Activities and their relation to cation distribution in NiAl2O4 MgAl2O4 spinel solid solutions

The activity of NiAl2O4 in NiAl2O4MgAl2O4 solid solutions has been measured by using a solid oxide galvanic cell of the type, Pt, Ni + NiAl2O4 + Al2O3(α)/CaOZrO2/Ni + NixMg1−xAl2O4 + Al2O3(α). Pt, in the temperature range 750–1150°C. The activities in the spinel solid solutions show negative deviations from Raoult's law. The cation distribution in the solid solutions has been calculated using site preference energies independent of composition for Ni2+, Mg2+, and Al3+ ions obtained from crystal field theory and measured cation disorder in pure NiAl2O4 and MgAl2O4, and assumi g ideal mixing of cations on the tetrahedral and octahedral positions. The calculated values correctly predict the decrease in the fraction, α, of Ni2+ ions on tetrahedral sites for 1>x>0.25, observed by Porta et al. [J. Solid State Chem.11, 135 (1974)] but do not support their tentative evidence for an increase in α for x < 0.25. The measured excess free energy of mixing can be completely accounted for by using either the calculated or the measured cation distributions. This suggests that the Madelung energy is approximately a linear function of composition in the solid solutions. The composition of NiOMgO solid solutions in equilibrium with NiAl2O4MgAl2O4 solid solutions has been calculated from the results and information available in literature.

Correlations between structure and thermodynamic properties of spinels and their applications in technology

Measurements a/the Gibbs' energy enthalpy and entrupy vffarmation oj chromites, vanadites and alumlnat.:s 0/ F", Ni. Co'. Mn, Zn Mg and Cd, using solid oxide galvanic cells over a ternperature range extending approximately lOOO°C, have shown that the '~'Ilir"!,,, J'JrIl/iJ~ tion 0/ cubic 2-3 oxide spinel phases (MX!O,), from component oxide (MO) with rock-salt and X.Os whir c(1f'l/!ldwn st!'llt'lw,·. call b,' represented by a semi-empirical correlalion, ~S~ = --LiS + L'i,SM +~S~:"d(±O.3) cal.deg-1 mol-1 where /',.SM Is the entropy 0/calian mixing oillhe tetrahedral alld octahedral sites o/the spinel and Sr:~ is tlie enfropy associaf,'d Wifh Ih,' randomization a/the lahn-Telier distortions. A review a/the methods/or evaluating the cation distriblltion lfl spille!s suggeJ{j' l/r,l! Ihe most promising scheme is based Oil octahedral site preference energies from the crystal field theory for the Iral1silioll IIIl'f"! IlIIL';. For I/""-Irallsifioll melal cal ions site preference energies are derived relative /0 thol'lt fLI, [ransilion metal ions from measured high tClllP('ftJi ure Cal iUlI disll iiJuriol1 in spine! phases thar contail! one IransilioJl metal and another non-transition metal carion. For 2-3 srinds compulatiorrs b,IS"J Oil i.!c[J;' Temkin mixing on each catioll subialtice predici JistributionJ that are In fair agreement with X-ray and 1I1'IIIrOll ditTraction, /IIdg""!ic dll.! electrical propcrries, and spectroscopic measurements. In 2-4 spineis mixing vI ions do not foliow strictly ideal slllIistli:al Jaws, Th,' OIl/up) associated with the randomizalion 0/the Jllhn-Teller dislOriioll" appear to be significant, only ill spinels witll 3d'. 3d', 3d' (ifld~UI' iOtls in tetrahedral and 3d' and 3d9 ions in octahedral positions. Application 0/this structural model for predicting the thermodynamic proputies ofspinel solid .,olutiofl5 or,' illustrated. F,lr complex systems additional contributions arising from strain fields, redox equilibria and off-center ions have to be qllalllififti. The entropy correlation for spinels provides a method for evaluating structure tran:.jormafiofl entropies in silllple o.\id.-s, ["founlllion on the relative stabilities ofoxides in different crystallCtructures is USe/III for computer ea/culaliof! a/phase dfugrullls ofIlIrer,',,1 III (N.lll1ie5 by method, similar to thost: used by Kaufman and Bernstein for refractory alloy systems. Examples oftechnoiogical appliCation tnclude the predictioll ofdeoxidation equilibria in Fe-Mn-AI-O s),slelll at 1600°C duj ,'Ulllpltfalion 0/phase relutions in Fe-Ni-Cr-S system,

