoO2 thin films is influenced by process parameters involved during deposition. The electrochemical performance of these films strongly depends on their microstructure, preferential orientation and stoichiometry. The transport process of sputtered Li and Co atoms from the LiCoO2 target to the substrate, through Ar plasma in a planar magnetron configuration, was investigated based on the Monte Carlo technique. The effect of sputtering gas pressure and the substrate-target distance (dst) on Li/Co ratio, as well as, energy and angular distribution of sputtered atoms on the substrate were examined. Stable Li/Co ratios have been obtained at 5 Pa pressure and dst in the range 5−11 cm. The kinetic energy and incident angular distribution of Li and Co atoms reaching the substrate have been found to be dependent on sputtering pressure. Simulations were extended to predict compositional variations in films prepared at various process conditions. These results were compared with the composition of films determined experimentally using x-ray photoelectron spectroscopy (XPS). Li/Co ratio calculated using XPS was in moderate agreement with that of the simulated value. The measured film thickness followed the same trend as predicted by simulation. These studies are shown to be useful in understanding the complexities in multicomponent sputtering.

Effect of capillarity and heterogeneity in the numerical modelling of multiphase flow of fluids in unsaturated porous medium

The multiphase flow of fluids in the unsaturated porous medium is considered as a three phase flow of water, NAPL, and air simultaneously in the porous medium. The adaptive solution fully implicit modified sequential method is used for the numerical modelling. The effect of capillarity and heterogeneity effect at the interface between the media is studied and it is observed that the interface criteria has to be taken into account for the correct prediction of NAPL migration especially in heterogeneous media. The modified Newton Raphson method is used for the linearization and Hestines and Steifel Conjugate Gradient method is used as the solver.

Compositional dependence optical properties study of As40Se60-xSbx thin films

Thin films were thermally evaporated from the bulk glasses of As40Se60-xSbx (with x = 0, 5, 10, 15 at.%) under high vacuum. We have characterized the deposited films by Fourier Transform Infrared spectroscopy. The relationship between the structural and optical properties and the compositional variation has been investigated. Increasing Sb content was found to affect the thermal and optical properties of these films. Non-direct electronic transition was found to be responsible for the photon absorption inside the investigated films. It was found that, the optical band gap E-o decreases while the width of localized states (Urbach energy) E-e increases. (C) 2011 Elsevier B.V. All rights reserved.

Multispecies coexistence of trees in tropical forests: spatial signals of topographic niche differentiation increase with environmental heterogeneity

Neutral and niche theories give contrasting explanations for the maintenance of tropical tree species diversity. Both have some empirical support, but methods to disentangle their effects have not yet been developed. We applied a statistical measure of spatial structure to data from 14 large tropical forest plots to test a prediction of niche theory that is incompatible with neutral theory: that species in heterogeneous environments should separate out in space according to their niche preferences. We chose plots across a range of topographic heterogeneity, and tested whether pairwise spatial associations among species were more variable in more heterogeneous sites. We found strong support for this prediction, based on a strong positive relationship between variance in the spatial structure of species pairs and topographic heterogeneity across sites. We interpret this pattern as evidence of pervasive niche differentiation, which increases in importance with increasing environmental heterogeneity.

Influence of annealing on structural, morphological, compositional and surface properties of magnetron sputtered nickel-titanium thin films

Thin films of NiTi were deposited by DC magnetron sputtering from an equiatomic alloy target (Ni/Ti: 50/50 at.%). The films were deposited without intentional heating of the substrates. The thickness of the deposited films was approximately 2 mu m. The structure and morphology of NiTi films annealed at different temperatures were analyzed in order to understand the effect of annealing on physical properties of the films. The compositional investigations of fresh and annealed films were also evaluated by energy dispersive X-ray spectroscopy (EDS) and X-ray photo-electron spectroscopy (XPS) techniques. X-ray diffraction (XRD) studies showed that as-deposited films were amorphous in nature whereas annealed films were found to poly-crystalline with the presence of Austenite phase as the dominant phase. AFM investigations showed higher grain size and surface roughness values in the annealed films. In annealed films, the grain size and film roughness values were increased from 10 to 85 nm and 2-18 nm. Film composition measured by EDS were found to 52.5 atomic percent of Ni and 47.5 atomic percent of Ti. XPS investigations, demonstrated the presence of Ni content on the surface of the films, in fresh films, whereas annealed films did not show any nickel. From HR-XPS investigations, it can be concluded that annealed NiTi films have higher tendency to form metal oxide (titanium dioxide) layer on the surface of the films than fresh NiTi films. (C) 2013 Elsevier B. V. All rights reserved.

Compositional hierarchical monitoring automaton construction for LTL

In this paper we give a compositional (or inductive) construction of monitoring automata for LTL formulas. Our construction is similar in spirit to the compositional construction of Kesten and Pnueli [5]. We introduce the notion of hierarchical Büchi automata and phrase our constructions in the framework of these automata. We give detailed constructions for all the principal LTL operators including past operators, along with proofs of correctness of the constructions.

