Hydrothermal synthesis of a monoclinic VO2 nanotube-graphene hybrid for use as cathode material in lithium ion batteries

The hydrothermal reaction of a mixture of a colloidal dispersion of graphite oxide and ammonium vanadate yielded a hybrid made of graphene and a nanotubular metastable monoclinic polymorph of VO2, known as VO2(B). The formation of VO2(B) nanotubes is accompanied by the reduction of graphite oxide. Initially the partially scrolled graphite oxide layers act as templates for the crystallization of VO2(B) in the tubular morphology. This is followed by the reduction of graphite oxide to graphene resulting in a hybrid in which VO2(B) nanotubes are dispersed in graphene. Electron microscopic studies of the hybrid reveal that the VO2(B) nanotubes are wrapped by and trapped between graphene sheets. The hybrid shows potential to be a high capacity cathode material for lithium ion batteries. It exhibits a high capacity (similar to 450 mAh/g) and cycling stability. The high capacity of the hybrid is attributed to the interaction between the graphene sheets and the VO2(B) tubes which improves the charge-transfer. The graphene matrix prevents the aggregation of the VO2(B) nanotubes leading to high cycling stability. (C) 2012 Elsevier Ltd. All rights reserved.

Polymer microfabrication by scanning based microstereolithography: Optical design and material functionality

Several research groups have attempted to optimize photopolymerization parameters to increase the throughput of scanning based microstereolithography (MSL) systems through modified beam scanning techniques. Efforts in reducing the curing line width have been implemented through high numerical aperture (NA) optical setups. However, the intensity contour symmetry and the depth of field of focus have led to grossly non-vertical and non-uniform curing profiles. This work tries to review the photopolymerization process in a scanning based MSL system from the aspect of material functionality and optical design. The focus has been to exploit the rich potential of photoreactor scanning system in achieving desired fabrication modalities (minimum curing width, uniform depth profile, and vertical curing profile) even with a reduced NA optical setup and a single movable stage. The present study tries to manipulate to its advantage the effect of optimized lower c] (photoinitiator (PI) concentration) in reducing the minimum curing width to similar to 10-20 mu m even with a higher spot size (similar to 21.36 mu m) through a judiciously chosen ``monomer-PI'' system. Optimization on grounds of increasing E-max (maximum laser exposure energy at surface) by optimizing the scan rate provides enough time for the monomer or resin to get cured across the entire resist thickness (surface to substrate similar to 10-100 mu m), leading to uniform depth profiles along the entire scan lengths. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4750975]

Lithium D-Isoascorbate Monohydrate, a New Nonlinear Optical Material

Single crystals of lithium D-isoascorbate monohydrate (LDAM), (C6H7O6Li center dot H2O), are grown by a solution growth method. The crystal structure of LDAM is solved using single crystal X-ray diffraction. The space group is orthorhombic P2(1)2(1)2(1) with four formula units per unit cell and lattice parameters a = 7.7836(3) angstrom, b = 8.7456(3) angstrom, and c = 11.0368(4) angstrom. Solubility of the material in water is determined thermogravimetrically and found to have a positive temperature coefficient of solubility. Large optical quality single crystals are subsequently grown from aqueous solution by a slow cooling method. The crystal has a bulky prismatic habit and among the prominent faces the c face appears as the only principal morphological face. The crystal exhibits a (010) cleavage. Dielectric spectroscopy reveals a nearly Debye type Cole-Cole behavior with anisotropy in relaxation. Optical transmission range is found to be from 300 to 1400 nm. The principal refractive indices of this biaxial crystal, measured using Brewster's angle method, at wavelengths 405, 543, and 632.8 nm, show high dispersion. The crystal is negative biaxial with 2V(z) = 107.8 degrees (405 nm) and belongs to the Hobden class 3. Theoretically generated type 1 and type 2 second order phase matching curves match very well with the experimental results. The second-order nonlinear coefficient d(14) was determined to be 7 x 10(-13) m/V. For the optimum phase matching direction (type 2), the second-order effective nonlinear coefficient and the walk off angle are determined to be 0.84 times d(14) and 3.5 degrees respectively. The crystal possesses high multiple surface damage thresholds of 18 GW/cm(2) and 8 GW/cm(2) at laser wavelengths 1064 and 532 nm, respectively.

Energy-efficient synthesis of ferrite powders and films

In recent years, there has been significant effort in the synthesis of nanocrystalline spinel ferrites due to their unique properties. Among them, zinc ferrite has been widely investigated for countless applications. As traditional ferrite synthesis methods are energy- and time-intensive, there is need for a resource-effective process that can prepare ferrites quickly and efficiently without compromising material quality. We report on a novel microwave-assisted soft-chemical synthesis technique in the liquid medium for synthesis of ZnFe2O4 powder below 100 °C, within 5 min. The use of β-diketonate precursors, featuring direct metal-to-oxygen bonds in their molecular structure, not only reduces process temperature and duration sharply, but also leads to water-soluble and non-toxic by-products. As synthesized powder is annealed at 300 °C for 2 hrs in a conventional anneal (CA) schedule. An alternative procedure, a 2-min rapid anneal at 300 °C (RA) is shown to be sufficient to crystallize the ferrite particles, which show a saturation magnetization (MS) of 38 emu/g, compared with 39 emu/g for a 2-hr CA. This signifies that our process is efficient enough to reduce energy consumption by ∼85% just by altering the anneal scheme. Recognizing the criticality of anneal process to the energy budget, a more energy-efficient variation of the reaction process was developed, which obviates the need for post-synthesis annealing altogether. It is shown that the process also can be employed to deposit crystalline thin films of ferrites.

