Correlated conformation and charge transport in multiwall carbon nanotube-conducting polymer nanocomposites

The strikingly different charge transport behaviours in nanocomposites of multiwall carbon nanotubes (MWNTs) and conducting polymer polyethylenedioxythiophene-polystyrene-sulfonic-acid (PEDOT-PSS) at low temperatures are explained by probing their conformational properties using small-angle x-ray scattering (SAXS). The SAXS studies indicate the assembly of elongated PEDOT-PSS globules on the walls of nanotubes, coating them partially, thereby limiting the interaction between the nanotubes in the polymer matrix. This results in a charge transport governed mainly by small polarons in the conducting polymer despite the presence of metallic MWNTs. At T > 4 K, hopping of the charge carriers following one-dimensional variable range hopping is evident which also gives rise to a positive magnetoresistance (MR) with an enhanced localization length (similar to 5 nm) due to the presence of MWNTs. However, at T < 4 K, the observation of an unconventional positive temperature coefficient of resistivity is attributed to small polaron tunnelling. The exceptionally large negative MR observed in this temperature regime is conjectured to be due to the presence of quasi-1D MWNTs that can aid in lowering the tunnelling barrier across the nanotube-polymer boundary resulting in large delocalization.

Thermal degradation processes in polysulfide copolymers investigated by direct pyrolysis mass spectrometry and flash pyrolysis-gas chromatography/mass spectrometry

This is the first report on the analysis of random block polysulfide copolymers containing different amounts of repeating units in the copolymer backbone, which has been studied by direct pyrolysis mass spectrometry (DPMS) and by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The homopolymers such as poly(ethylene sulfide) (PES), poly(styrene sulfide) (PSS), and two random copolymers, viz., poly(ethylene sulfide(x)-co-styrene sulfide(y)) [copolymer I (x = y = 0.5) and copolymer II (x = 0.74, y = 0.26)] were investigated by both DPMS and Py-GC/MS (except copolymer II) techniques. In the case of copolymer I, the thermal degradation products of SE1, SE2, S-2, and S2E (S = styrene sulfide, E = ethylene sulfide) were detected in DPMS, whereas the formation of SE1 and SE2 were observed by Py-GC/MS technique. However, for copolymer II, SE3 was also found along with SE1, SE2, S-2, and S2E in DPMS. The formation of additional product (SE3) observed in copolymer II could be due to an increase in the block length formed during copolymerization. Further, a comparative study on thermal degradation of PES, poly(ethylene disulfide) (PEDS), and poly(ethylene tetrasulfide) (PETS) were investigated by Py-GC/MS. The pyrolysis products detected by both DPMS and Py-GC/MS indicates that the thermal decomposition of these polymers yield cyclic sulfides through an intramolecular exchange or by backbiting processes. The linear products with thiol and vinyl groups were also observed by Py-GC/MS along with the cyclic products via carbon hydrogen transfer reaction.

Vasomodulatory effect of novel peroxovanadate compounds on rat aorta: Role of rho kinase and nitric oxide/cGMP pathway

The present study was undertaken to assess the role of reactive oxygen species (ROS) in rat aortic ring vasoreactivity and integrity by using various peroxovanadate (pV) compounds. All the pV compounds (1 nM-300 mu M) used in the present study exerted concentration-dependent contractions on endothelium intact rat aortic rings. All compounds with an exception of DPV-asparagine (DPV-asn) significantly altered vascular integrity as shown by diminished KCl responses. Phenylephrine (PE)-mediated contractions (3 nM-300 mu M) were unaltered in the presence of these compounds. Acetylcholine (Ach)-mediated relaxation in PE (1 mu M) pre-contracted rings was significantly reduced in presence of diperoxovanadate (DPV), poly (sodium styrene sulfonate-co-maleate)-pV (PSS-CoM-pV) and poly (sodium styrene 4-sulfonate)-pV (PSS-pV). However, no significant change in Ach-mediated responses was observed in the presence of poly (acrylate)-pV (PM-pV) and DPV-asn. DPV-asn was thus chosen to further elucidate mechanism involved in peroxide mediated modulation of vasoreactivity. DPV-asn (30 nM-300 mu M) exerted significantly more stable contractions, that was found to be catalase (100 U/ml) resistant in comparison with H(2)O(2) (30 nM-300 mu M) in endothelium intact aortic rings. These contractile responses were found to be dependent on extracellular Ca(2+) and were significantly inhibited in presence of ROS scavenger N-acetylcysteine (100 mu M). Intracellular calcium chelation by BAPTA-AM (10 mu M) had no significant effect on DPV-asn (30 nM-300 mu M) mediated contraction. Pretreatment of aortic rings by rho-kinase inhibitor Y-27632 (10 mu M) significantly inhibited DPV-asn-mediated vasoconstriction indicating role of voltage-dependent Ca(2+) influx and downstream activation of rho-kinase. The small initial relaxant effect obtained on addition of DPV-asn (30 nM-1 mu M) in PE (1 mu M) pre-contracted endothelium intact rings, was prevented in the presence of guanylate cyclase inhibitor, methylene blue (10 mu M) and/or nitric oxide synthase (NOS) inhibitor, L-NAME (100 mu M) suggesting involvement of nitric oxide and cGMP. DPV-asn, like H(2)O(2), exerted a response of vasoconstriction in normal arteries and vasodilation at low concentrations (30 nM-1 mu M) in PE-pre contracted rings with overlapping mechanisms. These findings suggest usefulness of DPV-asn having low toxicity, in exploring the peroxide-mediated effects on various vascular beds. The present study also convincingly demonstrates role of H(2)O(2) in the modulation of vasoreactivity by using stable peroxide DPV-asn and warrants future studies on peroxide mediated signaling from a newer perspective. (C) 2011 Published by Elsevier Ltd.

