Thermodynamic Properties of Niobium Oxides

Thermodynamic properties of three oxides of niobium have been measured using solid state electrochemical cells incorporating yttria-doped thoria (YDT) as the electrolyte in the temperature range T = (1000 to 1300) K. The standard Gibbs energies of formation of NbO, NbO2, and NbO2.422 from the elements can be expressed as: Delta(f)G(NbO)(o) +/- 547/J . mol(-1) = -414 986 + 86.861(T/K) Delta(f)G(NbO2)(o) +/- 548/J . mol(-1) = -779 864 + 164.438(T/K) Delta(f)G(NbO2.422)(o) +/- 775/J . mol(-1) = -911 045 + 197.932(T/K) The results are discussed in comparison with thermodynamic data reported in the literature. The new results refine data for NbO and NbO2 presented in standard data compilations. There are no data in thermodynamic compilations for NbO2.422 (Nb12O29). In the absence of the heat capacity and enthalpy of formation measurements, only the Gibbs energy of formation of NbO2.422 can be assessed. The free energy of formation of stoichiometric Nb2O5 is evaluated on the basis of measurements on NbO2.422 and information available in the literature on phase boundary compositions and isothermal variation of nonstoichiometric parameter with oxygen potential for Nb2O5-x. The results suggest a minor revision of data for Nb2O5. A minimum in the Gibbs energy of mixing for the system Nb-O occurs in the nonstoichiometric domain of Nb2O5-x with x = 0.036.

Thermodynamic properties of strontium titanates Sr2TiO4, Sr3Ti2O7, Sr4Ti3O10, and SrTiO3

The chemical potentials of SrO in two-phase fields (TiO2 + SrTiO3) (SrTiO3 + Sr4Ti3O10) (Sr4Ti3O10 + Sr3Ti2O7) and (Sr3Ti2O7 + Sr2TiO4) of the pseudo-binary system (SrO + TiO2) have been measured in the temperature range (900 to 1250) K relative to pure SrO as the reference state using solid-state galvanic cells incorporating single crystal SrF2 as the electrolyte The cells were operated under pure oxygen at ambient pressure The standard Gibbs free energies of formation of strontium titanates SrTiO3 Sr4Ti3O10 Sr3Ti2O7 and Sr2TiO4 from their component binary oxides were derived from the reversible electromotive force (EMF) of the cells For the formation of the four compounds from their component oxides TiO2 with rutile structure and SrO the standard Gibbs free energy changes are given by Delta G((ox))(SrTiO3) +/- 89/(J mol(-1)) = -121878 + 3 881(T/K) Delta G((ox))(Sr4Ti3O10) +/- 284/(J mol(-1)) = -409197 + 14 749(T/K) Delta G((ox))(Sr3Ti2O7) +/- 190/(J mol(-1)) = -285827 + 10 022(T/K) Delta G((ox))(Sr2TiO4) +/- 110/(J mol(-1))= -159385 + 3 770(T/K) The reference state for solid TiO2 is the rutile form The results of this study are in good agreement with Gibbs free energy of formation data reported in the literature for SrTiO3 but differ significantly with data for Sr4Ti3O10 For Si3Ti2O7 and Si2TiO4 experimental measurements are not available in the literature for direct comparison with the results obtained in this study (C) 2010 Elsevier Ltd All rights reserved

Phase relationships in the system Ni-W-O and thermodynamic properties of NiWO,

The phase diagram of the Ni-W-O system at 1200 K was established by metallographic and X-ray identification of the phases present after equilibration at controlled oxygen potentials. The oxygen partial pressures over the samples were fixed by metered streams of CO+CO2 gas mixtures. There was only one ternary oxide, nickel tungstate (NiWO4), in the Ni-W-O system at a total pressure of 1 atm, and this compound decomposed to a mixture of Ni+WO2.72 on lowering the oxygen potential. The Gibbs' free energy of formation of NiWO4 was determined from the measurement of the e.m.f. of the solid oxide galvanic cell, Pt, Ni+NiWO4+WO2.72/CaO-ZrO2/Ni+NiO, Pt and thermodynamic properties of tungsten and nickel oxides available in the literature. For the reaction, NiO(s)+WO3(s)rarrNiWO4(s) DeltaG°=–10500–0.708 T (±250) cal mol–1.

