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.

Dynamic Multiscaling in Two-Dimensional Fluid Turbulence

We obtain, by extensive direct numerical simulations, time-dependent and equal-time structure functions for the vorticity, in both quasi-Lagrangian and Eulerian frames, for the direct-cascade regime in two-dimensional fluid turbulence with air-drag-induced friction. We show that different ways of extracting time scales from these time-dependent structure functions lead to different dynamic-multiscaling exponents, which are related to equal-time multiscaling exponents by different classes of bridge relations; for a representative value of the friction we verify that, given our error bars, these bridge relations hold.

Softening and dynamic recrystallization in magnesium single crystals during c-axis compression

Commercial purity (99.8%) magnesium single crystals were subjected to plane strain compression (PSC) along the c-axis at 200 and 370 degrees C and a constant strain rate of 10(-3) s(-1). Extension was confined to the < 1 1 (2) over bar 0 > direction and the specimens were strained up to a logarithmic true strain of -1. The initial rapid increase in flow stress was followed by significant work softening at different stresses and comparable strains of about -0.05 related to macroscopic twinning events. The microstructure of the specimen after PSC at 200 degrees C was characterized by a high density of {1 0 (1) over bar 1} and {1 0 (1) over bar 3} compression twins, some of which were recrystallized. After PSC at 370 degrees C, completely recrystallized twin bands were the major feature of the observed microstructure. All new grains in these bands retained the same c-axis orientation of their compression twin hosts. The basal plane in these grains was randomly rotated around the c-axis, forming a fiber texture component. The obtained results are discussed with respect to the mechanism of recrystallization, the specific character of the boundaries between new grains and the initial matrix, and the importance of the dynamically recrystallized bands for strain accommodation in these deformed magnesium single crystals. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. 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]

Carbon Nanotube based Composite Fibers for Strain Sensing, Signal Processing and Computing

Carbon nanotubes dispersed in polymer matrix have been aligned in the form of fibers and interconnects and cured electrically and by UV light. Conductivity and effective semiconductor tunneling against reverse to forward bias field have been designed to have differentiable current-voltage response of each of the fiber/channel. The current-voltage response is a function of the strain applied to the fibers along axial direction. Biaxial and shear strains are correlated by differentiating signals from the aligned fibers/channels. Using a small doping of magnetic nanoparticles in these composite fibers, magneto-resistance properties are realized which are strong enough to use the resulting magnetostriction as a state variable for signal processing and computing. Various basic analog signal processing tasks such as addition, convolution and filtering etc. can be performed. These preliminary study shows promising application of the concept in combined analog-digital computation in carbon nanotube based fibers. Various dynamic effects such as relaxation, electric field dependent nonlinearities and hysteresis on the output signals are studied using experimental data and analytical model.

Dynamics of strain bifurcations in a magnetostrictive ribbon

We develop a coupled nonlinear oscillator model involving magnetization and strain to explain several experimentally observed dynamical features exhibited by forced magnetostrictive ribbon. Here we show that the model recovers the observed period-doubling route to chaos as function of the dc field for a fixed ac field and quasiperiodic route to chaos as a function of the ac field, keeping the dc field constant. The model also predicts induced and suppressed chaos under the influence of an additional small-amplitude near-resonant ac field. Our analysis suggests rich dynamics in coupled order-parameter systems such as magnetomartensitic and magnetoelectric materials.

Texture evolution in high strain rate deformed Cu-10Zn alloy

High strain rate deformation behavior of Cu-10Zn alloy was studied. A weak texture with fine grain size was observed at high strain rate. The weak texture has been attributed to activity of higher number of slip systems under dynamic loading conditions. Twinning has minimal role on texture. (C) 2012 Elsevier B.V. All rights reserved.

The influence of temperature and strain rate on the deformation response and microstructural evolution during hot compression of a titanium alloy Ti-6Al-4V-0.1B

Hot deformation behavior of a hypoeutectic Ti-6Al-4V-0.1B alloy in (alpha + beta) phase field is investigated in the present study with special reference to flow response, kinetics and microstructural evolution. For a comparison, the base alloy Ti-6Al-4V was also studied under identical conditions. Dynamic recovery of alpha phase occurs at low temperatures while softening due to globularization and/or dynamic recrystallization dominates at high temperatures irrespective of boron addition. Microstructural features for both the alloys display bending and kinking of alpha lamellae for near alpha test temperatures. Unlike Ti-6Al-4V, no sign of instability formation was observed in Ti-6Al-4V-0.1B for any deformation condition except for cavitation around TiB particles, due to deformation incompatibility and strain accumulation at the particle-matrix interface. The absence of macroscopic instabilities and early initiation of softening mechanisms as a result of boron addition has been attributed to microstructural features (e.g. refined prior beta grain and alpha colony size, absence of grain boundary alpha layer, presence of TiB particles at prior beta boundaries, etc.) of the respective alloys prior to deformation. (C) 2012 Elsevier B.V. All rights reserved.

