Studies on dielectric behavior of insulator‐conductor composites

This paper describes the dielectric behavior of an insulator‐conductor composite, namely, the wax‐graphite composite. The variation of specific capacitance of these composites with parameters such as volume fraction and grain size of the conducting particles and temperature has been studied. These observed variations have been explained using the same model [C. Rajagopal and M. Satyam, J. Appl. Phys. 49, 5536 (1978)] which explains electrical conduction in composites. The specific capacitance of these materials appears to be governed by the contact capacitance between the conducting particles and the number of contacts each particle has with its neighbors. The variation of specific capacitance with temperature is attributed to the change in contact area.

Leakage current behavior in pulsed laser deposited Ba(Zr0.05Ti0.95)O3 thin films

Barium zirconium titanate [Ba(Zr0.05Ti0.95)O3, BZT] thin films were prepared by pulsed laser ablation technique and dc leakage current conduction behavior was extensively studied. The dc leakage behavior study is essential, as it leads to degradation of the data storage devices. The current-voltage (I-V) of the thin films showed an Ohmic behavior for the electric field strength lower than 7.5 MV/m. Nonlinearity in the current density-voltage (J-V) behavior has been observed at an electric field above 7.5 MV/m. Different conduction mechanisms have been thought to be responsible for the overall I-V characteristics of BZT thin films. The J-V behavior of BZT thin films was found to follow Lampert’s theory of space charge limited conduction similar to what is observed in an insulator with charge trapping moiety. The Ohmic and trap filled limited regions have been explicitly observed in the J-V curves, where the saturation prevailed after a voltage of 6.5 V referring the onset of a trap-free square region. Two different activation energy values of 1.155 and 0.325 eV corresponding to two different regions have been observed in the Arrhenius plot, which was attributed to two different types of trap levels present in the film, namely, deep and shallow traps.

Quaternary association in beta-prism I fold plant lectins: Insights from X-ray crystallography, modelling and molecular dynamics

Dimeric banana lectin and calsepa, tetrameric artocarpin and octameric heltuba are mannose-specific beta-prism I fold lectins of nearly the same tertiary structure. MD simulations on individual subunits and the oligomers provide insights into the changes in the structure brought about in the protomers on oligomerization, including swapping of the N-terminal stretch in one instance. The regions that undergo changes also tend to exhibit dynamic flexibility during MD simulations. The internal symmetries of individual oligomers are substantially retained during the calculations. Energy minimization and simulations were also carried out on models using all possible oligomers by employing the four different protomers. The unique dimerization pattern observed in calsepa could be traced to unique substitutions in a peptide stretch involved in dimerization. The impossibility of a specific mode of oligomerization involving a particular protomer is often expressed in terms of unacceptable steric contacts or dissociation of the oligomer during simulations. The calculations also led to a rationale for the observation of a heltuba tetramer in solution although the lectin exists as an octamer in the crystal, in addition to providing insights into relations among evolution, oligomerization and ligand binding.

Investigation on the High Vacuum Tribological Characteristics of Surface Treated Nuclear Grade Stainless Steel Type AISI 316 LN at 25 to 500 degrees C

Although some researchers have published friction and wear data of Plasma Nitride (PN) coatings, the tribological behavior of PN/PN Pairs in high vacuum environment has not been published so far In order to bridge this knowledge gap, tribological tests under dry conditions have been conducted on PN/PN Pairs for varying temperatures of 25, 200, 400 and 500 degrees C in high vacuum (1.6 x 10(-4) bar) environment. The PN coatings showed good wear resistance layer on the ring surface. The PN coatings were removed only from the pin surface for all the tests since it contacts at a point. The friction and wear were low at lower temperatures and it eliminated adhesion between the contact surfaces until the coating was completely removed from the pin surface. (C) 2011 Journal of Mechanical Engineering. All rights reserved.

