Modified conformation and physical properties in conducting polymers due to varying conjugation and solvent interactions

Small angle X-ray scattering (SAXS) studies of poly2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) with varying conjugation, and polyethylene dioxythiophene complexed with polystyrene sulfonate (PEDOT-PSS) in different solvents have shown the importance of the role of pi-electron conjugation and solvent-chain interactions in controlling the chain conformation and assembly. In MEH-PPV, by increasing the extent of conjugation from 30 to 100%, the persistence length (l(p)) increases from 20 to 66 angstrom. Moreover, a pronounced second peak in the pair distribution function has been observed in the fully conjugated chain, at larger length scales. This feature indicates that the chain segments tend to self-assemble as the conjugation along the chain increases. In the case of PEDOT-PSS, the chains undergo solvent induced expansion and enhanced chain organization. The clusters formed by chains are better correlated in dimethyl sulfoxide (DMSO) solution than water, as observed in the scattered intensity profiles. The values of radius of gyration and the exponent (water: 2.6, DMSO: 2.31) of power-law decay, obtained from the unified scattering function (Beaucage) analysis, give evidence for chain expansion from compact (in water) to an extended coil in DMSO solutions, which is consistent with the Kratky plot analysis. The mechanism of this transition and the increase in dc conductivity of PEDOT-PSS in DMSO solution are discussed. The onset frequency for the increase in ac conduction, as well as its temperature dependence, probes the extent of the connectivity in the PEDOT-PSS system. The enhanced charge transport in PEDOT-PSS in DMSO is attributed to the extended chain conformation, as observed in the SAXS results.

Proton NMR study of molecular dynamics in ammonium tribromo stannate (NH4SnBr3)

The proton second moment M2 and spin-lattice relaxation time T1 have been measured in ammonium tribromo stannate (NH4SnBr3) in the temperature range 77–300 K, to determine the ammonium dynamics. The continuous wave signal is strong and narrow at 77 and 300 K but has revealed an interesting intensity anomaly between 210 and 125 K. T1 shows a maximum (13 s) around 220 K. No minimum in the T1 vs 1000/T plot was observed down to 77 K. M2 and T1 results are interpreted in terms of NH+4 ion dynamics. The activation energy Ea for NH+4 ion reorientation is estimated to be 1.4 kcal mol−1.

Interfaces and traps in pentacene field-effect transistor

The equivalent circuit parameters for a pentacene organic field-effect transistor are determined from low frequency impedance measurements in the dark as well as under light illumination. The source-drain channel impedance parameters are obtained from Bode plot analysis and the deviations at low frequency are mainly due to the contact impedance. The charge accumulation at organic semiconductor-metal interface and dielectric-semiconductor interface is monitored from the response to light as an additional parameter to find out the contributions arising from photovoltaic and photoconductive effects. The shift in threshold voltage is due to the accumulation of photogenerated carriers under source-drain electrodes and at dielectric-semiconductor interface, and also this dominates the carrier transport. The charge carrier trapping at various interfaces and in the semiconductor is estimated from the dc and ac impedance measurements under illumination. (c) 2010 American Institute of Physics. doi: 10.1063/1.3517085]

High-temperature low-cycle fatigue behavior of a NIMONIC PE-16 superalloy—Correlation with deformation and fracture

