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,

Spinel-Corundum Phase Equilibria in the Systems Mn-Cr-Al-O and Co-Cr-Al-O at 1373 K

The tie lines delineating ion-exchange equilibria between MCr2O4-MAl2O4 spinel solid solution, where M is either Mn or Co, and Cr2O3-Al2O3 solid solution with the corundum structure were determined at 1373 K by electron microprobe and E0AX point count analysis of the oxide phases equilibrated with metallic Co and Au-5% Mn. The component activities in the spinel solid solutions are derived from the tie lines and the thernodynamic data for Cr2O3-Al2O3 soiid solutions available hi the literature. The Gibbs free energies of mixing calculated from the experimental data are discussed in relation to the values derived from the cation distribution a.odel based on the site preference energies and assuming random mixing on both tetrahedral and octahedral sites. Positive deviations from ideality observed in this study suggest a miscibility gap for both series of spinel solid solutions at low temperatures in the absence of oxidation.

Metal-spinel-corundum three phase equilibria in the system Ni-Cr-Al-O at 1373 K

The tie-lines representing the inter-crystalline ion exchange equilibria between the NiCr2O4-NiAl2O4 spinet solid solution and Cr2O3-Al2O3 corundum solid solution are determined by electron microprobe andEDAX pointcountanalysis of the oxide phases equilibrated with metallic Ni at 1373 K. The component activities in the spinet solid solution are derived from the tie-lines and thermodynamic data for Cr2O3-Al2O3 solid solution available in the literature. The Gibbs energy of mixing of the spinet solid solution calculated from the experimental data is discussed in relation to the values derived from the cation distribution models which assume random mixing of cations on both tetrahedral and octahedral sites. Positive deviation from the models is observed indicating significant positive enthalpy contribution arising form the size mismatch between Al+3 and Ni+2 ions on the tetrahedral site and Al+3, Ni+2 and Cr+3 on the octahedral site. Variation of the oxygen potential for threephase equilibrium involving metallic nickel, spinet solid solution and corundum solid solution is computed as a function of composition of the solid solutions at 1373 K. The oxygen potential exhibits a minimum at aluminum cationic fraction eta(Al)/(eta(Al) + eta(Cr)) = 0.524 in the oxide solid solutions.

Suppression of spinel formation to induce reversible thermal behavior in the layered double hydroxides (LDHs) of Co with Al, Fe, Ga, and In

The layered double hydroxides (LDHs) of Co with trivalent cations decompose irreversibly to yield oxides with the spinel structure. Spinel formation is aided by the oxidation of Co(II) to Co(III) in the ambient atmosphere. When the decomposition is carried out under N-2, the oxidation of Co(II) is suppressed, and the resulting oxide has the rock salt structure. Thus, the Co-Al-CO32-/Cl- LDHs yield oxides of the type Co1- Al-x(2x/3)rectangle O-x/3, which are highly metastable, given the large defect concentration. This defect oxide rapidly reverts back to the original hydroxide on soaking in a Na2CO3 solution. Interlayer NO3- anions, on the other hand, decompose generating a highly oxidizing atmosphere, whereby the Co-Al-NO3- LDH decomposes to form the spinel phase even in a N-2 atmosphere. The oxide with the defect rock salt structure formed by the thermal decomposition of the Co-Fe-CO32- LDH under N2, on soaking in a Na2CO3 solution, follows a different kinetic pathway and undergoes a solution transformation into the inverse spinel Co(Co, Fe)(2)O-4. Fe3+ has a low octahedral crystal field stabilization energy and therefore prefers the tetrahedral coordination offered by the structure of the inverse spinel rather than the octahedral coordination of the parent LDH. Similar considerations do not hold in the case of Ga- and In-containing LDHs, given the considerable barriers to the diffusion of M3+ (M=Ga, In) from octahedral to tetrahedral sites owing to their large size. Consequently, the In-containing oxide residue reverts back to the parent hydroxide, whereas this reconstruction is partial in the case of the Ga-containing oxide. These studies show that the reversible thermal behavior offers a competing kinetic pathway to spinel formation. Suppression of the latter induces the reversible behavior in an LDH that otherwise decomposes irreversibly to the spinel.