Strain localization effect on system reliability based design of bridge abutments under earthquake loading

The component and system reliability based design of bridge abutments under earthquake loading is presented in the paper. Planar failure surface has been used in conjunction with pseudo-dynamic approach to compute seismic active earth pressures on an abutment. The pseudo-dynamic method, considers the effect of phase difference in shear waves, soil amplification along with the horizontal seismic accelerations, strain localization in backfill soil and associated post-peak reduction in the shear resistance from peak to residual values along a previously formed failure plane. Four modes of stability viz. sliding, overturning, eccentricity and bearing capacity of the foundation soil are considered in the analysis. The series system reliability is computed with an assumption of independent failure modes. The lower and upper bounds of system reliability are also computed by taking into account the correlations between four failure modes, which is evaluated using the direction cosines of the tangent planes at the most probable points of failure.

A unified model for the dynamics of driven ribbon with strain and magnetic order parameters

We develop a unified model to explain the dynamics of driven one dimensional ribbon for materials with strain and magnetic order parameters. We show that the model equations in their most general form explain several results on driven magnetostrictive metallic glass ribbons such as the period doubling route to chaos as a function of a dc magnetic field in the presence of a sinusoidal field, the quasiperiodic route to chaos as a function of the sinusoidal field for a fixed dc field, and induced and suppressed chaos in the presence of an additional low amplitude near resonant sinusoidal field. We also investigate the influence of a low amplitude near resonant field on the period doubling route. The model equations also exhibit symmetry restoring crisis with an exponent close to unity. The model can be adopted to explain certain results on magnetoelastic beam and martensitic ribbon under sinusoidal driving conditions. In the latter case, we find interesting dynamics of a periodic one orbit switching between two equivalent wells as a function of an ac magnetic field that eventually makes a direct transition to chaos under resonant driving condition. The model is also applicable to magnetomartensites and materials with two order parameters. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4790845]

Tension-compression asymmetry in an extruded Mg alloy AM30: temperature and strain rate effects

The effect of strain rate, (epsilon) over dot, and temperature, T, on the tension-compression asymmetry (TCA) in a dilute and wrought Mg alloy, AM30, over a temperature range that covers both twin accommodated deformation (below 250 degrees C in compression) as well as dislocation-mediated plasticity (above 250 degrees C) has been investigated. For this purpose, uniaxial tension and compression tests were conducted at T ranging from 25 to 400 degrees C with (epsilon) over dot varying between 10(-2) and 10 s(-1). In most of the cases, the stress-strain responses in tension and compression are distinctly different; with compression responses `concaving upward,' due to {10 (1) over bar2} tensile twinning at lower plastic strains followed by slip and strain hardening at higher levels of deformation, for T below 250 degrees C. This results in significant levels of TCA at T < 250 degrees C, reducing substantially at high temperatures. At T=150 and 250 degrees C, high (epsilon) over dot leads to high TCA, in particular at T=250 degrees C and (epsilon) over dot=10 s(-1), suggesting that twin-mediated plastic deformation takes precedence at high rates of loading even at sufficiently high T. TCA becomes negligible at T=350 degrees C; however at T=400 degrees C, as (epsilon) over dot increases TCA gets higher. Microscopy of the deformed samples, carried out by using electron back-scattered diffraction (EBSD), suggests that at T > 250 degrees C dynamic recrystallization begins between accompanied by reduction in the twinned fraction that contributes to the decrease of the TCA.

Effect of temperature and strain rate on the deformation behavior and microstructure of a homogenized AZ31 magnesium alloy

The plastic deformation behavior and dynamic recrystallization (DRX) in homogenized AZ31 Mg alloy was investigated in uniaxial compression in the temperature range between 150 and 400 degrees C with strain rates ranging from 10(-3) to 10(2) s(-1). Twinning was found to contribute significantly during the early stages of deformation. The onset of twinning was examined in detail by recourse to the examination of the appearance of first local maxima before peak strain in the stress-strain responses and the second derivative of stress with strain. High strain hardening rate was observed immediately after the onset of twinning and was found to increase with the Zener-Hollomon parameter. DRX was observed at temperatures above 250 degrees C whereas deformation at lower temperatures (< 250 degrees C) leads to extensive twinning at all the strain rates. At intermediate temperatures of 250-300 degrees C, plastic strains tend to localize near grain/twin boundaries, confining DRX only to these regions. Increase in the temperature promotes non-basal slip, which, in turn, leads to uniform deformation; DRX too becomes uniform. Deformation behavior in three different regimes of temperature is discussed. The dependence of critical stress for the onset of DRX and peak flow stress on temperature and strain rate are also described. (C) 2013 Elsevier B.V. All rights reserved.

