High-Temperature Phase Transition Studies in a Novel Fast Ion Conductor, Na2Cd(SO4)2, Probed by Raman Spectroscopy

Temperature-dependent Raman spectroscopic studies were carried out on Na2Cd(SO4)(2) from room temperature to 600 degrees C. We observe two transitions at around 280 and 565 degrees C. These transitions are driven by the change in the SO4 ion. On the basis of these studies, one can explain the changes in the conductivity data observed around 280 and 565 degrees C. At 280 degrees C, spontaneous tilting of the SO4 ion leads to restriction of Na+ mobility. Above 565 degrees C, the SO4 ion starts to rotate freely, leading to increased mobility of Na+ ion in the channel.

Unprecedented transformation of tetrathienoanthracene into pentacene on Ni(111)

The imaging and characterization of single-molecule reaction events is essential to both extending our basic understanding of chemistry and applying this understanding to challenges at the frontiers of technology, for example, in nanoelectronics. Specifically, understanding the behavior of individual molecules can elucidate processes critical to the controlled synthesis of materials for applications in multiple nanoscale technologies. Here, we report the synthesis of an important semiconducting organic molecule through an unprecedented reaction observed with submolecular resolution by scanning tunneling microscopy (STM) under ultrahigh vacuum (UHV) conditions. Our images reveal a sulfur abstraction and cyclization reaction that converts tetrathienoanthracene precursors into pentacene on the Ni(111) surface. The identity of the final reaction product was confirmed by time-of-flight secondary ion mass spectrometry (TOF-SIMS). This reaction has no known literature analogue, and highlights the power of local-probe techniques for exploring new chemical pathways.

Variable-Temperature EPR and Transport Studies on Poly(4,4'-methylenedianiline): Evidence for Bipolarons

The correlation between magnetic and transport properties is examined by studying poly(4,4'-methylenedianiline)(PMDA) salts and their bases using EPR and conductivity measurements. Five different PMDA salts (doped polymers)were prepared by chemical polymerization of 4,4'-methylenedianiline using different protonic acids. The PMDA bases were obtained by dedoping the salts using ammonium hydroxide. Ambient temperature electrical conductivity measurements show evidence for the doped PMDA system to be highly disordered. The EPR spectra of the samples were recorded in the range 20-200 "C, and the results were analyzed on the basis of the polaron-bipolaron model, which is typical of nondegenerate systems. Both PMDA salts and their bases consist of self-trapped, highly mobile polarons or radical cations. EPR studies on PMDA salts show evidence for the presence of thermally activated and temperature independent (or Pauli type) paramagnetism while the bases show thermally activated, Pauli and Curie-Weiss types of paramagnetism. The paramagnetism arises due to polarons.It is proposed that charge transport takes place through both polarons and bipolarons.

High-temperature deformation processing of Ti-24Al-20Nb

Power dissipation maps have been generated in the temperature range of 900 degrees C to 1150 degrees C and strain rate range of 10(-3) to 10 s(-1) for a cast aluminide alloy Ti-24Al-20Nb using dynamic material model. The results define two distinct regimes of temperature and strain rate in which efficiency of power dissipation is maximum. The first region, centered around 975 degrees C/0.1 s(-1), is shown to correspond to dynamic recrystallization of the alpha(2) phase and the second, centered around 1150 degrees C/0.001 s(-1), corresponds to dynamic recovery and superplastic deformation of the beta phase. Thermal activation analysis using the power law creep equation yielded apparent activation energies of 854 and 627 kJ/mol for the first and second regimes, respectively. Reanalyzing the data by alternate methods yielded activation energies in the range of 170 to 220 kJ/mol and 220 to 270 kJ/mol for the first and second regimes, respectively. Cross slip was shown to constitute the activation barrier in both cases. Two distinct regimes of processing instability-one at high strain rates and the other at the low strain rates in the lower temperature regions-have been identified, within which shear bands are formed.