Material uncertainty effect on vibration control of smart composite plate using polynomial chaos expansion

Polynomial Chaos Expansion with Latin Hypercube sampling is used to study the effect of material uncertainty on vibration control of a smart composite plate with piezoelectric sensors/actuators. Composite material properties and piezoelectric coefficients are considered as independent and normally distributed random variables. Numerical results show substantial variation in structural dynamic response due to material uncertainty of active vibration control system. This change in response due to material uncertainty can be compensated by actively tuning the feedback control system. Numerical results also show variation in dispersion of dynamic characteristics and control parameters with respect to ply angle and stacking sequence.

Conditions for the onset of elastic and material instabilities in hyperelastic materials

Several constitutive inequalities have been proposed in the literature to quantify the notion that ‘stress increases with strain’ in an elastic material. Due to some inherent shortcomings in them, which we discuss, we propose a new tensorial criterion for isotropic materials. We also present necessary conditions in terms of elasticity tensors for the onset of elastic instabilities.

Total internal reflection (TIR) Raman tribometer: a new tool for in situ study of friction-induced material transfer

The sliding history in friction-induced material transfer of dry 2H-MoS2 particles in a sheared contact was studied. Video images in contact showed fragmentation of lubricant particles and build-up of a transfer film, and were used to measure the speed of fragmented particles in the contact region. Total internal reflection (TIR) Raman spectroscopy was used to follow the build-up of the MoS2 transfer film. A combination of in situ and ex situ analysis of the mating bodies revealed the thickness of the transfer film at steady state to be of the order of 35 nm on the ball surface and 15 nm on the flat substrate. Insights into the mechanism of formation of the transfer film in the early stages of sliding contact are deduced.

Polyvinylbutyral based hybrid organic/inorganic films as a moisture barrier material

Flexible and thermally stable, freestanding hybrid organic/inorganic based polymer-composite films have been fabricated using a simple solution casting method. Polyvinylbutyral and amine functionalized mesoporous silica were used to synthesize the composite. An additional polyol-''tripentaerythritol''-component was also used to increase the -OH group content in the composite matrix. The moisture permeability of the composites was investigated by following a calcium degradation test protocol. This showed a reduction in the moisture permeability with the increase in functionalized silica loadings in the matrix. A reduction in permeability was observed for the composites as compared to the neat polymer film. The thermal and mechanical properties of these composites were also investigated by various techniques like thermogravimetric analysis, differential scanning calorimetry, tensile experiments, and dynamic mechanical analysis. It was observed that these properties detonate with the increase in the functionalized silica content and hence an optimized loading is required in order to retain critical properties. This deterioration is due to the aggregation of the fillers in the matrix. Furthermore, the films were used to encapsulate P3HT (poly 3 hexyl thiophene) based organic Schottky structured diodes, and the diode characteristics under accelerated aging conditions were studied. The weathered diodes, encapsulated with composite film showed an improvement in the lifetime as compared to neat polymer film. The initial investigation of these films suggests that they can be used as a moisture barrier layer for organic electronics encapsulation application.

Proactive control of sequential saccades in the human supplementary eye field

Our ability to regulate behavior based on past experience has thus far been examined using single movements. However, natural behavior typically involves a sequence of movements. Here, we examined the effect of previous trial type on the concurrent planning of sequential saccades using a unique paradigm. The task consisted of two trial types: no-shift trials, which implicitly encouraged the concurrent preparation of the second saccade in a subsequent trial; and target-shift trials, which implicitly discouraged the same in the next trial. Using the intersaccadic interval as an index of concurrent planning, we found evidence for context-based preparation of sequential saccades. We also used functional MRI-guided, single-pulse, transcranial magnetic stimulation on human subjects to test the role of the supplementary eye field (SEF) in the proactive control of sequential eye movements. Results showed that (i) stimulating the SEF in the previous trial disrupted the previous trial type-based preparation of the second saccade in the nonstimulated current trial, (ii) stimulating the SEF in the current trial rectified the disruptive effect caused by stimulation in the previous trial, and (iii) stimulating the SEF facilitated the preparation of second saccades based on previous trial type even when the previous trial was not stimulated. Taken together, we show how the human SEF is causally involved in proactive preparation of sequential saccades.