Segmental relaxations and crystallization-induced phase separation in PVDF/PMMA blends in the presence of surface-functionalized multiwall carbon nanotubes

Crystallization-induced phase separation and segmental relaxations in poly(vinylidene fluoride)/poly(methyl methacrylate) (PVDF/PMMA) blends was systematically investigated by melt-rheology and broadband dielectric spectroscopy in the presence of multiwall carbon nanotubes (MWNTs). Different functionalized MWNTs (amine, -NH2; acid, -COOH) were incorporated in the blends by melt-mixing above the melting temperature of PVDF, where the blends are miscible, and the crystallization induced phase separation was probed in situ by shear rheology. Interestingly, only -NH2 functionalized MWNTs (a-MWNTs) aided in the formation of beta-phase (trans-trans) crystals in PVDF, whereas both the neat blends and the blends with -COOH functionalized MWNTs (c-MWNTs) showed only alpha-phase (trans-gauche-trans-gauche') crystals as inferred from wide-angle X-ray diffraction (WXRD) and Fourier transform infrared (FTIR). Furthermore, blends with only a-MWNTs facilitated in heterogeneous nucleation in the blends manifesting in an increase in the calorimetric crystallization temperature and hence, augmented the theologically determined crystallintion induced phase separation temperature. The dielectric relaxations associated with the crystalline phase of PVDF (alpha(c)) was completely absent in the blends with a-MWNTs in contrast to neat blends and the blends with c-MWNTs in the dielectric loss spectra. The relaxations in the blends investigated here appeared to follow Havriliak-Negami (HN) empirical equations, and, more interestingly, the dynamic heterogeneity in the system could be mapped by an extra relaxation at higher frequency at the crystallization-induced phase separation temperature. The mean relaxation time (tau(HN)) was evaluated and observed to be delayed in the presence of MWNTs in the blends, more prominently in the case of blends with a-MWNTs. The latter also showed a significant increase in the dielectric relaxation strength (Delta epsilon). Electron microscopy and selective etching was used to confirm the localization of MWNTs in the amorphous phases of the interspherulitic regions as observed from scanning electron microscopy (SEM). The evolved crystalline morphology, during crystallization-induced phase separation, was observed to have a strong influence on the charge transport processes in the blends. These observations were further supported by the specific interactions (like dipole induced dipole interaction) between a-MWNTs and PVDF, as inferred from FTIR, and the differences in the crystalline morphology as observed from WXRD and polarized optical microscopy (POM).

Multiwalled-carbon-nanotube-induced miscibility in near-critical PS/PVME blends: assessment through concentration fluctuations and segmental relaxation

The effects of multiwalled carbon nanotubes (MWNTs) on the concentration fluctuations, interfacial driven elasticity, phase morphology, and local segmental dynamics of chains for near-critical compositions of polystyrene/poly(vinyl to methyl ether) (PS/PVME) blends were systematically investigated using dynamic shear rheology and dielectric spectroscopy. The contribution of the correlation length (xi) of the concentration fluctuations to the evolving stresses was monitored in situ to probe the different stages of demixing in the blends. The classical upturn in the dynamic moduli was taken as the rheological demixing temperature (T-rheo), which was also observed to be in close agreement with those obtained using concentration fluctuation variance, <(delta phi)(2)>, versus temperature curves. Further, Fredrickson and Larson's approach involving the mean-field approximation and the double-reptation self-concentration (DRSC) model was employed to evaluate the spinodal decomposition temperature (T-s). Interestingly, the values of both T-rheo and T-s shifted upward in the blends in the presence of MWNTs, manifesting in molecular-level miscibility. These phenomenal changes were further observed to be a function of the concentration of MWNTs. The evolution of morphology as a function of temperature was studied using polarized optical microscopy (POM). It was observed that PVME, which evolved as an interconnected network during the early stages of demixing, coarsened into a matrix-droplet morphology in the late stages. The preferential wetting of PVME onto MWNTs as a result of physicochemical interactions retained the interconnected network of PVME for longer time scales, as supported by POM and atomic force microscopy (AFM) images. Microscopic heterogeneity in macroscopically miscible systems was studied by dielectric relaxation spectroscopy. The slowing of segmental relaxations in PVME was observed in the presence of both ``frozen'' PS and MWNTs interestingly at temperatures much below the calorimetric glass transition temperature (T-g). This phenomenon was observed to be local rather than global and was addressed by monitoring the evolution of the relaxation spectra near and above the demixing temperature.

pH Induced switching in hydrogel coated fiber bragg grating sensor

In this paper we report a novel hydrogel functionalized optical Fiber Bragg Grating (FBG) sensor based on chemo-mechanical-optical sensing, and demonstrate its specific application in pH activated process monitoring. The sensing mechanism is based on the stress due to ion diffusion and polymer phase transition which produce strain in the FBG. This results in shift in the Bragg wavelength which is detected by an interrogator system. A simple dip coating method to coat a thin layer of hydrogel on the FBG has been established. The gel consists of sodium alginate and calcium chloride. Gel formation is observed in real-time by continuously monitoring the Bragg wavelength shift. We have demonstrated pH sensing in the range of pH of 2 to 10. Another interesting phenomenon is observed by swelling and deswelling of FBG functionalized with hydrogel by a sequence of alternate dipping between acidic and base solutions. It is observed that the Bragg wavelength undergoes reversible and repeatable pH dependent switching.