Variation of the partial thermodynamic properties of oxygen with composition in YBa2Cu3O7−δ

The variation of equilibrium oxygen potential with oxygen concentration inYBa 2Cu3O7-δhas been measured in the temperature range of 773 to 1223 K. For temperatures up to 1073 K, the oxygen content of theYBa 2Cu3O7-δsample, held in a stabilized-zirconia crucible, was altered by coulometric titration. The compound was in contact with the electrolyte, permitting direct exchange of oxygen ions. For measurements above 1073 K, the oxide was contained in a magnesia crucible placed inside a closed silica tube. The oxygen potential in the gas phase above the 123 compound was controlled and measured by a solid-state cell based on yttria-stabilized zirconia, which served both as a pump and sensor. Pure oxygen at a pressure of 1.01 × 105 Pa was used as the reference electrode. The oxygen pressure over the sample was varied from 10-1 to 105 Pa. The oxygen concentrations of the sample equilibrated with pure oxygen at 1.01 × 105 Pa at different temperatures were determined after quenching in liquid nitrogen by hydrogen reduction at 1223 K. The plot of chemical potential of oxygen as a function of oxygen non-stoichiometry shows an inflexion at δ ∼ 0.375 at 873 K. Data at 773 K indicate tendency for phase separation at lower temperatures. The partial enthalpy and entropy of oxygen derived from the temperature dependence of electromotive force (emf ) exhibit variation with composition. The partial enthalpy for °= 0.3, 0.4, and 0.5 also appears to be temperature dependent. The results are discussed in comparison with the data reported in the literature. An expression for the integral free energy of formation of YBa2Cu3O6.5 is evaluated based on measurements reported in the literature. By integration of the partial Gibbs’ energy of oxygen obtained in this study, the variation of integral property with oxygen concentration is obtained at 873 K.

A new matched thermochemical diagram for vacuum refining of nickel and cupronickel alloys

Sulfur and oxygen dissolved in nickel and cupronickel melts can be remwed as gaseous oxides of sulfur by a vacuum treatment. Presented in this paper is a new matched thermcxhemical disgran~ that permit.. direct evaluation of the equilibrium partial pressure of SO, as a function of temperature wer an alloy of specified compition. The matched thermochemical diagram consists of a central plot which shows the integral Gibbs' energy of mixing for the binary system SO, at different temperatures. The central plot is flanked on either side by terminal plots of the chemical potentials of oxygen and sulfur, as functions of temperature, for different alloy compositions. By projecting the chemical wtentials of oxygen and sulfur from the terminal lots on to the central diagram, ihe equilibrium partial pressure of S0,can be directly ;cad on the nomograms on the central plot at different temperatures. The matched therrnochemical diagrams are useful in assuring the efficiency of vacuum refining.

XXVI. The relation between thermo-optic and piezo-optic phenomena in crystals

It is pointed out that the change in refractive index with temperature of a crystal is different from what is calculated from the accompanying change in volume and the piezo-optic coefficients. The difference, which is a pure temperature effect, is explained as being due to the change in polarizability of the atoms produced by a change in the amplitude of vibration. The polarizability (α) can be expanded as a Taylor series in the changes of the distance (r) between the atoms and it is found that while the piezo-optic coefficient depends only on ∂α/∂r, the pure temperature effect is a function of ∂ 2 a/∂r 2. Making use of the experimental data, the values of a and its first two derivatives can be determined. These values are foundto be of the same order as those deduced from the intensities of Rayleigh and Raman scattering of light. The theory predicts that dn/dT should vary as the coefficient of cubical expansion at different temperatures and this is verified to be true. Finally, calculations are made of the thermo- and piezo-optic coefficients, considering the electrostatic interaction between the atoms. These do not adequately explain the observed facts, since no provision is made for the distortion of electron atmospheres around the atoms and the consequent changes in polarizability.