Mechanical Properties of Al-Mica Particulate Composite Material

Cast aluminium alloy mica particle composites of varying mica content were tested in tension, compression, and impact. With 2.2 percent mica (size range 40µm – 120µm) the tensile and compression strengths of aluminium alloy decreased by 56 and 22 percent, respectively. The corresponding decreases in percent elongation and percent reduction are 49 and 39 percent. Previous work [2] shows that despite this decrease in strength the composite with 2.5 percent mica and having an UTS of 15 kg/mm2 and compression strength of 28 kg/mm2 performs well as a bearing material under severe running conditions. The differences in strength characteristics of cast aluminium-mica particle composites between tension and compression suggests that, as in cast iron, expansion of voids at the matrix particle interface may be the guiding mechanism of the deformation. SEM studies show that on the tensile fractured specimen surface, there are large voids at the particle matrix interface.

Analysis of Nonlinear Optical Properties of Photonic Crystal Beam-splitters

The paper analyses electromagnetic wave propagation through nonlinear photonic crystal beam-splitters. Different lattice configurations of Y-junction beam-splitters are simulated and propagation properties are investigated with introducing nonlinearity with varying the rod size in crystal lattice. It is seen that nonlinear photonic crystal shows a considerable band-gap even at low refractive contrast. The division of power in both arms of beam-splitters can be controlled by varying the nonlinearity.

Optical properties of activated reactive evaporated TiO2 films

This paper discusses the optical properties of single-layer TiO2 films deposited using an activated reactive evaporation process. The combined effects of substrate temperature (in the range 70–200 °C) and discharge currents (0–400 mA) on refractive index, extinction coefficient and packing density of these films are investigated. Significant changes in refractive index values have been observed with increases in substrate temperature and discharge current. The change in refractive index is correlated with the variation in packing density. The variation in extinction coefficient was reduced using the combined effects of substrate temperature and discharge currents. A comparison with films deposited in neutral oxygen has also been made.

Effect Of Electroslag Refining On Microstructure And Mechanical-Properties Of Is-7670 Alloy

The electroslag refining technique is one of the modern tools which is capable of imparting superior mechanical and chemical properties to metals and alloys. Refining usually results in the elimination of a number of casting or solidification defects, such as shrinkage porosity, gas porosity, pipe, micro- and macro segregation. Remelting also imparts a directional grain structure apart from refining the size of the inclusions, grains and precipitates. This technique has over the years been used widely and successfully to improve the mechanical and chemical properties of steels and alloy steels which are used in the nuclear, missile, aerospace and marine industries for certain critical applications. But the application of ESR to aluminium and its alloys is only recent. This paper investigates the response of an aluminium alloy (corresponding to the Indian Specification IS: 7670) to ESR. Based on theoretical considerations and microstructural evidence it elucidates how ESR of aluminium alloys differs from that of ferrous alloys. The improvement achieved in mechanical properties of the alloy is correlated with the microstructure.

Effect of substrate temperature on the properties of ZrO2 films prepared by d.c. reactive magnetron sputtering

Studies of ZrO2 films prepared by d.c. reactive magnetron sputtering are described. The effects of substrate temperature on the packing density, refractive index, extinction coefficient and crystallinity phase have been investigated in the temperature range 25–450 °C. The refractive index varied from 1.84 to 1.95 and extinction coefficient from 2 × 10−3 to 9.6 × 10−3. This was explained on the basis of an increase in packing density from 0.686 to 0.813. The change in packing density has been attributed to a decrease in the oxygen condensation at higher temperatures. Annealing results in a decrease in refractive index and increase in extinction coefficient. The films deposited at 150 °C showed a monoclinic phase which transforms to a tetragonal phase at higher substrate temperatures.

Effects of thermal annealing on the properties of zirconia films prepared by ion-assisted deposition

The effect of thermal annealing in the range 300–800 °C on the properties of zirconia films prepared by ion assisted deposition was studied. It was found that at low temperature the cubic phase is formed. This phase is stable up to 700 °C. All the films exhibit a monophasic monoclinic structure at 800 °C. The stress, estimated from X-ray patterns, shows a transition from tensile to compressive with increasing ion fluence. The refractive index and extinction coefficient do not seem to change appreciably up to 700 °C, showing a marked degradation thereafter. Single step annealing to the highest temperature was found to result in better stability than multistep annealing.

Electrical properties of cobalt‐zinc ferrites

The electrical properties of Co1−xZnxFe2O4 (x=0–1) spinel ferrites were investigated by impedance spectroscopy. The grain‐boundary resistance was found to increase as a function of composition up to x=0.6, and decreases beyond x=0.6. The variation in the bulk resistance and the activation energy as a function of composition is found to exhibit a similar trend whereas the grain resistance appears to be an independent parameter. The observed results suggest that the bulk properties of solid solution spinel ferrites are primarily controlled by the grain‐boundary phase.

