Physical properties of a new Deep Eutectic Solvent based on lithium bis[(trifluoromethyl)sulfonyl]imide and N-methylacetamide as superionic suitable electrolyte for lithium ion batteries and electric double layer capacitors

Herein we present a study on the physical/chemical properties of a new Deep Eutectic Solvent (DES) based on N-methylacetamide (MAc) and lithium bis[(trifluoromethyl)sulfonyl]imide (LiTFSI). Due to its interesting properties, such as wide liquid-phase range from -60°C to 280°C, low vapor pressure, and high ionic conductivity up to 28.4mScm at 150°C and at x=1/4, this solution can be practically used as electrolyte for electrochemical storage systems such as electric double-layer capacitors (EDLCs) and/or lithium ion batteries (LiBs). Firstly, relationships between its transport properties (conductivity and viscosity) as a function of composition and temperature were discussed through Arrhenius' Law and Vogel-Tamman-Fulcher (VTF) equations, as well as by using the Walden classification. From this investigation, it appears that this complex electrolyte possesses a number of excellent transport properties, like a superionic character for example. Based on which, we then evaluated its electrochemical performances as electrolyte for EDLCs and LiBs applications by using activated carbon (AC) and lithium iron phosphate (LiFePO) electrodes, respectively. These results demonstrate that this electrolyte has a good compatibility with both electrodes (AC and LiFePO) in each testing cell driven also by excellent electrochemical properties in specific capacitance, rate and cycling performances, indicating that the LiTFSI/MAc DES can be a promising electrolyte for EDLCs and LiBs applications especially for those requiring high safety and stability. © 2013 Elsevier Ltd.

Fatigue behavior of laser-welded NiTi wires in small-strain cyclic bending

NiTi wires and their weldments are commonly used in micro-electro-mechanical systems (MEMS), and in such applications, cyclic loading are commonly encountered. In this paper, the bending-rotation fatigue (BRF) test was used to study the bending fatigue behavior of NiTi wire laser weldment in the small-strain regime. The fracture mechanism, which includes crack initiation, crack growth and propagation of the weldment in the BRF test, was investigated with the aid of SEM fractography and discussed in terms of the microstructure. It was found that crack initiation was primarily surface-condition dependent. The cracks were found to initiate at the surface defects at the weld zone (WZ) surface, and the crack propagation was assisted by the gas inclusions in the WZ. The weldment was finally fractured in a ductile manner. The fatigue life was found to decrease with increasing surface strain and also with increasing bending frequency (controlled by the rotational speed in the BRF test). In comparison, the fatigue life of the unwelded NiTi wires was higher than their welded counterparts at all strain levels and bending frequencies. The decrease in fatigue resistance of the weldment could be attributed to the surface and microstructural defects introduced during laser welding.

Effect of post-weld-annealing on the tensile deformation characteristics of laser-welded NiTi thin foil

Laser welding is an important process for fabricating complex components involving NiTi shape memory
alloy. As welding is a thermal process, the amount of heat input and the rate of cooling have significant
impact on the microstructure and hence the resultant characteristics of NiTi. In this study, the effect of
laser welding and post-weld-annealing from 573 K to 1173 K on the thermal phase transformation behaviors,
tensile deformation and micro-hardness characteristics of the laser-welded NiTi thin foils were investigated.
It was found that the as-welded sample exhibited inferior super-elasticity compared to the base
material, and the super-elasticity could be partially restored by annealing at 573 K. On the other hand,
annealing of the weldment above the recrystallization temperature would lower the super-elasticity.

Susceptibility to stress corrosion cracking of NiTi laser weldment in Hanks’ solution

In this study, the susceptibility to stress corrosion cracking (SCC) of laser-welded NiTi wires in Hanks’ solution at 37.5 °C was studied by the slow strain-rate test (SSRT) at open-circuit potential and at different applied anodic potentials. The weldment shows high susceptibility to SCC when the applied potential is near to the pitting potential of the heat-affected zone (HAZ). The pits formed in the HAZ become sites of crack initiation when stress is applied, and cracks propagate in an intergranular mode under the combined effect of corrosion and stress. In contrast, the base-metal is immune to SCC under similar conditions. The increase in susceptibility to SCC in the weldment could be attributed to the poor corrosion resistance in the coarse-grained HAZ.