ZnFe(2)O(4): Rapid and sub-100 degrees C synthesis and anneal-tuned magnetic properties

Nanocrystalline zinc ferrite (ZFO) has been synthesized from metal acetylacetonates by microwave irradiation for 5 min in the presence of a surfactant. The as-prepared material is ZFO and has been subjected in air to conventional furnace annealing and to rapid annealing at different temperatures. Both annealing protocols lead to well-crystallized ZFO, with crystallite sizes in the range similar to 8-20 nm, which is ferrimagnetic, even at room temperature, with magnetization attaining saturation. While the magnetization M(S) of conventionally annealed ZFO varies with crystallite size in the expected manner, rapid annealing leads to high M(S) even when the crystallite size is relatively large. The coercivity is greater in the conventionally annealed ZFO. Thermal and magnetic measurements suggest that the inhomogeneous site cationic distribution within each crystallite caused by rapid annealing can be used to tailor the magnetic behaviour of nanocrystalline ferrites.

Removal of Nitrogen Oxides in Diesel Engine Exhaust by Plasma Assisted Molecular Sieves

This paper reports the studies conducted on removal of oxides of nitrogen (NOx) from diesel engine exhaust using electrical discharge plasma combined with adsorbing materials such as molecular sieves. This study is being reported for the first time. The exhaust is taken from a diesel engine of 6 kW under no load conditions. The characteristic behavior of a pulse energized dielectric barrier discharge reactor in the diesel exhaust treatment is reported. The NOx removal was not significant (36%) when the reactor without any packing was used. However, when the reactor was packed with molecular sieves (MS -3A, -4A & -13X), the NOx removal efficiency was increased to 78% particularly at a temperature of 200 °C. The studies were conducted at different temperatures and the results were discussed.

Nonthermal-Plasma-Promoted Catalysis for the Removal of NOx From a Stationary Diesel-Engine Exhaust

A detailed study on the removal of oxides of nitrogen (NOx) from the exhaust of a stationary diesel engine was carried out using nonthermal-plasma (pulsed electrical-discharge plasma)-promoted catalytic process. In this paper, the filtered exhaust from the diesel engine is made to pass through a combination of nonthermal plasma reactor and a catalytic reactor connected in series. This combination is referred to as cascade. Two types of cascaded systems were studied. In one type, the plasma treating filtered exhaust was cascaded with a reduction catalyst V2O5/TiO2 using ammonia as reducing agent, and in the other type, the plasma treating filtered exhaust was cascaded with activated-alumina catalyst without any additive. Improved NOx-removal performance of both the cascaded processes and the role of nonthermal plasma in promoting catalysis are explained. Along with the NOx, total hydrocarbon and aldehydes were also removed. Furthermore, experiments were conducted at different temperatures and engine-loading conditions.

Influence of the Methane-Zeolite A Interaction Potential on the Concentration Dependence of Self-diffusivity

Studies on the diffusion of methane in a zeolite structure type LTA (as per IZA nomenclature) have indicated that different types of methane zeolite potentials exist in the literature in which methane is treated within the united-atom model. One set of potentials, referred to as model A, has a methane oxygen diameter of 3.14 angstrom, while another set of potential parameters, model B, employs a larger value of 3.46 angstrom. Fritzsche and co-workers (1993) have shown that these two potentials lead to two distinctly different energetic barriers for the passage of methane through the eight-ring window in the cation-free form of zeolite A. Here, we compute the variation of the self-diffusivity (D) with loading (c) for these two types of potentials and show that this slight variation in the diameter changes the concentration dependence qualitatively: thus, D decreases monotonically with c for model A, while D increases and goes through a maximum before finally decreasing for model B. This effect and the surprising congruence of the diffusion coefficients for both models at high loadings is examined in detail at the molecular level. Simulations for different temperatures reveal the Arrhenius behaviour of the self-diffusion coefficient. The apparent activation energy is found to vary with the loading. We conclude that beside the cage-to-cage jumps, which are essential for the migration of the guest molecules, at high concentrations migration within the cage and guest guest interactions with other molecules become increasingly dominant influences on the diffusion coefficient and make the guest zeolite interaction less important for both model A and model B.

