Influence of Geometrical Factors on the Physico-Chemical Properties of Perovskite and Layered Perovskite Oxides

A brief qualitative comparison is made of perovskite ABO sub 3 and layered perovskite ABO sub 3 and layered perovskite A sub 2 BO sub 4 oxides with special emphasis on the influence of geometrical factors on certain physico-chemical properties. The layered perovskite oxides are distinguished from three-dimensional oxides by a looser packing, frustration in three-dimensional interactions, more internal pressure on B--O bonds for small tolerance factors, and by different values of site-percolation thresholds. Their influence on electronic configurations of metal ions, stabilities and syntheses of compounds is discussed. The influence of increased anisotropy in layered oxides on localisation of charge carriers and in suppressing the onset of long-range ferromagnetic ordering is also discussed.

Synthesis, crystal structures and magnetic behavior of two 3D coordination polymers using N-(4/3-arboxyphenyl)iminodiacetic acids as bridging ligands

Research on structure and magnetic properties of polynuclear metal complexes to understand the structural and chemical factors governing the electronic exchange coupling mediated by multi-atom bridging ligands is of growing interest. Hydrothermal treatment of Ni(NO3)(2)center dot 6H(2)O with N-(4-carboxyphenyl)iminodiacetic acid N-4(H(3)CPIDA)] at 150 degrees C yielded a 3D coordination polymer of general formula Ni-3{N-4( CPIDA)}(2)(H2O)(3)]center dot 6H(2)O (1). An analogous network of general formula Co-3{N-3(CPIDA)}(2)(H2O)(3)]center dot 3H(2)O (2) was synthesized using N-(3-carboxyphenyl) iminodiacetic acid N-3(H(3)CPIDA)] in combination with Co(NO3)(2)center dot 6H(2)O under identical reaction condition. Both the complexes contain trinuclear secondary building unit, and crystallized in monoclinic system with space groups C2/c (1) and P2(1)/c (2), respectively. Variable temperature magnetic characterization of these complexes in the temperature range of 2-300 K indicated the presence of overall ferromagnetic and antiferromagnetic behavior for 1 and 2, respectively. Density functional theory calculations (B3LYP functional) were performed for further insight on the trinuclear units to provide a qualitative theoretical interpretation on the overall magnetic behavior of the complexes 1 and 2. (C) 2010 Elsevier B.V. All rights reserved.

Conformations of synthetic alamethicin fragments. Evidence for 310 helical folding from 270-MHz hydrogen-1 nuclear magnetic resonance and circular dichroism studies

IH NMR studies at 270 MHz on the synthetic alamethicin fragments Z-Aib-Pro-Aib-Ala-Aib-Ala-OMe (1-6), Boc-Gln-Aib-Val-Aib-Gly-Leu-Aib-OMe (7-1 3), Boc-Leu-Aib-Pro-Val-Aib-OMe (1 2-16), and Boc-Gly-Leu- Aib-Pro-Val-Aib-OMe (1 1-16) have been carried out in CDC13 and (CD3)2S0. The intramolecularly hydrogen bonded amide hydrogens in these peptides have been delineated by using solvent titration experiments and temperature coefficientsof NH chemical shifts in (CD3)+30. All the peptides adopt highly folded structures, characterized by intramolecular 4 - 1 hydrogen bonds. The 1-6 fragment adopts a 310 helical conformation with four hydrogen bonds, in agreement with earlier studies (Rao, Ch. P., Nagaraj, R., Rao, C. N. R., & Balaram, P. (1980) Biochemistry 19, 425-4311. The 7-13

Magnetic fabrics indicating Late Quaternary seismicity in the Himalayan foothills

The anisotropy of magnetic susceptibility (AMS) study was performed on soft sediment samples from a trenched fault zone across the Himalayan frontal thrust (HFT), western Himalaya. AMS orientation of K-min axes in the trench sediments is consistent with lateral shortening revealed by geometry of deformed regional structures and recent earthquakes. Well-defined vertical magnetic foliation parallel to the flexure cleavage in which a vertical magnetic lineation is developed, high anisotropy, and triaxial ellipsoids suggest large overprinting of earth-quake- related fabrics. The AMS data suggest a gradual variation from layer parallel shortening (LPS) at a distance from the fault trace to a simple shear fabric close to the fault trace. An abrupt change in the shortening direction (K-min) from NE-SW to E-W suggests a juxtaposition of pre-existing layer parallel shortening fabric, and bending-related flexure associated with an earthquake. Hence the orientation pattern of magnetic susceptibility axes helps in identifying co-seismic structures in Late Holocene surface sediments.