Low-cycle fatigue (LCF) responses of NIMONIC PE-16 for various prior microstructures and strain amplitudes have been evaluated and the fatigue behavior has been explained in terms of the operative deformation mechanisms. Total strain-controlled LCF tests were performed at 923 K on samples possessing three different prior microstructures: alloy A in solution-annealed condition (free of γ′ and carbides), alloy B with double aging treatment (spherical γ′ of 18-nm diameter and M23C6), and alloy C with another double aging treatment (γ′ of size 35 nm, MC and M23C6). All three microstructures exhibited an intial cyclic hardening followed by a period of gradual softening at 923 K. Coffin-Manson plots describing the plastic strain amplitudevs number of reversals to failure showed that alloy A had maximum fatigue life while C showed the least. Alloy B exhibited a two-slope behavior in the Coffin-Manson plot over the strain amplitudes investigated. This has been ascribed to the change in the degree of homogeneity of deformation at high and low strain amplitudes. Transmission electron microscopic studies were carried out to characterize the various deformation mechanisms and precipitation reactions occurring during fatigue testign. Fresh precipitation of fine γ′ was confirmed by the development of “mottled contrast” in alloy C. Evidence for the shearing of the ordered γ′ precipitates was revealed by the presence of superdislocations in alloy C. Repeated shearing during cyclic loading led to the reduction in the size of the γ′ and consequent softening. Coarser γ′ precipitates were associated with Orowan loops. The observed fatigue behavior has been rationalized based on the micromechanisms stated above and on the degree of homogenization of slip assessed by slipband spacing measurements on tested samples.

Improved velocity method for the determination of coefficient of consolidation

Parkin (1978) suggested the velocity method based on the observation that the theoretical rate of consolidation and time factor plot on a log-log scale yields an initial slope of 1:2 up to 50% consolidation. A new method is proposed that is an improvement over Parkin's velocity method because it minimizes the problems encountered in using that method. The results obtained agree with the other methods in use.

Stretch effects extracted from inwardly and outwardly propagating spherical premixed flames

Unsteady propagation of spherical flames, both inward and outward, are studied numerically extensively for single-step reaction and for different Lewis numbers of fuel/oxidizer. The dependence of flame speed ratio (s) and flame temperature ratio are obtained for a range of Lewis numbers and stretch (kappa) values. These results of s versus kappa show that the asymptotic theory by Frankel and Sivashinsky is reasonable for outward propagation. Other theories are unsatisfactory both quantitatively and qualitatively. The stretch effects are much higher for negative stretch than for positive stretch, as also seen in the theory of Frankel and Sivashinsky. The linearity of the flame speed ratio vs stretch relationship is restricted to nondimensional stretch of +/-0.1. It is shown further that the results from cylindrical flames are identical to the spherical flame on flame speed ratio versus nondimensional stretch plot thus confirming the generality of the concept of stretch. The comparison of the variation of (ds/dkappa)kappa=0 with beta(Lc - 1) show an offset between the computed and the asymptotic results of Matalon and Matkowsky. The departure of negative stretch results from this variation is significant. Several earlier experimental results are analysed and set out in the form of s versus kappa plot. Comparison of the results with experiments seem reasonable for negative stretch. The results for positive stretch are satisfactory qualitatively for a few cases. For rich propane-air, there are qualitative differences pointing to the need for full chemistry calculations in the extraction of stretch effects.

Consolidation behavior of clayey soils under radial drainage

For Barren's degree of consolidation, U-r, versus the time factor, T-r, relationship for soils undergoing consolidation with radial drainage for the equal vertical strain condition, a simple method has been developed to determine the value of the coefficient of consolidation with radial drainage c(r). Theoretical log(10)(d(e)(2)/t) versus U-r curves where d(e) is the diameter of influence and r is the real time for the different known value of c(r) have been generated. A method has been developed wherein both the theoretical and experimental behaviors of soils undergoing consolidation with radial drainage can be simultaneously compared and studied on the same plot. The experimental log(10)(d(e)(2)/t) versus U-r curves have been compared with the theoretical curves. Effects of initial compression, secondary compression, and duration of load increment are studied. Simple procedures are presented for calculating the values of c(r) using the experimental log(10)(d(e)(2)/t) versus U-r curves. A comparative study of the coefficient of consolidation and the coefficient of permeability between the cases of vertical and radial drainage has been done.

Correlation of Kauzman temperature with odd-even effect in n-alkanes

A unique correlation has been established between Kauzmann temperature (Tk1) and the odd–even effect in n‐alkanes. The derived new parameter, i.e., Tm/Tk1 obtained from entropy conservation at Tk1, when plotted against chain length, provides a much sharper odd–even contrast than entropy of fusion plot reported earlier. © 1996 American Institute of Physics.

