Study of Brittle-to-ductile-transition in Pt-aluminide bond coat using micro-tensile testing method

The Brittle-to-ductile-transition-temperature (BDTT) of free-standing Pt-aluminide (PtAl) coating specimens, i.e. stand-alone coating specimens without any substrate, was determined by micro-tensile testing technique. The effect of Pt content, expressed in terms of the thickness of initial electro-deposited Pt layer, on the BDTT of the coating has been evaluated and an empirical correlation drawn. Increase in the electrodeposited Pt layer thickness from nil to 10 mu m was found to cause an increase in the BDTT of the coating by about 100 degrees C.

Field emission properties of carbon nanotube arrays with defects and impurities

Field emission from carbon nanotubes (CNTs) in the form of arrays or thin films give rise to several strongly correlated process of electromechanical interaction and degradation. Such processes are mainly due to (1) electron-phonon interaction (2) electromechanical force field leading to stretching of CNTs (3) ballistic transport induced thermal spikes, coupled with high dynamic stress, leading to degradation of emission performance at the device scale. Fairly detailed physics based models of CNTs considering the aspects (1) and (2) above have already been developed by these authors, and numerical results indicate good agreement with experimental results. What is missing in such a system level modeling approach is the incorporation of structural defects and vacancies or charge impurities. This is a practical and important problem due to the fact that degradation of field emission performance is indeed observed in experimental I-V curves. What is not clear from these experiments is whether such degradation in the I-V response is due to dynamic reorientation of the CNTs or due to the defects or due to both of these effects combined. Non-equilibrium Green’s function based simulations using a tight-binding Hamiltonian for single CNT segment show up the localization of carrier density at various locations of the CNTs. About 11% decrease in the drive current with steady difference in the drain current in the range of 0.2-0.4V of the gate voltage was reported in literature when negative charge impurity was introduced at various locations of the CNT over a length of ~20nm. In the context of field emission from CNT tips, a simplistic estimate of defects have been introduced by a correction factor in the Fowler-Nordheim formulae. However, a more detailed physics based treatment is required, while at the same time the device-scale simulation is necessary. The novelty of our present approach is the following. We employ a concept of effective stiffness degradation for segments of CNTs, which is due to structural defects, and subsequently, we incorporate the vacancy defects and charge impurity effects in the Green’s function based approach. Field emission induced current-voltage characteristics of a vertically aligned CNT array on a Cu-Cr substrate is then simulated using a detailed nonlinear mechanistic model of CNTs coupled with quantum hydrodynamics. An array of 10 vertically aligned and each 12 m long CNTs is considered for the device scale analysis. Defect regions are introduced randomly over the CNT length. The result shows the decrease in the longitudinal strain due to defects. Contrary to the expected influence of purely mechanical degradation, this result indicates that the charge impurity and hence weaker transport can lead to a different electromechanical force field, which ultimately can reduce the strain. However, there could be significant fluctuation in such strain field due to electron-phonon coupling. The effect of such fluctuations (with defects) is clearly evident in the field emission current history. The average current also decreases significantly due to such defects.

Quantum destruction of spiral order in two-dimensional frustrated magnets

We study the fate of spin-1/2 spiral-ordered two-dimensional quantum antiferromagnets that are disordered by quantum fluctuations. A crucial role is played by the topological point defects of the spiral phase, which are known to have a Z(2) character. Previous works established that a nontrivial quantum spin-liquid phase results when the spiral is disordered without proliferating the Z(2) vortices. Here, we show that when the spiral is disordered by proliferating and condensing these vortices, valence-bond solid ordering occurs due to quantum Berry phase effects. We develop a general theory for this latter phase transition and apply it to a lattice model. This transition potentially provides a new example of a Landau-forbidden deconfined quantum critical point.