Ionomer based blend as water vapor barrier material for organic device encapsulation

Blends of poly (ethylene-co-methacrylic acid) (PEMA) and poly (vinyl alcohol-co-ethylene) (EVOH) were studied for encapsulating Schottky structured organic devices. A calcium degradation test was used to determine water vapor transmission rates and to determine the moisture barrier performance of neat and blend films. Moisture barrier analysis for the neat and blend compositions was discussed concerning the interactions in the blend, diffusivity of water molecules through the unit cell systems, and the occupiable free volumes available in the unit cells using molecular dynamics simulations. The experimental results of water vapor permeation were correlated with diffusion behavior predicted from molecular dynamics simulations results. The effectiveness of the blend as a suitable barrier material in increasing the lifetime of an encapsulated Schottky structured organic device was determined.

Ellagic acid - a novel organic electrode material for high capacity lithium ion batteries

Ellagic acid, a naturally occurring polyphenol, extracted from pomegranate husk, is found to be a very good organic electrode material for rechargeable lithium batteries with high reversible capacities of similar to 450 and 200 mA h g(-1) at C/10 and C/2.5 discharge rates, respectively; ex situ NMR studies reveal possible lithiation-delithiation modes at different stages of the charge-discharge process.

Spatial Wavelet Approach to Local Matrix Crack Detection in Composite Beams with Ply Level Material Uncertainty

Wavelet coefficients based on spatial wavelets are used as damage indicators to identify the damage location as well as the size of the damage in a laminated composite beam with localized matrix cracks. A finite element model of the composite beam is used in conjunction with a matrix crack based damage model to simulate the damaged composite beam structure. The modes of vibration of the beam are analyzed using the wavelet transform in order to identify the location and the extent of the damage by sensing the local perturbations at the damage locations. The location of the damage is identified by a sudden change in spatial distribution of wavelet coefficients. Monte Carlo Simulations (MCS) are used to investigate the effect of ply level uncertainty in composite material properties such as ply longitudinal stiffness, transverse stiffness, shear modulus and Poisson's ratio on damage detection parameter, wavelet coefficient. In this study, numerical simulations are done for single and multiple damage cases. It is observed that spatial wavelets can be used as a reliable damage detection tool for composite beams with localized matrix cracks which can result from low velocity impact damage.

Novel piezoelectric thin film impact sensor: application in non-destructive material discrimination

We report on the design, development, and performance study of a packaged piezoelectric thin film impact sensor, and its potential application in non-destructive material discrimination. The impact sensing element employed was a thin circular diaphragm of flexible Phynox alloy. Piezoelectric ZnO thin film as an impact sensing layer was deposited on to the Phynox alloy diaphragm by RF reactive magnetron sputtering. Deposited ZnO thin film was characterized by X-ray diffraction (XRD), Atomic Force Microscopy (AFM), and Scanning Electron Microscopy (SEM) techniques. The d(31) piezoelectric coefficient value of ZnO thin film was 4.7 pm V-1, as measured by 4-point bending method. ZnO film deposited diaphragm based sensing element was properly packaged in a suitable housing made of High Density Polyethylene (HDPE) material. Packaged impact sensor was used in an experimental set-up, which was designed and developed in-house for non-destructive material discrimination studies. Materials of different densities (iron, glass, wood, and plastic) were used as test specimens for material discrimination studies. The analysis of output voltage waveforms obtained reveals lots of valuable information about the impacted material. Impact sensor was able to discriminate the test materials on the basis of the difference in their densities. The output response of packaged impact sensor shows high linearity and repeatability. The packaged impact sensor discussed in this paper is highly sensitive, reliable, and cost-effective.

Growth and characterization of L-histidinium 2-nitrobenzoate single crystals: A new NLO material

Crystals of a new nonlinear optical (NLO) material, viz., L-histidinium 2-nitrobenzoate (LHNB) (1) were grown by slow evaporation of an aqueous solution containing equimolar concentrations of L-histidine and 2-nitrobenzoic acid. The structure of the title compound which crystallizes in the non-centrosymmetric monoclinic space group P2(1) was elucidated using single crystal X-ray intensity data. The UV-Vis-NIR spectrum of 1 reveals its transparent nature while the vibrational spectra confirm the presence of the functional groups in 1. The thermal stability and second harmonic generation (SHG) conversion efficiency of 1 were also investigated. (C) 2012 Elsevier GmbH. All rights reserved.

Li diffusion through doped and defected graphene

We investigate the effect of nitrogen and boron doping on Li diffusion through defected graphene using first principles based density functional theory. While a high energy barrier rules out the possibility of Li-diffusion through the pristine graphene, the barrier reduces with the incorporation of defects. Among the most common defects in pristine graphene, Li diffusion through the divacancy encounters the lowest energy barrier of 1.34 eV. The effect of nitrogen and boron doping on the Li diffusion through doped defected-graphene sheets has been studied. N-doping in graphene with a monovacancy reduces the energy barrier significantly. The barrier reduces with the increasing number of N atoms. On the other hand, for N doped graphene with a divacancy, Li binds in the plane of the sheet, with an enhanced binding energy. The B doping in graphene with a monovacancy leads to the enhancement of the barrier. However, in the case of B-doped graphene with a divacancy, the barrier reduces to 1.54 eV, which could lead to good kinetics. The barriers do not change significantly with B concentration. Therefore, divacancy, B and N doped defected graphene has emerged as a better alternative to pristine graphene as an anode material for Li ion battery.