System Gd-Rh-O: Thermodynamics and phase relations

Thermodynamic properties of GdRhO3 are investigated in the temperature range from 900 to 1300 K by employing a solid-state electrochemical cell, incorporating calcia-stabilized zirconia as the electrolyte. The standard Gibbs free energy of formation of GdRhO3 from component binary oxide Gd2O3 with C-rare earth structure and Rh2O3 with orthorhombic structure can be expressed as; Delta G(f(ox))(o)(+/- 60)/J mol(-1) = -56603 + 3.78(T/K) Based on the thermodynamic information on GdRhO3 from experiment and auxiliary data for binary oxides from the literature and estimated properties of Gd-Rh alloys, phase relations are computed for the system Gd-Rh-O at 1273 K. Gibbs free energies for intermetallic phases in the binary Gd-Rh are evaluated using calorimetric data available in the literature for two compositions and Miedema's model, consistent with the binary phase diagram. Isothermal section of the ternary phase diagram, oxygen potential-composition diagram and a 3-D chemical potential diagram for the system Gd-Rh-O at 1273 K are developed. Phase relations in the ternary Gd-Rh-O are also computed as a function of temperature at constant oxygen partial pressures. The ternary oxide, GdRhO3 decomposes to Gd2O3 with B-rare earth structure, metallic Rh and O-2 at 1759(+/- 2) K in pure O-2 and 1649(+/- 2) K in air at a total pressure P-0 -0.1 MPa. (c) 2012 Elsevier B.V. All rights reserved.

Phase equilibria in the system Sm-Rh-O and thermodynamic and thermal studies on SmRhO3

Using isothermal equilibration, phase relations are established in the system Sm-Rh-O at 1273 K. SmRhO3 with GdFeO3-type perovskite structure is found to be the only ternary phase. Solid-state electrochemical cells, containing calcia-stabilized zirconia as an electrolyte, are used to measure the thermodynamic properties of SmRhO3 formed from their binary component oxides Rh2O3 (ortho) and Sm2O3 (C-type and B-type) in two different temperature ranges. Results suggest that C-type Sm2O3 with cubic structure transforms to B-type Sm2O3 with monoclinic structure at 1110 K. The standard Gibbs energy of transformation is . Standard Gibbs energy of formation of SmRhO3 from binary component oxides Rh2O3 and Sm2O3 with B-type rare earth oxide structure can be expressed as . The decomposition temperature of SmRhO3 estimated from the extrapolation of electrochemical data is 1665 (+/- 2) K in air and 1773 (+/- 3) K in pure oxygen. Temperature-composition diagrams at constant oxygen pressures are constructed for the system Sm-Rh-O. Employing the thermodynamic data for SmRhO3 from emf measurement and auxiliary data for other phases from the literature, oxygen potential-composition phase diagram and 3-D chemical potential diagram for the system Sm-Rh-O at 1273 K are developed.

C. N. R. Rao and the Growth of Solid State and Materials Chemistry as a Central Domain of Research

In celebrating Professor C. N. R. Rao's 80th birthday, this article recalls his singular contributions to solid state and materials chemistry for about sixty years. In so doing, the article also traces the growth of the field as a central domain of research in chemical sciences from its early origins in Europe. Although Rao's major work lies in solid state and materials chemistry - a field which he started and nurtured in India while its importance was being recognized internationally - his contributions to other areas of chemistry (and physics), viz., molecular spectroscopy, phase transitions, fullerenes, graphene, nanomaterials and multiferroics are equally significant. Illustrative examples of his work devoted to rare earth and transition metal oxides, defects and nonstoichiometry, metal-insulator transitions, investigation of crystal and electronic structures of a variety of solids by means of electron microscopies and photoelectron spectroscopy, superconducting cuprates, magnetoresistive manganites, multiferroic metal oxides of various structures and, last but not the least, development of new strategies for chemical synthesis of a wide variety of solids including nanomaterials and framework solids in different dimensionalities, are highlighted. The article also captures his exemplary role as a science teacher, science educationist and institution builder in post-Independence India.