Effect of postweld heat treatment on the microstructure and cyclic deformation behavior of laser-welded NiTi-shape memory wires

NiTi wires of 0.5 mm diameter were laser welded using a CW 100-W fiber laser in an argon shielding environment with or without postweld heat-treatment (PWHT). The microstructure and the phases present were studied by scanning-electron microscopy (SEM), transmission-electron microscopy (TEM), and X-ray diffractometry (XRD). The phase transformation behavior and the cyclic stress–strain behavior of the NiTi weldments were studied using differential scanning calorimetry (DSC) and cyclic tensile testing. TEM and XRD analyses reveal the presence of Ni4Ti3 particles after PWHT at or above 623 K (350 °C). In the cyclic tensile test, PWHT at 623 K (350 °C) improves the cyclic deformation behavior of the weldment by reducing the accumulated residual strain, whereas PWHT at 723 K (450 °C) provides no benefit to the cyclic deformation behavior. Welding also reduces the tensile strength and fracture elongation of NiTi wires, but the deterioration could be alleviated by PWHT.

Parameter study on laser welding of nitinol wire by Taguchi method

A L27 Taguchi experiment was done to investigate the effect of laser power, welding time, laser mode (CW and two pulsed modes), focus position, and their possible interactions on the weld-bead aspect ratio of laser-welded NiTi wires by using a 100W fibre laser. The optimized parameter setting to produce the full penetrated weldment with minimum welding defects is successfully determined in the Taguchi experiment. The laser mode is found to be the most important parameter that directly controls the weld-bead aspect ratio. The focus position is the secondly important parameter for the laser welding of NiTi wires. Strong interaction between the power and focus position is found in the Taguchi experiment. The optimized weldment produced by the Taguchi experiment is mainly of columnar dendritic structure in the weld zone (WZ) with the size of 1-3µm, while the HAZ exhibits equiaxed grain structure with the size of 5-10µm. The Vickers micro-hardness test indicted that the WZ and HAZ in the weldment are softened to certain extends after fibre laser welding.

Strain dependent microstructural modifications of BiCrO3 epitaxial thin films

Strain-dependent microstructural modifications were observed in epitaxial BiCrO3 (BCO) thin films fabricated on single crystalline substrates, utilizing pulsed laser deposition. The following conditions were employed to modify the epitaxial-strain: (i) in-plane tensile strain, BCOSTO [BCO grown on buffered SrTiO3 (001)] and in-plane compressive strain, BCONGO [BCO grown on buffered NdGaO3 (110)] and (ii) varying BCO film thickness. A combination of techniques like X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (TEM) was used to analyse the epitaxial growth quality and the microstructure of BCO. Our studies revealed that in the case of BCOSTO, a coherent interface with homogeneous orthorhombic phase is obtained only for BCO film with thicknesses, d < 50 nm. All the BCOSTO films with d = 50 nm were found to be strain-relaxed with an orthorhombic phase showing 1/2 <100> and 1/4 <101> satellite reflections, the latter oriented at 45° from orthorhombic diffraction spots. High angle annular dark field scanning TEM of these films strongly suggested that the satellite reflections, 1/2 <100> and 1/4 <101>, originate from the atomic stacking sequence changes (or “modulated structure”) as reported for polytypes, without altering the chemical composition. The unaltered stoichiometry was confirmed by estimating both valency of Bi and Cr cations by surface and in-depth XPS analysis as well as the stoichiometric ratio (1 Bi:1 Cr) using scanning TEM–energy dispersive X-ray analysis. In contrast, compressively strained BCONGO films exhibited monoclinic symmetry without any structural modulations or interfacial defects, up to d ~ 200 nm. Our results indicate that both the substrate-induced in-plane epitaxial strain and the BCO film thickness are the crucial parameters to stabilise a homogeneous BCO phase in an epitaxially grown film.

Generation of hemispherical fast electron waves in the presence of preplasma in ultraintense laser-matter interaction

Hemispherical electron plasma waves generated from ultraintense laser interacting with a solid target having a subcritical preplasma is studied using particle-in-cell simulation. As the laser pulse propagates inside the preplasma, it becomes self-focused due to the response of the plasma electrons to the ponderomotive force. The electrons are mainly heated via betatron resonance absorption and their thermal energy can become higher than the ponderomotive energy. The hot electrons easily penetrate through the thin solid target and appear behind it as periodic hemispherical shell-like layers separated by the laser wavelength.