Increased glycosidic bond stabilities in 4-C-hydroxymethyl linked disaccharides

Three new hydroxymethyl-linked non-natural disaccharide analogues, containing an additional methylene group in between the glycosidic linkage, were synthesized by utilizing 4-C-hydroxymethyl-alpha-D-glucopyranoside as the glycosyl donor. A kinetic study was undertaken to assess the hydrolytic stabilities of these new disaccharide analogues toward acid-catalyzed hydrolysis, at 60 degrees C and 70 degrees C. The studies showed that the disaccharide analogues were stable, by an order of magnitude, than naturally-occurring disaccharides, such as, cellobiose, lactose, and maltose. The first order rate constants were lower than that of methyl glycosides and the trend of hydrolysis rate constants followed that of naturally-occurring disaccharides. alpha-Anomer showed faster hydrolysis than the beta-anomer and the presence of axial hydroxyl group also led to faster hydrolysis among the disaccharide analogues. Energy minimized structures, derived through molecular modeling, showed that dihedral angles around the glycosidic bond in disaccharide analogues were nearly similar to that of naturally-occurring disaccharides. (C) 2011 Elsevier Ltd. All rights reserved.

Efficacies of multivalent vs monovalent poly(ether imine) dendritic catalysts within a generation in multiple C-C bond forming reactions

Dendrimers are ideal platforms to study multivalent effects due to the presence of uniform end groups at their peripheries. This report concerns with a study of multivalent dendritic catalysts, both within and across dendrimer generations, and their effects to mediate C-C bond forming reactions on multivalent substrates that have two and three acrylate reactive sites. As many as fourteen multivalent dendritic catalysts were prepared using 0-3 generations of poly(propyl ether imine) dendrimers, incorporated with Pd(II) catalytic sites, both within and across the dendrimer generations. C-C Bond forming reactions of these substrates with iodobenzene, mediated by uniform concentration of the metal across all catalysts, showed formation of partially and fully functionalized cinnamates in varying ratios, depending on the extent of clustering of catalytic moieties at the peripheries of dendrimers within a dendrimer generation. In a given generation, higher clustering of catalytic moieties greatly assisted multiple C-C bond formations than presenting the same in lesser number. The studies demonstrate true benefits of clustering catalytic moieties within a dendrimer generation and the beneficial effects applicable to catalysis of substrates presenting more than one reactive center. (C) 2011 Elsevier B.V. All rights reserved.

Influence of Si-C bond density on the properties of a-Si(1-x)C(x) thin films

Amorphous silicon carbide (a-Si(1-x)C(x)) films were deposited on silicon (100) and quartz substrates by pulsed DC reactive magnetron sputtering of silicon in methane (CH(4))-Argon (Ar) atmosphere. The influence of substrate temperature and target power on the composition, carbon bonding configuration, band gap, refractive index and hardness of a-SiC films has been investigated. Increase in substrate temperature results in slightly decreasing the carbon concentration in the films but favors silicon-carbon (Si-C) bonding. Also lower target powers were favorable towards Si-C bonding. X-ray photoelectron spectroscopy (XPS) results agree with the Fourier Transform Infrared (FTIR), UV-vis spectroscopy results. Increase in substrate temperature resulted in increased hardness of the thin films from 13 to 17 GPa and the corresponding bandgap varied from 2.1 to 1.8 eV. (C) 2011 Elsevier B.V. All rights reserved.

Origin of structural defects in multiwall carbon nanotube

We investigate the walls of the defective multiwall carbon nanotube (MWCNT), and give possible mechanism for the formation of defective structure. A generalized model has been proposed for the MWCNT. which consists of (a) catalyst part, (b) embryo part and (c) full grown part. We claim that the weak embryo portion of the MWCNT, is structurally undeveloped. The stress due to pressure imbalance between inside and outside of the MWCNT during growth along with axial load at the embryo portion causes distortion, which is the source of bending and making the walls of the MWCNT off-concentric. At the later stage the stressed embryo retain the distorted structure and get transformed into fully gown defective CNT. Published by Elsevier B.V.

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.

Fatigue de-bond growth in adhesively bonded single lap joints

The fatigue de-bond growth studies have been conducted on adhesively bonded lap joint specimens between aluminium and aluminium with Redux-319A adhesive with a pre-defined crack of 3 mm at the bond end. The correlations between fracture parameters and the de-bond growth data are established using both numerical and experimental techniques. In the numerical method, geometrically non-linear finite element analyses were carried out on adhesively bonded joint specimen for various de-bond lengths measured from the lap end along the mid-bond line of the adhesive. The finite element results were post processed to estimate the SERR components G (I) and G (II) using the Modified Virtual Crack Closure Integral (MVCCI) procedure. In experimental work, specimens were fabricated and fatigue de-bond growth tests were conducted at a stress ratio R = -1. The results obtained from both numerical analyses and testing have been used to generate de-bond growth curve and establish de-bond growth law in the Paris regime for such joints. The de-bond growth rate is primarily function of mode-I SERR component G (I) since the rate of growth in shear mode is relatively small. The value of Paris exponent m is found to be 6.55. The high value of de-bond growth exponent in Paris regime is expected, since the adhesive is less ductile than conventional metallic materials. This study is important for estimating the life of adhesively bonded joints under both constant and variable amplitude fatigue loads.