Thermodynamics of Cobalt (II, III) Oxide (Co3O4): Evidence of Phase Transition

The Gibbs' energy change for the reaction, 3CoO (r.s.)+1/2O2(g)→Co3O4(sp), has been measured between 730 and 1250 K using a solid state galvanic cell: Pt, CuO+Cu2O|(CaO)ZrO2|CoO+Co3O4,Pt. The emf of this cell varies nonlinearly with temperature between 1075 and 1150 K, indicating a second or higher order phase transition in Co3O4around 1120 (±20) K, associated with an entropy change of ∼43 Jmol-1K-1. The phase transition is accompanied by an anomalous increase in lattice parameter and electrical conductivity. The cubic spinel structure is retained during the transition, which is caused by the change in CO+3 ions from low spin to high spin state. The octahedral site preference energy of CO+3 ion in the high spin state has been evaluated as -24.8 kJ mol-1. This is more positive than the value for CO+2 ion (-32.9 kJ mol-1). The cation distribution therefore changes from normal to inverse side during the phase transition. The transformation is unique, coupling spin unpairing in CO+3 ion with cation rearrangement on the spinel lattice, DTA in pure oxygen revealed a small peak corresponding to the transition, which could be differentiated from the large peak due to decomposition. TGA showed that the stoichiometry of oxide is not significantly altered during the transition. The Gibbs' energy of formation of Co3O4 from CoO and O2 below and above phase transition can be represented by the equations:ΔG0=-205,685+170.79T(±200) J mol-1(730-1080 K) and ΔG0=-157,235+127.53T(±200) J mol-1(1150-1250 K).

The effect of aluminosilicate on the delayed onset of upturn voltages of zinc oxide varistor ceramics

The effect of aluminosilicate (Al2SiO5) on the upturn characteristics of ZnO varistor ceramics has been investigated. Addition of Al2SiO5 shifts the point of upturn above 10(4) A cm(-2). The extended nonlinearity in the high current density region is better correlatable to the presence of higher density of trap stales and changing pattern of trap depths at the grain boundary interface as much as the grain interior conductivity. Microstructure studies show the formation and involvement of a liquid phase during sintering. The secondary phases, predominantly are antimony spinel, Zn7Sb2O12, zinc silicate, Zn2SiO4 and magnesium aluminium silicate. MgAl2Si3O10. Energy dispersive X-ray analyses (EDAX) show that Al and Si are distributed more in the grain boundaries and within the secondary phases than in the grain interiors. Capacitance-voltage analyses and dielectric dispersion studies indicate the presence of negative capacitance and associated resonance, indicative of the oscillatory charge redistribution involving increased trapping at the interface states. The admittance spectroscopy data show that the type of trap slates remains unaltered whereas the addition of Al2SiO5 increases the density of low energy traps. (C) 1997 Published by Elsevier Science S.A.

An investigation of carbon nanotubes obtained from the decomposition of methane over reduced Mg1− xM xAl2O4 spinel catalysts

Carbon nanotubes produced by the treatment of Mg1−xMxAl2O4 (M = Fe, Co, or Ni; x = 0.1, 0.2, 0.3, or 0.4) spinels with an H2–CH4 mixture at 1070 °C have been investigated systematically. The grains of the oxide-metal composite particles are uniformly covered by a weblike network of carbon nanotube bundles, several tens of micrometers long, made up of single-wall nanotubes with a diameter close to 4 nm. Only the smallest metal particles (<5 nm) are involved in the formation of the nanotubes. A macroscopic characterization method involving surface area measurements and chemical analysis has been developed in order to compare the different nanotube specimens. An increase in the transition metal content of the catalyst yields more carbon nanotubes (up to a metal content of 10.0 wt% or x = 0.3), but causes a decrease in carbon quality. The best compromise is to use 6.7 wt% of metal (x = 0.2) in the catalyst. Co gives superior results with respect to both the quantity and quality of the nanotubes. In the case of Fe, the quality is notably hampered by the formation of Fe3C particles.

Evidence of residual entropy in the cubic spinel Zn2TiO4

The standard free energies of formation of Zn2Ti04 and ZnTi03 have been determined in the temperature range 930° to i ioo'x from electromotive force measurements on reversible solid oxide galvanic cells;Ag-5at%znll I Pt, + CaO-Zr02 ZnO I II Ag-5at%Zn Y20r Th02 CaO-Zr02 + ,Pt Zn2Ti04+ ZnTi03 and II Ag-5at%Zn CaO-Zr02 + ,Pt ZnTi03+ Ti02 The values may be expressed by the equations,2ZnO (wurtz) + Ti02(rut) -> Zn2Ti04(sp), f:!:.Go = -750-2-46T (±75)cal;ZnO(wurtz) +Ti02(rut) -> ZnTi03(ilmen) ,f:!:.Co = -]600-0·]99T(±50)cal.Combination of the free energy values with the calorimetric heat of formation, and low-temperature and high-temperature heat capacity of Zn2Ti04 reported in literature, suggests a residual entropy of ],9 (±0·6) cal K-1 mol ? for the cubic spinel. Ideal mixing of Zn2+ and Ti4+ ions on the octahedral sites would result in a configurational contribution to the entropy of 2· 75 cal K-1 rnol ".The difference is indicative of short-range ordering of cations on octahedral sites.