Nanoscale compositional analysis of NiTi shape memory alloy films deposited by DC magnetron sputtering

The formation of surface oxide layer as well as compositional changes along the thickness for NiTi shape memory alloy thin films deposited by direct current magnetron sputtering at substrate temperature of 300 degrees C in the as-deposited condition as well as in the postannealed (at 600 degrees C) condition have been thoroughly studied by using secondary ion mass spectroscopy, x-ray photoelectron spectroscopy, and scanning transmission electron microscopy-energy dispersive x-ray spectroscopy techniques. Formation of titanium oxide (predominantly titanium dioxide) layer was observed in both as-deposited and postannealed NiTi films, although the oxide layer was much thinner (8 nm) in as-deposited condition. The depletion of Ti and enrichment of Ni below the oxide layer in postannealed films also resulted in the formation of a graded microstructure consisting of titanium oxide, Ni3Ti, and B2 NiTi. A uniform composition of B2 NiTi was obtained in the postannealed film only below a depth of 200-250 nm from the surface. Postannealed film also exhibited formation of a ternary silicide (NixTiySi) at the film-substrate interface, whereas no silicide was seen in the as-deposited film. The formation of silicide also caused a depletion of Ni in the film in a region similar to 250-300 nm just above the film substrate interface. (C) 2013 American Vacuum Society.

Non-Syndromic Hearing Impairment in India: High Allelic Heterogeneity among Mutations in TMPRSS3, TMC1, USHIC, CDH23 and TMIE

Mutations in the autosomal genes TMPRSS3, TMC1, USHIC, CDH23 and TMIE are known to cause hereditary hearing loss. To study the contribution of these genes to autosomal recessive, non-syndromic hearing loss (ARNSHL) in India, we examined 374 families with the disorder to identify potential mutations. We found four mutations in TMPRSS3, eight in TMC1, ten in USHIC, eight in CDH23 and three in TMIE. Of the 33 potentially pathogenic variants identified in these genes, 23 were new and the remaining have been previously reported. Collectively, mutations in these five genes contribute to about one-tenth of ARNSHL among the families examined. New mutations detected in this study extend the allelic heterogeneity of the genes and provide several additional variants for structure-function correlation studies. These findings have implications for early DNA-based detection of deafness and genetic counseling of affected families in the Indian subcontinent.

Structural Investigations on the Compositional Anomalies in Lanthanum Zirconate System Synthesized by Coprecipitation Method

The study set out to investigate the compositional inconsistency in lanthanum zirconate system revealed the presence of nonstoichiometry in lanthanum zirconate powders when synthesized by coprecipitation route. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) investigations confirmed the depletion of La3+ ions in the system. Analysis using Vegard's law showed the La/Zr mole ratio in the sample to be around 0.45. An extra step of ultrasonication, introduced during the washing stage followed by the coprecipitation reaction, ensured the formation of stoichiometric La2Zr2O7. Noteworthy is also the difference between crystal sizes in the samples prepared by with and without ultrasonication step. This difference has been explained in light of the formation of individual nuclei and their scope of growth within the precipitate core. The differential scanning calorimetry (DSC) analyses revealed that optimum pH for the synthesis of La2Zr2O7 is about 11. The ultrasonication step was pivotal in assuring consistency in mixing and composition for the lanthanum zirconate powders.

Deformation field heterogeneity in punch indentation

Plastic heterogeneity in indentation is fundamental for understanding mechanics of hardness testing and impression-based deformation processing methods. The heterogeneous deformation underlying plane-strain indentation was investigated in plastic loading of copper by a flat punch. Deformation parameters were measured, in situ, by tracking the motion of asperities in high-speed optical imaging. These measurements were coupled with multi-scale analyses of strength, microstructure and crystallographic texture in the vicinity of the indentation. Self-consistency is demonstrated in description of the deformation field using the in situ mechanics-based measurements and post-mortem materials characterization. Salient features of the punch indentation process elucidated include, among others, the presence of a dead-metal zone underneath the indenter, regions of intense strain rate (e. g. slip lines) and extent of the plastic flow field. Perhaps more intriguing are the transitions between shear-type and compression-type deformation modes over the indentation region that were quantified by the high-resolution crystallographic texture measurements. The evolution of the field concomitant to the progress of indentation is discussed and primary differences between the mechanics of indentation for a rigid perfectly plastic material and a strain-hardening material are described.

Fluctuating micro-heterogeneity in water-tert-butyl alcohol mixtures and lambda-type divergence of the mean cluster size with phase transition-like multiple anomalies

Water-tert-butyl alcohol (TBA) binary mixture exhibits a large number of thermodynamic and dynamic anomalies. These anomalies are observed at surprisingly low TBA mole fraction, with x(TBA) approximate to 0.03-0.07. We demonstrate here that the origin of the anomalies lies in the local structural changes that occur due to self-aggregation of TBA molecules. We observe a percolation transition of the TBA molecules at x(TBA) approximate to 0.05. We note that ``islands'' of TBA clusters form even below this mole fraction, while a large spanning cluster emerges above that mole fraction. At this percolation threshold, we observe a lambda-type divergence in the fluctuation of the size of the largest TBA cluster, reminiscent of a critical point. Alongside, the structure of water is also perturbed, albeit weakly, by the aggregation of TBA molecules. There is a monotonic decrease in the tetrahedral order parameter of water, while the dipole moment correlation shows a weak nonlinearity. Interestingly, water molecules themselves exhibit a reverse percolation transition at higher TBA concentration, x(TBA) approximate to 0.45, where large spanning water clusters now break-up into small clusters. This is accompanied by significant divergence of the fluctuations in the size of largest water cluster. This second transition gives rise to another set of anomalies around. Both the percolation transitions can be regarded as manifestations of Janus effect at small molecular level. (C) 2014 AIP Publishing LLC.