Use of Composition-Graded Bi-Electrolyte Cells for Thermodynamic Studies on Lanthanum Aluminates

Innovative bi-electrolyte solid-state cells incorporating single crystal CaF2 and composition-graded solid electrolyte (LaF3) y (CaF2) 1-y (y = 0 to 0.32) were used for measurement of the standard Gibbs energy of formation of hexagonal La0.885Al11.782O19 and cubic LaAlO3 from component binary oxides La2O3 and alpha-Al2O3 in the temperature range from 875 to 1175 K. The cells were designed based on experimentally verified relevant phase relations in the systems La2O3-Al2O3LaF3 and CaF2-LaF3. The results can be summarized as: 5.891 alpha-Al2O3 + 0.4425 La2O3 (A-rare earth)-> La0.885Al11.782O19 (hex), Delta G(f(ox))(degrees)(+/- 2005)/Jmol(-1) = -80982 + 7.313(T/K); 1/2 La2O3 (A-rare earth) + 1/2 a-Al2O3 -> LaAlO3 (cubic), Delta G(f(ox))(degrees)(+/- 2100)/Jmol(-1) = -59810 + 4.51(T/K). Electron probe microanalysis was used to ascertain the non-stoichiometric range of the hexaaluminate phase. The results are critically analyzed in the light of earlier electrochemical measurements. Several imperfections in the electrochemical cells used by former investigators are identified. Data obtained in the study for LaAlO3 are consistent with calorimetric enthalpy of formation and entropy derived from heat capacity data. Estimated are the standard entropy and the standard enthalpy of formation from elements of hexagonal La0.885Al11.782O19 and rhombohedral LaAlO3 at 298.15 K. c 2014 The Electrochemical Society. All rights reserved.

Conductivity noise study of the insulator-metal transition and phase coexistence in epitaxial samarium nickelate thin films

Interaction between the lattice and the orbital degrees of freedom not only makes rare-earth nickelates unusually ``bad metal,'' but also introduces a temperature-driven insulator-metal phase transition. Here we investigate this insulator-metal phase transition in thin films of SmNiO3 using the slow time-dependent fluctuations (noise) in resistivity. The normalized magnitude of noise is found to be extremely large, being nearly eight orders of magnitude higher than thin films of common disordered metallic systems, and indicates electrical conduction via classical percolation in a spatially inhomogeneous medium. The higher-order statistics of the fluctuations indicate a strong non-Gaussian component of noise close to the transition, attributing the inhomogeneity to the coexistence of the metallic and insulating phases. Our experiment offers insight into the impact of lattice-orbital coupling on the microscopic mechanism of electron transport in the rare-earth nickelates.

Contrasting geochemical signatures on land from the Middle and Late Permian extinction events

The end of the Palaeozoic is marked by two mass-extinction events during the Middle Permian (Capitanian) and the Late Permian (Changhsingian). Given similarities between the two events in geochemical signatures, such as large magnitude negative C-13 anomalies, sedimentological signatures such as claystone breccias, and the approximate contemporaneous emplacement of large igneous provinces, many authors have sought a common causal mechanism. Here, a new high-resolution continental record of the Capitanian event from Portal Mountain, Antarctica, is compared with previously published Changhsingian records of geochemical signatures of weathering intensity and palaeoclimatic change. Geochemical means of discriminating sedimentary provenance (Ti/Al, U/Th and La/Ce ratios) all indicate a common provenance for the Portal Mountain sediments and associated palaeosols, so changes spanning the Capitanian extinction represent changes in weathering intensity rather than sediment source. Proxies for weathering intensity chemical index of alteration, W and rare earth element accumulation all decline across the Capitanian extinction event at Portal Mountain, which is in contrast to the increased weathering recorded globally at the Late Permian extinction. Furthermore, palaeoclimatic proxies are consistent with unchanging or cooler climatic conditions throughout the Capitanian event, which contrasts with Changhsingian records that all indicate a significant syn-extinction and post-extinction series of greenhouse warming events. Although both the Capitanian and Changhsingian event records indicate significant redox shifts, palaeosol geochemistry of the Changhsingian event indicates more reducing conditions, whereas the new Capitanian record of reduced trace metal abundances (Cr, Cu, Ni and Ce) indicates more oxidizing conditions. Taken together, the differences in weathering intensity, redox and the lack of evidence for significant climatic change in the new record suggest that the Capitanian mass extinction was not triggered by dyke injection of coal-beds, as in the Changhsingian extinction, and may instead have been triggered directly by the Emeishan large igneous province or by the interaction of Emeishan basalts with platform carbonates.