Tuning the structure of surfactant complexes with DNA and other polyelectrolytes

We have carried out small-angle X-ray diffraction studies on complexes formed by the anionic polyelectrolytes, namely, sodium salts of double and single stranded (ds and ss) DNA, poly( glutamic acid) ( PGA), poly( acrylic acid) (PAA), and poly( styrene sulfonate) (PSS) with a cationic surfactant system consisting of cetyltrimethylammonium bromide ( CTAB) and sodium 3-hydroxy-2-naphthoate (SHN). All complexes have a two-dimensional (2D) hexagonal structure at low SHN concentrations. DNA-CTAB-SHN complexes exhibit a hexagonal to lamellar transition near the SHN concentration at which CTAB-SHN micelles show a cylinder to bilayer transformation. On the other hand, PGA and PAA complexes form a 2D centered rectangular phase at higher SHN concentrations, and PSS complexes show a primitive rectangular structure. These results provide a striking example of polyion specificity in polyelectrolytesurfactant interactions.

Synchronizing and Damping Torques Analysis of Nonlinear Voltage Regulators

This paper makes an attempt to assess the benefits of replacing a conventional generator excitation system (AVR + PSS) with a nonlinear voltage regulator using the concepts of synchronizing and damping torque components in a single machine infinite bus (SMIB) system. In recent years, there has been considerable interest in designing nonlinear excitation controllers, which are expected to give better dynamic performance over a wider range of system and operating conditions. The performance of these controllers is often justified by simulation studies on few test cases which may not adequately represent the diverse operating conditions of a typical power system. The performance of two such nonlinear controllers which are designed based on feedback linearization and include automatic voltage regulation with good dynamic performance have been analyzed using an SMIB model. Linearizing the nonlinear control laws along with the SMIB system equations, a Heffron Phillip's type of a model has been derived. Concepts of synchronizing and damping torque components have been used to show that such controllers can impair the small signal stability under certain operating conditions. This paper shows the possibility of negative damping contribution due to nonlinear voltage regulators and gives a new insight on understanding the physical impact of complex nonlinear control laws on power system dynamics.

Evaluation of bentonite and sand mixtures as liners

Compacted clay liners are widely used for waste contaminant facilities because of their low cost, large leachate attenuation capacity and resistance to damage and puncture. Commonly used bentonite possess many limitations such as high swelling and shrinkage potential, sensitivity to waste fluid characteristics etc. The paper proposes the use of bentonite-sand mixture containing optimal clay content as liner material. It has been brought out, based on detailed geotechnical investigations, that a mixture containing only about 20 to 39% of bentonite is more suited than the clay alone and they possess.

Effect of pore medium chemistry on hydraulic conductivity of fine grained soils

Hydraulic conductivity of fine-grained soils has assumed greater importance in waste disposal facilities. It is necessary to understand better the factors controlling hydraulic conductivity of fine-grained soils which are used as liners in waste disposal facilities. Hydraulic Conductivity study with ten soils with two fluids having extreme dielectric constants(epsilon) namely water and CCl4 has shown that intrinsic permeability (K) increases drastically with decrease in epsilon. These changes are attributed to the significant reduction in the thickness of diffuse double layer which in turn mainly dependent on the epsilon of the permeant. Hydraulic Conductivity with water of each pair of soils having nearly same liquid limit but different plasticity properties is found to be vastly different, but found to correlate well with shrinkage index, defined as difference between the liquid and the shrinkage limits. Also the ratio Kccl(4)/K-w is found to significantly increase with the increase in the shrinkage index.

Geotechnical properties of some Indian fly ashes

To reduce the cost of disposal of large quantities of fly ash generated and environmental problems associated with it, efforts are made to utilize fly ash for geotechnical applications. Geotechnical properties of fly ash play a key role in enhancing their application. Physical properties and chemical composition control the index properties arid engineering behaviour. The paper brings out the rob of surface area, surface characteristics, reactive silica and lime content of fly ashes on index, compaction, consolidation and strength properties of fly ashes.

