Gray to transmissive electrochromic switching based on electropolymerized PEDOT-ionic liquid functionalized graphene films

A supporting electrolyte based on lithium perchlorate has been functionalized with graphene (ionic liquid functionalized graphene (IFGR)) by facile electrochemical exfoliation of graphite rods in aq. LiClO4 solution. Poly(3,4-ethylenedioxythiophene) (PEDOT)-IFGR films were prepared by electropolymerization of EDOT monomer with IFGR as supporting electrolyte in ethanol at static potential of 1.5 V. The Raman, SEM, and XPS analysis of PEDOT-IFGR film confirmed the presence of functionalized graphene in the film. The PEDOT-IFGR films showed good electrochemical properties, better ionic and electrical conductivity, significant band gap, and excellent spectroelectrochemical and electrochromic properties. The electrical conductivity of PEDOT-IFGR film was measured as about 3968 S cm(-1). PEDOT-IFGR films at reduced state showed strong and broad absorption in the whole visible region and remarkable absorption at near-IR region. PEDOT-IFGR film showed electrochromic response between transmissive blue and darkish gray at redox potential. The color contrast (%T) between fully reduced and oxidized states of PEDOT-IFGR film is 25 % at lambda (max) of 485 nm. The optical switching stability of PEDOT-IFGR film has retained 80 % of its electroactivity even after 500 cycles.

COMPUTATIONAL MODELING OF A MULTI-LAYERED PIEZO-COMPOSITE BEAM MADE UP OF MFC

The Variational Asymptotic Method (VAM) is used for modeling a coupled non-linear electromechanical problem finding applications in aircrafts and Micro Aerial Vehicle (MAV) development. VAM coupled with geometrically exact kinematics forms a powerful tool for analyzing a complex nonlinear phenomena as shown previously by many in the literature 3 - 7] for various challenging problems like modeling of an initially twisted helicopter rotor blades, matrix crack propagation in a composite, modeling of hyper elastic plates and various multi-physics problems. The problem consists of design and analysis of a piezocomposite laminate applied with electrical voltage(s) which can induce direct and planar distributed shear stresses and strains in the structure. The deformations are large and conventional beam theories are inappropriate for the analysis. The behavior of an elastic body is completely understood by its energy. This energy must be integrated over the cross-sectional area to obtain the 1-D behavior as is typical in a beam analysis. VAM can be used efficiently to approximate 3-D strain energy as closely as possible. To perform this simplification, VAM makes use of thickness to width, width to length, width multiplied by initial twist and strain as small parameters embedded in the problem definition and provides a way to approach the exact solution asymptotically. In this work, above mentioned electromechanical problem is modeled using VAM which breaks down the 3-D elasticity problem into two parts, namely a 2-D non-linear cross-sectional analysis and a 1-D non-linear analysis, along the reference curve. The recovery relations obtained as a by-product in the cross-sectional analysis earlier are used to obtain 3-D stresses, displacements and velocity contours. The piezo-composite laminate which is chosen for an initial phase of computational modeling is made up of commercially available Macro Fiber Composites (MFCs) stacked together in an arbitrary lay-up and applied with electrical voltages for actuation. The expressions of sectional forces and moments as obtained from cross-sectional analysis in closed-form show the electro-mechanical coupling and relative contribution of electric field in individual layers of the piezo-composite laminate. The spatial and temporal constitutive law as obtained from the cross-sectional analysis are substituted into 1-D fully intrinsic, geometrically exact equilibrium equations of motion and 1-D intrinsic kinematical equations to solve for all 1-D generalized variables as function of time and an along the reference curve co-ordinate, x(1).

