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 relations and activities in the Co Ni O system at 1373 K

The tie-lines delineating equilibria between CoO-NiO and Co-Ni solid solutions in the ternary Co-Ni-O system at 1373 K have been determined by electron microprobe andedax point count analysis of the oxide phase equilibrated with the alloy. The oxygen potentials corresponding to the tie-line compositions have been measured using a solid oxide galvanic cell with calcia-stabilized zirconia electrolyte and Ni + NiO reference electrode. Activities in the metallic and oxide solid solution have been derived using a new Gibbs-Duhem integration technique. Both phases exhibit small positive deviations from ideality; the values ofG E/X 1 X 2 are 2640 J mol−1 for the metallic phase and 2870 J mol−1 for the oxide solid solution.

Gibbs energy of formation of CuCrO4 and phase relations in the system Cu-Cr-O below 735 K

A solid state galvanic cell incorporating yttria-stabilized zirconia electrolyte and ruthenium(IV) oxide electrodes has been used to measure the equilibrium chemical potential of oxygen corresponding to the decomposition of CuCrO4 in the range 590–760 K. For the reaction CuO(tenorite) + CuCr2O4(spinel) + 1.5O2(g)→2CuCrO4(orth), ΔGXXX = −183540 + 249.6T(±900) J mol−1. The decomposition temperature of CuCrO4 in pure oxygen at a pressure of 1.01 × 105 Pa is 735(±1) K. By combining the results obtained in this study with data on the Gibbs energy of formation of CuCr2O4 and CuCrO2 reported earlier, the standard Gibbs energy of formation of CuCrO4 and the phase relations in the system Cu-Cr-O at temperatures below 735 K have been deduced. Electron microscopic studies have indicated that the decomposition of CuCrO4 to CuCr2O4 is topotactic.

Phase relations in the system SrO-Y2O3-CuO-O2 and CaO-Y2O3-CuO-O2 at 1173 K

Phase relations in the systems SrO-Y2O3-CuO-O2 and CaO-Y2O3-CuO-O2 at 1173 K were established by equilibrating different compositions in flowing oxygen gas at a pressure of 1.01 × 105 Pa. The quenched samples were examined by optical microscopy, X-ray diffraction (XRD), energy dispersive analysis of X-rays (EDAX), and electron spin resonance (ESR). In the system SrO-Y2O3-CuO-O2, except for the limited substitution of Y3+ for Sr2+ ions in the ternary oxide Sr14Cu24O41, no new quaternary phase was found to be stable. The compositions corresponding to the solid solution Sr14−xYxCu24O41 and the compound SrCuO2+δ lie above the plane containing SrO, Y2O3, and CuO,displaced towards the oxygen apex. However, in the system CaO-Y203-CuO-O2 at 1173 K, all the condensed phases lie on the plane containing CaO, Y203, and CuO, and a new quaternary oxide YCa2Cu306.s is present. The quaternary phase has a composition that lies at the center of the nonstoichiometric field of the analogous phase YBa2Cu307_~ in the BaO-Y203-CuO-O2 system. The compound YCa2Cu306.s has the tetragonal structure and does not become superconducting at low temperature. Surprisingly, phase relations in the three systems CaO-Y203-CuO-O2, SrO-Y203-CuO-O2, and BaO-Y203-CuO-O2 are found to be quite different.

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.

Phase relations in the system Cu-La-O and thermodynamic properties of CuLaO2 and CuLa2O4

Phase relations in the system Cu-La-O at 1200 K have been determined by equilibrating samples of different average composition at 1200 K, and phase analysis of quenched samples using optical microscopy, XRD, SEM and EDX. The equilibration experiments were conducted in evacuated ampoules, and under flowing inert gas and pure oxygen. There is only one stable binary oxide La2O3 along the binary La-O, and two oxides Cu2O and CuO along the binary Cu-O. The Cu-La alloys were found to be in equilibrium with La2O3. Two ternary oxides CuLaO2 and CuLa2O4+

Phase relations in the system Cu-Eu-O and thermodynamic properties of CuEu2O4 and CuEuO2

Phase relations in the system Cu-Eu-O have been determined by equilibrating samples of different average composition at 1200 K and by phase analysis after quenching using optical microscopy (OM), x-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive x-ray (EDX). The equilibration experiments were conducted in evacuated ampoules and under flowing inert gas and pure oxygen. The Cu-Eu alloys were found to be in equilibrium with EuO. The higher oxides of europium, Eu3O4 and Eu2O3, coexist with metallic copper. Two ternary oxides CuEu2O4 and CuEuO2 were found to be stable. The ternary oxide CuEuO2, with copper in the monovalent state, can coexist with Cu, Cu2O, Eu2O3 and CuEu2O4 in different phase fields. The compound CuEu2O4 can be in equilibrium with Cu2O, CuO, CuEuO2, Eu2O3, and O2 gas under different conditions at 1200 K. Thermodynamic properties of the ternary oxides were determined using three solid-state cells based on yttria-stabilized zirconia as the electrolyte in the temperature range from 875 to 1250 K. The cells essentially measure the oxygen chemical potential in the three-phase fields: Cu+Eu2O3+CuEuO2, Cu2O+CuEuO2+CuEu2O4, and Eu2O3+CuEuO2+CuEu2O4. The thermodynamic properties of the ternary oxides can be represented by the equations: $\begin{gathered} {\raise0.5ex\hbox{$Couldn't find \end for begin{gathered} Thermogravimetric analysis (TGA) studies in Ar+O2 mixtures confirmed the results from emf measurements. An oxygen potential diagram for the system Cu-Eu-O at 1200 K was evaluated from the results of this study and information available in the literature on the binary phases.