A neural network based power system stabilizer suitable for on-line training-a practical case study for EGAT system

This paper presents the development of a neural network based power system stabilizer (PSS) designed to enhance the damping characteristics of a practical power system network representing a part of Electricity Generating Authority of Thailand (EGAT) system. The proposed PSS consists of a neuro-identifier and a neuro-controller which have been developed based on functional link network (FLN) model. A recursive on-line training algorithm has been utilized to train the two neural networks. Simulation results have been obtained under various operating conditions and severe disturbance cases which show that the proposed neuro-PSS can provide a better damping to the local as well as interarea modes of oscillations as compared to a conventional PSS

Unusual photoresponse of indium doped ZnO/organic thin film heterojunction

Photoresponse of n-type indium-doped ZnO and a p-type polymer (PEDOT:PSS) heterojunction devices are studied, juxtaposed with the photoluminescence of the In-ZnO samples. In addition to the expected photoresponse in the ultraviolet, the heterojunctions exhibit significant photoresponse to the visible (532 nm). However, neither the doped ZnO nor PEDOT: PSS individually show any photoresponse to visible light. The sub-bandgap photoresponse of the heterojunction originates from visible photon mediated e-h generation between the In-ZnO valence band and localized states lying within the band gap. Though increased doping of In-ZnO has limited effect on the photoluminescence, it significantly diminishes the photoresponse. The study indicates that optimally doped devices are promising for the detection of wavelengths in selected windows in the visible. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4704655]

Layer-by-Layer Self-Assembled Metal-Ion- (Ag-, Co-, Ni-, and Pd-) Doped TiO2 Nanoparticles: Synthesis, Characterisation, and Visible Light Degradation of Rhodamine B

Metal-ion- (Ag, Co, Ni and Pd) doped titania nanocatalysts were successfully deposited on glass slides by layer-by-layer (LbL) self-assembly technique using a poly(styrene sulfonate sodium salt) (PSS) and poly(allylamine hydrochloride) (PAH) polyelectrolyte system. Solid diffuse reflectance (SDR) studies showed a linear increase in absorbance at 416 nm with increase in the number of m-TiO2 thin films. The LbL assembled thin films were tested for their photocatalytic activity through the degradation of Rhodamine B under visible-light illumination. From the scanning electron microscope (SEM), the thin films had a porous morphology and the atomic force microscope (AFM) studies showed ``rough'' surfaces. The porous and rough surface morphology resulted in high surface areas hence the high photocatalytic degradation (up to 97% over a 6.5 h irradiation period) using visible-light observed. Increasing the number of multilayers deposited on the glass slides resulted in increased film thickness and an increased rate of photodegradation due to increase in the availability of more nanocatalysts (more sites for photodegradation). The LbL assembled thin films had strong adhesion properties which made them highly stable thus displaying the same efficiencies after five (5) reusability cycles.

Tunable device properties of free-standing inorganic/organic flexible hybrid structures obtained by exfoliation

We report the fabrication of free-standing flexible inorganic/organic hybrid structures by exfoliating ZnO nanostructured films from the flat indium tin oxide (ITO)/silicon/sapphire substrates using poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS). Strong interaction between ZnO and PEDOT: PSS and the thermomechanical response of PEDOT: PSS are the key issues for the exfoliation to prevail. The performance of the free-standing hybrid structures as rectifiers and photodetectors is better as compared to ITO supported hybrid structures. It is also shown that device properties of hybrid structures can be tuned by using different electrode materials. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4729550]

Synthesis of zinc oxide porous structures by anodization with water as an electrolyte

We report a simple, reliable and one-step method of synthesizing ZnO porous structures at room temperature by anodization of zinc (Zn) sheet with water as an electrolyte and graphite as a counter electrode. We observed that the de-ionized (DI) water used in the experiment is slightly acidic (pH=5.8), which is due to the dissolution of carbon dioxide from the atmosphere forming carbonic acid. Porous ZnO is characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy and photoluminescence (PL) studies. The current-transient measurement is carried out using a Gamry Instruments Reference 3000 and the thickness of the deposited films is measured using a Dektak surface profilometer. The PL, Raman and X-ray photoelectron spectroscopy are used to confirm the presence of ZnO phase. We have demonstrated that the hybrid structures of ZnO and poly (3,4-ethylenedioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) exhibit good rectifying characteristics. The evaluated barrier height and the ideality factor are 0.45 eV and 3.6, respectively.

Decentralized linear quadratic power system stabilizers for multi-machine power systems

Linear quadratic stabilizers are well-known for their superior control capabilities when compared to the conventional lead-lag power system stabilizers. However, they have not seen much of practical importance as the state variables are generally not measurable; especially the generator rotor angle measurement is not available in most of the power plants. Full state feedback controllers require feedback of other machine states in a multi-machine power system and necessitate block diagonal structure constraints for decentralized implementation. This paper investigates the design of Linear Quadratic Power System Stabilizers using a recently proposed modified Heffron-Phillip's model. This model is derived by taking the secondary bus voltage of the step-up transformer as reference instead of the infinite bus. The state variables of this model can be obtained by local measurements. This model allows a coordinated linear quadratic control design in multi machine systems. The performance of the proposed controller has been evaluated on two widely used multi-machine power systems, 4 generator 10 bus and 10 generator 39 bus systems. It has been observed that the performance of the proposed controller is superior to that of the conventional Power System Stabilizers (PSS) over a wide range of operating and system conditions.