Phase equilibria in the system NiO-CaO-SiO2 and Gibbs energy of formation of CaNiSi2O6

Phase relations in the pseudoternary system NiO-CaO-SiO2 at 1373 K are established. The coexisting phases are identified by X-ray diffraction and energy-dispersive X-ray analysis of equilibrated samples. There is only one quaternary oxide CaNiSi2O6 with clinopyroxene structure. The Gibbs energy of formation of CaNiSi2O6 is measured using a solid state galvanic cell incorporating stabilized zirconia as the solid electrolyte in the temperature range of 1000 to 1400 K:Pt, Ni + SiO2 + CaSiO3 + CaNiSi2O6 \ (Y2O3)ZrO2 \ Ni + NiO, Pt From the electromotive force (emf) of the cell, the Gibbs energy of formation of CaNiSi2O6 from NiO, SiO2, and CaSiO3 is obtained. To derive the Gibbs energy of formation of the quaternary oxide from component binary oxides, the free energy of formation of CaSiO, is determined separately using a solid state cell based on single crystal CaF2 as the electrolyte: Pt, O-2, CaO + CaF2 \ CaF2 \ CaSiO3 + SiO2 + CaF2, O-2, Pt The results can be expressed by the following equations: NiO (r.s) + CaO (r.s) + 2SiO(2) (qz) --> CaNiSi2O6 (pyr) Delta G degrees = -115,700 + 10.63T (+/-100) J mol(-1) CaO (r.s) + SiO2 (qz) --> CaSiO3 (wol) Delta G degrees = -90,030 -0.61T (+/-60) J mol(-1).

Phase relations in the system Sr–Ir–O and thermodynamic measurements on SrIrO3, Sr2IrO4 and Sr4IrO6 using solid-state cells with buffer electrodes

The standard Gibbs energies of formation of SrIrO3, Sr2IrO4 and Sr4IrO6 have been determined in the temperature range from 975 to 1400 K using solid-state cells with (Y2O3) ZrO2 as the electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode. For the design of appropriate working electrodes, phase relations in the ternary system Sr–Ir–O were investigated at 1350 K. The only stable oxide detected along the binary Ir–O was IrO2. Three ternary oxides, SrIrO3, Sr2IrO4 and Sr4IrO6, compositions of which fall on the join SrO–IrO2, were found to be stable. Each of the oxides coexisted with pure metal Ir. Therefore, three working electrodes were prepared consisting of mixtures of Ir+SrO+Sr4IrO6, Ir+Sr4IrO6+Sr2IrO4, and Ir+Sr2IrO4+SrIrO3. These mixtures unambiguously define unique oxygen chemical potentials under isothermal and isobaric conditions. Used for the measurements was a novel apparatus, in which a buffer electrode was introduced between reference and working electrodes to absorb the electrochemical flux of oxygen through the solid electrolyte. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. The standard Gibbs energies of formation of the compounds, obtained from the emf of the cells, can be represented by the following equations: View the MathML sourcem View the MathML source View the MathML source where Δf (ox)Go represents the standard Gibbs energy of formation of the ternary compound from its component binary oxides SrO and IrO2. Based on the thermodynamic information, chemical potential diagrams for the system Sr–Ir–O were developed.

Thermodynamics of SmMnO3 and SmMn2O5 phases determined by the E.M.F. method

Streszczenie angielskie: Using solid oxide galvanic cells of the type: MnO + Sm2O3 + SmMnO3 / O-2/ Ni + NiO and Mn3O4 + SmMnO3 + SmMn2O5 / O-2 / air the equilibrium oxygen pressure for three-phase equilibria described by the following reactions of formation of ternary phases: MnO + 1/2Sm2O3 + 1/4O2 = SmMnO3 1/3Mn3O4 + SmMnO3 + 1/3O2 = SmMn2O5 was determined in the temperature range from 1173 to 1450 K. From the obtained experimental data the corresponding Gibbs free energy change for above reactions of phases formation was derived: ΔG0f,SmMnO3(+/ - 250J) = -131321(+/ - 2000) + 48.02(+/ - 0:35)T / K ΔG0f,SmMn2O5(+/ - 2000 J) = -107085(+/ - 2200) + 69.74(+/ - 1:70)T / K Using obtained results and available literature data, thermodynamic data tables for the two ternary phases have been compiled from 298.15 to 1400 K. Streszczenie polskie: W pracy przedstawiono wyniki badań dotyczące własności termodynamicznych manganinów samaru, wyznaczone metodą pomiaru SEM ogniw ze stałym elektrolitem: MnO + Sm2O3 + SmMnO3 / O-2/ Ni + NiO ogniwo I Mn3O4 + SmMnO3 + SmMn2O5 / O-2 / powietrze ogniwo II oraz określono równowagowe ciśnienie parcjalne tlenu dla reakcji tworzenia SmMnO3 i SmMn2O5 w zakresie temperatur 1173�1450 K: MnO + 1/2Sm2O3 + 1/4O2 = SmMnO3 1/3Mn3O4 + SmMnO3 + 1/3O2 = SmMn2O5 Z tych danych doświadczalnych wyznaczono zależności temperaturowe energii swobodnych tworzenia powyższych manganinów samaru: ΔG0f,SmMnO3(+/ - 250J) = -131321(+/ - 2000) + 48.02(+/ - 0:35)T / K ΔG0f,SmMn2O5(+/ - 2000 J) = -107085(+/ - 2200) + 69.74(+/ - 1:70)T / K W tablicach I i II zamieszczono dane termodynamiczne dla dwóch potrójnych faz otrzymane poprzez kompilacje własnych danych doświadczalnych z danymi literaturowymi.