Deep eutectic solvents based on N-methylacetamide and a lithium salt as suitable electrolytes for lithium-ion batteries

In this work, we present a study on the physical and electrochemical properties of three new Deep Eutectic Solvents (DESs) based on N-methylacetamide (MAc) and a lithium salt (LiX, with X = bis[(trifluoromethyl)sulfonyl]imide, TFSI; hexafluorophosphate, PF; or nitrate, NO). Based on DSC measurements, it appears that these systems are liquid at room temperature for a lithium salt mole fraction ranging from 0.10 to 0.35. The temperature dependences of the ionic conductivity and the viscosity of these DESs are correctly described by using the Vogel-Tammann-Fulcher (VTF) type fitting equation, due to the strong interactions between Li, X and MAc in solution. Furthermore, these electrolytes possess quite large electrochemical stability windows up to 4.7-5 V on Pt, and demonstrate also a passivating behavior toward the aluminum collector at room temperature. Based on these interesting electrochemical properties, these selected DESs can be classified as potential and promising electrolytes for lithium-ion batteries (LIBs). For this purpose, a test cell was then constructed and tested at 25 °C, 60 °C and 80 °C by using each selected DES as an electrolyte and LiFePO (LFP) material as a cathode. The results show a good compatibility between each DES and LFP electrode material. A capacity of up to 160 mA h g with a good efficiency (99%) is observed in the DES based on the LiNO salt at 60 °C despite the presence of residual water in the electrolyte. Finally preliminary tests using a LFP/DES/LTO (lithium titanate) full cell at room temperature clearly show that LiTFSI-based DES can be successfully introduced into LIBs. Considering the beneficial properties, especially, the cost of these electrolytes, such introduction could represent an important contribution for the realization of safer and environmentally friendly LIBs. © 2013 the Owner Societies.

Who Feels Inferior? A Test of the Status Anxiety Hypothesis of Social Inequalities in Health

The empirical association between income inequality, population health and other social problems is now well established and the research literature suggests that the relationship is not artefactual. Debate is still ongoing as to the cause of this association. Wilkinson, Marmot and colleagues have argued for some time that the relationship stems from the psycho-social effects of status comparisons. Here, income inequality is a marker of a wider status hierarchy that provokes an emotional stress response in individuals that is harmful to health and well-being. We label this the ‘status anxiety hypothesis’. If true, this would imply a structured relationship between income inequality at the societal level, individual income rank and anxiety relating to social status. This paper sets out strong and weak forms of the hypothesis and then presents three predictions concerning the structuring of ‘status anxiety’ at the individual level given different levels of national income inequality and varying individual income. We then test these predictions using data from a cross-national survey of over 34,000 individuals carried out in 2007 in 31 European countries. Respondents from low inequality countries reported less status anxiety than those in higher inequality countries at all points on the income rank curve. This is an important precondition of support for the status anxiety hypothesis and may be seen as providing support for the weaker version of the hypothesis. However, we do not find evidence to support the stronger version of the hypothesis which requires the negative effect of income rank on status anxiety to be exacerbated by increasing income inequality.

Tailoring Alphabetical Metamaterials in Optical Frequency: Plasmonic Coupling, Dispersion, and Sensing

Tailoring optical properties of artificial metamaterials, whose optical properties go beyond the limitations of conventional and naturally occurring materials, is of importance in fundamental research and has led to many important applications such as security imaging, invisible cloak, negative refraction, ultrasensitive sensing, transformable and switchable optics. Herein, by precisely controlling the size, symmetry and topology of alphabetical metamaterials with U, S, Y, H, U-bar and V shapes, we have obtained highly tunable optical response covering visible-to-infrared (Vis-NIR) optical frequency. In addition, we show a detailed study on the physical origin of resonance modes, plasmonic coupling, the dispersion of electronic and magnetic surface plasmon polaritons, and the possibility of negative refraction. We have found that all the electronic and magnetic modes follow the dispersion of surface plasmon polaritons thus essentially they are electronic- and magnetic-surface-plasmon-polaritons-like (ESPP-like and MSPP-like) modes resulted from diffraction coupling between localized surface plasmon and freely-propagating light. Based on the fill factor and formula of magnetism permeability, we predict that the alphabetical metamaterials should show the negative refraction capability in visible optical frequency. Furthermore, we have demonstrated the specific ultrasensitive surface enhanced Raman spectroscopy (SERS) sensing of monolayer molecules and femtomolar food contaminants by tuning their resonance to match the laser wavelength, or by tuning the laser wavelength to match the plasmon resonance of metamaterials. Our tunable alphabetical metamaterials provide a generic platform to study the electromagnetic properties of metamaterials and explore the novel applications in optical frequency.

