Kinetics of hydrogen evolution on submicron size Co, Ni, Pd and CoNi alloy powder electrodes by d.c. polarization and a.c. impedance studies

Submicron size Co, Ni and Co-Ni alloy powders have been synthesized by the polyol method using the corresponding metal malonates and Pd powder by reduction of PdOx in methanol. The kinetics of the hydrogen evolution reaction ( HER) in 6 M KOH electrolyte have been studied on electrodes made from the pressed powders. The d.c. polarization measurements have resulted in a value close to 120 mV decade(-1) for the Tafel slope, suggesting that the HER follows the Volmer-Heyrovsky mechanism. The values of exchange current density (i(o)) are in the range 1-10 mA cm(-2) for electrodes fabricated in the study. The a.c. impedance spectra measured at several potentials in the HER region showed a single semicircle in the Nyquist plots. Exchange current density (i(o)) and energy transfer coefficient (alpha) have been calculated by employing a nonlinear least square-fitting program.

Synthesis and characterization of mono- and bis-D-pi-A cryptand derivatives for second-order nonlinear optics and its modulation with different metal ion inputs

Two new classes of mono- and bis-D-pi-A cryptand derivatives with a flexible and a rigid cryptand core have been synthesized. The linear and nonlinear optical properties of these molecules are probed. The three dimensional cavity of the cryptand moiety has been utilized to modulate the SHG intensity to different extents in solution with metal ion inputs such as Ni-II,Cu-II,Zn-II, and Cd-II. We also report that decomplexation events can be used to reversibly modulate their NLO responses.

Crystal structures of open and closed forms of D-serine deaminase from Salmonella typhimurium - implications on substrate specificity and catalysis

Metabolism of D-amino acids is of considerable interest due to their key importance in cell structure and function. Salmonella typhimurium D-serine deaminase (StDSD) is a pyridoxal 5' phosphate (PLP) dependent enzyme that catalyses degradation of D-Ser to pyruvate and ammonia. The first crystal structure of D-serine deaminase described here reveals a typical Foldtype II or tryptophan synthase beta subunit fold of PLP-dependent enzymes. Although holoenzyme was used for crystallization of both wild-type StDSD (WtDSD) and selenomethionine labelled StDSD (SeMetDSD), significant electron density was not observed for the cofactor, indicating that the enzyme has a low affinity for the cofactor under crystallization conditions. Interestingly, unexpected conformational differences were observed between the two structures. The WtDSD was in an open conformation while SeMetDSD, crystallized in the presence of isoserine, was in a closed conformation suggesting that the enzyme is likely to undergo conformational changes upon binding of substrate as observed in other Foldtype II PLP-dependent enzymes. Electron density corresponding to a plausible sodium ion was found near the active site of the closed but not in the open state of the enzyme. Examination of the active site and substrate modelling suggests that Thr166 may be involved in abstraction of proton from the C alpha atom of the substrate. Apart from the physiological reaction, StDSD catalyses a, b elimination of D-Thr, D-Allothr and L-Ser to the corresponding alpha-keto acids and ammonia. The structure of StDSD provides a molecular framework necessary for understanding differences in the rate of reaction with these substrates.

Stabilizing a pulsed field emission from an array of carbon nanotubes

In this paper, we propose a new design configuration for a carbon nanotube (CNT) array based pulsed field emission device to stabilize the field emission current. In the new design, we consider a pointed height distribution of the carbon nanotube array under a diode configuration with two side gates maintained at a negative potential to obtain a highly intense beam of electrons localized at the center of the array. The randomly oriented CNTs are assumed to be grown on a metallic substrate in the form of a thin film. A model of field emission from an array of CNTs under diode configuration was proposed and validated by experiments. Despite high output, the current in such a thin film device often decays drastically. The present paper is focused on understanding this problem. The random orientation of the CNTs and the electromechanical interaction are modeled to explain the self-assembly. The degraded state of the CNTs and the electromechanical force are employed to update the orientation of the CNTs. Pulsed field emission current at the device scale is finally obtained by using the Fowler-Nordheim equation by considering a dynamic electric field across the cathode and the anode and integration of current densities over the computational cell surfaces on the anode side. Furthermore we compare the subsequent performance of the pointed array with the conventionally used random and uniform arrays and show that the proposed design outperforms the conventional designs by several orders of magnitude. Based on the developed model, numerical simulations aimed at understanding the effects of various geometric parameters and their statistical features on the device current history are reported.

Electrical and magneto-resistance of Co/CNT/epoxy thin film for strain and magnetic field sensing

Cobalt and iron nanoparticles are doped in carbon nanotube (CNT)/polymer matrix composites and studied for strain and magnetic field sensing properties. Characterization of these samples is done for various volume fractions of each constituent (Co and Fe nanoparticles and CNTs) and also for cases when only either of the metallic components is present. The relation between the magnetic field and polarization-induced strain are exploited. The electronic bandgap change in the CNTs is obtained by a simplified tight-binding formulation in terms of strain and magnetic field. A nonlinear constitutive model of glassy polymer is employed to account for (1) electric bias field dependent softening/hardening (2) CNT orientations as a statistical ensemble and (3) CNT volume fraction. An effective medium theory is then employed where the CNTs and nanoparticles are treated as inclusions. The intensity of the applied magnetic field is read indirectly as the change in resistance of the sample. Very small magnetic fields can be detected using this technique since the resistance is highly sensitive to strain. Its sensitivity due to the CNT volume fraction is also discussed. The advantage of this sensor lies in the fact that it can be molded into desirable shape and can be used in fabrication of embedded sensors where the material can detect external magnetic fields on its own. Besides, the stress-controlled hysteresis of the sample can be used in designing memory devices. These composites have potential for use in magnetic encoders, which are made of a magnetic field sensor and a barcode.

