Thermal stress-induced charge and structure heterogeneity in emerging cathode materials

Nickel-rich layered oxide cathode materials are attractive near-term candidates for boosting the energy density of next generation lithium-ion batteries. The practical implementation of these materials is, however, hindered by unsatisfactory capacity retention, poor thermal stability, and oxygen release as a consequence of structural decomposition, which may have serious safety consequences. The undesired side reactions are often exothermic, causing complicated electro-chemo-mechanical interplay at elevated temperatures. In this work, we explore the effects of thermal exposure on chemically delithiated LiNi0.8Mn0.1Co0.1O2 (NMC-811) at a practical state-of-charge (50% Li content) and an over-charged state (25% Li content). A systematic study using a suite of advanced synchrotron radiation characterization tools reveals the dynamics of thermal behavior of the charged NMC-811, which involves sophisticated structural and chemical evolution; e.g. lattice phase transformation, transition metal (TM) cation migration and valence change, and lithium redistribution. These intertwined processes exhibit a complex 3D spatial heterogeneity and, collectively, form a valence state gradient throughout the particles. Our study sheds light on the response of NMC-811 to elevated temperature and highlights the importance of the cathode's thermal robustness for battery performance and safety

Laser diagnostics of pulverized coal combustion in O<inf>2</inf>/N<inf>2</inf> and O<inf>2</inf>/CO<inf>2</inf> conditions: velocity and scalar field measurements

Optical diagnostic techniques are applied to a 21 kW laboratory-scale pulverized coal–methane burner to map the reaction zone during combustion, in mixtures with varying fractions of O_2, N_2 and CO_2. Simultaneous Mie scatter and OH planar laser-induced fluorescence (PLIF) measurements have been carried out to study the effect of the oxidizer/diluent concentrations as well as the coal-loading rate. The spatial distribution of soot is captured using laser-induced incandescence (LII). Additionally, velocity profiles at selected axial locations are measured using the pairwise two-dimensional laser Doppler velocimetry technique. The OH PLIF images capture the reaction zones of pilot methane–air flames and the variation of the coal flame structure under various O_2/CO_2 compositions. Coal particles devolatilize immediately upon crossing the flame interface, so that the Mie scatter signal almost vanishes. Increasing coal-loading rates leads to higher reaction rates and shorter flames. LII measurements show that soot is formed primarily in the wake of remaining coal particles in the product regions. Finally, differences in the mean and RMS velocity field are explained by the combined action of thermal expansion and the changes in particle diameter between reacting and non-reacting flows.This work is supported by EPSRC research Grant (#EP/G062153/1). Yi Gao is supported by EPSRC Grant (#EP/K02924X/1), S. Lowe acknowledges support through an EPSRC DTA grant, M. Kamal is supported by University of Engineering and Technology Peshawar (Pakistan), and Bo Tian acknowledges support from CSC.This is the final version of the article. It first appeared from Springer via http://dx.doi.org/10.1007/s00348-015-1965-

Two distinct sequences of blue straggler stars in the globular cluster M30

Stars in globular clusters are generally believed to have all formed at the same time, early in the Galaxy's history. 'Blue stragglers' are stars massive enough that they should have evolved into white dwarfs long ago. Two possible mechanisms have been proposed for their formation: mass transfer between binary companions and stellar mergers resulting from direct collisions between two stars. Recently, the binary explanation was claimed to be dominant. Here we report that there are two distinct parallel sequences of blue stragglers in M30. This globular cluster is thought to have undergone 'core collapse', during which both the collision rate and the mass transfer activity in binary systems would have been enhanced. We suggest that the two observed sequences arise from the cluster core collapse, with the bluer population arising from direct stellar collisions and the redder one arising from the evolution of close binaries that are probably still experiencing an active phase of mass transfer.Comment: Published on the 24th December 2009 issue of Natur

Longer telomere length in peripheral white blood cells is associated with risk of lung cancer and the rs2736100 (CLPTM1L-TERT) polymorphism in a prospective cohort study among women in China.

A recent genome-wide association study of lung cancer among never-smoking females in Asia demonstrated that the rs2736100 polymorphism in the TERT-CLPTM1L locus on chromosome 5p15.33 was strongly and significantly associated with risk of adenocarcinoma of the lung. The telomerase gene TERT is a reverse transcriptase that is critical for telomere replication and stabilization by controlling telomere length. We previously found that longer telomere length measured in peripheral white blood cell DNA was associated with increased risk of lung cancer in a prospective cohort study of smoking males in Finland. To follow up on this finding, we carried out a nested case-control study of 215 female lung cancer cases and 215 female controls, 94% of whom were never-smokers, in the prospective Shanghai Women's Health Study cohort. There was a dose-response relationship between tertiles of telomere length and risk of lung cancer (odds ratio (OR), 95% confidence interval [CI]: 1.0, 1.4 [0.8-2.5], and 2.2 [1.2-4.0], respectively; P trend = 0.003). Further, the association was unchanged by the length of time from blood collection to case diagnosis. In addition, the rs2736100 G allele, which we previously have shown to be associated with risk of lung cancer in this cohort, was significantly associated with longer telomere length in these same study subjects (P trend = 0.030). Our findings suggest that individuals with longer telomere length in peripheral white blood cells may have an increased risk of lung cancer, but require replication in additional prospective cohorts and populations