Dimethyl sulfoxide induced structural transformations and non-monotonic concentration dependence of conformational fluctuation around active site of lysozyme

Experimental studies have observed significant changes in both structure and function of lysozyme (and other proteins) on addition of a small amount of dimethyl sulfoxide (DMSO) in aqueous solution. Our atomistic molecular dynamic simulations of lysozyme in water-DMSO reveal the following sequence of changes on increasing DMSO concentration. (i) At the initial stage (around 5% DMSO concentration) protein's conformational flexibility gets markedly suppressed. From study of radial distribution functions, we attribute this to the preferential solvation of exposed protein hydrophobic residues by the methyl groups of DMSO. (ii) In the next stage (10-15% DMSO concentration range), lysozome partially unfolds accompanied by an increase both in fluctuation and in exposed protein surface area. (iii) Between 15-20% concentration ranges, both conformational fluctuation and solvent accessible protein surface area suddenly decrease again indicating the formation of an intermediate collapse state. These results are in good agreement with near-UV circular dichroism (CD) and fluorescence studies. We explain this apparently surprising behavior in terms of a structural transformation which involves clustering among the methyl groups of DMSO. (iv) Beyond 20% concentration of DMSO, the protein starts its final sojourn towards the unfolding state with further increase in conformational fluctuation and loss in native contacts. Most importantly, analysis of contact map and fluctuation near the active site reveal that both partial unfolding and conformational fluctuations are centered mostly on the hydrophobic core of active site of lysozyme. Our results could offer a general explanation and universal picture of the anomalous behavior of protein structure-function observed in the presence of cosolvents (DMSO, ethanol, tertiary butyl alcohol, dioxane) at their low concentrations. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3694268]

The Nature of Bond Critical Points in Dinuclear Copper(I) Complexes

Closed-shell contacts between two copper(I) ions are expected to be repulsive. However, such contacts are quite frequent and are well documented. Crystallographic characterization of such contacts in unsupported and bridged multinuclear copper(I) complexes has repeatedly invited debates on the existence of cuprophilicity. Recent developments in the application of Baders theory of atoms-in-molecules (AIM) to systems in which weak hydrogen bonds are involved suggests that the copper(I)copper(I) contacts would benefit from a similar analysis. Thus the nature of electron-density distributions in copper(I) dimers that are unsupported, and those that are bridged, have been examined. A comparison of complexes that are dimers of symmetrical monomers and those that are dimers of two copper(I) monomers with different coordination spheres has also been made. AIM analysis shows that a bond critical point (BCP) between two Cu atoms is present in most cases. The nature of the BCP in terms of the electron density, ?, and its Laplacian is quite similar to the nature of critical points observed in hydrogen bonds in the same systems. The ? is inversely correlated to Cu?Cu distance. It is higher in asymmetrical systems than what is observed in corresponding symmetrical systems. By examining the ratio of the local electron potential-energy density (Vc) to the kinetic energy density (Gc), |Vc|/Gc at the critical point suggests that these interactions are not perfectly ionic but have some shared nature. Thus an analysis of critical points by using AIM theory points to the presence of an attractive metallophilic interaction similar to other well-documented weak interactions like hydrogen bonding.

Evidence for the ``Amphoteric'' Nature of Fluorine in Halogen Bonds: An Instance of Cl center dot center dot center dot F Contact

This study presents unambiguous experimental evidence in support of the highly debated ``halogen bond donor'' character of organic fluorine. Two examples of intermolecular Cl center dot center dot center dot F contacts, with F-atom as halogen bond acceptor and donor, have been analyzed by in situ cryocrystallography and theoretical charge density studies.

About the transparent electrode of the organic photovoltaic cells

Electrodes and the nature of their contact with organic materials play a crucial role in the realization of efficient optoelectronic components. Whether the injection (organic light-emitting diodes - OLEDs) or collection (organic photovoltaic cells - OPV cells) of carriers, contacts must be as efficient as possible. To do this, it is customary to refer to electrode surface treatment and/or using a buffer layer all things to optimize the contact. Efficiency of organic photovoltaic cells based on organic electron donor/organic electron acceptor junctions can be strongly improved when the transparent conductive anode is coated with a buffer layer (ABL). We show that an ultra-thin gold (0.5 nm) or a thin molybdenum oxide (3-5 nm) can be used as efficient ABL. However, the effects of these ABL depend on the highest occupied molecular orbital (HOMO) of different electron donors of the OPV cells. The results indicate that, in the case of metal ABL, a good matching between the work function of the anode and the highest occupied molecular orbital of the donor material is the major factor limiting the hole transfer efficiency. Indeed, gold is efficient as ABL only when the HOMO of the organic donor is close to its work function Phi(Au). MoO3 has a wider field of application as ABL than gold. The role of the oxide is not so clearly understood than that of Au, different models proposed to interpret the experimental results are discussed.