Effect of annealing on phase transition in poly(vinylidene fluoride) films prepared using polar solvent

The gamma-phase poly (vinylidene fluoride) (PVDF) films are usually prepared using dimethyl sulfoxide (DMSO) solvent, regardless of preparation temperature. Here we report the crystallization of both alpha and gamma-phase PVDF films by varying preparation temperature using DMSO solvent. The gamma-phase PVDF films were annealed at 70, 90, 110, 130 and 160 degrees C for five hours. The changes in the phase contents in the PVDF at different annealing conditions have been described. When thin films were annealed at 90 degrees C for 5 h, maximum percentage of beta-phase appears in PVDF thin films. The gamma-phase PVDF films completely converted to alpha-phase when they were annealed at 160 degrees C for 5 h. From X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), differential scanning calorimetry (DSC) and Raman studies, it is confirmed that the PVDF thin films, cast from solution and annealed at 90 degrees C for 5 h, have maximum percentage of beta-phase. The beta-phase PVDF shows a remnant polarization of 4.9 mu C/cm(2) at 1400 kV/cm at 1 Hz.

Polymer thin film structures for ultra-low cost biosensing

Reflectance change due to binding of molecules on thin film structures has been exploited for bio-molecular sensing by several groups due to its potential in the development of sensitive, low cost, easy to fabricate, large area sensors with high multiplexing capabilities. However, all of these sensing platforms have been developed using traditional semiconductor materials and processing techniques, which are expensive. This article presents a method to fabricate disposable thin film reflectance biosensors using polymers, such as polycarbonate, which are 2-3 orders of magnitude cheaper than conventional semiconductor and dielectric materials and can be processed by alternate low cost methods, leading to significant reduction in consumable costs associated with diagnostic biosensing. (C) 2011 Elsevier GmbH. All rights reserved.

Lithium D-Isoascorbate Monohydrate, a New Nonlinear Optical Material

Single crystals of lithium D-isoascorbate monohydrate (LDAM), (C6H7O6Li center dot H2O), are grown by a solution growth method. The crystal structure of LDAM is solved using single crystal X-ray diffraction. The space group is orthorhombic P2(1)2(1)2(1) with four formula units per unit cell and lattice parameters a = 7.7836(3) angstrom, b = 8.7456(3) angstrom, and c = 11.0368(4) angstrom. Solubility of the material in water is determined thermogravimetrically and found to have a positive temperature coefficient of solubility. Large optical quality single crystals are subsequently grown from aqueous solution by a slow cooling method. The crystal has a bulky prismatic habit and among the prominent faces the c face appears as the only principal morphological face. The crystal exhibits a (010) cleavage. Dielectric spectroscopy reveals a nearly Debye type Cole-Cole behavior with anisotropy in relaxation. Optical transmission range is found to be from 300 to 1400 nm. The principal refractive indices of this biaxial crystal, measured using Brewster's angle method, at wavelengths 405, 543, and 632.8 nm, show high dispersion. The crystal is negative biaxial with 2V(z) = 107.8 degrees (405 nm) and belongs to the Hobden class 3. Theoretically generated type 1 and type 2 second order phase matching curves match very well with the experimental results. The second-order nonlinear coefficient d(14) was determined to be 7 x 10(-13) m/V. For the optimum phase matching direction (type 2), the second-order effective nonlinear coefficient and the walk off angle are determined to be 0.84 times d(14) and 3.5 degrees respectively. The crystal possesses high multiple surface damage thresholds of 18 GW/cm(2) and 8 GW/cm(2) at laser wavelengths 1064 and 532 nm, respectively.