Growth and study of antiferroelectric lead zirconate thin films by pulsed laser ablation

Antiferroelectric lead zirconate (PZ) thin films were deposited by pulsed laser ablation on platinum-coated silicon substrates. Films showed a polycrystalline pervoskite structure upon annealing at 650 degrees C for 5-10 min. Dielectric properties were investigated as a function of temperature and frequency. The dielectric constant of PZ films was 220 at 100 kHz with a dissipation factor of 0.03. The electric field induced transformation from the antiferroelectric phase to the ferroelectric phase was observed through the polarization change, using a Sawyer-Tower circuit. The maximum polarization value obtained was 40 mu C/cm(2). The average fields to excite the ferroelectric state, and to reverse to the antiferroelectric state were 71 and 140 kV/cm, respectively. The field induced switching was also observed through double maxima in capacitance-voltage characteristics. Leakage current was studied in terms of current versus time and current versus voltage measurements. A leakage current density of 5x10(-7) A/cm(2) at 3 V, for a film of 0.7 mu m thickness, was noted at room temperature. The trap mechanism was investigated in detail in lead zirconate thin films based upon a space charge limited conduction mechanism. The films showed a backward switching time of less than 90 ns at room temperature.

High temperature time-dependent low cycle fatigue behaviour of a type 316L(N) stainless steel

Total strain controlled low cycle fatigue tests on 316L(N) stainless steel have been conducted in air at various strain rates in the temperature range of 773-873 K to identify the operative time-dependent mechanisms and to understand their influence on the cyclic deformation and fracture behaviour of the alloy. The cyclic stress response at all the testing conditions was marked by an initial hardening followed by stress saturation. A negative strain rate stress response is observed under specific testing conditions which is attributed to dynamic strain ageing (DSA). Transmission electron microscopy studies reveal that there is an increase in the dislocation density and enhanced slip planarity in the DSA regime. Fatigue life is found to decrease with a decrease in strain rate. The degradation in fatigue resistance is attributed to the detrimental effects associated with DSA and oxidation. Quantitative measurement of secondary cracks indicate that both transgranular and intergranular cracking are accelerated predominantly under conditions conducive to DSA.

Study of texture evolution in metastable beta-Ti alloy as a function of strain path and its effect on alpha transformation texture

Texture evolution in a low cost beta titanium alloy was studied for different modes of rolling and heat treatments. The alloy was cold rolled by unidirectional and multi-step cross rolling. The cold rolled material was either aged directly or recrystallized and then aged. The evolution of texture in alpha and beta phases were studied. The rolling texture of beta phase that is characterized by the gamma fiber is stronger for MSCR than UDR; while the trend is reversed on recrystallization. The mode of rolling affects alpha transformation texture on aging with smaller alpha lath size and stronger alpha texture in UDR than in MSCR. The defect structure in beta phase influences the evolution of a texture on aging. A stronger defect structure in beta phase leads to variant selection with the rolled samples showing fewer variants than the recrystallized samples.

Role of predictors in downscaling surface temperature to river basin in India for IPCC SRES scenarios using support vector machine