Mutations in Drosophila Myosin Rod Cause Defects in Myofibril Assembly

The roles of myosin during muscle contraction are well studied, but how different domains of this protein are involved in myofibril assembly in vivo is far less understood. The indirect flight muscles (IFMs) of Drosophila melanogaster provide a good model for understanding muscle development and function in vivo. We show that two missense mutations in the rod region of the myosin heavy-chain gene, Mhc, give rise to IFM defects and abnormal myofibrils. These defects likely result from thick filament abnormalities that manifest during early sarcomere development or later by hypercontraction. The thick filament defects are accompanied by marked reduction in accumulation of flightin, a myosin binding protein, and its phosphorylated forms, which are required to stabilise thick filaments. We investigated with purified rod fragments whether the mutations affect the coiled-coil structure, rod aggregate size or rod stability. No significant changes in these parameters were detected, except for rod thermodynamic stability in one mutation. Molecular dynamics simulations suggest that these mutations may produce localised rod instabilities. We conclude that the aberrant myofibrils are a result of thick filament defects, but that these in vivo effects cannot be detected in vitro using the biophysical techniques employed. The in vivo investigation of these mutant phenotypes in IFM development and function provides a useful platform for studying myosin rod and thick filament formation generically, with application to the aetiology of human myosin rod myopathies. (C) 2012 Elsevier Ltd. All rights reserved.

Non-monotonic, distance-dependent relaxation of water in reverse micelles: Propagation of surface induced frustration along hydrogen bond networks

Layer-wise, distance-dependent orientational relaxation of water confined in reverse micelles (RM) is studied using theoretical and computational tools. We use both a newly constructed ``spins on a ring'' (SOR) Ising-type model (with Shore-Zwanzig rotational dynamics) and atomistic simulations with explicit water. Our study explores the effect of reverse micelle size and role of intermolecular correlations, compromised by the presence of a highly polar surface, on the distance (from the interface) dependence of water relaxation. The ``spins on a ring'' model can capture some aspects of distance dependence of relaxation, such as acceleration of orientational relaxation at intermediate layers. In atomistic simulations, layer-wise decomposition of hydrogen bond formation pattern clearly reveals that hydrogen bond arrangement of water at a certain distance away from the surface can remain frustrated due to the interaction with the polar surface head groups. This layer-wise analysis also reveals the presence of a non-monotonic slow relaxation component which can be attributed to this frustration effect and which is accentuated in small to intermediate size RMs. For large size RMs, the long time component decreases monotonically from the interface to the interior of the RMs with slowest relaxation observed at the interface. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4732095]

A method for stabilizing the cis prolyl peptide bond: influence of an unusual n -> pi* interaction in 1,3-oxazine and 1,3-thiazine containing peptidomimetics

The cis/trans isomer ratios of the Xaa-Pyr (Pyr = pyrrolidine) 3 degrees amide bonds are significantly high (similar to 90% cis) in the novel peptidomimetics where Pyr contains 1,3-oxazine (Oxa) or 1,3-thiazine (Thi) at its 2 position. We find that an unusual n -> pi(i-1)* interaction, selectively stabilizes the cis conformer and the n X n repulsion destabilizes the trans conformer of these molecules. Both these electronic effects oppose the steric effects in the 3 degrees amide bond. The structural requirements for manifestation of these electronic effects are determined. (c) 2012 Elsevier Ltd. All rights reserved.

Bond Graph Modeling for Energy-Harvesting Wireless Sensor Networks

Researchers can use bond graph modeling, a tool that takes into account the energy conservation principle, to accurately assess the dynamic behavior of wireless sensor networks on a continuous basis.