Long term monitering of vegetation in a tropical deciduous forest in Mudumalai,southern India

As part of an international network of large plots to study tropical vegetation dynamics on a long-term basis, a 50-hectare permanent plot was set up during 1988-89 in the deciduous forests of Mudumalai, southern India. Within this plot 25,929 living woody plants (71 species) above 1 cm DBH (diameter at breast height) were identified, measured, tagged and mapped. Species abundances corresponded to the characteristic log-normal distribution. The four most abundant species (Kydia calycina, Lagerstroemia microcarpa, Terminalia crenulata and Helicteres isora) constituted nearly 56% of total stems, while seven species were represented by only one individual each in the plot. Variance/mean ratios of density showed most species to have clumped distributions. The population declined overall by 14% during the first two years, largely due to elephant and fire-mediated damage to Kydia calycina and Helicteres isora. In this article we discuss the need for large plots to study vegetation dynamics.

Computing Fractal Dimension of Signals using Multiresolution Box-counting Method

In this paper, we have developed a method to compute fractal dimension (FD) of discrete time signals, in the time domain, by modifying the box-counting method. The size of the box is dependent on the sampling frequency of the signal. The number of boxes required to completely cover the signal are obtained at multiple time resolutions. The time resolutions are made coarse by decimating the signal. The loglog plot of total number of boxes required to cover the curve versus size of the box used appears to be a straight line, whose slope is taken as an estimate of FD of the signal. The results are provided to demonstrate the performance of the proposed method using parametric fractal signals. The estimation accuracy of the method is compared with that of Katz, Sevcik, and Higuchi methods. In ddition, some properties of the FD are discussed.

Thermodynamics of flow and vaporization processes in long-chain liquids

The flow and vaporization behaviors of long-chain esters of varying molecular weights (300-900) ana branching (linear, Y-shaped, and +-shaped molecules) have been studied. The flow behavior is found to depend on the structure as well as the molecular weight. Below a molecular weight of 600, the molecules flow wholly but above this, segmental motion occurs, and the flow becomes independent of the molecular weight which is explained from the blob model. The blob concept demonstrates that the hole of a size of about 11 angstrom is needed for the flow to occur and it is much less than the size of the molecule. The blob size is observed to slightly decrease along the series linear and Y- and +-branched esters. The heat of vaporization is found to be independent of the molecular structure since the molecules acquire a coiled spherical shape during vaporization and hence depends only on the molecular weight. A significant structural effect is observed for the esters on their glass transition temperature (T(g)). The T(g) vs molecular weight plot displays contrasting trend for linear and +-branched esters, with Y esters showing an intermediate behavior. It is explained from their molecular packing and entanglement as visualized by the blob model.

Nature of the Oxygen Species at Ni(110) and Ni(100) Surfaces Revealed by Exposure to Oxygen and Oxygen-Ammonia Mixtures: Evidence for the Surface Reactivity of O- Type Species

Adsorption of dioxygen at clean Ni(110) and Ni(100) surfaces gives rise to two prominent features in the O(1s) spectra at 530 and 531 eV due to O2- and O- type species, respectively. Interaction of ammonia with a Ni(100)-O surface where theta(oxygen) < 0.1 ML favors the dissociation of NH3 giving NHn, (n = 1, 2) and N(a) species. This is accompanied by a decrease in the intensity of the 531 eV feature. On the other hand. a Ni(100)-O surface where the oxygen species are mainly of the O2- type is unreactive, Coadsorption studies of NH3-O-2 mixtures show that at Ni(110) surfaces the uptake of both oxygen and ammonia increase with the proportion of oxygen in the NH3-O-2 mixture. The surface concentrations of the O- species and the NHn species also increase with the increase in the O-2/NH3 ratio while the slope of the plot of sigma(N) versus sigma(O-) is around unity. The results demonstrate the high surface reactivity of the O- species and its role in the dissociation of ammonia. Based on these observations, the possibility of the formation of a surface complex between ammonia and oxygen (specifically O-) is suggested. Results from vibrational spectroscopic studies of the coadsorption of NH3-O-2 mixtures are consistent with those from core-level spectroscopic studies.