Synthesis and supramolecular assembly of the bifunctional borinic acid 1,2-fcB(OH)](2)

Treatment of the chloro-substituted diboradiferrocene derivative 1 with Me3SiOMe and subsequent hydrolysis resulted in formation of the novel organometallic bis(borinic acid) derivative 3. The assembly of 3 into supramolecular structures via hydrogen bonding and reversible covalent boron-oxygen bond formation was explored. Upon crystallization from acetone or THF one-dimensional chains form in which molecules of 3 alternately serve as hydrogen bond donors and acceptors. The additional OH hydrogens that are not involved in hydrogen bonding within the polymeric chains undergo hydrogen bonding to the solvent molecules. Removal of the solvent was achieved at moderate temperature under high vacuum. While the polymeric chains remain intact, in the absence of the solvent as a hydrogen bond acceptor, short contacts to the Cp rings of neighboring polymer strands lead to a network-like structure. At higher temperatures, further dehydration occurs with formation of B-O-B linkages as confirmed by MALDI-TOF mass spectrometry. Oligomers with up to 15 repeating units (30 ferrocenes) were detected.

Structure of a carbon nanotube-dendrimer composite

Using all atomistic molecular dynamics (MD) simulations we report a microscopic picture of the carbon nanotube (6,5)-dendrimer complex for PAMAM dendrimers of generations 2 to 4. We study the compact wrapping conformations of the dendrimer onto the nanotube surface for all the three generations of PAMAM dendrimer. A high degree of wrapping for the non-protonated dendrimer is observed as compared to the protonated dendrimer. For comparison, we also study the interaction of another dendrimer, poly(propyl ether imine) (PETIM), with the nanotube. The results of the distance of closest approach as well as the number of close contacts between the nanotube and the dendrimer reveal that the PAMAM dendrimer interacts strongly as compared to the PETIM dendrimer. We also calculate the binding energy between the nanotube and the dendrimer using MM/PBSA methods and attribute the strong binding to the charge transfer between them. Dendrimer wrapping on the CNT will make it soluble and the dendrimer can act as an efficient dispersing agent for the nanotubes.

Effect of Temperature Cycling on Conduction Mechanisms in CdTe Thin Films

CdTe thin films of 500 thickness prepared by thermal evaporation technique were analyzed for leakage current and conduction mechanisms. Metal-insulator-metal (MIM) capacitors were fabricated using these films as a dielectric. These films have many possible applications, such as passivation for infrared diodes that operate at low temperatures (80 K). Direct-current (DC) current-voltage (I-V) and capacitance-voltage (C-V) measurements were performed on these films. Furthermore, the films were subjected to thermal cycling from 300 K to 80 K and back to 300 K. Typical minimum leakage currents near zero bias at room temperature varied between 0.9 nA and 0.1 mu A, while low-temperature leakage currents were in the range of 9.5 pA to 0.5 nA, corresponding to resistivity values on the order of 10(8) a''broken vertical bar-cm and 10(10) a''broken vertical bar-cm, respectively. Well-known conduction mechanisms from the literature were utilized for fitting of measured I-V data. Our analysis indicates that the conduction mechanism in general is Ohmic for low fields < 5 x 10(4) V cm(-1), while the conduction mechanism for fields > 6 x 10(4) V cm(-1) is modified Poole-Frenkel (MPF) and Fowler-Nordheim (FN) tunneling at room temperature. At 80 K, Schottky-type conduction dominates. A significant observation is that the film did not show any appreciable degradation in leakage current characteristics due to the thermal cycling.

An efficient hybrid approach for design of automotive wheel bearings

Wheel bearings play a crucial role in the mobility of a vehicle by minimizing motive power loss and providing stability in cornering maneuvers. Detailed engineering analysis of a wheel bearing subsystem under dynamic conditions poses enormous challenges due to the nonlinearity of the problem caused by multiple factional contacts between rotating and stationary parts and difficulties in prediction of dynamic loads that wheels are subject to. Commonly used design methodologies are based on equivalent static analysis of ball or roller bearings in which the latter elements may even be represented with springs. In the present study, an advanced hybrid approach is suggested for realistic dynamic analysis of wheel bearings by combining lumped parameter and finite element modeling techniques. A validated lumped parameter representation serves as an efficient tool for the prediction of radial wheel load due to ground reaction which is then used in detailed finite element analysis that automatically accounts for contact forces in an explicit formulation.