Gibbs energy of formation of CaCu3Ti4O12 and phase relations in the system CaO-CUO/CU2O-TiO2

he standard Gibbs energy of formation of CaCu3Ti4O12 (CCTO) from CaTiO3, CuO and TiO2 has been determined as a function of temperature from 925 to 1350 K using a solid-state electrochemical cell with yttria-stabilized zirconia as the solid electrolyte. Combining this result with information in the literature on CaTiO3, the standard Gibbs energy of formation of CCTO from its component binary oxides, CaO, CuO and TiO2, has been obtained: View the MathML source (CaCu3Ti4O12)/J mol−1 (±600) = −125231 + 6.57 (T/K). The oxygen chemical potential corresponding to the reduction of CCTO to CaTiO3, TiO2 and Cu2O has been calculated from the electrochemical measurements as a function of temperature and compared on an Ellingham diagram with those for the reduction of CuO to Cu2O and Cu2O to Cu. The oxygen partial pressures corresponding to the reduction reactions at any chosen temperature can be read using the nomograms provided on either side of the diagram. The effect of the oxygen partial pressure on phase relations in the pseudo-ternary system CaO–CuO/Cu2O–TiO2 at 1273 K has been evaluated. The phase diagrams allow identification of secondary phases that may form during the synthesis of the CCTO under equilibrium conditions. The secondary phases may have a significant effect on the extrinsic component of the colossal dielectric response of CCTO.

Phase relations and Gibbs energies of spinel phases and solid solutions in the system Mg-Rh-O

Pure stoichiometric MgRh(2)O(4) could not be prepared by solid state reaction from an equimolar mixture of MgO and Rh(2)O(3) in air. The spinel phase formed always contained excess of Mg and traces of Rh or Rh(2)O(3). The spinel phase can be considered as a solid solution of Mg(2)RhO(4) in MgRh(2)O(4). The compositions of the spinel solid solution in equilibrium with different phases in the ternary system Mg-Rh-O were determined by electron probe microanalysis. The oxygen potential established by the equilibrium between Rh + MgO + Mg(1+x)Rh(2-x)O(4) was measured as a function of temperature using a solid-state cell incorporating yttria-stabilized zirconia as an electrolyte and pure oxygen at 0.1 MPa as the reference electrode. To avoid polarization of the working electrode during the measurements, an improved design of the cell with a buffer electrode was used. The standard Gibbs energies of formation of MgRh(2)O(4) and Mg(2)RhO(4) were deduced from the measured electromotive force (e.m.f.) by invoking a model for the spinel solid solution. The parameters of the model were optimized using the measured composition of the spinel solid solution in different phase fields and imposed oxygen partial pressures. The results can be summarized by the equations: MgO + beta -Rh(2)O(3) -> MgRh(2)O(4); Delta G degrees (+ 1010)/J mol(-1) = -32239 + 7.534T; 2MgO + RhO(2) -> Mg(2)RhO(4); Delta G degrees(+/- 1270)/J mol(-1) = 36427 -4.163T; Delta G(M)/J mol(-1) = 2RT(xInx + (1-x)In(1-x)) + 4650x(1-x), where Delta G degrees is the standard Gibbs free energy change for the reaction and G(M) is the free energy of mixing of the spinel solid solution Mg(1+x)Rh(2-x)O(4). (C) 2011 Elsevier B. V. All rights reserved.

Statistical properties of entropy-consuming fluctuations in jammed states of laponite suspensions: Fluctuation relations and generalized Gumbel distribution

We report a universal large deviation behavior of spatially averaged global injected power just before the rejuvenation of the jammed state formed by an aging suspension of laponite clay under an applied stress. The probability distribution function (PDF) of these entropy consuming strongly non-Gaussian fluctuations follow an universal large deviation functional form described by the generalized Gumbel (GG) distribution like many other equilibrium and nonequilibrium systems with high degree of correlations but do not obey the Gallavotti-Cohen steady-state fluctuation relation (SSFR). However, far from the unjamming transition (for smaller applied stresses) SSFR is satisfied for both Gaussian as well as non-Gaussian PDF. The observed slow variation of the mean shear rate with system size supports a recent theoretical prediction for observing GG distribution.

Ultrasound Assisted Optical Tomography: Estimation of phase Shift experienced by photon on transit through US insonified region for detection of breast tumor

A Monte Carlo model of ultrasound modulation of multiply scattered coherent light in a highly scattering media has been carried out for estimating the phase shift experienced by a photon beam on its transit through US insonified region. The phase shift is related to the tissue stiffness, thereby opening an avenue for possible breast tumor detection. When the scattering centers in the tissue medium is exposed to a deterministic forcing with the help of a focused ultrasound (US) beam, due to the fact that US-induced oscillation is almost along particular direction, the direction defined by the transducer axis, the scattering events increase, thereby increasing the phase shift experienced by light that traverses through the medium. The phase shift is found to increase with increase in anisotropy g of the medium. However, as the size of the focused region which is the region of interest (ROI) increases, a large number of scattering events take place within the ROI, the ensemble average of the phase shift (Delta phi) becomes very close to zero. The phase of the individual photon is randomly distributed over 2 pi when the scattered photon path crosses a large number of ultrasound wavelengths in the focused region. This is true at high ultrasound frequency (1 MHz) when mean free path length of photon l(s) is comparable to wavelength of US beam. However, at much lower US frequencies (100 Hz), the wavelength of sound is orders of magnitude larger than l(s), and with a high value of g (g 0.9), there is a distinct measurable phase difference for the photon that traverses through the insonified region. Experiments are carried out for validation of simulation results.

Gibbs Energy of Formation of Ca3Ti8Al12O37 and Phase Relations and Chemical Potentials in the System Al2O3-TiO2-CaO

The quaternary oxide in the system Al2O3-CaO-TiO2 is found to have the composition Ca3Ti8Al12O37 rather than CaTi3Al8O19 as reported in the literature. The standard Gibbs energy of formation of Ca3Ti8Al12O37 from component binary oxides is measured in the temperature range from 900 to 1250 K using a solid-state electrochemical cell incorporating single crystal CaF2 as the solid electrolyte. The results can be represented by the equation: delta G(f(0x))(0) (+/- 70)/J mol(-1) = -248474 - 15.706(T/K). Combining this information with thermodynamic data on calcium aluminates and titanates available in the literature, subsolidus phase relations in the pseudo-ternary system Al2O3-CaO-TiO2 are computed and presented as isothermal sections. The evolution of phase relations with temperature is highlighted. Chemical potential diagrams are computed at 1200 K, showing the stability domains of the various phases in the chemical potential-composition space. In each chemical potential diagram, chemical potential of one component is plotted against the cationic fraction of the other two components. The diagrams are valid at relatively high oxygen potentials where Ti is present in its four-valent state in all the oxide phases.

Similarity relations in visual search predict rapid visual categorization

How do we perform rapid visual categorization?It is widely thought that categorization involves evaluating the similarity of an object to other category items, but the underlying features and similarity relations remain unknown. Here, we hypothesized that categorization performance is based on perceived similarity relations between items within and outside the category. To this end, we measured the categorization performance of human subjects on three diverse visual categories (animals, vehicles, and tools) and across three hierarchical levels (superordinate, basic, and subordinate levels among animals). For the same subjects, we measured their perceived pair-wise similarities between objects using a visual search task. Regardless of category and hierarchical level, we found that the time taken to categorize an object could be predicted using its similarity to members within and outside its category. We were able to account for several classic categorization phenomena, such as (a) the longer times required to reject category membership; (b) the longer times to categorize atypical objects; and (c) differences in performance across tasks and across hierarchical levels. These categorization times were also accounted for by a model that extracts coarse structure from an image. The striking agreement observed between categorization and visual search suggests that these two disparate tasks depend on a shared coarse object representation.

Electrochemical determination of thermodynamic properties of DyRhO3 and phase relations in the system Dy-Rh-O

Thermodynamic properties of Dysprosium rhodite (DyRhO3) are measured in the temperature range from 900 to 1,300 K using a solid-state electrochemical cell incorporating yttria-stabilized zirconia as the electrolyte. The standard Gibbs free energy of formation of DyRhO3 with O-type perovskite structure from its components binary oxides, Dysprosia with C-rare earth structure and beta-Rh2O3 with orthorhombic structure, can be represented by the equation: Delta G(f(OX))(O) (+/- 182)/J mol(-1) = -52710+3.821(T/K). By using the thermodynamic data for DyRhO3 from experiment and auxiliary data for other phases from the literature, the phase relations in the system Dy-Rh-O are computed. Thermodynamic data for intermetallic phases in the binary system Dy-Rh, required for constructing the chemical potential diagrams, are evaluated using calorimetric data available in the literature for three intermetallics and Miedema's model, consistent with the phase diagram. The results are presented in the form of Gibbs triangle, oxygen potential-composition diagram, and three-dimensional chemical potential diagram at 1,273 K. Temperature-composition diagrams at constant oxygen partial pressures are also developed. The decomposition temperature of DyRhO3 is 1,732 (+/- 2.5) K in pure oxygen and 1,624 (+/- 2.5) K and in air at standard pressure.