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.

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.

Determination of coefficient of consolidation from early stage of log t plot

The standard curve-fitting methods, Casagrande's log t method and Taylor's root t method, for the determination of the coefficient of consolidation use the later part of the consolidation curve and are influenced by secondary compression effects. Literature shows that secondary compression is concurrent with primary consolidation and that its effect is to decrease the value of the coefficient of consolidation. If the early part of the time-compression data is used, the values obtained will be less influenced by secondary compression effects. A method that uses the early part of the log t plot is proposed in this technical note. As the influence of secondary compression is reduced, the value obtained by this method is greater than that yielded by both the standard methods. The permeability values computed from C-v (obtained from the proposed method) rue more in agreement with the measured values than the standard methods showing that the effects of secondary compression are minimized. Time-compression data for a shorter duration is sufficient for the determination of C-v if the coefficient of secondary compression is not required.

Ultrasonic Degradation of Poly(acrylic acid)

The ultrasonic degradation of poly(acrylic acid), a water-soluble polymer, was studied in the presence of persulfates at different temperatures in binary solvent Mixtures of methanol and water. The degraded samples were analyzed by gel permeation chromatography for the time evolution of the molecular weight distributions. A continuous distribution kinetics model based on midpoint chain scission was developed, and the degradation rate coefficients were determined. The decline in the rate of degradation of poly(acrylic acid) with increasing temperature and with an increment in the methanol content in the binary solvent mixture of methanol and water was attributed to the increased vapor pressure of the solutions. The experimental data showed an augmentation of the degradation rate of the polymer with increasing oxidizing agent (persulfate) concentrations. Different concentrations of three persulfates-potassium persulfate, ammonium persulfate, and sodium persulfate-were used. It was found that the ratio of the polymer degradation rate coefficient to the dissociation rate constant of the persulfate was constant. This implies that the ultrasonic degradation rate of poly(acrylic acid) can be determined a priori in the presence of any initiator.

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.

Structural and optical investigations of TiO2 films deposited on transparent substrates by sol-gel technique

An inexpensive and effective simple method for the preparation of nano-crystalline titanium oxide (anatase) thin films at room temperature on different transparent substrates is presented. This method is based on the use of peroxo-titanium complex, i.e. titanium isopropoxide as a single initiating organic precursor. Post-annealing treatment is necessary to convert the deposited amorphous film into titanium oxide (TiO2) crystalline (anatase) phase. These films have been characterized for X-ray diffraction (XRD) studies, atomic force microscopic (AFM) studies and optical measurements. The optical constants such as refractive index and extinction coefficient have been estimated by using envelope technique. Also, the energy gap values have been estimated using Tauc's formula for on glass and quartz substrates are found to be 3.35 eV and 3.39 eV, respectively.

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

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.

Some studies on TiO2 films deposited by sol-gel technique

TiO2 films are extensively used in various applications including optical multi-layers, sensors, photo catalysis, environmental purification, and solar cells etc. These are prepared by both vacuum and non-vacuum methods. In this paper, we present the results on TiO2 thin films prepared by a sol-gel spin coating process in non-aqueous solvent. Titanium isopropoxide is used as TiO2 precursor. The films were annealed at different temperatures up to 3000 C for 5 hours in air. The influence of the various deposition parameters like spinning speed, spinning time and annealing temperature on the thickness of the TiO2 films has been studied. The variation of film thickness with time in ambient atmosphere was also studied. The optical, structural and morphological characteristics were investigated by optical transmittance-reflectance measurements, X-ray diffraction (XRD) and scanning electron microscopy (SEM) respectively. The refractive index and extinction coefficient of the films were determined by envelope technique and spectroscopic ellipsometry. TiO2 films exhibited high transparency (92%) in the visible region with a refractive index of 2.04 at 650 nm. The extinction coefficient was found to be negligibly small. The X-ray diffraction analysis showed that the TiO2 film deposited on glass substrate changes from amorphous to crystalline (anatase) phase with annealing temperature above 2500 C. SEM results show that the deposited films are uniform and crack free.

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.

Unsteady Natural Convection Flow in a Square Cavity Filled with a Porous Medium Due to Impulsive Change in Wall Temperature

Unsteady natural convection flow in a two- dimensional square cavity filled with a porous material has been studied. The flow is initially steady where the left- hand vertical wall has temperature T-h and the right- hand vertical wall is maintained at temperature T-c ( T-h > T-c) and the horizontal walls are insulated. At time t > 0, the left- hand vertical wall temperature is suddenly raised to (T-h) over bar ((T-h) over bar > T-h) which introduces unsteadiness in the flow field. The partial differential equations governing the unsteady natural convection flow have been solved numerically using a finite control volume method. The computation has been carried out until the final steady state is reached. It is found that the average Nusselt number attains a minimum during the transient period and that the time required to reach the final steady state is longer for low Rayleigh number and shorter for high Rayleigh number.

Stability of pargasite during ultrahigh-temperature metamorphism:A consequence of titanium and REE partitioning

Orthopyroxene-clinopyroxene-plagioclase needles and symplectite along the cleavage planes and grain boundaries of fluorine-bearing titanian-ferroan pargasite from the Highland Complex, Sri Lanka, are interpreted as evidence for dehydration melting at ultrahigh-temperature conditions. High Ti (up to 0.4 pfu) and F (XF up to 0.56) content in pargasite extends its stability to higher temperatures, and the composition indicates the dehydration melting reaction may take place at ultrahigh-temperatures (~950 °C) at a pressure around 10 kbar, close to peak metamorphic conditions. The increase of Ti content close to the grain boundaries and cleavage planes in pargasite indicates titanium partitioning from the melt during dehydration melting enhanced the stability of the mineral toward ultrahigh-temperature conditions. The REE content in the pargasite shows a similar behavior to that of titanium. The cores with no breakdown assemblage consist of low and flat REE concentrations with respect to the high and Eu-depleted rim. Clinopyroxene in symplectite and needle-shaped lamellae within the pargasite porphyroblasts have similar REE patterns with slightly low-concentrations relative to that of pargasite. In the breakdown assemblage, LREEs are partitioned mainly into plagioclase while the HREEs are partitioned into orthopyroxene. The REE enrichment in the pargasite rims signals their relative partitioning between pargasite rims and melt. Modeling of the partitioning of Ti and REEs associated with pargasite breakdown demonstrates that its stability is greatly enhanced at UHT conditions. This investigation implies that the stability of hydrous minerals such as amphibole can be extended to UHT conditions, and expands our knowledge of metamorphism in the lower crust.