Low temperature giant magnetocaloric effect in multiferroic GdMnO3 single crystals

Magnetocaloric (MC) properties of GdMnO3 single crystals are investigated using magnetic and magneto-thermal measurements. GdMnO3 exhibits a giant MC effect (isothermal change in magnetic entropy (-Delta S-M) similar to 31 J (kg K)(-1) at 7 K and adiabatic change in temperature similar to 10 K at 19 K for magnetic field variation 0-80 kOe). Complex interactions between 3d and 4f magnetic sublattices influence MC properties. The rare-earth antiferromagnetic ordering induces an inverse MC effect (positive Delta S-M) along `a' and `c' axes whereas it's not seen along the `b' axis, revealing complex anisotropic magnetic ordering. The antiferromagnetic ordering possibly changes to ferromagnetic ordering at higher fields.

Common effect of chemical and external pressures on the magnetic properties of RCoPO (R = La, Pr, Nd, Sm). II.

We investigate the direct correspondence between Co band ferromagnetism and structural parameters in the pnictide oxides RCoPO for different rare-earth ions (R = La, Pr, Nd, Sm) by means of muon-spin spectroscopy and ab initio calculations, complementing our results published previously G. Prando et al., Common effect of chemical and external pressures on the magnetic properties of RCoPO (R = La, Pr), Phys. Rev. B 87, 064401 (2013)]. We find that both the transition temperature to the ferromagnetic phase T-C and the volume of the crystallographic unit cell V are conveniently tuned by the R ionic radius and/or external pressure. We report a linear correlation between T-C and V and our ab initio calculations unambiguously demonstrate a full equivalence of chemical and external pressures. As such, we show that R ions influence the ferromagnetic phase only via the induced structural shrinkage without involving any active role from the electronic f degrees of freedom, which are only giving a sizable magnetic contribution at much lower temperatures.

Thermal, magnetic and electrical properties of Tb1-xDyxMnO3 multiferroics

A series of multiferroic materials with the compositional formula, Tb1 - xDyxMnO3 (where x=0, 0.1, 0.2, 0.3 and 0.4) were prepared by the sol gel method. After characterizing the samples structurally, a systematic investigation of specific heat, magnetization and dielectric properties over the temperature range, 4-300 K, was undertaken. Based on these studies, it was found that all the samples exhibit a transition at 40 K and the observed behavior may be attributed to the ordering of Mn3+ ions. Further, all the five samples are found to exhibit a ferroelectric transition in the temperature range 20-24 K. Finally, yet another transition was also exhibited by all the samples at temperatures below 10 K and is attributed to the antiferromagnetic (AF) ordering of rare-earth ionic moments. The magnetic entropy of all the samples was also computed with the help of their heat capacity data. (C) 2015 Elsevier B.V. All rights reserved.

Tuning Photoluminescence Response by Electric Field in Electrically Soft Ferroelectrics

We show that an electrically soft ferroelectric host can be used to tune the photoluminescence (PL) response of rare-earth emitter ions by external electric field. The proof of this concept is demonstrated by changing the PL response of the Eu3+ ion by electric field on a model system Eu-doped 0.94(Na1/2Bi1/2TiO3)-0.06(BaTiO3). We also show that new channels of radiative transitions, forbidden otherwise, open up due to positional disorder in the system, which can as well be tuned by electric field.