Thermodynamic Properties of LaCrO4, La2CrO6, and La2Cr3O12, and Subsolidus Phase Relations in the System Lanthanum-Chromium-Oxygen

In the system La-Cr-O, there are three ternary oxides (LaCrO4, La2Cr3O12, and La2CrO6) that contain Cr in higher valence states (V or VI). On heating, LaCrO4 decomposes to LaCrO3, La2Cr3O12 to a mixture of LaCrO4 and Cr2O3, and La2CrO6 to LaCrO3 and La2O3 with loss of oxygen. The oxygen potentials corresponding to these decomposition reactions are determined as a function of temperature using solid-state cells incorporating yttria-stabilized zirconia as the electrolyte. Measurements are made from 840K to the decomposition temperature of the ternary oxides in pure oxygen. The standard Gibbs energies of formation of the three ternary oxides are derived from the reversible electromotive force (EMF) of the three cells. The standard enthalpy of formation and standard entropy of the three ternary oxides at 298.15K are estimated. Subsolidus phase relations in the system La-Cr-O are computed from thermodynamic data and displayed as isothermal sections at several temperature intervals. The decomposition temperatures in air are 880 (+/- 3)K for La2Cr3O12, 936 (+/- 3)K for LaCrO4, and 1056 (+/- 4)K for La2CrO6.

A Rodinian suture in western India: New insights on India-Madagascar correlations

We report detailed evidence for a new paleo-suture zone (the Kumta suture) on the western margin of southern India. The c. 15-km-wide, westward dipping suture zone contains garnet-biotite, fuchsite-haematite, chlorite-quartz, quartz-phengite schists, biotite augen gneiss, marble and amphibolite. The isochemical phase diagram estimations and the high-Si phengite composition of quartz-phengite schist suggest a near-peak condition of c. 18 kbar at c. 550 degrees C, followed by near-isothermal decompression. The detrital SHRIMP U-Pb zircon ages from quartz-phengite schist give four age populations ranging from 3280 to 2993 Ma. Phengite from quartz-phengite schist and biotite from garnet-biotite schist have K-Ar metamorphic ages of ca. 1326 and ca. 1385 Ma respectively. Electron microprobe-CHIME ages of in situ zircons in quartz-phengite schist (ca. 3750 Ma and ca. 1697 Ma) are consistent with the above results. The Bondla ultramafic-gabbro complex in the west of the Kumta suture compositionally represents an arc with K-Ar biotite ages from gabbro in the range 1644-1536 Ma. On the eastern side of the suture are weakly deformed and unmetamorphosed shallow westward-dipping sedimentary rocks of the Sirsi shelf, which has the following upward stratigraphy: pebbly quartzite/sandstone, turbidite, magnetite iron formation, and limestone; farther east the lower lying quartzite has an unconformable contact with ca. 2571 Ma quartzo-feldspathic gneisses of the Dharwar block with a ca. 1733 Ma biotite cooling age. To the west of the suture is a c. 60-km-wide Karwar block mainly consisting of tonalite-trondhjemite-granodiorite (TTG) and amphibolite. The TTGs have U-Pb zircon magmatic ages of ca. 3200 Ma with a rare inherited core age of ca. 3601 Ma. The K-Ar biotite cooling age from the TTGs (1746 Ma and 1796 Ma) and amphibolite (ca. 1697 Ma) represents late-stage uplift. Integration of geological, structural and geochronological data from western India and eastern Madagascar suggest diachronous ocean closure during the amalgamation of Rodinia; in the north at around ca. 1380 Ma, and a progression toward the south until ca. 750 Ma. Satellite imagery based regional structural lineaments suggests that the Betsimisaraka suture continues into western India as the Kumta suture and possibly farther south toward a suture in the Coorg area, representing in total a c. 1000 km long Rodinian suture. (C) 2013 Elsevier B.V. All rights reserved.

CFD Analysis of two phase flow with a prediction of torque demand of a Bi-lobe rotor of a mixing chamber

An attempt to study the fluid dynamic behavior of two phase flow comprising of solid and liquid with nearly equal density in a geometrical case that has an industrial significance in theareas like processing of polymers, food, pharma ceutical, paints. In this work,crystalline silica is considered as the dispersed medium in glycerin. In the CFD analysis carried out,the two phase components are considered to be premixed homogeneously at the initial state. The flow in a cylinder that has an axially driven bi-lobe rotor, a typical blender used in polymer industry for mixing or kneading to render the multi-component mixture to homogeneous condition is considered. A viscous, incompressible, isothermal flow is considered with an assumption that the components do not undergo any physical change and the solids are rigid and mix in fully wetting conditions. Silica with a particle diameter of 0.4 mm is considered and flow is analyzed for different mixing fractions. An industry standard CFD code is used for solving 3D-RANS equations. As the outcome of the study the torque demand by the bi-lobe rotor for different mixture fractions which are estimated show a behavioral consistency to the expected physical phenomena occurring in the domain considered.

Size dependent structural relaxations and dielectric properties induced by surface functionalized MWNTs in poly(vinylidene fluoride)/poly(methyl methacrylate) blends

Structural dynamics, dielectric permittivity and ferroelectric properties in poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) (PVDF/PMMA) blends with respect to crystalline morphology was systematically investigated in presence of amine functionalized MWNTs (NH2-MWNTs) using dielectric spectroscopy. The crystalline morphology and the crystallization driven demixing in the blends was assessed by light microscopy (LM), wide angle X-ray diffraction (WXRD) and, in situ, by shear rheology. The crystal nucleation activity of PVDF was greatly induced by NH2-MWNTs, which also showed two distinct structural relaxations in dielectric loss owing to mobility confinement of PVDF chains and smaller cooperative lengths. The presence of crystal-amorphous interphase was supported by the presence of interfacial polarization at lower frequencies in the dielectric loss spectra. On contrary, the control blends showed a single broad relaxation at higher frequency due to defective crystal nuclei. This was further supported by monitoring the dielectric relaxations during isothermal crystallization of PVDF in the blends. These observations were addressed with respect to the spherulite sizes which were observed to be larger in case of blends with NH2-MWNTs. Higher dielectric permittivity with minimal losses was also observed in blends with NH2-MWNTs as compared to neat PVDF. Polarization obtained using P-E (polarization-electric field) hysteresis loops was higher in case of blends with NH2-MWNTs in contrast to control blends and PVDF. These observations were corroborated with the charge trapped at the crystal-amorphous interphase and larger crystal sizes in the blends with NH2-MWNTs. The microstructure and localization of MWNTs were assessed using SEM.

Calculation of Chemical Potentials and Occupancies in Clathrate Hydrates through Monte Carlo Molecular Simulations

The flexibility of the water lattice in clathrate hydrates and guest-guest interactions has been shown in previous studies to significantly affect the values of the thermodynamic properties, such as chemical potentials and free energies. Here we describe methods for computing occupancies, chemical potentials, and free energies that account for the flexibility of water lattice and guest-guest interactions in the hydrate phase. The methods are validated for a wide variety of guest molecules, such as methane, ethane, carbon dioxide, and tetrahydrodfuran by comparing the predicted occupancy values of guest molecules with those obtained from isothermal isobaric semigrand Monte Carlo simulations. The proposed methods extend the van der Waals and Platteuw theory for clathrate hydrates, and the Langmuir constant is calculated based on the structure of the empty hydrate lattice. These methods in combination with development of advanced molecular models for water and guest molecules should lead to a more thermodynamically consistent theory for clathrate hydrates.

Tuning solubility and stability of hydrochlorothiazide co-crystals

Hydrochlorothiazide (HCT), C7H8ClN3O4S2, is a diuretic BCS (Biopharmaceutics Classification System) class IV drug which has primary and secondary sulfonamide groups. To modify the aqueous solubility of the drug, co-crystals with biologically safe co-formers were screened. Multi-component molecular crystals of HCT were prepared with nicotinic acid, nicotinamide, succinamide, p-aminobenzoic acid, resorcinol and pyrogallol using liquid-assisted grinding. The co-crystals were characterized by FT-IR spectroscopy, powder X-ray diffraction (PXRD) and differential scanning calorimetry. Single crystal structures were obtained for four of them. The N-H center dot center dot center dot O sulfonamide catemer synthons found in the stable polymorph of pure HCT are replaced in the co-crystals by drug-co-former heterosynthons. Isostructural co-crystals with nicotinic acid and nicotinamide are devoid of the common sulfonamide dimer/catemer synthons. Solubility and stability experiments were carried out for the co-crystals in water (neutral pH) under ambient conditions. Among the six binary systems, the co-crystal with p-aminobenzoic acid showed a sixfold increase in solubility compared with pure HCT, and stability up to 24 h in an aqueous medium. The co-crystals with nicotinamide, resorcinol and pyrogallol showed only a 1.5-2-fold increase in solubility and transformed to HCT within 1 h of the dissolution experiment. An inverse correlation is observed between the melting points of the co-crystals and their solubilities.

Structural, thermal and electrical properties of poly(methyl methacrylate)/CaCu3Ti4O12 composite sheets fabricated via melt mixing

Poly(methyl methacrylate) (PMMA) and CaCu3Ti4O12 (CCTO) composites were fabricated via melt mixing followed by hot pressing technique. These were characterized using X-ray diffraction, thermo gravimetric, thermo mechanical, differential scanning calorimetry, fourier transform infrared (FTIR) and Impedance analyser for their structural, thermal and dielectric properties. Composites were found to have better thermal stability than that of pure PMMA. However, there was no significant difference in the glass transition (T (g) ) temperature between the polymer and the composite. The appearance of additional vibrational frequencies in the range 400-600 cm(-1) in FTIR spectra indicated a possible interaction between PMMA and CCTO. The composite, with 38 vol% of CCTO (in PMMA), exhibited remarkably low dielectric loss at high frequencies and the low-frequency relaxation is attributed to the interfacial polarization/MWS effect. The origin of AC conductivity particularly in the high-frequency region was attributed to the electronic polarization.

Evaluation of chitosan nanoformulations as potent anti-HIV therapeutic systems

Background: Antiretroviral Therapy (ART) is currently the major therapeutic intervention in the treatment of AIDS. ART, however, is severely limited due to poor availability, high cytotoxicity, and enhanced metabolism and clearance of the drug molecules by the renal system. The use of nanocarriers encapsulating the antiretroviral drugs may provide a solution to the aforementioned problems. Importantly, the application of mildly immunogenic polymeric carrier confers the advantage of making the nanoparticles more visible to the immune system leading to their efficient uptake by the phagocytes. Methods: The saquinavir-loaded chitosan nanopartides were characterized by transmission electron microscopy and differential scanning calorimetry and analyzed for the encapsulation efficiency, swelling characteristics, particle size properties, and the zeta potential. Furthermore, cellular uptake of the chitosan nanocarriers was evaluated using confocal microscopy and Flow cytometry. The antiviral efficacy was quantified using viral infection of the target cells. Results: Using novel chitosan carriers loaded with saquinavir, a protease inhibitor, we demonstrate a drug encapsulation efficiency of 75% and cell targeting efficiency greater than 92%. As compared to the soluble drug control, the saquinavir-loaded chitosan carriers caused superior control of the viral proliferation as measured by using two different viral strains, NL4-3 and Indie-C1, and two different target T-cells, Jurkat and CEM-CCR5. Conclusion: Chitosan nanoparticles loaded with saquinavir were characterized and they demonstrated superior drug loading potential with greater cell targeting efficiency leading to efficient control of the viral proliferation in target T-cells. General significance: Our data ascertain the potential of chitosan nanocarriers as novel vehicles for HIV-1 therapeutics. (C) 2013 Elsevier B.V. All rights reserved.

Rheological characterization of semi-solid A356 aluminium alloy

Rheological behavior of semi-solid slurries forms the backbone of semi-solid processing of metallic alloys. In particular, the effects of several process and metallurgical parameters such as shear rate, shear time, temperature, rest time and size, distribution and morphology of the primary phase on the viscosity of the slurry needs in-depth characterization. In the present work, rheological behaviour of the semisolid aluminium alloy (A356) slurry is investigated by using a high temperature Searle type Rheometer using concentric cylinders. Three different types of experiment are carried out: isothermal test, continuous cooling test and steady state test. Continuous decrease in viscosity is observed with increasing shear rate at a fixed temperature (isothermal test). It is also found that the viscosity increases with decreasing temperature for a particular shear rate due to increasing solid fraction (continuous cooling test). Thixotropic nature of the slurry is confirmed from the hysteresis loops obtained during experimentation. Time dependence of slurry viscosity has been evaluated from the steady state tests. After a longer shearing time under isothermal conditions the starting dendritic structure of the said alloy is transformed into globular grains due to abrasion, agglomeration, welding and ripening.

Studies on rheocasting using cooling slope

In the present work, a cooling channel is employed to produce semi-solid A356 alloy slurry. To understand the transport process involved, a 3D non-isothermal, multiphase volume averaging model has been developed for simulation of the semi-solid slurry generation process in the cooling channel. For simulation purpose, the three phases considered are the parent melt, the nearly spherical grains and air as separated but highly coupled interpenetrating continua. The conservation equations of mass, momentum, energy and species have been solved for each phase and the thermal and mechanical interactions (drag force) among the phases have been considered using appropriate model. The superheated liquid alloy is poured at the top of the cooling slope/channel, where specified velocity inlet boundary condition is used in the model, and allowed to flow along gravity through the channel. The melt loses its superheat and becomes semisolid up to the end of cooling channel due to the evolving -Al grains with decreasing temperature. The air phase forms a definable air/liquid melt interface, i.e. free surface, due its low density. The results obtained from the present model includes volume fractions of three different phases considered, grain evolution, grain growth rate, size and distribution of solid grains. The effect of key process variables such as pouring temperature, slope angle of the cooling channel and cooling channel wall temperature on temperature distribution, velocity distribution, grain formation and volume fraction of different phases are also studied. The results obtained from the simulations are validated by microstructure study using SEM and quantitative image analysis of the semi-solid slurry microstructure obtained from the experimental set-up.

Phase equilibria in the system Sm-Rh-O and thermodynamic and thermal studies on SmRhO3

Using isothermal equilibration, phase relations are established in the system Sm-Rh-O at 1273 K. SmRhO3 with GdFeO3-type perovskite structure is found to be the only ternary phase. Solid-state electrochemical cells, containing calcia-stabilized zirconia as an electrolyte, are used to measure the thermodynamic properties of SmRhO3 formed from their binary component oxides Rh2O3 (ortho) and Sm2O3 (C-type and B-type) in two different temperature ranges. Results suggest that C-type Sm2O3 with cubic structure transforms to B-type Sm2O3 with monoclinic structure at 1110 K. The standard Gibbs energy of transformation is . Standard Gibbs energy of formation of SmRhO3 from binary component oxides Rh2O3 and Sm2O3 with B-type rare earth oxide structure can be expressed as . The decomposition temperature of SmRhO3 estimated from the extrapolation of electrochemical data is 1665 (+/- 2) K in air and 1773 (+/- 3) K in pure oxygen. Temperature-composition diagrams at constant oxygen pressures are constructed for the system Sm-Rh-O. Employing the thermodynamic data for SmRhO3 from emf measurement and auxiliary data for other phases from the literature, oxygen potential-composition phase diagram and 3-D chemical potential diagram for the system Sm-Rh-O at 1273 K are developed.

Nonlinear optical second harmonic generation in ZnS quantum dots and observation on optical properties of ZnS/PMMA nanocomposites

ZnS quantum dots (QDs) of different sizes are synthesized by a simple chemical co-precipitation method at room temperature, by varying pH value of the reaction mixture. Samples are characterized by an X-ray diffractometer, transmission electron microscope, energy-dispersive X-ray analysis, etc. Linear optical properties, including UV-visible absorption and photoluminescence emission characteristics, of as-prepared QDs are measured. Size dependent nonlinear optical property, such as second harmonic generation (SHG) of 1064 nm Nd:YAG laser fundamental radiation in the synthesized ZnS QDs, is reported for the first time, to the best of our knowledge, by using the standard Kurtz-Perry powder method. In not to study the possibility of the synthesized ZnS QDs in different device applications ZnS/PMMA (polymethylmethacrylate) nanocomposites are also synthesized. The presence of weak chemical interaction between the polymer matrix and ZnS QDs is confirmed by Fourier transform infrared spectroscopy. Thermal properties of the nanocomposites are studied by differential scanning calorimetry and thermo-gravimetric analysis techniques, which show that the composites are stable up to similar to 300 degrees C temperature. (C) 2013 Elsevier B.V. All rights reserved.

Structural Investigations on the Compositional Anomalies in Lanthanum Zirconate System Synthesized by Coprecipitation Method

The study set out to investigate the compositional inconsistency in lanthanum zirconate system revealed the presence of nonstoichiometry in lanthanum zirconate powders when synthesized by coprecipitation route. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) investigations confirmed the depletion of La3+ ions in the system. Analysis using Vegard's law showed the La/Zr mole ratio in the sample to be around 0.45. An extra step of ultrasonication, introduced during the washing stage followed by the coprecipitation reaction, ensured the formation of stoichiometric La2Zr2O7. Noteworthy is also the difference between crystal sizes in the samples prepared by with and without ultrasonication step. This difference has been explained in light of the formation of individual nuclei and their scope of growth within the precipitate core. The differential scanning calorimetry (DSC) analyses revealed that optimum pH for the synthesis of La2Zr2O7 is about 11. The ultrasonication step was pivotal in assuring consistency in mixing and composition for the lanthanum zirconate powders.

Performance of an ionomer blend-nanocomposite as an effective gas barrier material for organic devices

A new, flexible, gas barrier material has been synthesized by exfoliating organically modified nano-clays (MMT) in the blends of Surlyn (PEMA) using a copolymer of vinyl alcohol (EVOH) and demonstrated as a gas barrier material. The materials were characterized by Fourier transform infra red (FTIR) and UV-visible spectroscopy, differential scanning calorimetry (DSC), thermo-gravimetric analysis (TGA) and tensile studies. The oxygen and water-vapor permeabilities of the fabricated films were determined by calcium degradation test and a novel permeability setup based on cavity ring down spectroscopy, respectively. Hierarchical simulations of these materials helped us to understand the effect of intermolecular interactions on diffusivities of oxygen and water molecules in these materials. Schottky structured poly(3-hexylthiophene) based organic devices were encapsulated with the fabricated films and aging studies were carried under accelerated conditions. Based on permeability test results and accelerated aging studies, the fabricated PEMA/EVOH/MMT composites were found to be effective in decreasing the permeabilities for gases by about two orders of magnitude and maintaining the lifetime of organic devices.

Structural, Electrical and Magnetic Behaviour of FeTe0.5Se0.5 Superconductor

We report the synthesis as well as structural and physical properties of the bulk polycrystalline FeTe and FeTe0.5Se0.5 compounds. These samples are synthesised by the solid state-reaction method via vacuum encapsulation. Both studied compounds are crystallized in a tetragonal phase with space group P4/nmm. The parent FeTe compound shows an anomaly in resistivity measurement at around 78 K, which is due to the structural change along with a magnetic phase transition. The superconductivity in the FeTe0.5Se0.5 sample at 13 K is confirmed by the resistivity measurements. DC magnetisation along with an isothermal (M-H) loop shows that FeTe0.5Se0.5 possesses bulk superconductivity. The upper critical field is estimated through resistivity rho (T,H) measurements using Gingzburg-Landau (GL) theory and is above 50 T with 50 % resistivity drop criterion. The origin of the resistive transition broadening under magnetic field is investigated by thermally activated flux flow. The magnetic field dependence of the activation energy of the flux motion is discussed.