Influence of tool rotation speed and feed rate on the forming limit of friction stir welded AA6061-T6 sheets

In this study, the influence of tool rotation speed and feed rate on the forming limit of friction stir welded Al 6061-T651 sheets has been investigated. The forming limit curve was evaluated by limit dome height test performed on all the friction stir welded sheets. The welding trials were conducted at a tool rotation speed of 1300 and 1400 r/min and feed rate of 90 and 100 mm/min. A third trial of welding was performed at a rotational speed of 1500 r/min and feed rate 120 mm/min. It is found that with increase in the tool rotation speed, from 1300 to 1400 r/min, for a constant feed rate, the forming limit of friction stir welded blank has improved and with increase in feed rate, from 90 to 100 mm/min, for a constant tool rotation speed, it has decreased. The forming limit of friction stir welded sheets is better than unwelded sheets. The thickness gradient after forming is severe in the cases of friction stir welded blanks made at higher feed rate and lower rotation speed. The strain hardening exponent of weld (n) increases with increase in tool rotation speed and it decreases with increase in feed rate. It has been demonstrated that the change in the forming limit of friction stir welded sheets with respect to welding parameters is due to the thickness distribution severity and strain hardening exponent of the weld region during forming. There is not much variation in the dome height among the friction stir welded sheets tested. When compared with unwelded sheets, dome height of friction stir welded sheets is higher in near-plane-strain condition, but it is lesser in stretching strain paths.

``On-the-fly'' kinetics of enzymatic racemization using deuterium NMR in DNA-based chiral oriented media

We report the in situ and real-time monitoring of the interconversion of L- and D-alanine-d(3) by alanine racemase from Bacillus stearothermophilus directly observed by H-2 NMR spectroscopy in anisotropic phase. The enantiomers are distinguished by the difference of their H-2 quadrupolar splittings in a chiral liquid crystal containing short DNA fragments. The proof-of-principle, the reliability, and the robustness of this new method is demonstrated by the determination of the turnover rates of the enzyme using the Michaelis Menten model.

Scale-dependent relationships between tree species richness and ecosystem function in forests

1. The relationship between species richness and ecosystem function, as measured by productivity or biomass, is of long-standing theoretical and practical interest in ecology. This is especially true for forests, which represent a majority of global biomass, productivity and biodiversity. 2. Here, we conduct an analysis of relationships between tree species richness, biomass and productivity in 25 forest plots of area 8-50ha from across the world. The data were collected using standardized protocols, obviating the need to correct for methodological differences that plague many studies on this topic. 3. We found that at very small spatial grains (0.04ha) species richness was generally positively related to productivity and biomass within plots, with a doubling of species richness corresponding to an average 48% increase in productivity and 53% increase in biomass. At larger spatial grains (0.25ha, 1ha), results were mixed, with negative relationships becoming more common. The results were qualitatively similar but much weaker when we controlled for stem density: at the 0.04ha spatial grain, a doubling of species richness corresponded to a 5% increase in productivity and 7% increase in biomass. Productivity and biomass were themselves almost always positively related at all spatial grains. 4. Synthesis. This is the first cross-site study of the effect of tree species richness on forest biomass and productivity that systematically varies spatial grain within a controlled methodology. The scale-dependent results are consistent with theoretical models in which sampling effects and niche complementarity dominate at small scales, while environmental gradients drive patterns at large scales. Our study shows that the relationship of tree species richness with biomass and productivity changes qualitatively when moving from scales typical of forest surveys (0.04ha) to slightly larger scales (0.25 and 1ha). This needs to be recognized in forest conservation policy and management.

Adsorption Isotherms and Heat of Adsorption of Difluoromethane on Activated Carbons

Experimental adsorption data of difluoromethane (HFC-32) on activated carbon in powder (ACP) and fiber (ACF) forms over a range of (25 to 75) degrees C and pressures up to 1400 kPa are reported. The data are fitted to Toth and Dubinin-Astakhov isotherm equations. Adsorbed phase volume is derived from the data. Isosteric heats of adsorption are extracted, and their dependence on relative loading and relative pressure is analyzed.

Studies on microscopic structure of diesel sprays under atmospheric and high gas pressures

In the present work, the spray structure of diesel from a 200-mu m, single-hole solenoid injector is studied using microscopic imaging at injection pressures of 700, 1000 and 1400 bar for various gas pressures. A long-distance microscope with a high resolution camera is used for spray visualization with a direct imaging technique. This study shows that even at very high injection pressures, the spray structure in an ambient environment of atmospheric pressure reveals presence of entangled ligaments and non-spherical droplets during the injection period. With increase in the injection pressure, the ligaments tend to get smaller and spread radially. The spray structure studies are also conducted at high gas pressures in a specially designed high pressure chamber with optical access. The near nozzle spray structure at the end of the injection shows that the liquid jet breakup is improved with increase in gas density. The droplet size measurement is possible only late in the injection duration when the breakup appears to be complete and mostly spherical droplets are observed. Hence, droplet size measurements are performed after 1.3 ms from start of the injection pulse. Spatial and temporal variation in Sauter Mean `Diameter (SMD) is observed and reported for the case corresponding to an injection pressure of 700 bar. Overall, this study has highlighted the importance of verifying the extentof atomization and droplet shape even in dense sprays before using conventional dropsizing methods such as PDPA.