Shear strength characteristics of mechanically biologically treated municipal solid waste (MBT-MSW) from Bangalore

Strength and stiffness properties of municipal solid waste (MSW) are important in landfill design. This paper presents the results of comprehensive testing of shear strength properties of mechanically biologically treated municipal solid waste (MBT-MSW) in laboratory. Changes in shear strength of MSW as a function of unit weight and particle size were investigated by performing laboratory studies on the MSW collected from Mavallipura landfill site in Bangalore. Direct shear tests, small scale and large scale consolidated undrained and drained triaxial tests were conducted on reconstituted compost reject MSW samples. The triaxial test results showed that the MSW samples exhibited a strain-hardening behaviour and the strength of MSW increased with increase in unit weight. Consolidated drained tests showed that the mobilized shear strength of the MSW increased by 40% for a unit weight increase from 7.3 kN/m(3) to 10.3 kN/m(3) at 20% strain levels. The mobilized cohesion and friction angle ranged from 5 to 9 kPa and 8 degrees to 33 degrees corresponding to a strain level of 20%. The consolidated undrained tests exhibited reduced friction angle values compared to the consolidated drained tests. The friction angle increased with increase in the unit weight from 8 degrees to 55 degrees in the consolidated undrained tests. Minor variations were found in the cohesion values. Relationships for strength and stiffness of MSW in terms of strength and stiffness ratios are developed and discussed. The stiffness ratio and the strength ratio of MSW were found to be 10 and 0.43. (c) 2015 Elsevier Ltd. All rights reserved.

Effect of Manganese (II) Oxide on microstructure and ionic transport properties of nanostructured cubic zirconia

Effect of MnO addition on microstructure and ionic transport properties of nanocrystalline cubic(c)-ZrO2 is reported. Monoclinic (m) ZrO2 powders with 10-30 mol% MnO powder are mechanically alloyed in a planetary ball mill at room temperature for 10 h and annealed at 550 degrees C for 6 h. In all compositions m-ZrO2 transforms completely to nanocrystalline c-ZrO2 phase and MnO is fully incorporated into c-ZrO2 lattice. Rietveld's refinement technique is employed for detailed microstructure analysis by analyzing XRD patterns. High resolution transmission electron microscopy (HRTEM) analysis confirms the complete formation of c-ZrO2 phase. Presence of stoichiometric Mn in c-ZrO2 powder is confirmed by Electron Probe Microscopy analysis. XPS analysis reveals that Mn is mostly in Mn2+ oxidation state. A correlation between lattice parameter and oxygen vacancy is established. A detailed ionic conductivity measurement in the 250 degrees-575 degrees C temperature range describes the effect of MnO on conductivity of c-ZrO2. The ionic conductivity (s) of 30 mol% MnO alloyed ZrO2 at 550 degrees C is 0.04 s cm(-1). Electrical relaxation studies are carried out by impedance and modulus spectroscopy. Relaxation frequency is found to increase with temperature and MnO mol fraction. Electrical characterization predicts that these compounds have potentials for use as solid oxide fuel cell electrolyte material. (C) 2015 Elsevier Ltd. All rights reserved.

Solid-state optical absorption from optimally tuned time-dependent range-separated hybrid density functional theory

We present a framework for obtaining reliable solid-state charge and optical excitations and spectra from optimally tuned range-separated hybrid density functional theory. The approach, which is fully couched within the formal framework of generalized Kohn-Sham theory, allows for the accurate prediction of exciton binding energies. We demonstrate our approach through first principles calculations of one- and two-particle excitations in pentacene, a molecular semiconducting crystal, where our work is in excellent agreement with experiments and prior computations. We further show that with one adjustable parameter, set to produce the known band gap, this method accurately predicts band structures and optical spectra of silicon and lithium fluoride, prototypical covalent and ionic solids. Our findings indicate that for a broad range of extended bulk systems, this method may provide a computationally inexpensive alternative to many-body perturbation theory, opening the door to studies of materials of increasing size and complexity.

