Nonlinear electrical conduction and broad band noise in the charge-ordered rare earth manganate Nd0.5Ca0.5MnO3

Measurements of the dc transport properties and the low-frequency conductivity noise in films of charge-ordered Nd0.5Ca0.5MnO3 grown on Si substrate reveal the existence of a threshold field in the charge-ordered regime beyond which strong nonlinear conduction sets in along with a large broad band conductivity noise. Threshold-dependent conduction disappears as T --> T-CO, the charge-ordering temperature. This observation suggests that the charge-ordered state gets depinned at the onset of the nonlinear conduction. (C) 1999 American Institute of Physics. [S0003-6951(99)05247-X].

Grain size effects on charge-ordering, phase segregation and related properties of rare-earth manganates, Nd(0.5)A(0.5)MnO(3) (A = Ca or Sr)

Grain size has marked effects on charge-ordering and other properties of Nd(0.5)A(0.5)MnO(3) (A=Ca or Sr). Thus, the anti-ferromagnetic (AFM) transition in Nd0.5Ca0.5MnO3 is observed distinctly only in samples sintered at 1273 K or higher. The sample with a small grain size (sintered at 1173 K) shows evidence for greater ferromagnetic (FM) interaction at low temperatures, probably due to phase segregation. The FM transition as well as the charge-ordering transition in Nd0.5Sr0.5MnO3 becomes sharper in samples sintered at 1273 K or higher. The sample sintered at 1173 K does not show the AFM-CO transition around 150 K and is FM down to low temperatures; the apparent T-c-T-co gap decreases with the increase in the grain size. The samples sintered at lower temperatures (<1673 K) show evidence for greater segregation of the AFM and FM domains. (C) 2002 Elsevier Science Ltd. All rights reserved.

An infrared spectroscopic study of the low-spin to intermediate-spin state (1A1–3T1) transition in rare earth cobaltates, LnCoO3 (Ln=La, Pr and Nd)

Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO3 (Ln=La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoO3 and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition.

An infrared spectroscopic study of the low-spin to intermediate-spin state ((1)A(1)-T-3(1)) transition in rare earth cobaltates, LnCoO(3) (Ln = La, Pr and Nd)

Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO(3) (Ln = La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoo(3) and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition. (C) 2001 Published by Elsevier Science B.V.

Complexes of rare-earth perchlorates with ditbutyl amides of di, tri and tetraglycolic acids

New complexes of lanthanide perchlorates with di-t-butyl amides of di, tri and tetraglycolic acids have been synthesised. The complexes have the general formula Ln(DiGA)3(ClO4)3; Ln(TriGA)2 (ClO4)3 and Ln(TetGA)2 (C1O4)3, where Ln = La-Yb and Y and DiGA = N,N′, di-t-butyl diglycolamide, TriGA N,N′, di-t-butyl triglycolamide and TetGA = N,N′ di-t-butyl tetraglycolamide, respectively. The complexes have been characterized by analysis, electrolytic conductance, infrared,1H and13C nuclear magnetic resonance and electronic spectral data.Infrared spectra indicate the coordination of all the available ether oxygens and the amide carbonyls in each of the ligands, to the metal ions. IR and conductance data show that the perchlorate groups in all the complexes are ionic.1H and13C NMR data support the IR data regarding the mode of coordination of ligands to the metal ions. Electronic spectral shapes have been interpreted in terms of nine, eight and ten coordination in DiGA, TriGA and TetGA complexes respectively.

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.

Raman spectroscopic investigation of pure and ytterbium-doped rare earth silicate crystals

Raman spectroscopy was used to study the molecular structure of a series of selected rare earth (RE) silicate crystals including Y2SiO5 (YSO), LU2SiO5 (LSO), (Lu0.5Y0.5)(2)SiO5 (LYSO) and their ytterbium-doped samples. Raman spectra show resolved bands below 500 cm(-1) region assigned to the modes of SiO4 and oxygen vibrations. Multiple bands indicate the nonequivalence of the RE-O bonds and the lifting of the degeneracy of the RE ion vibration. Low intensity bands below 500 cm(-1) are an indication of impurities. The (SiO4)(4-) tetrahedra are characterized by bands near 200 cm(-1) which show a separation of the components of nu(4) and nu(2), in the 500-700 cm(-1) region which are attributed to the distorting bending vibration and in the 880-1000 cm(-1) region which are attributed to the symmetric and antisymmetric stretching vibrational modes. The majority of the bands in the 300-610 cm(-1) region of Re2SiO5 were found to arise from vibrations involving both Si and RE ions, indicating that there is considerable mixing of Si displacements with Si-O bending modes and RE-0 stretching modes. The Raman spectra of RE silicate crystals were analyzed in terms of the molecular structure of the crystals, which enabled separation of the bands attributed to distinct vibrational units. Copyright (C) 2007 John Wiley & Sons, Ltd.

Kinetic studies on the effects of rare earth elements (REES) on the growth of Microcystis and their accumulation by Microcystis

In the paper the kinetic effects of La3+ and Ce4+ on the growth of Microcystis and the accumulation kinetics of Microcystis in the single and combined systems of La3+ and Ce4+ were studied. The mechanism of the effects of La3+ and Ce4+ on the growth of Microcystis and their accumulation kinetics were also discussed. In the single system, La3+ stimulated the growth of Microcystis at initial concentrations below 2 mg / 1, but inhibited it above 2 mg / 1. Ce4+ accelerated the growth of Microcystis at initial concentrations below 0.2 mg / 1 and inhibited at above 0.2 mg /l. Furthermore, the stimulation weakened with the increase of initial concentrations of La3+ and Ce4+. In the combined system, the growth of Microcystis was accelerated in the over all cases. In the single system, the amount of La3+ and Ce4+ uptake was more at higher initial concentrations than at lower ones. At the same initial concentrations, La3+ and Ce4+ uptake in the combined system was less than that in the single system. The kinetic process of La3+ and Ce4+ adsorpted by Microcystis can be explained with the second order kinetics adsorption model.