In this paper, downscaling models are developed using a support vector machine (SVM) for obtaining projections of monthly mean maximum and minimum temperatures (T-max and T-min) to river-basin scale. The effectiveness of the model is demonstrated through application to downscale the predictands for the catchment of the Malaprabha reservoir in India, which is considered to be a climatically sensitive region. The probable predictor variables are extracted from (1) the National Centers for Environmental Prediction (NCEP) reanalysis dataset for the period 1978-2000, and (2) the simulations from the third-generation Canadian Coupled Global Climate Model (CGCM3) for emission scenarios A1B, A2, B1 and COMMIT for the period 1978-2100. The predictor variables are classified into three groups, namely A, B and C. Large-scale atmospheric variables Such as air temperature, zonal and meridional wind velocities at 925 nib which are often used for downscaling temperature are considered as predictors in Group A. Surface flux variables such as latent heat (LH), sensible heat, shortwave radiation and longwave radiation fluxes, which control temperature of the Earth's surface are tried as plausible predictors in Group B. Group C comprises of all the predictor variables in both the Groups A and B. The scatter plots and cross-correlations are used for verifying the reliability of the simulation of the predictor variables by the CGCM3 and to Study the predictor-predictand relationships. The impact of trend in predictor variables on downscaled temperature was studied. The predictor, air temperature at 925 mb showed an increasing trend, while the rest of the predictors showed no trend. The performance of the SVM models that are developed, one for each combination of predictor group, predictand, calibration period and location-based stratification (land, land and ocean) of climate variables, was evaluated. In general, the models which use predictor variables pertaining to land surface improved the performance of SVM models for downscaling T-max and T-min

Introduction: Japan’s gradual transformation in corporate governance

Japan has recovered from a ‘lost decade’ of economic stagnation over the 1990s. Anyway, it has been a ‘found decade’ for civil and criminal justice law reform, especially in corporate and securities law. Yet, have liberalisation and globalisation in those fields led to major changes in the ‘law in action’? Does this represent ‘Americanisation’ of Japan’s corporate governance system, focusing on shareholders rather than other key stakeholders such as ‘main banks’, core employees, and partners within diffuse corporate groups (keiretsu)? This version of our introductory chapter explains how our forthcoming book argues for a more complex ‘gradual transformation’. Such shifts are also found in many other post-industrial economies, but Japan appears to give greater emphasis given to certain modes of achieving change. The book brings together contributions from academics and practitioners from Japan, Australia, New Zealand, Canada and the United States. An early chapter introduces methodology for effective cross-country comparisons and for evaluating the burgeoning but divergent literature on Japanese corporate governance. The concluding chapter compares continuities and changes in Japan’s largest companies now and two decades ago. Other chapters cover ‘lifelong employment’, main banks, the untold story of closely-held companies, the limited uptake of the Committee-based governance form, and the procedural, substantive and FDI policy dimensions of takeovers law and practice.

Lowering of relaxor transition temperature in Lead-based perovskites under pressure

The dielectric constants of lead iron niobate (PFN) and 40% lead zinc niobate (PZN) added to lead iron niobate (PFN0.6-PZN(0.4)) have been measured as a function of pressure up to 6 GPa under isothermal conditions between room temperature and 348 K. The relaxer transition temperature measured at 1 kHz excitation frequency varies at a rate -24.5 K/GPa for PFN and at a rate of - 28.8 K/GPa for the PFN0.6-PZN(0.4) composition.

Development of temperature-tolerant strains of Thiobacillus ferrooxidans to improve bioleaching kinetics

An isolate of Thiobacillus ferrooxidans derived from gold mine water samples was repeatedly subcultured at increasing temperatures (from 30 degrees to 42 degrees C) in 9K medium. The temperature-adapted strain was found to be more efficient in the bioleaching of pyrite mineral than the wild type. When temperature-tolerant strains were cultured repeatedly in 9K medium at 30 degrees C, the temperature tolerance was completely lost, These results indicate that the temperature tolerance was stress-dependent and not a permanent trait of the adapted strain, The potential utility of such temperature-tolerant strains of Thiobacillus ferrooxidans in sulphide mineral dissolution is demonstrated.