Coupled electro-mechanical response of an electroactive polymer cantilever structure and its application in energy harvesting

Ionic polymer-metal composites (IPMC), piezoelectric polymer composites and nematic elastomer composites are materials, which exhibit characteristics of both sensors and actuators. Large deformation and curvature are observed in these systems when electric potential is applied. Effects of geometric non-linearity due to the chargeinduced motion in these materials are poorly understood. In this paper, a coupled model for understanding the behavior of an ionic polymer beam undergoing large deformation and large curvature is presented. Maxwell's equations and charge transport equations are considered which couple the distribution of the ion concentration and the pressure gradient along length of a cantilever beam with interdigital electrodes. A nonlinear constitutive model is derived accounting for the visco-elasto-plastic behavior of these polymers and based on the hypothesis that the presence of electrical charge stretches/contracts bonds, which give rise to electrical field dependent softening/hardening. Polymer chain orientation in statistical sense plays a role on such softening or hardening. Elementary beam kinematics with large curvature is considered. A model for understanding the deformation due to electrostatic repulsion between asymmetrical charge distributions across the cross-sections is presented. Experimental evidence that Silver(Ag) nanoparticle coated IPMCs can be used for energy harvesting is reported. An IPMC strip is vibrated in different environments and the electric power against a resistive load is measured. The electrical power generated was observed to vary with the environment with maximum power being generated when the strip is in wet state. IPMC based energy harvesting systems have potential applications in tidal wave energy harvesting, residual environmental energy harvesting to power MEMS and NEMS devices.

Lamb wave based identification and parameter estimation of corrosion in metallic plate structure using a circular PWAS array

A circular array of Piezoelectric Wafer Active Sensor (PWAS) has been employed to detect surface damages like corrosion using lamb waves. The array consists of a number of small PWASs of 10 mm diameter and 1 mm thickness. The advantage of a circular array is its compact arrangement and large area of coverage for monitoring with small area of physical access. Growth of corrosion is monitored in a laboratory-scale set-up using the PWAS array and the nature of reflected and transmitted Lamb wave patterns due to corrosion is investigated. The wavelet time-frequency maps of the sensor signals are employed and a damage index is plotted against the damage parameters and varying frequency of the actuation signal (a windowed sine signal). The variation of wavelet coefficient for different growth of corrosion is studied. Wavelet coefficient as function of time gives an insight into the effect of corrosion in time-frequency scale. We present here a method to eliminate the time scale effect which helps in identifying easily the signature of damage in the measured signals. The proposed method becomes useful in determining the approximate location of the corrosion with respect to the location of three neighboring sensors in the circular array. A cumulative damage index is computed for varying damage sizes and the results appear promising.

Viscoelastic phenomenology based structure assignment for closed-loop vibration control of a beam with sensors and actuators

In this paper we incorporate a novel approach to synthesize a class of closed-loop feedback control, based on the variational structure assignment. Properties of a viscoelastic system are used to design an active feedback controller for an undamped structural system with distributed sensor, actuator and controller. Wave dispersion properties of onedimensional beam system have been studied. Efficiency of the chosen viscoelastic model in enhancing damping and stability properties of one-dimensional viscoelastic bar have been analyzed. The variational structure is projected on a solution space of a closed-loop system involving a weakly damped structure with distributed sensor and actuator with controller. These assign the phenomenology based internal strain rate damping parameter of a viscoelastic system to the usual elastic structure but with active control. In the formulation a model of cantilever beam with non-collocated actuator and sensor has been considered. The formulation leads to the matrix identification problem of two dynamic stiffness matrices. The method has been simplified to obtain control system gains for the free vibration control of a cantilever beam system with collocated actuator-sensor, using quadratic optimal control and pole-placement methods.

Effects of phase inhomogeneity and boundary conditions on the dynamic response of SMA wire actuators

This paper reports the simulation results from the dynamic analysis of a Shape Memory Alloy (SMA) actuator. The emphasis is on understanding the dynamic behavior under various loading rates and boundary conditions, resulting in complex scenarios such as thermal and stress gradients. Also, due to the polycrystalline nature of SMA wires, presence of microstructural inhomogeneity is inevitable. Probing the effect of inhomogeneity on the dynamic behavior can facilitate the prediction of life and characteristics of SMA wire actuator under varieties of boundary and loading conditions. To study the effect of these factors, an initial boundary value problem of SMA wire is formulated. This is subsequently solved using finite element method. The dynamic response of the SMA wire actuator is analyzed under mechanical loading and results are reported. Effect of loading rate, micro-structural inhomogeneity and thermal boundary conditions on the dynamic response of SMA wire actuator is investigated and the simulation results are reported.