Graphene scavenges free radicals to synergistically enhance structural properties in a gamma-irradiated polyethylene composite through enhanced interfacial interactions

A unique strategy for scavenging free radicals in situ on exposure to gamma irradiation in polyethylene (PE) nanocomposites is presented. Blends of ultra-high molecular weight PE and linear low-density PE (PEB) and their nanocomposites with graphene (GPEB) were prepared by melt mixing to develop materials for biomedical implants. The effect of gamma irradiation on the microstructure and mechanical properties was systematically investigated. The neat blend and the nanocomposite were subjected to gamma-ray irradiation in order to improve the interfacial adhesion between PE and graphene sheets. Structural and thermal characterization revealed that irradiation induced crosslinking and increased the crystallinity of the polymer blend. The presence of graphene further enhanced the crystallinity via crosslinks between the polymer matrix and the filler on irradiation. Graphene was found to scavenge free radicals as confirmed by electron paramagnetic resonance spectroscopy. Irradiation of graphene-containing polymer composites resulted in the largest increase in modulus and hardness compared to either irradiation or addition of graphene to PEB alone. This study provides new insight into the role of graphene in polymer matrices during irradiation and suggests that irradiated graphene-polymer composites could emerge as promising materials for use as articulating surfaces in biomedical implants.

A 1 V supercapacitor device with nanostructured graphene oxide/polyaniline composite materials

Polyaniline and graphene oxide composite on activated carbon cum reduced graphene oxide-supported supercapacitor electrodes are fabricated and electrochemically characterized in a three-electrode cell assembly. Attractive supercapacitor performance, namely high-power capability and cycling stability for graphene oxide/polyaniline composite, is observed owing to the layered and porous-polymeric-structured electrodes. Based on the materials characterization data in a three-electrode cell assembly, 1 V supercapacitor devices are developed and performance tested. A comparative study has also been conducted for polyaniline and graphene oxide/polyaniline composite-based 1 V supercapacitors for comprehending the synergic effect of graphene oxide and polyaniline. Graphene oxide/polyaniline composite-based capacitor that exhibits about 100 F g(-1) specific capacitance with faradaic efficiency in excess of 90% has its energy and power density values of 14 Wh kg(-1) and 72 kW kg(-1), respectively. Cycle-life data for over 1000 cycles reflect 10% capacitance degradation for graphene oxide/polyaniline composite supercapacitor.

A novel in-situ polymer derived nano ceramic MMC by friction stir processing

Fiction stir processing (FSP) is a solid state technique used for material processing. Tool wear and the agglomeration of ceramic particles have been serious issues in FSP of metal matrix composites. In the present study, FSP has been employed to disperse the nanoscale particles of a polymer-derived silicon carbonitride (SiCN) ceramic phase into copper by an in-situ process. SiCN cross linked polymer particles were incorporated using multi-pass ESP into pure copper to form bulk particulate metal matrix composites. The polymer was then converted into ceramic through an in-situ pyrolysis process and dispersed by ESP. Multi-pass processing was carried out to remove porosity from the samples and also for the uniform dispersion of polymer derived ceramic particles. Microstructural observations were carried out using Field Emission Scanning Electron Microscopy (FE-SEM) and Transmission Electron Microscopy (TEM) of the composite. The results indicate a uniform distribution of similar to 100 nm size particles of the ceramic phase in the copper matrix after ESP. The nanocomposite exhibits a five fold increase in microhardness (260HV(100)) which is attributed to the nano scale dispersion of ceramic particles. A mechanism has been proposed for the fracturing of PDC particles during multi pass FSP. (C) 2015 Elsevier Ltd. All rights reserved

Noble metal ions in CeO2 and TiO2: synthesis, structure and catalytic properties

In the past four decades, CeO2 has been recognized as an attractive material in the area of auto exhaust catalysis because of its unique redox properties. In the presence of CeO2, the catalytic activity of noble metals supported on Al2O3 is enhanced due to higher dispersion of noble metals in their ionic form. In the last few years, we have been exploring an entirely new approach of dispersing noble metal ions on CeO2 and TiO2 matrices for redox catalysis. In this study, the dispersion of noble metal ions by solution combustion as well as other methods over CeO2 and TiO2 resulting mainly in Ce1-xMxO2-delta, Ce1-x-yTixMyO2-delta, Ce1-x-ySnxMyO2-delta, Ce1-x-yFexMyO2-delta, Ce1-x-yZrxMyO2-delta and Ti1-xMxO2-delta (M = Pd, Pt, Rh and Ru) catalysts, the structure of these materials, their catalytic properties toward different types of catalysis, structure-property relationships and mechanisms of catalytic reactions are reviewed. In these catalysts, noble metal ions are incorporated into a substrate matrix to a certain limit in a solid solution form. Lower valent noble metal-ion substitution in CeO2 and TiO2 creates noble metal ionic sites and oxide ion vacancies that act as adsorption sites for redox catalysis. It has been demonstrated that these new generation noble metal ionic catalysts (NMIC) have been found to be catalytically more active than conventional nanocrystalline noble metal catalysts dispersed on oxide supports.