Dynamical Transition of Water in the Grooves of DNA Duplex at Low Temperature

At low temperature (below its freezing/melting temperature), liquid water under confinement is known to exhibit anomalous dynamical features. Here we study structure and dynamics of water in the grooves of a long DNA duplex using molecular dynamics simulations with TIP5P potential at low temperature. We find signatures of a dynamical transition in both translational and orientational dynamics of water molecules in both the major and the minor grooves of a DNA duplex. The transition occurs at a slightly higher temperature (TGL ≈ 255 K) than the temperature at which the bulk water is found to undergo a dynamical transition, which for the TIP5P potential is at 247 K. Groove water, however, exhibits markedly different temperature dependence of its properties from the bulk. Entropy calculations reveal that the minor groove water is ordered even at room temperature, and the transition at T ≈ 255 K can be characterized as a strong-to-strong dynamical transition. Confinement of water in the grooves of DNA favors the formation of a low density four-coordinated state (as a consequence of enthalpy−entropy balance) that makes the liquid−liquid transition stronger. The low temperature water is characterized by pronounced tetrahedral order, as manifested in the sharp rise near 109° in the O−O−O angle distribution. We find that the Adams−Gibbs relation between configurational entropy and translational diffusion holds quite well when the two quantities are plotted together in a master plot for different region of aqueous DNA duplex (bulk, major, and minor grooves) at different temperatures. The activation energy for the transfer of water molecules between different regions of DNA is found to be weakly dependent on temperature.

Temperature measurements in the boron carbide manufacturing process - A hot model study

Boron carbide is produced in a heat resistance furnace using boric oxide and petroleum coke as the raw materials. The product yield is very low. Heat transfer plays an important role in the formation of boron carbide. Temperature at the core reaches up to 2600 K. No experimental study is available in the open literature for this high temperature process particularly in terms of temperature measurement and heat transfer. Therefore, a laboratory scale hot model of the process has been setup to measure the temperatures in harsh conditions at different locations in the furnace using various temperature measurement devices such as pyrometer and various types of thermocouple. Particular attention was paid towards the accuracy and reliability of the measured data. The recorded data were analysed to understand the heat transfer process inside the reactor and the effect of it on the formation of boron carbide.

trans-Dichloro-bis-(arylazoimidazole)palladium(II): Synthesis, Structure, Photoisomerization, and DFT Calculation

Reaction between PdCl2 and 1-alkyl-2-(arylazo)imidazole (RaaiR') or 1-alkyl-2-(naphthyl-alpha/beta-azo)imidazole (alpha/beta-NaiR') under reflux in ethanol has isolated complexes of compositions Pd(RaaiR')(2)Cl-2 (5, 6) and Pd(alpha/beta-NaiR')(2)Cl-2 (7, 8). The X-ray structure determination of one of the molecules, Pd(alpha-NaiBz)(2)Cl-2 (7c), has reported a trans-PdCl2 configuration, and alpha-NaiBz acts as monodentate N(imidazole) donor ligand. The spectral (IR, UV-vis, H-1 NMR) data support the structure. UV light irradiation (light source: Perkin-Elmer LS 55 spectrofluorimeter, Xenon discharge lamp, lambda = 360-396 nm) in a MeCN solution of the complexes shows E-to-Z isomerization of the coordinated azoimidazole unit. The reverse transformation, Z-to-E, is very slow with visible light irradiation. Quantum yields (phi(E-Z)) of E-to-Z isomerization are calculated, and phi is lower than that of the free ligand but comparable with those of Cd(II) and Hg(II) complexes of the same ligand. The Z-to-E isomerization is a thermally induced process. The activation energy (E-a) of Z-to-E isomerization is calculated by controlled-temperature experimentation. cis-Pd(azoimidazole)Cl-2 complexes (azomidazole acts as N(imidazole) and N(azo) Chelating ligand) do not respond upon light irradiation, which supports the idea that the presence of noncoordinated azo-N to make free azo (-N=N-) function is important to reveal photochromic activity. DFT calculation of Pd(alpha-NaiBz)(2)Cl-2 (7c) has suggested that the HOMO of the molecule is constituted of Pd (32%) and Cl (66%), and hence photo excitation may use the energy of Pd and Cl instead of that of the photofunctional -N=N-Ar motif; thus, the rate of photoisomerization and quantum yield decrease versus the free ligand values.