Synergistic use of thermogravimetric and electrochemical techniques for thermodynamic study of TiOx (1.67 <= x <= 2.0) at 1573 K

A thermodynamic study of the Ti-O system at 1573 K has been conducted using a combination of thermogravimetric and emf techniques. The results indicate that the variation of oxygen potential with the nonstoichiometric parameter delta in stability domain of TiO2-delta with rutile structure can be represented by the relation, Delta mu o(2) = -6RT In delta - 711970(+/-1600) J/mol. The corresponding relation between non-stoichiometric parameter delta and partial pressure of oxygen across the whole stability range of TiO2-delta at 1573 K is delta proportional to P-O2(-1/6). It is therefore evident that the oxygen deficient behavior of nonstoichiometric TiO2-delta is dominated by the presence of doubly charged oxygen vacancies and free electrons. The high-precision measurements enabled the resolution of oxygen potential steps corresponding to the different Magneli phases (Ti-n O2n-1) up to n = 15. Beyond this value of n, the oxygen potential steps were too small to be resolved. Based on composition of the Magneli phase in equilibrium with TiO2-delta, the maximum value of n is estimated to be 28. The chemical potential of titanium was derived as a function of composition using the Gibbs-Duhem relation. Gibbs energies of formation of the Magneli phases were derived from the chemical potentials of oxygen and titanium. The values of -2441.8(+/-5.8) kJ/mol for Ti4O7 and -1775.4(+/-4.3) kJ/mol for Ti3O5 Obtained in this study refine values of -2436.2(+/-26.1) kJ/mol and-1771.3(+/-6.9) kJ/mol, respectively, given in the JANAF thermochemical tables.

Use of Polyazaheterocycles in the Assembly of New Cadmium Sulfate Frameworks: Synthesis, Structure, and Properties

The reaction of cadmium sulfate in the presence of polyazaheterocyclic organic molecules gave rise to a variety of new cadmium sulfate phases in water containing solvothermal reaction. The compounds have two- (I) and three-dimensionally (II-VI) extended structures. All the compounds have structures built up by the connectivity involving the cadmium octahedra and the sulfate tetrahedra in which the heterocyclic organic molecules act as the ligand. The linkages between the Cd2+ and (SO4)2- ions form one- (II), two- (I, III, and IV), and three- (V and VI) dimensionally extended cadmium sulfate phases. The connectivity between Cd2+ ion and the heterocyclic ligand also gives rise to one- and two-dimensional structures. The inter-connectivity between the two units gives rise to the observed structures. The presence of Cd-O-Cd chains and Cd-O-Cd layers in some of the structures is noteworthy. The adsorption/desorption studies suggest that the cadmium sulfate phases adsorb/desorb anionic dyes selectively in the presence of water/ethanol, respectively. The photocatalytic degradation studies on cationic dyes under UV-irradiation indicate modest activity. The cyanosilylation of imines using the present compounds as heterogeneous catalyst indicate good catalytic behavior. The various properties exhibited by the cadmium sulfate phases suggest that these compounds are versatile. All the compounds were characterized by powder X-ray diffraction, thermogravimetric analysis, infrared (IR) and UV-visible studies.

Fabrication of device quality films of high loaded PPy/MWCNT nanocomposites using pulsed laser deposition

Polypyrrole (PPy) - multiwalled carbonnanotubes (MWCNT) nanocomposites with various MWCNT loading were prepared by in situ inversion emulsion polymerization technique. High loading of the nano filler were evaluated because of available inherent high interface area for charge separation in the nanocomposites. Solution processing of these conducting polymer nanocomposites is difficult because, most of them are insoluble in organic solvents. Device quality films of these composites were prepared by using pulsed laser deposition techniques (PLD). Comparative study of X-ray photoelectron spectroscopy (XPS) of bulk and film show that there is no chemical modification of polymer on ablation with laser. TEM images indicate PPy layer on MWCNT surface. SEM micrographs indicate that the MWCNT's are distributed throughout the film. It was observed that MWCNT in the composite held together by polymer matrix. Further more MWCNT diameter does not change from bulk to film indicating that the polymer layer remains intact during ablation. Even for very high loadings (80 wt.% of MWCNT's) of nanocomposites device quality films were fabricated, indicating laser ablation is a suitable technique for fabrication of device quality films. Conductivity of both bulk and films were measured using collinear four point probe setup. It was found that overall conductivity increases with increase in MWCNT loading. Comparative study of thickness with conductivity indicates that maximum conductivity was observed around 0.2 mu m. (C) 2010 Elsevier B.V. All rights reserved.

Use of metastable equilibria for determination of Gibbs energy of solids

Attempts are made to measure activities of both components of a binary alloy (A�B) at 650 K using a solid-state galvanic cell incorporating a new composite solid electrolyte. Since the ionic conductivity of the composite solid electrolyte is three orders of magnitude higher than that of pure CaF2, the cell can be operated at lower temperatures. The alloy phase is equilibrated in separate experiments with flourides of each component and fluorine potential is measured. The mixture of the alloy (A�B) and the fluoride of the more reactive component (BF2) is stable, while (A�B) + AF2 mixture is metastable, Factors governing the possible use of metastable equilibria have been elucidated in this study. In the Co�Ni system, where the difference in Gibbs energies of formation of the fluorides is 21.4 kJ/mol, emf of the cell with metastable phases at the electrode is constant for periods ranging from 90 to 160 ks depending on alloy composition. Subsequently, the emf decreases because of the onset of the displacement reaction. In the Ni�Mn system, measurement of the activity of Ni using metastable equilibria is not fully successful at 650 K because of the large driving force for the displacement reaction (208.8 kJ/mol). Critical factors in the application of metastable equilibria are the driving force for displacement reaction and diffusion coefficients in both the alloy and fluoride solid solution.

Use of modal energy distribution in the design of honeycomb sandwich decks

Through the example of a spacecraft equipment deck, which is generally made of honeycomb sandwich construction, it is shown that modal energy distribution can be used as an effective guideline in improving the deck's frequencies to meet the restrictions imposed upon it. The kinetic energy distribution is employed as a basis for redistributing various packages on the deck. Strain energy distribution is used to identify areas which can be stiffened by bonding �doublers� on the face sheets and the doubler thickness is obtained from a sensitivity analysis.