Electron-beam weld microstructures and properties of aluminium-lithium alloy 8090

Lithium-containing aluminium alloys are of considerable current interest in the aerospace and aircraft industries because lithium additions to aluminium improve the modulus and decrease the density compared to conventional aluminium alloys. Few commercial aluminium-lithium alloys have emerged for use in the aerospace industry. One such candidate is 8090, a precipitation-hardenable Al-Li-Cu-Mg alloy. The influence of electron-beam welding on the microstructure and mechanical properties of alloy 8090 material has been evaluated through microscopical observations and mechanical tests. Microscopic observations of the electronbeam welds revealed an absence of microporosity and hot cracking, but revealed presence of microporosity in the transverse section of the weld. Mechanical tests revealed the electronbeam weld to have lower strength, elongation and joint efficiency. A change in microscopic fracture mode was observed for the welded material when compared to the unwelded counterpart. An attempt is made to rationalize the behaviour in terms of competing mechanistic effects involving the grain structure of the material, the role of matrix deformation characteristics, grain-boundary chemistry and grain-boundary failure.

Influence of Starch Polysaccharide on the Remolded Properties of 2 Indian clay Samples

The reported presence in marine clays and the recognized role of polysaccharide as a bonding agent provided the motivation to examine the role of starch polysaccharide in the remoulded properties of nonswelling (kaolinite) and swelling (bentonite) groups of clays. The starch polysaccharide belongs to a group of naturally occurring, large-sized organic molecules (termed polymers) and is built up by extensive repetition of simple chemical units called repeat units. The results of the study indicate that the impact of the starch polysaccharide on the remoulded properties of clays is dependent on the mineralogy of the clays. On addition to bentonite clay, the immensely large number of segments (repeat units) of the starch polysaccharide create several polymer segment - clay surface bonds that cause extensive aggregation of the bentonite units layers. The aggregation of the bentonite unit layers greatly curtails the available surface area of the clay mineral for diffuse ion layer formation. The reduction in diffuse ion layer thickness markedly lowers the consistency limits and vane shear strength of the bentonite clay. On addition to kaolinite, the numerous polymer segment - clay surface bonds enhance the tendency of the kaolinite particles to flocculate. The enhanced particle flocculation is responsible apparently for a small to moderate increase in the liquid limit and remoulded undrained strength of the nonswelling clay.

Mechanical and swelling properties of HTPB-based copolyurethane networks

Copolyurethanes of hydroxy terminated polybutadiene (HTPB) and ISRO–Polyol (ISPO), an indigenously developed castor-oil based polyol, have been prepared using toluene diiso-cyanate and hexamethylenediisocyanate. The mechanical strength and swelling characteristics of the copolyurethanes cured with trimethylol propane and triethanolamine have been studied to evolve improved solid propellant binders. By varying the ratios of the two hydroxy pre-polymers, chain extenders, and crosslinkers, copolyurethanes having a wide range of tensile strength and elongation could be obtained. Many of these systems are desirable for their use as propellant binders. The results have been explained in terms of the measured crosslink densities and other swelling properties. © 1993 John Wiley & Sons, Inc.

Phase relations and thermodynamic properties of condensed phases in the system calcium-copper-oxygen

The isothermal sections of the phase diagram for the system Ca-Cu-0 at 1073 and 1223 K have been determined. Several compositions in the ternary system were quenched after equilibration, and the phases present were identified by optical microscopy, X-ray diffraction, and electron probe microanalysis. Two ternary compounds Ca2CuO3 and Cao.8&uO1.9s were identified at 1073 K. However, only Ca2CuO3 was found to be stable at 1223 K. The thermodynamic properties of the two ternary compounds were determined using solid-state cells incorporating either an oxide or a fluoride solid electrolyte. The results for both types of cells were internally consistent. The compound C ~ O . ~ & U Ow~h.i~ch~ c, a n also be represented as Ca15Cu18035h, as been identified in an earlier investigation as Cao.828CuOz. Using a novel variation of the galvanic cell technique, in which the emf of a cell incorporating a fluoride electrolyte is measured as a function of the oxygen potential of the gas phase in equilibrium with the condensed phase electrodes, it has been confirmed that the compound Cao.828CuO1.93 (Ca15Cu18035d) oes not have significant oxygen nonstoichiometry. Phase relations have been deduced from the thermodynamic data as a function of the partial pressure of oxygen for the system Ca-Cu-0 at 873, 1073, and 1223 K.