Infiltration of Matrix-Non-producers Weakens the Salmonella Biofilm and Impairs Its Antimicrobial Tolerance and Pathogenicity

Bacterial biofilms display a collective lifestyle, wherein the cells secrete extracellular polymeric substances (EPS) that helps in adhesion, aggregation, stability, and to protect the bacteria from antimicrobials. We asked whether the BPS could act as a public good for the biofilm and observed that infiltration of cells that do not produce matrix components weakened the biofilm of Salmonella enterica serovar Typhimurium. PS production was costly for the producing cells, as indicated by a significant reduction in the fitness of wild type (WT) cells during competitive planktonic growth relative to the non-producers. Infiltration frequency of non-producers in the biofilm showed a concomitant decrease in overall productivity. It was apparent in the confocal images that the non producing cells benefit from the BPS produced by the Wild Type (WT) to stay in the biofilm. The biofilm containing non-producing cells were more significantly susceptible to sodium hypochlorite and ciprofloxacin treatment than the WT biofilm. Biofilm infiltrated with non-producers delayed the pathogenesis, as tested in a murine model. The cell types were spatially assorted, with non producers being edged out in the biofilm. However, cellulose was found to act as a barrier to keep the non-producers away from the WT microcolony. Our results show that the infiltration of non-cooperating cell types can substantially weaken the biofilm making it vulnerable to antibacterials and delay their pathogenesis. Cellulose, a component of BPS, was shown to play a pivotal role of acting as the main public good, and to edge-out the non-producers away from the cooperating microcolony.

Efficient density matrix renormalization group algorithm to study Y junctions with integer and half-integer spin

An efficient density matrix renormalization group (DMRG) algorithm is presented and applied to Y junctions, systems with three arms of n sites that meet at a central site. The accuracy is comparable to DMRG of chains. As in chains, new sites are always bonded to the most recently added sites and the superblock Hamiltonian contains only new or once renormalized operators. Junctions of up to N = 3n + 1 approximate to 500 sites are studied with antiferromagnetic (AF) Heisenberg exchange J between nearest-neighbor spins S or electron transfer t between nearest neighbors in half-filled Hubbard models. Exchange or electron transfer is exclusively between sites in two sublattices with N-A not equal N-B. The ground state (GS) and spin densities rho(r) = < S-r(z)> at site r are quite different for junctions with S = 1/2, 1, 3/2, and 2. The GS has finite total spin S-G = 2S(S) for even (odd) N and for M-G = S-G in the S-G spin manifold, rho(r) > 0(< 0) at sites of the larger (smaller) sublattice. S = 1/2 junctions have delocalized states and decreasing spin densities with increasing N. S = 1 junctions have four localized S-z = 1/2 states at the end of each arm and centered on the junction, consistent with localized states in S = 1 chains with finite Haldane gap. The GS of S = 3/2 or 2 junctions of up to 500 spins is a spin density wave with increased amplitude at the ends of arms or near the junction. Quantum fluctuations completely suppress AF order in S = 1/2 or 1 junctions, as well as in half-filled Hubbard junctions, but reduce rather than suppress AF order in S = 3/2 or 2 junctions.

Composite Guidance for Impact Angle Control Against Higher Speed Targets

In the literature, the impact angle control problem has been addressed mostly against lower speed or stationary targets. However, in the current defense scenario, targets of much higher speeds than interceptors are a reality. Moreover, approaching a higher speed target from a specified angle is important for effective seeker acquisition and enhanced warhead effectiveness. This paper proposes a composite proportional navigation guidance law using a combination of the standard proportional navigation and the recently proposed retroproportional navigation guidance laws for intercepting higher speed nonmaneuvering targets at specified impact angles in three-dimensional engagements. An analysis of the set of achievable impact angles by the composite proportional navigation guidance law is presented. It is shown that there exists an impulse bias that, when added to the composite proportional navigation guidance command, expands this set further by reversing the direction of the line-of-sight angular rotation vector. A bound on the magnitude of the bias is also derived. Finally, an implementation of this impulse bias, in the form of a series of pulses, is proposed and analyzed. Simulation results are also presented to support the analysis.