Complex Interactions between Dioxin-Like and Non-Dioxin-Like Compounds for in Vitro Cellular Responses: Implications for the Identification of Dioxin Exposure Biomarkers

Despite considerable advances in reducing the production of dioxin-like toxicants in recent years, contamination of the food chain still occasionally occurs resulting in huge losses to the agri-food sector and risk to human health through exposure. Dioxin-like toxicity is exhibited by a range of stable and bioaccumulative compounds including polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), produced by certain types of combustion, and man-made coplanar polychlorinated biphenyls (PCBs), as found in electrical transformer oils. While dioxinergic compounds act by a common mode of action making exposure detection biomarker based techniques a potentially useful tool, the influence of co-contaminating toxicants on such approaches needs to be considered. To assess the impact of possible interactions, the biological responses of H4IIE cells to challenge by 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in combination with PCB-52 and benzo-a-pyrene (BaP) were evaluated by a number of methods in this study. Ethoxyresorufin-O-deethylase (EROD) induction in TCDD exposed cells was suppressed by increasing concentrations of PCB-52, PCB-153, or BaP up to 10 mu M. BaP levels below 1 mu M suppressed TCDD stimulated EROD induction, but at higher concentrations, EROD induction was greater than the maximum observed when cells were treated with TCDD alone. A similar biphasic interaction of BaP with TCDD co-exposure was noted in the AlamarBlue assay and to a lesser extent with PCB-52. Surface enhanced laser desorption/ionization-time of flight mass spectrometry (SELDI-TOF) profiling of peptidomic responses of cells exposed to compound combinations was compared. Cells co-exposed to TCDD in the presence of BaP or PCB-52 produced the most differentiated spectra with a substantial number of non-additive interactions observed. These findings suggest that interactions between dioxin and other toxicants create novel, additive, and non-additive effects, which may be more indicative of the types of responses seen in exposed animals than those of single exposures to the individual compounds.

Effect of laser treatment on the attachment and viability of mesenchymal stem cell responses on shape memory NiTi alloy

The objectives of this study were to investigate the effect of laser-induced surface features on the morphology, attachment and viability of mesenchymal stem cells (MSCs) at different periods of time, and to evaluate the biocompatibility of different zones: laser-melted zone (MZ), heat-affected zone (HAZ) and base metal (BM) in laser-treated NiTi alloy. The surface morphology and composition were studied by scanning electron microscope (SEM) and X-ray photoemission spectroscopy (XPS), respectively. The cell morphology was examined by SEM while the cell counting and viability measurements were done by haemocytometer and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) colorimetric assay. The results indicated that the laser-induced surface features, such as surface roughening, presence of anisotropic dendritic pattern and complete surface Ni oxidation were beneficial to improve the biocompatibility of NiTi as evidenced by the highest cell attachment (4 days of culture) and viability (7 days of culture) found in the MZ. The biocompatibility of the MZ was the best, followed by the BM with the HAZ being the worst. The defective and porous oxide layer as well as the coarse grained structure might attribute to the inferior cell attachment (4 days of culture) and viability (7 days of culture) on the HAZ compared with the BM which has similar surface morphology.

Instrumentation for diagnostics and control of laser-accelerated proton (ion) beams

Suitable instrumentation for laser-accelerated proton (ion) beams is critical for development of integrated, laser-driven ion accelerator systems. Instrumentation aimed at beam diagnostics and control must be applied to the driving laser pulse, the laser-plasma that forms at the target and the emergent proton (ion) bunch in a correlated way to develop these novel accelerators. This report is a brief overview of established diagnostic techniques and new developments based on material presented at the first workshop on 'Instrumentation for Diagnostics and Control of Laser-accelerated Proton (Ion) Beams' in Abingdon, UK. It includes radiochromic film (RCF), image plates (IP), micro-channel plates (MCP), Thomson spectrometers, prompt inline scintillators, time and space-resolved interferometry (TASRI) and nuclear activation schemes. Repetition-rated instrumentation requirements for target metrology are also addressed. (C) 2013 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

Nanosecond imaging of shock-and jet-like features

The production of shock- and collimated jet-like features is recorded from the self-emission of a plasma using a 16- frame camera, which can show the progression of the interaction over short (100s ns) durations. A cluster of laser beams, with intensity 10¹⁵ W/cm², was focused onto a planar aluminum foil to produce a plasma that expanded into 0.7 mbar of argon gas. The acquisition of 16 ultrafast images on a single shot allows prompt spatial and temporal characterization of the plasma and enables the velocity of the jet- and shock-like features to be calculated.