Microstructure and damping behaviour of consolidated magnesium chips

Chips produced by turning a commercial grade pure magnesium billet were consolidated by solid state recycling technique of cold compaction followed by hot extrusion. The cold compacted billets were extruded at four different temperatures: 250 degrees C, 300 degrees C, 350 degrees C and 400 degrees C. For the purpose of comparison, cast magnesium (pure) billets were extruded under similar conditions. Extruded products were characterized for damping properties. Damping capacity and dynamic modulus was measured as a function of time and temperature at a fixed frequency of 5 Hz 10 to 14% increase in damping capacity was observed in chip consolidated products compared to reference material. Microstructural changes after the temperature sweep tests were examined. Chip boundaries present in consolidated products were observed to suppress grain coarsening which otherwise was significant in reference material. The present work is significant from the viewpoint of recycling of machined chips and development of sustainable manufacturing processes. (C) 2012 Elsevier B.V. All rights reserved.

Dielectric Barrier Discharge Cascaded with Red Mud Waste to Enhance NOX Removal from Diesel Engine Exhaust

Red mud is a waste by-product generated during the processing of bauxite, the most common ore of aluminium. With the presence of ferric oxide, high surface area, resistance to poisoning and low cost, red mud made itself a good alternative to the existing commercial automobile catalyst. The cascading of dielectric barrier discharge plasma with red mud improved the NOX removal from diesel engine exhaust significantly. The DeNO(X) efficiency with discharge plasma was 74% and that with red mud was 31%. The efficiency increased to 92% when plasma was cascaded with red mud catalyst operating at a temperature of 400 degrees C. The NOX removal was dominated by NO2 removal. The studies were conducted at different temperatures and the results were discussed.

Size-mediated cytotoxicity of nanocrystalline titanium dioxide, pure and zinc-doped hydroxyapatite nanoparticles in human hepatoma cells

Nanoparticles are highly used in biological applications including nanomedicine. In this present study, the interaction of HepG2 hepatocellular carcinoma cells (HCC) with hydroxyapatite (HAp), zinc-doped hydroxyapatite, and titanium dioxide (TiO2) nanoparticles were investigated. Hydroxyapatite, zinc-doped hydroxyapatite and titanium dioxide nanoparticles were prepared by wet precipitation method. They were subjected to isochronal annealing at different temperatures. Particle morphology and size distribution were characterized by X-ray diffraction and transmission electron microscope. The nanoparticles were co-cultured with HepG2 cells. MTT assay was employed to evaluate the proliferation of tumor cells. The DNA damaging effect of HAp, Zn-doped HAp, and TiO2 nanoparticles in human hepatoma cells (HepG2) were evaluated using DNA fragmentation studies. The results showed that in HepG2 cells, the anti-tumor activity strongly depend on the size of nanoparticles in HCC cells. Cell cycle arrest analysis for HAp, zinc-doped HAp, and TiO2 nanoparticles revealed the influence of HAp, zinc-doped HAp, and titanium dioxide nanoparticles on the apoptosis of HepG2 cells. The results imply that the novel nano nature effect plays an important role in the biomedicinal application of nanoparticles.

Microstructure and compression behavior of chip consolidated magnesium

Chips produced by turning a commercial purity magnesium billet were cold compacted and then hot extruded at four different temperatures: 250, 300, 350, and 400 degrees C. Cast billets, of identical composition, were also extruded as reference material. Chip boundaries, visible even after 49: 1 extrusion at 400 degrees C, were observed to suppress grain coarsening. Although 250 degrees C extruded chip-consolidated product showed early onset of yielding and lower ductility, fully dense material (extruded at 400 degrees C) had nearly 40% reduction in grain size with 22% higher yield strength and comparable ductility as that of the reference. The study highlights the role of densification and grain refinement on the compression behavior of chip consolidated specimens.