Thermodynamic properties of Ln-O (Ln = La, Pr, Nd) solid solutions and their deoxidation by molten salt electrolysis

The lanthanide metals lanthanum, praseodymium and neodymium containing 2,200, 2,600, 1,850 mass ppm oxygen, respectively, were deoxidized to 20-30 ppm level at 1,073 K by an electrochemical method. The metal to be deoxidized was used as the cathode in an electrolysis cell which consisted of a graphite anode and molten CaCl2 electrolyte. The calcium metal produced at the cathode by electrolysis effectively deoxidized the lanthanide metal. Calcium oxide produced by deoxidation, dissolved in the melt. The liberation of carbon monoxide/dioxide at the anode was found to prevent accumulation of oxygen in the melt. For a quantitative discussion of the limits of deoxidation achievable by this technique, a thermodynamic investigation of the lanthanide-oxygen (Ln-O ; Ln = La, Pr, Nd) solid solutions was conducted. The lanthanide metal, yttrium and titanium samples were immersed in calcium-saturated CaCl2 melt, containing a small quantity of dissolved CaO, at 1,093 K. The oxygen potential of the melt and the Ln-O solid solutions were obtained from the oxygen content of yttrium samples at equilibrium, and the known thermodynamic properties of yttrium-oxygen solid solution. The results were confirmed by using Y/Y2O3 equilibrium to control the oxygen potential of the molten salt reservoir. The oxygen affinity of the metals was found to decrease in the order : Y > Ti > Nd > Pr > La. The deoxidation results are consistent with the thermodynamic properties of the RE-O solid solutions.

Extending the Supramolecular Synthon Based Fragment Approach (SBFA) for Transferability of Multipole Charge Density Parameters to Monofluorobenzoic Acids and their Cocrystals with Isonicotinamide: Importance of C-H center dot center dot center dot O, C-H center dot center dot center dot F, and F center dot center dot center dot F Intermolecular Regions

An extension of the supramolecular synthon-based fragment approach (SBFA) method for transferability of multipole charge density parameters to include weak supramolecular synthons is proposed. In particular, the SBFA method is applied to C-H center dot center dot center dot O, C-H center dot center dot center dot F, and F center dot center dot center dot F containing synthons. A high resolution charge density study has been performed on 4-fluorobenzoic acid to build a synthon library for C-H center dot center dot center dot F infinite chain interactions. Libraries for C-H center dot center dot center dot O and F center dot center dot center dot F synthons were taken from earlier work. The SBFA methodology was applied successfully to 2- and 3-fluorobenzoic acids, data sets for which were collected in a routine manner at 100 K, and the modularity of the synthons was demonstrated. Cocrystals of isonicotinamide with all three fluorobenzoic acids were also studied with the SBFA method. The topological analysis of inter- and intramolecular interaction regions was performed using Bader's AIM approach. This study shows that the SBFA method is generally applicable to generate charge density maps using information from multiple intermolecular regions.

Microwave cavity resonators. Some perturbation effects and their applications

Lagrange's equation is utilized to show the analogy of a lossless microwave cavity resonator with the conventional LC network. A brief discussion on the resonant frequencies of a microwave cavity resonator and the two degenerate companion modes H01 and E11 appearing in a cavity is given. The first order perturbation theory of a small deformation of the wall of a cavity is discussed. The effects of perturbation, such as the change in the resonant frequency and the Q of a cavity, the change in the electromagnetic field configurations and hence mixing of modes are also discussed. An expression for the coupling coefficient between the two degenerate modes H01 and E11 is derived with the help of the field equations. Results indicate that in the absence of perturbation the above two degenerate modes can co-exist without losing their individual identities. Several applications of the perturbation theory, such as the measurement of the dielectric properties of matter, study of ferromagnetic resonance, etc., are described.