Non-covalent C-Cl center dot center dot center dot pi interaction in acetylene-carbon tetrachloride adducts: Matrix isolation infrared and ab initio computational studies

Non-covalent halogen-bonding interactions between n cloud of acetylene (C2H2) and chlorine atom of carbon tetrachloride (CCl4) have been investigated using matrix isolation infrared spectroscopy and quantum chemical computations. The structure and the energies of the 1:1 C2H2-CCl4 adducts were computed at the B3LYP, MP2 and M05-2X levels of theory using 6-311++G(d,p) basis set. The computations indicated two minima for the 1:1 C2H2-CCl4 adducts; with the C-Cl center dot center dot center dot pi adduct being the global minimum, where pi cloud of C2H2 is the electron donor. The second minimum corresponded to a C-H...Cl adduct, in which C2H2 is the proton donor. The interaction energies for the adducts A and B were found to be nearly identical. Experimentally, both C-Cl center dot center dot center dot pi and C-H center dot center dot center dot Cl adducts were generated in Ar and N2 matrixes and characterized using infrared spectroscopy. This is the first report on halogen bonded adduct, stabilized through C-Cl center dot center dot center dot pi interaction being identified at low temperatures using matrix isolation infrared spectroscopy. Atoms in Molecules (AIM) and Natural Bond Orbital (NBO) analyses were performed to support the experimental results. The structures of 2:1 ((C2H2)(2)-CCl4) and 1:2 (C2H2-(CCl4)(2)) multimers and their identification in the low temperature matrixes were also discussed. (C) 2015 Elsevier B.V. All rights reserved.

Composite Guidance for Impact Angle Control Against Higher Speed Targets

In the literature, the impact angle control problem has been addressed mostly against lower speed or stationary targets. However, in the current defense scenario, targets of much higher speeds than interceptors are a reality. Moreover, approaching a higher speed target from a specified angle is important for effective seeker acquisition and enhanced warhead effectiveness. This paper proposes a composite proportional navigation guidance law using a combination of the standard proportional navigation and the recently proposed retroproportional navigation guidance laws for intercepting higher speed nonmaneuvering targets at specified impact angles in three-dimensional engagements. An analysis of the set of achievable impact angles by the composite proportional navigation guidance law is presented. It is shown that there exists an impulse bias that, when added to the composite proportional navigation guidance command, expands this set further by reversing the direction of the line-of-sight angular rotation vector. A bound on the magnitude of the bias is also derived. Finally, an implementation of this impulse bias, in the form of a series of pulses, is proposed and analyzed. Simulation results are also presented to support the analysis.

Electrical and Plasmonic Properties of Ligand-Free Sn4+-Doped In2O3 (ITO) Nanocrystals

Sn4+-doped In2O3 (ITO) is a benchmark transparent conducting oxide material. We prepared ligand-free but colloidal ITO (8nm, 10% Sn4+) nanocrystals (NCs) by using a post-synthesis surface-modification reaction. (CH3)(3)OBF4 removes the native oleylamine ligand from NC surfaces to give ligand-free, positively charged NCs that form a colloidal dispersion in polar solvents. Both oleylamine-capped and ligand-free ITO NCs exhibit intense absorption peaks, due to localized surface plasmon resonance (LSPR) at around =1950nm. Compared with oleylamine-capped NCs, the electrical resistivity of ligand-free ITO NCs is lower by an order of magnitude (approximate to 35mcm(-1)). Resistivity over a wide range of temperatures can be consistently described as a composite of metallic ITO grains embedded in an insulating matrix by using a simple equivalent circuit, which provides an insight into the conduction mechanism in these systems.