Lopsidedness in WHISP galaxies II. Morphological lopsidedness

The distribution of stars and gas in many galaxies is asymmetric. This so-called lopsidedness is expected to significantly affect the dynamics and evolution of the disc, including the star formation activity. Here, we measure the degree of lopsidedness for the gas distribution in a selected sample of 70 galaxies from the Westerbork Hi Survey of Spiral and Irregular Galaxies. This complements our earlier work (Paper I) where the kinematic lopsidedness was derived for the same galaxies. The morphological lopsidedness is measured by performing a harmonic decomposition of the surface density maps. The amplitude of lopsidedness A(1), the fractional value of the first Fourier component, is typically quite high (about 0.1) within the optical disc and has a constant phase. Thus, lopsidedness is a common feature in galaxies and indicates a global mode. We measure A(1) out to typically one to four optical radii, sometimes even further. This is, on average, four times larger than the distance to which lopsidedness was measured in the past using near-IR as a tracer of the old stellar component, and therefore provides a new, more stringent constraint on the mechanism for the origin of lopsidedness. Interestingly, the value of A(1) saturates beyond the optical radius. Furthermore, the plot of A(1) versus radius shows fluctuations that we argue are due to local spiral features. We also try to explain the physical origin of this observed disc lopsidedness. No clear trend is found when the degree of lopsidedness is compared to a measure of the isolation or interaction probability of the sample galaxies. However, this does not rule out a tidal origin if the lopsidedness is long-lived. In addition, we find that the early-type galaxies tend to be more morphologically lopsided than the late-type galaxies. Both results together indicate that lopsidedness has a tidal origin.

Mechanism of “Autoacceleration” in the Thermal Oxidative Polymerization of R-Methylstyrene

Thermal oxidative polymerization of alpha-methylstyrene (AMS) has been studied at various temperatures(45-70 degrees C) and pressures (50-400 psi). Due to its high electron dense double bond, it undergoes thermal oxidative polymerization even at low temperatures fairly easily. The major products are poly(alpha-methylstyrene peroxide) (PMSP), and its decomposition products are acetophenone and formaldehyde. Above 45 degrees C the rate of polymerization increases sharply at a particular instant showing an ''autoacceleration'' with the formation of a knee point. The ''autoacceleration'' is supported from the fact that the plot, of R-p vs T shows a rapid rise, and the plot of ln R-p vs 1/T is non-Arrhenius. The occurrence of autoacceleration is explained on the basis of acetophenone-induced cleavage of PMSP during polymerization, generating more initiating alkoxy radicals, which subsequently leads to the rapid rise in the rate of polymerization. The mechanism of autoacceleration is supported by the change in. order, activation energy, and activation volume before and after the knee point.

Profiling of late Tertiary-early Quaternary surface in the lower reaches of Narmada valley using microtremors

In this paper, we propose the first approximation for thickness of Quaternary sediment and late Quaternary early Tertiary topography for the part of lower reaches of Narmada valley in a systematic way using the shallow seismic method, that records both horizontal and vertical components of the microtremor (ambient noise) caused by natural processes. The measurements of microtremors were carried out at 31 sites spaced at a grid interval of 5 km s using Lennartz seismometer (5 s period) and City shark-II data acquisition system. The signals recorded were analysed for horizontal to the vertical (H/V) spectral ratio using GEOPSY software. For the present study, we concentrate on frequency range between 0.2 Hz and 10 Hz. The thickness of unconsolidated sediments at various sites is calculated based on non-linear regression equations proposed by Ibs-von Seht and Wohlenberg (1999) and Parolai et al. (2002). The estimated thickness is used to plot digital elevation model and cross profiles correlating with geomorphology and geology of the study area. (C) 2011 Elsevier Ltd. All rights reserved.