Ultrasonic performance of the PVDF thin film sensors under thermal fatigue

In the present work, the ultrasonic strain sensing performance of the large area PVDF thin film subjected to the thermal fatigue is studied. The PVDF thin film is prepared using hot press and the piezoelectric phase (beta-phase) has been achieved by thermo-mechanical treatment and poling under DC field. The sensors used in aircrafts for structural health monitoring applications are likely to be subjected to a wide range of temperature fluctuations which may create thermal fatigue in both aircraft structures and in the sensors. Thus, the sensitivity of the PVDF sensors for thermal fatigue needs to be studied for its effective implementation in the structural health monitoring applications. In present work, the fabricated films have been subjected to certain number of thermal cycles which serve as thermal fatigue and are further tested for ultrasonic strain sensitivity at various different frequencies. The PVDF sensor is bonded on the beam specimen at one end and the ultrasonic guided waves are launched with a piezoelectric wafer bonded on another end of the beam. Sensitivity of PVDF sensor in terms of voltage is obtained for increasing number of thermal cycles. Sensitivity variation is studied at various different extent of thermal fatigue. The variation of the sensor sensitivity with frequency due to thermal fatigue at different temperatures is also investigated. The present investigation shows an appropriate temperature range for the application of the PVDF sensors in structural health monitoring.

Asymmetric and symmetric rolling of magnesium: Evolution of microstructure, texture and mechanical properties

In the present study, asymmetric rolling was carried out for incorporating a shear component during the rolling at different temperatures, and was compared with conventional (symmetric) rolling. The microstructures were investigated using electron back-scatter diffraction (EBSD). The strain incorporated was compared with the help of grain orientation spread (GOS). GOS was eventually used as a criterion to partition the microstructure for separating the deformed and the dynamically recrystallized (DRX) grains. The texture of the partitioned DRX grains was shifted by similar to 30 degrees along the c-axis from the deformed grains. The mechanism of dynamic recrystallization (DRX) has been identified as continuous dynamic recovery and recrystallization (CDRR). The partitioned deformed grains for the higher temperature rolled specimens exhibited a texture similar to the room temperature rolled specimen. The asymmetric rolling introduces a shear component which shifts the texture fibre by similar to 5-10 degrees from the conventional rolling texture. This led to an increase in ductility with little compromise on strength. (c) 2012 Elsevier B.V. All rights reserved.

Influence of Sn doping on structural, optical and electrical properties of ZnO thin films prepared by cost effective sol-gel process

Tin (Sn) doped zinc oxide (ZnO) thin films were synthesized by sol-gel spin coating method using zinc acetate di-hydrate and tin chloride di-hydrate as the precursor materials. The films were deposited on glass and silicon substrates and annealed at different temperatures in air ambient. The agglomeration of grains was observed by the addition of Sn in ZnO film with an average grain size of 60 nm. The optical properties of the films were studied using UV-VIS-NIR spectrophotometer. The optical band gap energies were estimated at different concentrations of Sn. The MOS capacitors were fabricated using Sn doped ZnO films. The capacitance-voltage (C-V), dissipation vs. voltage (D-V) and current-voltage (I-V) characteristics were studied and the electrical resistivity and dielectric constant were estimated. The porosity and surface area of the films were increased with the doping of Sn which makes these films suitable for opto-electronic applications. (C) 2012 Elsevier B.V. All rights reserved.

Sensitivity of polyvinylidene fluoride films to mechanical vibration modes and impact after optimizing stretching conditions

The β-phase of polyvinylidene fluoride (PVDF) is well known for its piezoelectric properties. PVDF films have been developed using solvent cast method. The films thus produced are in α-phase. The α-phase is transformed to piezoelectric β-phase when the film is hot-stretched with various different stretching factors at various different temperatures. The films are then characterized in terms of their mechanical properties and surface morphological changes during the transformation from α- to β-phases by using X-ray diffraction, differential scanning calorimeter, Raman spectra, Infrared spectra, tensile testing, and scanning electron microscopy. The films showed increased crystallinity with stretching at temperature up to 80°C. The optimum conditions to achieve β-phase have been discussed in detail. The fabricated PVDF sensors have been tested for free vibration and impact on plate structure, and its response is compared with conventional piezoelectric wafer type sensor. The resonant and antiresonant peaks in the frequency response of PVDF sensor match well with that of lead zirconate titanate wafer sensors. Effective piezoelectric properties and the variations in the frequency response spectra due to free vibration and impact loading conditions are reported. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers.