Investigation of activated transport in hole doped rare earth manganites in the high temperature paramagnetic regime

Electronic transport in the high temperature paramagnetic regime of the colossal magnetoresistive oxides, La(1-x)A(x)MnO(3), A=Ca, Sr, Ba, x similar or equal to 0.1-0.3, has been investigated using resistivity measurements. The main motivation for this work is to relook into the actual magnitude of the activation energy for transport in a number of manganites and study its variation as a function of hole doping (x), average A-site cation radius (< r(A)>), cationic disorder (sigma(2)) and strain (epsilon(zz)). We show that contrary to current practice, the description of a single activation energy in this phase is not entirely accurate. Our results clearly reveal a strong dependence of the activation energy on the hole doping as well as disorder. Comparing the results across different substituent species with different < r(A)> reveals the importance of sigma(2) as a metric to qualify any analysis based on (r(A)). (c) 2006 Elsevier Ltd. All rights reserved.

High-temperature reactions of alkali and plagioclase feldspars with alkali and alkaline-earth chlorides-formation of celsian

High-temperature reactions (Ca 900-degrees-C) involving albite, K-feldspar or plagioclase and K, Ba-or K, Sr chlorides were experimentally studied. These experiments reveal that the reaction between K-exchanged albite, potash feldspar, or plagioclase and Ba-chloride/Ba-K chloride results in the formation of celsian by the breakdown of the starting feldspar structure above 800-degrees-C. Sr-feldspar does not form under similar conditions. A size-effect of the large M-site cation appears to be responsible for the formation of celsian. The reaction between K-feldspar and barium chloride may be used as a method for synthesizing celsian.

New uniform solid catalyst for the low-temperature oxidation of carbon monoxide: A triple-layered rare earth perovskite containing Co and Cu ions

Oxygen reactivity and catalytic activity of the cobalt-containing layered defect perovskites, YBa2Cu2CoO7+delta and LaBa2Cu2CoO7+delta, in comparison with LaBa2Cu3O7-delta have been investigated employing temperature-programmed desorption (TPD) and temperature-programmed surface reactions (TPSR) in the stoichiometric and catalytic mode using carbon monoxide as a probe molecule. TPD studies showed evidence for the presence of two distinct labile oxygen species, one at (0 0 1/2) sites and the other at (0 1/2 0) sites in LaBa2Cu2CoO7+delta against a single labile species at (0 1/2 0) in the case of two other oxides. The activation energies for the catalytic oxidation of carbon monoxide by oxygen over LaBa2Cu3O7-delta, YBa2Cu2CoO7+delta, and LaBa2Cu2CoO7+delta have been estimated to be 24.2, 15.9, and 13.6 kcal/mol, respectively. The reactivity and catalytic activity of the oxide systems have been interpreted in terms of the structural changes brought about by substituents, guided by a directing effect of the larger rare earth cation. TPSR profiles, structural analysis, and infrared spectroscopic investigations suggest that the oxygen present at (0 0 1/2) sites in the case of LaBa2Cu2CoO7+delta is accessible to catalytic oxidation of CO through a Mars-Van Krevelen pathway. Catalytic conversion of CO to CO2 over LaBa2Cu2CoO7+delta occurs at 200 degrees C. The enhanced reactivity is explained in terms of changes brought about in the coordination polyhedra around transition metals, enhanced basal plane oxygen diffusivity, and redox potentials of the different transition metal cations.

Energetics of rare earth manganese perovskites A1-xA ' xMnO3 (A = La, Nd, Y and A ' = Sr, La) systems

High temperature reaction calorimetry using molten lead berate as solvent has been used to study the thermochemistry of NdMnO3, YMnO3, La1-xSrxMnO3 (with 0 < x < 0.5), and Ln(0.5)Ca(0.5)MnO(3) (with Ln = La, Nd, Y), The enthalpies of formation of these multicomponent oxides from their binary constituents have been calculated from the measured enthalpy of drop solution, The energetic stability of the perovskite depends on the size of the A cation, The enthalpy of formation of YMnO3 (smallest A cation) is more endothermic than those of NdMnO3 and LaMnO3. The energetics of the perovskite also depends on the oxidation state of the B site's ions. In the La1-xSrxMnO3 system, the energetic stability of the structure increases with the Mn4+/Mn3+ ratio, The new values of the enthalpies of oxidations, with reliable standard entropies, were used to plot the phase stability diagram of the lanthanum-manganese-oxygen system in the temperature range 300-1100 K, The LaMnO3/MnO phase boundary evaluated in this study agrees with the one published by Atsumi et nl. calculated from thermogravimetric and conductivity measurements.

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.

Role of predictors in downscaling surface temperature to river basin in India for IPCC SRES scenarios using support vector machine

In this paper, downscaling models are developed using a support vector machine (SVM) for obtaining projections of monthly mean maximum and minimum temperatures (T-max and T-min) to river-basin scale. The effectiveness of the model is demonstrated through application to downscale the predictands for the catchment of the Malaprabha reservoir in India, which is considered to be a climatically sensitive region. The probable predictor variables are extracted from (1) the National Centers for Environmental Prediction (NCEP) reanalysis dataset for the period 1978-2000, and (2) the simulations from the third-generation Canadian Coupled Global Climate Model (CGCM3) for emission scenarios A1B, A2, B1 and COMMIT for the period 1978-2100. The predictor variables are classified into three groups, namely A, B and C. Large-scale atmospheric variables Such as air temperature, zonal and meridional wind velocities at 925 nib which are often used for downscaling temperature are considered as predictors in Group A. Surface flux variables such as latent heat (LH), sensible heat, shortwave radiation and longwave radiation fluxes, which control temperature of the Earth's surface are tried as plausible predictors in Group B. Group C comprises of all the predictor variables in both the Groups A and B. The scatter plots and cross-correlations are used for verifying the reliability of the simulation of the predictor variables by the CGCM3 and to Study the predictor-predictand relationships. The impact of trend in predictor variables on downscaled temperature was studied. The predictor, air temperature at 925 mb showed an increasing trend, while the rest of the predictors showed no trend. The performance of the SVM models that are developed, one for each combination of predictor group, predictand, calibration period and location-based stratification (land, land and ocean) of climate variables, was evaluated. In general, the models which use predictor variables pertaining to land surface improved the performance of SVM models for downscaling T-max and T-min

Stability of pargasite during ultrahigh-temperature metamorphism:A consequence of titanium and REE partitioning

Orthopyroxene-clinopyroxene-plagioclase needles and symplectite along the cleavage planes and grain boundaries of fluorine-bearing titanian-ferroan pargasite from the Highland Complex, Sri Lanka, are interpreted as evidence for dehydration melting at ultrahigh-temperature conditions. High Ti (up to 0.4 pfu) and F (XF up to 0.56) content in pargasite extends its stability to higher temperatures, and the composition indicates the dehydration melting reaction may take place at ultrahigh-temperatures (~950 °C) at a pressure around 10 kbar, close to peak metamorphic conditions. The increase of Ti content close to the grain boundaries and cleavage planes in pargasite indicates titanium partitioning from the melt during dehydration melting enhanced the stability of the mineral toward ultrahigh-temperature conditions. The REE content in the pargasite shows a similar behavior to that of titanium. The cores with no breakdown assemblage consist of low and flat REE concentrations with respect to the high and Eu-depleted rim. Clinopyroxene in symplectite and needle-shaped lamellae within the pargasite porphyroblasts have similar REE patterns with slightly low-concentrations relative to that of pargasite. In the breakdown assemblage, LREEs are partitioned mainly into plagioclase while the HREEs are partitioned into orthopyroxene. The REE enrichment in the pargasite rims signals their relative partitioning between pargasite rims and melt. Modeling of the partitioning of Ti and REEs associated with pargasite breakdown demonstrates that its stability is greatly enhanced at UHT conditions. This investigation implies that the stability of hydrous minerals such as amphibole can be extended to UHT conditions, and expands our knowledge of metamorphism in the lower crust.

59Co NMR studies of the spin-state equilibria in rare-earth cobaltites

Hyperfine interaction parameters reveal differences in the nature of spin-state equilibria in the lighter and heavier rare-earth cobaltites; the crystal-field parameter is lower in the lighter cobaltites. Temperature variation of the quadrupolar coupling constant is also more marked in the lighter rare-earth cobaltites, with NdCoO3 showing evidence for a structural phase transition.

Counterclockwise exhumation of a hot orogen: The Paleoproterozoic ultrahigh-temperature granulites in the North China Craton

Regional metamorphic belts provide important constraints on the plate tectonic architecture of orogens. We report here a detailed petrologic examination of the sapphirine-bearing ultra-high temperature (UHT) granulites from the Jining Complex within the Khondalite Belt of the North China Craton (NCC). These granulites carry diagnostic UHT assemblages and their microstructures provide robust evidence to trace the prograde, peak and retrograde metamorphic evolution. The P–T conditions of the granulites estimated from XMgGrt(Mg/Fe + Mg) − XMgSpr isopleth calculations indicate temperature above 970 °C and pressures close to 7 kbar. We present phase diagrams based on thermodynamic computations to evaluate the mineral assemblages and microstructures and trace the metamorphic trajectory of the rocks. The evolution from Spl–Qtz–Ilm–Crd–Grt–Sil to Spr–Qtz–Crd–Opx–Ilm marks the prograde stage. The Spl–Qtz assemblage appears on the low-pressure side of the P–T space with Spr–Qtz stable at the high-pressure side, possibly representing an increase in pressure corresponding to compression. The spectacular development of sapphirine rims around spinel enclosed in quartz supports this inference. An evaluation of the key UHT assemblages based on model proportion calculation suggests a counterclockwise P–T path. With few exceptions, granulite-facies rocks developed along collisional metamorphic zones have generally been characterized by clockwise exhumation trajectories. Recent evaluation of the P–T paths of metamorphic rocks developed within collisional orogens indicates that in many cases the exhumation trajectories follow the model subduction geotherm, in accordance with a tectonic model in which the metamorphic rocks are subducted and exhumed along a plate boundary. The timing of UHT metamorphism in the NCC (c. 1.92 Ga) coincides with the assembly of the NCC within the Paleoproterozoic Columbia supercontinent, a process that would have involved subduction of passive margins sediments and closure of the intervening ocean. Thus, the counterclockwise P–T path obtained in this study correlates well with a tectonic model involving subduction and final collisional suturing, with the UHT granulites representing the core of the hot or ultra-hot orogen developed during Columbia amalgamation.

An investigation of structural, magnetic and dielectric properties of R2NiMnO6 (R = rare earth, Y)

We have investigated the structure, magnetic and dielectric properties of the double perovskite oxides, R2NiMnO6 (R = Pr, Nd, Sm, Gd, Tb, Dy, Ho and Y). We could refine powder X-ray diffraction patterns of all the phases on the basis of monoclinic (P2(1)/n) double perovskite structure where Ni and Mn atoms are ordered at 2c and 2d sites, respectively. All the phases are ferromagnetic insulators exhibiting relatively low dielectric loss and dielectric constants in the range 15-25. The ferromagnetic ordering temperature of the R2NiMnO6 series seems to correlate better with the radius of R3+ atoms than with the average Ni-O-Mn angle (phi) in the double perovskite structure. These results are consistent with all samples having Mn4+ and Ni2+ With minimal antisite disorder.

A Magnetic Susceptibility Study of Spin-state Transitions in Rare-earth TrioxocobaItates( III)

Rare-earth trioxocobaltates(lll), Ln[CoO,], with Ln = Pr, Nd, Tb, Dy. and Yb exhibit low-spin to high-spin transitions of cobalt characterised by a maximum in the Ax-l against temperature plots where Ax is the cobalt contribution to the magnetic susceptibility. The susceptibility behaviour is distinct from that of La[CoO,] which shows a plateau in the x-I-T curve accompanied by a structural transition. The temperature at which the AX- I-T curve shows a maximum increases with the decrease in the size of the rare-earth ion. The susceptibility behavior of solid solutions of La,,Nd,CoO, has been investigated to see how the behaviour characteristic of Nd[CoO,] changes to that of La[CoO,].

Gibbs energies of formation of rare earth oxysulfides

The standard Gibbs energy change accompanying the conversion of rare earth oxides to oxysulfides by reaction of rare earth oxides with diatomic sulfur gas has been measured in the temperature range 870 to 1300 K using the solid state cell: Pt/Cu+Cu2S/R2O2S+R2O3‖(CaO)ZrO2‖Ni+NiO, Pt where R=La, Nd, Sm, Gd, Tb, and Dy. The partial pressure of diatomic sulfur over a mixture of rare earth oxide (R2O3) and oxysulfide (R2O2S) is fixed by the dissociation of Cu2S to Cu in a closed system. The buffer mixture of Cu+Cu2S is physically separated from the rare earth oxide and oxysulfide to avoid complications arising from interaction between them. The corresponding equilibrium oxygen partial pressure is measured with an oxide solid electrolyte cell. Gibbs energy change for the conversion of oxide to the corresponding oxysulfide increases monotonically with atomic number of the rare earth element. Second law enthalpy of formation also shows a similar trend. Based on this empirical trend Gibbs energies of formation of oxysulfides of Pr, Eu, Ho, and Er are estimated as a function of temperature.

Magnetic superconductors: Model theories and experimental properties of rare-earth compounds

Superconducting and magnetically long-range ordered states were believed to be mutually exclusive phenomena. The discovery of rare-earth compounds in recent years, which exhibit both superconductivity and magnetic ordering (ferromagnetic, antiferromagnetic or sinusoidal), has led to considerable theoretical and experimental work on such systems. In the present article, we give a review of various theoretical models and important experimental results. In the theoretical sections, we start with the Abrikosov-Gorkov pair breaking theory for dilute alloys and discuss its improvement in the work of Müller-Hartmann and Zittartz. Then, in the context of magnetic superconductors, various microscopic theories that have been advanced are presented. These predict re-entrant behaviour in some systems (ferromagnetic superconductors) and coexistence regions in others (particularly antiferromagnetic superconductors). Following this, phenomenological generalized Ginzburg-Landau theories for two kinds of orders (superconducting and magnetic) are presented. A section dealing with renormalization group analysis of phase diagrams in magnetic superconductors is given. In experimental sections, the properties of each rare-earth compounds (ternary as well as some tetranery) are reviewed. These involve susceptibility, heat capacity, resistivity, upper critical field, neutron scattering and magnetic resonance measurements. The anomalous behaviour of the upper critical field of antiferromagnetic superconductors near the Néel temperature is discussed both in theory sections and experimental section for various systems.

Oxidation of alkaline earth sulfides to sulfates: Thermodynamic aspects

The emf of the galvanic cell, Pt, Ni + NiO/(CaO) ZrO2/MS + MSO4, Ir, Pt, where M is calcium, strontium, or barium, has been measured in the temperature range 850 to 1100 K. From these measurements the Gibbs’ energy changes for the oxidation of sulfides of alkaline earth metals to their respective sulfates have been calculated. The results are compared with available thermodynamic data in the literature. The agreement varies from ±2 kJ for the strontium system to ±20 kJ in the case of barium. Trends in the stabilities of alkaline earth sulfates are discussed in relation to the properties of the cationic species involved.

Itinerant electron ferromagnetism in Sr2+-, Ca2+-, and Ba2+-doped rare-earth orthocobaltites (Ln3+1�xM2+xCoO3)

Electronic and magnetic properties of Ln1�xSrxCoO3 (Ln = Pr, Nd, Sm, Eu, and Gd) systems show that above a critical value of x, the d electrons become itinerant while the materials become ferromagnetic at low temperatures. The ferromagnetic component increases with increase in x and decrease in temperature. The Curie temperature increases with x and decreases with decrease in the size of the rare-earth ion. Incorporation of Ba2+ in LaCoO3 favors itinerant electron ferromagnetism relative to Sr2+ while Ca2+ is less favorable than Sr2+.