Ion exchange equilibria between (Mn,Co)O solid solution and (Mn,Co)Cr2O4 and (Mn,Co)Al2O4 spinel solid solutions at 1100oC

The compositions of the (Mn,Co)O solid solution with rock salt structure in equilibrium with (Mn,Co)Cr2O4 and (Mn,Co)Al2O4 spinel solid solutions have been determined by X-ray diffraction measurements at 1100° C and an oxygen partial pressure of 10–10 atm. The ion exchange equilibria are quantitatively analysed, using values for activities in the (Mn,Co)O solid solution available in the literature, in order to obtain activities in the spinel solid solutions. The MnAl2O4-CoAl2O4 solid solution exhibits negative deviations from Raoult's law, consistent with the estimated cation disorder in the solid solution, while the MnCr2O4-CoCr2O4 solid solution shows slightly positive deviations. The difference in the Gibbs free energy of formation of the two pure chromites and aluminates derived from the results of this study are in good agreement with recent results obtained from solid oxide galvanic cells and gas-equilibrium techniques.

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.

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.

Thermodynamic properties of Fe3O4 FeAl2O4 spinel solid solution

The Gibbs energy of mixing for the system Fe3O4-FeAl2O4 was determined at 1573 K using a gas-metal-oxide equilibration technique. Oxide solid solution samples were equilibrated with Pt foils under controlled CO+CO2 gas streams. The equilibrium iron concentration in the foil was determined by chemical analysis. The cation distribution between tetrahedral and octahedral sites in the spinel crystal can be calculated from site-preference energies and used as an alternate method of determining some thermodynamic properties, including the Gibbs energy of mixing. The solvus occurring at low temperatures in the system Fe3C4-FeAl2C4 was used to derive the effect of lattice distortion due to cation size difference on the enthalpy of mixing and to obtain a better approximation to the measured thermodynamic quantities.

Giant Magnetoresistance and Related Properties of Rare Earth Manganates and Other Oxide Systems

Giant magnetoresistance (GMR), which was until recently confined to magnetic layered and granular materials, as well as doped magnetic semiconductors, occurs in manganate perovskites of the general formula Ln(1-x)A(x)MnO(3) (Ln = rare earth; A = divalent ion). These manganates are ferromagnetic at or above a certain value of x (or Mn4+ content) and become metallic at temperatures below the curie temperature, T-c. GMR is generally a maximum close to T-c or the insulator-metal (I-M) transition temperature, T-im. The T-c and %MR are markedly affected by the size of the A site cation, [r(A)], thereby affording a useful electronic phase diagram when T-c or T-im is plotted against [r(A)]. We discuss GMR and related properties of manganates in polycrystalline, thin-film, and single-crystal forms and point out certain commonalities and correlations. We also examine some unusual features in the electron-transport properties of manganates, in particular charge-ordering effects. Charge ordering is crucially dependent on [r(A)] or the e(g) band width, and the charge-ordered insulating state transforms to a metallic ferromagnetic state on the application of a magnetic field.

Studies on aluminum-isopropoxide doped poly(ethylene oxide), poly(vinyl alcohol), and poly(ethylene oxide)-poly(vinyl alcohol) blends

Poly( ethylene oxide), poly(vinyl alcohol): and their blend in a 40 : 60 mole ratio were doped with aluminum isopropoxide. Their structural, thermal, and electrical properties were studied. Aluminum isopropoxide acts as a Lewis acid and thus significantly influences the electrical properties of the polymers and the blend. It also acts as a scavanger for the trace quantities of water p-resent in them, thereby reducing the magnitude of proton transport. It also affects the structure of polymers that manifests in the thermal transformation and decomposition characteristics.

Mesostructured lamellar chromium oxide

Mesostructured lamellar chromium oxide with an interlayer separation of 29 Angstrom has been prepared by employing a cationic surfactant. The introduction of phosphate groups in the oxide increases the interlayer separation to 32 Angstrom.