CTFS-ForestGEO: a worldwide network monitoring forests in an era of global change

Global change is impacting forests worldwide, threatening biodiversity and ecosystem services including climate regulation. Understanding how forests respond is critical to forest conservation and climate protection. This review describes an international network of 59 long-term forest dynamics research sites (CTFS-ForestGEO) useful for characterizing forest responses to global change. Within very large plots (median size 25ha), all stems 1cm diameter are identified to species, mapped, and regularly recensused according to standardized protocols. CTFS-ForestGEO spans 25 degrees S-61 degrees N latitude, is generally representative of the range of bioclimatic, edaphic, and topographic conditions experienced by forests worldwide, and is the only forest monitoring network that applies a standardized protocol to each of the world's major forest biomes. Supplementary standardized measurements at subsets of the sites provide additional information on plants, animals, and ecosystem and environmental variables. CTFS-ForestGEO sites are experiencing multifaceted anthropogenic global change pressures including warming (average 0.61 degrees C), changes in precipitation (up to +/- 30% change), atmospheric deposition of nitrogen and sulfur compounds (up to 3.8g Nm(-2)yr(-1) and 3.1g Sm(-2)yr(-1)), and forest fragmentation in the surrounding landscape (up to 88% reduced tree cover within 5km). The broad suite of measurements made at CTFS-ForestGEO sites makes it possible to investigate the complex ways in which global change is impacting forest dynamics. Ongoing research across the CTFS-ForestGEO network is yielding insights into how and why the forests are changing, and continued monitoring will provide vital contributions to understanding worldwide forest diversity and dynamics in an era of global change.

On the Origin of Steep I-V Nonlinearity in Mixed-Ionic-Electronic-Conduction-Based Access Devices

Numerical modeling is used to explain the origin of the large ON/OFF ratios, ultralow leakage, and high ON-current densities exhibited by back-end-of-the-line-friendly access devices based on copper-containing mixed-ionic-electronic-conduction (MIEC) materials. Hall effect measurements confirm that the electronic current is hole dominated; a commercial semiconductor modeling tool is adapted to model MIEC. Motion of large populations of copper ions and vacancies leads to exponential increases in hole current, with a turn-ON voltage that depends on material bandgap. Device simulations match experimental observations as a function of temperature, electrode aspect ratio, thickness, and device diameter.

Texture evolution during hot deformation of Moly-TZM

Moly-TZM was deformed at constant strain rate of 1.0 s(-1) to investigate the high strain rate deformation behaviour by microstructural and stress response change within a temperature range of 1400-1700 degrees C. To correlate the deformation behaviour with orientational change, recrystallization and recovery of the material, the microstructural investigation was undertaken using scanning electron microscopy (SEM) of electron back scattered diffraction (EBSD). Depending on the grain size and orientation spread recrystallized grains were identified and texture was calculated. Change in grain boundary characteristics with increasing temperature was determined by the misorientation angle distribution for the deformed and recrystallized grains. Subgrain coalescence and increase in subgrain size with increasing temperature was observed, indicating recrystallization not only occurred from the nucleation of the dislocation free grains in grain boundaries but also from the subgrain rotation and merging of the subgrains by annihilation of the low angle grain boundaries. Detailed studies on the evolution of texture of recrystallized grains showed continuous increase in <001> fiber texture in recrystallised grains, in contrast to a mixed fiber <001> +<111> for the deformed grains.

High temperature thermoelectric properties of Zr and Hf based transition metal dichalcogenides: A first principles study

We investigate the electronic and thermal transport properties of bulk MX2 compounds (M = Zr, Hf and X = S, Se) by first-principles calculations and semi-classical Boltzmann transport theory. The band structure shows the confinement of heavy and light bands along the out of plane and in-plane directions, respectively. This results in high electrical conductivity (sigma) and large thermopower leading to a high power factor (S-2 sigma) for moderate n-type doping. The phonon dispersion demonstrates low frequency flat acoustical modes, which results in low group velocities (v(g)). Consequently, lowering the lattice thermal conductivity (kappa(latt)) below 2 W/m K. Low kappa(latt) combined with high power factor results in ZT > 0.8 for all the bulk MX2 compounds at high temperature of 1200 K. In particular, the ZT(max) of HfSe2 exceeds 1 at 1400 K. Our results show that Hf/Zr based dichalcogenides are very promising for high temperature thermoelectric application. (C) 2015 AIP Publishing LLC.