Gallium hydride vapor phase epitaxy of GaN nanowires

Straight GaN nanowires (NWs) with diameters of 50 nm, lengths up to 10 μm and a hexagonal wurtzite crystal structure have been grown at 900°C on 0.5 nm Au/Si(001) via the reaction of Ga with NH3 and N2:H2, where the H2 content was varied between 10 and 100%. The growth of high-quality GaN NWs depends critically on the thickness of Au and Ga vapor pressure while no deposition occurs on plain Si(001). Increasing the H2 content leads to an increase in the growth rate, a reduction in the areal density of the GaN NWs and a suppression of the underlying amorphous (α)-like GaN layer which occurs without H2. The increase in growth rate with H2 content is a direct consequence of the reaction of Ga with H2 which leads to the formation of Ga hydride that reacts efficiently with NH3 at the top of the GaN NWs. Moreover, the reduction in the areal density of the GaN NWs and suppression of the α-like GaN layer is attributed to the reaction of H2 with Ga in the immediate vicinity of the Au NPs. Finally, the incorporation of H2 leads to a significant improvement in the near band edge photoluminescence through a suppression of the non-radiative recombination via surface states which become passivated not only via H2, but also via a reduction of O2-related defects

ADP Ribosylation Factor Like 2 (Arl2) Regulates Breast Tumor Aggressivity in Immunodeficient Mice

We have previously reported that ADP ribosylation factor like 2 (Arl2), a small GTPase, content influences microtubule dynamics and cell cycle distribution in breast tumor cells, as well as the degree and distribution of phosphorylated P53. Here we show, in two different human breast adenocarcinoma models, that Arl2 content has a major impact on breast tumor cell aggressivity both in vitro and in vivo. Cells with reduced content of Arl2 displayed reduced contact inhibition, increased clonogenic or cluster formation as well as a proliferative advantage over control cells in an in vitro competition assay. These cells also caused larger tumors in SCID mice, a phenotype which was mimicked by the in vivo administration of siRNA directed against Arl2. Cells with increased Arl2 content displayed reduced aggressivity, both in vitro and in vivo, with enhanced necrosis and were also found to contain increased PP2A phosphatase activity. A rt-PCR analysis of fresh human tumor breast samples suggested that low Arl2 expression was associated with larger tumor size and greater risk of lymph node involvement at diagnosis. These data underline the role of Arl2, a small GTPase, as an important regulator of breast tumor cell aggressivity, both in vitro and in vivo

The sudden change phenomenon of quantum discord

Even if the parameters determining a system's state are varied smoothly, the behavior of quantum correlations alike to quantum discord, and of its classical counterparts, can be very peculiar, with the appearance of non-analyticities in its rate of change. Here we review this sudden change phenomenon (SCP) discussing some important points related to it: Its uncovering, interpretations, and experimental verifications, its use in the context of the emergence of the pointer basis in a quantum measurement process, its appearance and universality under Markovian and non-Markovian dynamics, its theoretical and experimental investigation in some other physical scenarios, and the related phenomenon of double sudden change of trace distance discord. Several open questions are identified, and we envisage that in answering them we will gain significant further insight about the relation between the SCP and the symmetry-geometric aspects of the quantum state space.Comment: Lectures on General Quantum Correlations and their Applications, F. F. Fanchini, D. O. Soares Pinto, and G. Adesso (Eds.), Springer (2017), pp 309-33

Interval estimation and optimal design for the within-subject coefficient of variation for continuous and binary variables

BACKGROUND: In this paper we propose the use of the within-subject coefficient of variation as an index of a measurement's reliability. For continuous variables and based on its maximum likelihood estimation we derive a variance-stabilizing transformation and discuss confidence interval construction within the framework of a one-way random effects model. We investigate sample size requirements for the within-subject coefficient of variation for continuous and binary variables. METHODS: We investigate the validity of the approximate normal confidence interval by Monte Carlo simulations. In designing a reliability study, a crucial issue is the balance between the number of subjects to be recruited and the number of repeated measurements per subject. We discuss efficiency of estimation and cost considerations for the optimal allocation of the sample resources. The approach is illustrated by an example on Magnetic Resonance Imaging (MRI). We also discuss the issue of sample size estimation for dichotomous responses with two examples. RESULTS: For the continuous variable we found that the variance stabilizing transformation improves the asymptotic coverage probabilities on the within-subject coefficient of variation for the continuous variable. The maximum like estimation and sample size estimation based on pre-specified width of confidence interval are novel contribution to the literature for the binary variable. CONCLUSION: Using the sample size formulas, we hope to help clinical epidemiologists and practicing statisticians to efficiently design reliability studies using the within-subject coefficient of variation, whether the variable of interest is continuous or binary

Electro-plating and characterisation of cadmium sulphide thin films using ammonium thiosulphate as the sulphur source

Cadmium sulphide (CdS) thin films have been successfully prepared from an aqueous electrolyte bath containing CdCl2 and ammonium thiosulphate ((NH4)2S2O3) using electrodeposition technique. The structural, compositional, optical, morphological and electrical properties of these thin films have been characterized using X-ray diffraction (XRD), Raman spectroscopy, energy dispersive X-ray spectroscopy, UV–Vis spectrophotometry, scanning electron microscopy (SEM), atomic force microscopy (AFM), photoelectrochemical cell and D.C. current–voltage (I–V) measurements. The optimum deposition cathodic potential has been observed at 1,455 mV, in a 2-electrode system with respect to carbon anode. Structural analysis using XRD shows a mixture of hexagonal and cubic phases in the as-deposited CdS samples and a phase transformation to the hexagonal structure occurred after heat treatment at 400 °C for 20 min. Optical studies demonstrate an improvement in the band edge, producing 2.42 eV for the band gap of the films after heat treatment. The heat treated CdS thin films show better transmission for wavelengths longer than 500 nm. SEM and AFM show that the heat-treated samples are more uniform, smoother and have larger grain size. Electrical studies confirm that the CdS thin films have n-type electrical conductivity and heat treated CdS thin films have resistivities of the order of 105 Ω cm