Synthesis, structure and IR absorption studies of LnBaCuCoO(5) (Ln equal earth) oxides

A series of oxides LnBaCuCoO(5) (Ln = Pr, Nd, Sm, Dy, Gd, Ho and Er) have been synthesized by ceramic method. The oxides crystallize in a tetragonal structure, isostructural to YBaCuCoO5. All the oxides in the series are semiconducting. IR spectra of these oxides show distinct absorption bands at 630 cm(-1), 550 cm(-1) and 330 cm(-1) which are assigned to E, A(2) and A(1) modes respectively. Doping of holes in these oxides, by calcium substitution in Er1-xCaxBaCuCoO5-x (up to x similar or equal to 0.3) was done but, these oxides did not show metallic behaviour.

Synthesis and properties of rare earth doped lamp phosphors

Red, blue and green emitting lamp phosphors such as EU(3+) doped Y2O3 (red phosphor), EU(2+) doped Ba0.64Al12O18.64, BaMgAl10O17 and BaMg2Al16O27 (blue phosphors) and Ce0.67Tb0.33MgAl11O19 and Eu2+, Mn2+ doped BaMgAl10O17 (green phosphors) have been prepared by the combustion of the corresponding metal nitrates (oxidizer) and oxalyl dihydrazide/urea/carbohydrazide (fuel) mixtures at 400 degrees-500 degrees C within 5 min. The formation of these phosphors has been confirmed by their characteristic powder X-ray diffraction patterns and fluorescence spectra. The phosphors showed characteristic emission bands at 611 nm (red emission), 430-450 nm (blue emission) and 515-540 nm (green emission). The fine-particle nature of the combustion derived phosphors has been investigated using powder density, particle size and BET surface area measurements.

The nature of charge ordering in rare earth manganates and its strong dependence on the size of the A-site cations

Charge ordering in rare earth manganates of the type Ln(0.5)A(0.5)MnO(3) (Ln = rare earth, A = alkaline earth) is highly sensitive to the average radius of the A-site cations, [r(A)]. Tn the small [r(A)] regime (e.g., Y0.5Ca0.5MnO3), charge ordering occurs in the paramagnetic state, the transformation to an antiferromagnetic state occurring at still lower temperatures. At moderate [r(A)] values (e.g., Nd0.5Sr0.5MnO3), a ferromagnetic metallic state transforms to a charge-ordered antiferromagnetic state with cooling. These two distinct types of charge ordering and associated properties are explained in terms of the variation of the exchange couplings J(FM) and J(AFM) with [r(A)] and the invariance of the single-ion Jahn-Teller energy with [r(A)]. A qualitative temperature-[r(A)] phase diagram, consistent with the experimental observations, has been constructed to describe the properties of the manganates in the different [r(A)] regimes. (C) 1997 Academic Press.

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].

Studies on strontium substituted rare earth manganites

Sintering, electrical conductivity and thermal expansion behaviour of combustion synthesised strontium substituted rare earth manganites with the general formula Ln(1-x)Sr(x)MnO(3) (Ln = Pr, Nd and Sm; x = 0, 0.16 and 0.25) have been investigated as solid oxide fuel cell cathode materials. The combustion derived rare earth manganites have surface area in the range of 13-40 m(2)/g. Strontium substitution increases the electrical conductivity values in all the rare earth manganites. With the decreasing ionic radii of rare earth ions, the conductivity value decreases. Among the rare earth manganites studied, (Pr/Nd)(0.75)Sr0.25MnO3 show high electrical conductivity ( > 100 S/cm). The thermal expansion coefficients of Pr0.75Sr0.25MnO3 and Nd0.75Sr0.25MnO3 were found to be 10.2 x 10(-6) and 10.7 x 10(-6) K-1 respectively, which is very close to that of the electrolyte (YSZ) used in solid oxide fuel cells. (C) 1999 Elsevier Science B.V. All rights reserved.

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.

Removal of As(V) by adsorption onto mixed rare earth oxides

Arsenic pollution of water is a major problem faced worldwide. Arsenic is a suspected carcinogen in human beings and is harmful to other living beings. In the present study, a novel adsorbent was used to remove arsenate [As(V)] from synthetic solutions. The adsorbent, which is a mixture of rare earth oxides, was found to adsorb As(V) rapidly and effectively. The effect of various parameters such as contact time, initial concentration, pH, and adsorbent dose on adsorption efficiency was investigated. More than 90% of the adsorption occurred within the first 10 min and the kinetic rate constant was found to be about 3.5 mg min(-1). Adsorption efficiency was found to be dependent on the initial As(V) concentration, and the adsorption behavior followed the Langmuir adsorption model. The optimum pH was found to be 6.5. The presence of other ions such as nitrate, phosphate, sulphate, and silicate decreased the adsorption of As(V) by about 20-30%. The adsorbed As(V) could be desorbed easily by washing the adsorbent with pH 12 solution. This study demonstrates the applicability of naturally occurring rare earth oxides as selective adsorbents for As(V) from solutions.

Seismic passive earth pressure coefficients using the method of characteristics

The method of characteristics was used to generate passive earth pressure coefficients for an inclined wall retaining cohesionless backfill material in the presence of pseudostatic horizontal earthquake body forces. The variation of the passive earth pressure coefficients K-pq and K-pgamma with changes in horizontal earthquake acceleration coefficient due to the components of soil unit weight and surcharge pressure, respectively, has been obtained; a closed-form solution for K-pq is also provided. The passive earth resistance has been found to decrease sharply with an increase in the magnitude of horizontal earthquake acceleration. The computed passive earth pressure coefficients were found to be the lowest when compared to all of the previous solutions available in the literature.

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.

Role of clay content and moisture on characteristics of cement stabilised rammed earth

Rammed earth is an energy efficient and low carbon emission alternative for load bearing walls. This paper attempts to examine the influence of clay content and moisture content on the compressive strength of cement stabilised rammed earth (CSRE) through experimental investigations. Compressive strength of CSRE prisms was monitored both in dry and wet (saturated) conditions. Major conclusions of the study are:(a) Optimum clay content for maximum compressive strength is about 16%, (b) the strength of CSRE is sensitive to the moisture content at the time of testing, (c) Strength in saturated condition is less than half of the dry strength and (d) Water absorption (saturated water content) increases as the clay content of the soil mix increases and it is in the range of 12 to 16% for the CRSE prisms with 8% cement.

Magnetic order of the hexagonal rare-earth manganite Dy(0.5)Y(0.5)MnO(3)

Hexagonal Dy(0.5)Y(0.5)MnO(3), a multiferroic rare-earth manganite with geometrically frustrated antiferromagnetism, has been investigated with single-crystal neutron diffraction measurements. Below 3.4 K magnetic order is observed on both the Mn (antiferromagnetic) and Dy (ferrimagnetic) sublattices that is identical to that of undiluted hexagonal DyMnO(3) at low temperature. The Mn moments undergo a spin reorientation transition between 3.4 K and 10 K, with antiferromagnetic order of the Mn sublattice persisting up to 70 K; the antiferromagnetic order in this phase is distinct from that observed in undiluted (h) DyMnO(3), yielding a qualitatively new phase diagram not seen in other hexagonal rare-earth manganites. A magnetic field applied parallel to the crystallographic c axis will drive a transition from the antiferromagnetic phase into the low-temperature ferrimagnetic phase with little hysteresis.

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.