Geometry of static balancing during posture transition

The interaction between the digital human model (DHM) and environment typically occurs in two distinct modes; one, when the DHM maintains contacts with the environment using its self weight, wherein associated reaction forces at the interface due to gravity are unidirectional; two, when the DHM applies both tension and compression on the environment through anchoring. For static balancing in first mode of interaction, it is sufficient to maintain the projection of the centre of mass (COM) inside the convex region induced by the weight supporting segments of the body on a horizontal plane. In DHM, static balancing is required while performing specified tasks such as reach, manipulation and locomotion; otherwise the simulations would not be realistic. This paper establishes the geometric relationships that must be satisfied for maintaining static balance while altering the support configurations for a given posture and altering the posture for a given support condition. For a given location of the COM for a system supported by multiple point contacts, the conditions for simultaneous withdrawal of a specified set of contacts have been determined in terms of the convex hulls of the subsets of the points of contact. When the projection of COM must move beyond the existing support for performing some task, new supports must be enabled for maintaining static balance. This support seeking behavior could also manifest while planning for reduction of support stresses. Feasibility of such a support depends upon the availability of necessary features in the environment. Geometric conditions necessary for selection of new support on horizontal,inclined and vertical surfaces within the workspace of the DHM for such dynamic scenario have been derived. The concepts developed are demonstrated using the cases of sit-to-stand posture transition for manipulation of COM within the convex supporting polygon, and statically stable walking gaits for support seeking within the kinematic capabilities of the DHM. The theory developed helps in making the DHM realize appropriate behaviors in diverse scenarios autonomously.

Can the viscosity in astrophysical black hole accretion disks be close to its string theory bound?

String theory and gauge/gravity duality suggest the lower bound of shear viscosity (eta) to entropy density (s) for any matter to be mu h/4 pi k(B), when h and k(B) are reduced Planck and Boltzmann constants respectively and mu <= 1. Motivated by this, we explore eta/s in black hole accretion flows, in order to understand if such exotic flows could be a natural site for the lowest eta/s. Accretion flow plays an important role in black hole physics in identifying the existence of the underlying black hole. This is a rotating shear flow with insignificant molecular viscosity, which could however have a significant turbulent viscosity, generating transport, heat and hence entropy in the flow. However, in presence of strong magnetic field, magnetic stresses can help in transporting matter independent of viscosity, via celebrated Blandford-Payne mechanism. In such cases, energy and then entropy produces via Ohmic dissipation. In,addition, certain optically thin, hot, accretion flows, of temperature greater than or similar to 10(9) K, may be favourable for nuclear burning which could generate/absorb huge energy, much higher than that in a star. We find that eta/s in accretion flows appears to be close to the lower bound suggested by theory, if they are embedded by strong magnetic field or producing nuclear energy, when the source of energy is not viscous effects. A lower bound on eta/s also leads to an upper bound on the Reynolds number of the flow.

Chemical unfolding of chicken villin headpiece in aqueous dimethyl sulfoxide solution: cosolvent concentration dependence, pathway, and microscopic mechanism

Unfolding of a protein often proceeds through partial unfolded intermediate states (PUIS). PUIS have been detected in several experimental and simulation studies. However, complete analyses of transitions between different PUIS and the unfolding trajectory are sparse. To understand such dynamical processes, we study chemical unfolding of a small protein, chicken villin head piece (HP-36), in aqueous dimethyl sulfoxide (DMSO) solution. We carry out molecular dynamics simulations at various solution compositions under ambient conditions. In each concentration, the initial step of unfolding involves separation of two adjacent native contacts, between phenyl alanine residues (11-18 and 7-18). This first step induces, under appropriate conditions, subsequent separation among other hydrophobic contacts, signifying a high degree of cooperativity in the unfolding process. The observed sequence of structural changes in HP-36 on increasing DMSO concentration and the observed sequence of PUIS, are in approximate agreement with earlier simulation results (in pure water) and experimental observations on unfolding of HP-36. Peculiar to water-DMSO mixture, an intervening structural transformation (around 15% of DMSO) in the binary mixture solvent retards the progression of unfolding as composition is increased. This is reflected in a remarkable nonmonotonic composition dependence of RMSD, radius of gyration and the fraction of native contacts. At 30% mole fraction of DMSO, we find the extended randomly coiled structure of the unfolded protein. The molecular mechanism of DMSO induced unfolding process is attributed to the initial preferential solvation of the hydrophobic side chain atoms through the methyl groups of DMSO, followed by the hydrogen bonding of the oxygen atom of DMSO to the exposed backbone NH groups of HP-36.