Activities in the spinel solid solution, phase equilibria and thermodynamic properties of ternary phases in the system Cu Fe O

A review of the structural and thermodynamic information and phase equilibria in the Cu-Fe-O system suggested that a consistent, quantitative description of the system is hampered by lack of data on activities in the spinel solid solution CuFe2O4-Fe3O4. Therefore the activity of Fe3O4 in this solid solution is derived from measurements of the oxygen potentials established at 1000°C by mixtures containing Fe2O3 and spinel solid solutions of known composition. The oxygen pressures were measured manometrically for solid solutions rich in CuFe2O4, while for Fe3O4-rich compositions the oxygen potentials were obtained by an emf technique. The activities show significant negative deviations from Raoult’s law. The compositions of the spinel solid solutions in equilibrium with CuO + CuFeO2 and Cu + CuFeO2 were obtained from chemical analysis of the solid solution after magnetic separation. The oxygen potential of the three-phase mixture Cu + CuFeO2 + Fe3O4(spinel s.s.) was determined by a solid oxide galvanic cell. From these measurements a complete phase diagram and consistent thermodynamic data on the ternary condensed phases, CuFeO2 and CuFeO2O4, were obtained. An analysis of the free energy of mixing of the spinel solid solution furnished information on the distribution of cations and their valencies between the tetrahedral and octahedral sites of the spinel lattice, which is consistent with X-ray diffraction, magnetic and Seebeck coefficient measurements.

Phase relations in the Fe Ni Cr S system and the sulfidation of an austenitic stainless steel

The stability fields of various sulfide phases that form on Fe-Cr, Fe-Ni, Ni-Cr, and Fe-Cr-Ni alloys have been developed as a function of temperature and the partial pressure of sulfur. The calculated stability fields in the ternary A-B-S system are displayed on plots of log \textpS2 pS2 vs. the conjugate extensive variable (nA/nA–nB), which provides a better framework for following the sulfidation of Fe-Cr-Ni alloys at high temperatures. Experimental and estimated thermodynamic data were used in developing the sulfur potential diagrams. Current models and correlations were employed to estimate the unknown thermodynamic behavior of solid solutions of sulfides and to supplement the incomplete phase-diagram data of geophysical literature. These constructed stability field diagrams are in excellent agreement with the sulfide phases and compositions determined experimentally during the sulfidation of SAE 310 stainless steel. The sulfur potential plots appear to be very useful in predicting and correlating the sulfidation of commercial alloys.

Phase relationships in the system Cr W O and thermodynamic properties of CrWO4 and Cr2WO6

The phase diagram of the Cr-W-O system at 1000° C was established by metallographic and X-ray identification of the phases present after equilibration in evacuated silica capsules. Two ternary oxide phases, CrWO4 and Cr2WO6 were detected. The oxygen potential over the three-phase mixtures, W+Cr2O3 s+CrWO4, WO2.90+CrWO4+Cr2WO6 and Cr2O3+CrWO4+Cr2WO6, were measured by solid state cells incorporating Y2O3 stabilized ZrO2 electrolyte and Ni+NiO reference electrode. The Gibbs' energies of formation of the two ternary phases can be represented by the following equations

First-order structural transition in the magnetically ordered phase of Fe(1.13)Te

Specific heat, resistivity, magnetic susceptibility, linear thermal expansion (LTE), and high-resolution synchrotron x-ray powder diffraction investigations of single crystals Fe(1+y) Te (0.06 <= y <= 0.15) reveal a splitting of a single, first-order transition for y <= 0.11 into two transitions for y >= 0.13. Most strikingly, all measurements on identical samples Fe(1.13)Te consistently indicate that, upon cooling, the magnetic transition at T(N) precedes the first-order structural transition at a lower temperature T(s). The structural transition in turn coincides with a change in the character of the magnetic structure. The LTE measurements along the crystallographic c axis display a small distortion close to T(N) due to a lattice striction as a consequence of magnetic ordering, and a much larger change at T(s). The lattice symmetry changes, however, only below T(s) as indicated by powder x-ray diffraction. This behavior is in stark contrast to the sequence in which the phase transitions occur in Fe pnictides.

Functionalized and Postfunctionalizable Porous Polymeric Films through Evaporation-Induced Phase Separation Using Mixed Solvents

Condensation of water droplets during rapid evaporation of a polymer solution, under humid conditions, has been known to generate uniformly porous polymer films. Similar porous films are also formed when a solution of the polymer in THF containing small amounts of water, is allowed to evaporate rapidly under air flow; this suggests that water droplets may be formed during the final stages of film formation. In the presence of added surfactants, the interface of water droplets could become lined with the surfactants and consequently the internal walls of the pores generated, upon removal of the water, could become decorated with the hydrophilic head groups of the surfactant molecules. In a series of carefully designed experiments, we have examined the effect of added surfactants, both anionic and cationic, on the formation of porous PMMA films; the films were prepared by evaporating a solution of the polymer in THF containing controlled amounts of aqueous surfactant solutions. We observed that the average size of the pores decreases with increasing surfactant concentration, while it increases with increasing amounts of added water. The size of the pores and their distribution were examined using AFM and IR imaging methods. Although IR imaging possessed inadequate resolution to confirm the presence of surfactants at the pore surface, exchange of the inorganic counterion, such as the sodium-ion of SDS, with suitable ionic organic dyes permitted the unequivocal demonstration of the presence of the surfactants at the interface by the use of confocal fluorescence microscopy.

Three phase equilibria for activity determinations: system Co Mn

A solid state e.m.f. cell with yttria-doped thoria as the electrolyte and a mixture of Cr + Cr sub 2 O sub 3 as the reference electrode, was employed for the measurement of the activity of manganese in the Co--Mn system at 1760 deg K, for 0.3 > X sub Mn > 0.05. The liquid alloy was contained in an alumina crucible and saturated with MnAl sub 2+2x O sub 4+3x . The cell can be represented by Pt, W, (Co--Mn) + MnAl sub 2+2x O sub 4+3x + Al sub 2 O sub 3 /ThO sub 2 --Y sub 2 O sub 3 /Cr + Cr sub 2 O sub 3 , Pt. The activity of manganese shows negative deviations from Raoult's law. The activities in the Co--Mn system are intermediate between those in the Fe--Mn and Ni--Mn systems. The Gibbs' energies of mixing in these systems follow the trends given by Miedema's model. 14 ref.--AA.