Sonochemical Synthesis of Pt Ion Substituted TiO2 (Ti0.9Pt0.1O2): A High Capacity Anode Material for Lithium Battery

Doping of TiO2 with a suitable metal ion where dopant redox potential couples with that of titanium (Ti4+) and act as catalyst for additional reduction of Ti4+ to Ti2+ (Ti4+ -> Ti3+ -> Ti2+) is envisaged here to enhance lithium storage even higher than one Li/TiO2. Accordingly, 10 atom% Pt ion substituted TiO2, Ti0.9Pt0.1O2 nanocrystallites was synthesized by sonochemical method using diethylenetriamine (DETA) as complexing agent. Powder X-ray diffraction pattern (XRD), Rietveld refinement and TEM study reveals that Ti0.9Pt0.1O2 nanocrystallites of similar to 4 nm size crystallize in anatase structure. X-ray photo-electron spectroscopy (XPS) study confirms that and both Ti and Pt are in 4+ oxidation state. Due to Pt4+ ion substitution in TiO2, reducibility of TiO2 was enhanced and Ti4+ was reduced up to Ti2+ state via coupling of Pt states (Pt4+/Pt2+/Pt-0) with Ti states (Ti4+/Ti3+/Ti2+). Galvanostatic cycling of Ti0.9Pt0.1O2 against lithium showed very high capacity of 430 mAhg(-1) or exchange of similar to 1.5Li/Ti0.9Pt0.1O2. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.029208jes] All rights reserved.

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.

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.

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.

Polymer template-assisted microemulsion synthesis of large surface area, porous Li2MnO3 and its characterization as a positive electrode material of Li-ion cells

Lithium-rich manganese oxide (Li2MnO3) is prepared by reverse microemulsion method employing Pluronic acid (P123) as a soft template and studied as a positive electrode material. The as-prepared sample possesses good crystalline structure with a broadly distributed mesoporosity but low surface area. As expected, cyclic voltammetry and charge-discharge data indicate poor electrochemical activity. However, the sample gains surface area with narrowly distributed mesoporosity and also electrochemical activity after treating in 4 M H2SO4. A discharge capacity of about 160 mAh g(-1) is obtained. When the acid-treated sample is heated at 300 A degrees C, the resulting porous sample with a large surface area and dual porosity provides a discharge capacity of 240 mAh g(-1). The rate capability study suggests that the sample provides about 150 mAh g(-1) at a specific discharge current of 1.25 A g(-1). Although the cycling stability is poor, the high rate capability is attributed to porous nature of the material.

How much land-based greenhouse gas mitigation can be achieved without compromising food security and environmental goals?

Feeding 9-10billion people by 2050 and preventing dangerous climate change are two of the greatest challenges facing humanity. Both challenges must be met while reducing the impact of land management on ecosystem services that deliver vital goods and services, and support human health and well-being. Few studies to date have considered the interactions between these challenges. In this study we briefly outline the challenges, review the supply- and demand-side climate mitigation potential available in the Agriculture, Forestry and Other Land Use AFOLU sector and options for delivering food security. We briefly outline some of the synergies and trade-offs afforded by mitigation practices, before presenting an assessment of the mitigation potential possible in the AFOLU sector under possible future scenarios in which demand-side measures codeliver to aid food security. We conclude that while supply-side mitigation measures, such as changes in land management, might either enhance or negatively impact food security, demand-side mitigation measures, such as reduced waste or demand for livestock products, should benefit both food security and greenhouse gas (GHG) mitigation. Demand-side measures offer a greater potential (1.5-15.6Gt CO2-eq. yr(-1)) in meeting both challenges than do supply-side measures (1.5-4.3Gt CO2-eq. yr(-1) at carbon prices between 20 and 100US$ tCO(2)-eq. yr(-1)), but given the enormity of challenges, all options need to be considered. Supply-side measures should be implemented immediately, focussing on those that allow the production of more agricultural product per unit of input. For demand-side measures, given the difficulties in their implementation and lag in their effectiveness, policy should be introduced quickly, and should aim to codeliver to other policy agenda, such as improving environmental quality or improving dietary health. These problems facing humanity in the 21st Century are extremely challenging, and policy that addresses multiple objectives is required now more than ever.