Composite instantaneous comparators basis for design and their transient performance

Principles of design of composite instantaneous comparators (a combination of amplitude- and phase- comparison techniques) are laid out to provide directional, directional-reactance, nonoffset-resistance and conductance characteristices. The respective signals provided by the voltage transformer and the current transformer are directly used as relaying signals without resorting to any form of mixing. Phase shifts required, are obtained by using magnetic ferrite cores in a novel manner. Sampling units employing a combination of ferrite cores and semiconductor devices provide highly reliable designs. Special attention is paid to the choice of relaying signals, to eliminate the need for any synchronisation or modification and to avoid `image¿ characteristics. These factors have resulted in a considerable simplification of the practical circuitry. A thyristor AND circuit is employed in dual comparator units to provide the final tripping, and leads to a circuit which is much less sensitive to extraneous signals than a single-thyristor unit.

Quasicrystals and their crystalline homologues in the Al–Mn–Cu ternary alloys

Electron diffraction and high-resolution electron microscopy have been employed to differentiate among icosahedral, decagonal and crystalline particles that occur in as-cast and rapidly solidified Al-Mn-Cu alloys. The resemblance between decagonal quasicrystals and crystals in their electron diffraction patterns is striking. The crystalline structure is based on the orthorhombic ‘Al3Mn’ structure, but also a new monoclinic phase called ‘X’ has been discovered and described here. The present observations are also closely related to the orthorhombic structures in Al60Mn11Ni4. The occurrence of fine-scale twinning and fragmentation into domains explains the complex diffraction effects.

Studies of phosphazenes .11. syntheses and structures of bis(primary amino)hexachlorocyclotetraphosphazenes and their dimethylamino derivatives

The bis(amino)hexachlorocyclotetraphosphazenes, 2-trans-6-N4P4 (NHR)2Cl6, R [dbnd] Me, Pr n Pr i , Bu n , CH2Ph, Ph, are obtained from the reaction of N4P4Cl8 with four mol. equivalents of the appropriate amine. Isomers with 2,4-structures have been isolated for R [dbnd] Bu n , CH2Ph. The 1H and 31P NMR spectra of these bis(amino) compounds and of their dimethylamino derivatives, 2-trans-6-N4P4 (NMe2)6 (NHR)2 are discussed.

Minor mergers and their impact on the kinematics of old and young stellar populations in disk galaxies

By means of N-body simulations we investigate the impact of minor mergers on the angular momentum and dynamical properties of the merger remnant. Our simulations cover a range of initial orbital characteristics and gas-to-stellar mass fractions (from 0 to 20%), and include star formation and supernova feedback. We confirm and extend previous results by showing that the specific angular momentum of the stellar component always decreases independently of the orbital parameters or morphology of the satellite, and that the decrease in the rotation velocity of the primary galaxy is accompanied by a change in the anisotropy of the orbits. However, the decrease affects only the old stellar population, and not the new population formed from gas during the merging process. This means that the merging process induces an increasing difference in the rotational support of the old and young stellar components, with the old one lagging with respect to the new. Even if our models are not intended specifically to reproduce the Milky Way and its accretion history, we find that, under certain conditions, the modeled rotational lag found is compatible with that observed in the Milky Way disk, thus indicating that minor mergers can be a viable way to produce it. The lag can increase with the vertical distance from the disk midplane, but only if the satellite is accreted along a direct orbit, and in all cases the main contribution to the lag comes from stars originally in the primary disk rather than from stars in the satellite galaxy. We also discuss the possibility of creating counter-rotating stars in the remnant disk, their fraction as a function of the vertical distance from the galaxy midplane, and the cumulative effect of multiple mergers on their creation.