Use of 2-pyrimidineamidoxime to generate polynuclear homo-/heterometallic assemblies: synthesis, crystal structures and magnetic study with theoretical investigations on the exchange mechanism

Three new transition metal complexes using 2-pyrimidineamidoxime (pmadH(2)) as multidentate chelating and/or bridging ligand have been synthesized and characterized. The ligand pmadH(2) has two potential bridging functional groups mu-O and mu-(N-O)] and consequently shows several coordination modes. While a polymeric 1D Cu-II complex Cu(pmadH(2))(2)(NO3)](NO3) (1) was obtained upon treatment of Cu(NO3)(2)center dot 3H(2)O with pmadH(2) at room temperature in the absence of base, a high temperature reaction in the presence of base yielded a tetranuclear Cu-II-complex Cu-4(pmad)(2)(pmadH)(2)(NO3)](NO3)(H2O) (2). One of the Cu-II centers is in a square pyramidal environment while the other three are in a square planar geometry. Reaction of the same ligand with an equimolar mixture of both Cu(NO3)(2)center dot 3H(2)O and NiCl2 center dot 6H(2)O yielded a tetranuclear heterometallic (Cu2Ni2II)-Ni-II complex Cu2Ni2(pmad)(2)(pmadH)(2)Cl-2]center dot H2O (3) containing both square planar (Ni-II) and square pyramidal (Cu-II) metal centers. Complexes 1-3 represent the first examples of polynuclear metal complexes of 2-pyrimidineamidoxime. The analysis of variable temperature magnetic susceptibility data of 2 reveals that both ferromagnetic and antiferromagnetic interactions exist in this complex (J(1) = +10.7 cm(-1) and J(2) = -2.7 cm(-1) with g = 2.1) leading to a resultant ferromagnetic behavior. Complex 3 shows expected antiferromagnetic interaction between two Cu-II centers through -N-O- bridging pathway with J(1) = -3.4 cm(-1) and g = 2.08. DFT calculations have been used to corroborate the magnetic results.

Electric and magnetic polarizabilities of hexagonal Ln(2)CuTiO(6)(Ln = Y, Dy, Ho, Er, and Yb)

We investigated the rare-earth transition-metal oxide series, Ln(2)CuTiO(6) (Ln = Y, Dy, Ho, Er, and Yb), crystallizing in the hexagonal structure with noncentrosymmetric P6(3)cm space group for possible occurrences of multiferroic properties. Our results show that while these compounds, except Ln = Y, exhibit a low-temperature antiferromagnetic transition due to the ordering of the rare-earth moments, the expected ferroelectric transition is frustrated by the large size difference between Cu and Ti at the B site. Interestingly, this leads these compounds to attain a rare and unique combination of desirable paraelectric properties with high dielectric constants, low losses, and weak temperature and frequency dependencies. First-principles calculations establish these exceptional properties result from a combination of two effects. A significant difference in the MO5 polyhedral sizes for M = Cu and M = Ti suppress the expected cooperative tilt pattern of these polyhedra, required for the ferroelectric transition, leading to relatively large values of the dielectric constant for every compound investigated in this series. Additionally, it is shown that the majority contribution to the dielectric constant arises from intermediate-frequency polar vibrational modes, making it relatively stable against any temperature variation. Changes in the temperature stability of the dielectric constant among different members of this series are shown to arise from changes in relative contributions from soft polar modes.

Correlations between frequency of infra-red active vibrational modes and copper-oxygen distance in copper oxides. Application to superconductors

The infra-red spectra of a large number of ternary Cu(II) oxides with at least a quasi square-planar coordination of oxygen around the copper ions have been studied. The frequency of the bands with the highest frequency,v max, is found to correlate extremely well with the shortest Cu–O distance.v max increases at an impressive rate of sim20 cm–1 per 0.01 Å when the Cu–O distance becomes less than 1.97 Å, which is the Cu2+–O2– distance in square-planar CuO4 complexes as obtained from empirical ionic radii considerations. The marked sensitivity may be used as a ldquotitrationrdquo procedure not only to assign bands but also to obtain diagnostic information about local coordination in compounds derived, for example, from the YBa2Cu3O7–d structure such as LaCaBaCu3O7–d . The only example where this correlation fails is in the two-layer non-superconducting oxides derived from La2(Ca, Sr)Cu2O6. The significance of this result is discussed. The marked dependence of frequency on the bond-distance is qualitatively examined in terms of an increased electron-phonon coupling to account for the observed tendency of the superconducting transition temperature to go through a maximum as the average basal plane Cu–O distance is decreased.

Direct current electrical resistivity of zinc borate glasses containing transition metal oxides

The resistivities of zinc borate glasses containing Fe2O3, V2O5, and Fe2O3 + V2O5 have been measured as a function of composition and temperature. The values of resistivity and activation energy decrease as the transition metal oxide content is increased. The conductivities of the glasses containing Fe2O3 + V2O5 are more than the sum of those of the glasses containing only Fe2O3 or V2O5 (i.e. the activation energies are less than the sum of those in the glasses containing only Fe2O3 or V2O5). The results are discussed in terms of existing theories.

Flow And Heat-Transfer Over An Upstream Moving Wall With A Magnetic-Field And A Parallel Free Stream

The flow and heat transfer over an upstream moving non-isothermal wall with a parallel free stream have been considered. The magnetic field has been applied in the free stream parallel to the wall and the effect of induced magnetic field has been included in the analysis. The boundary layer equations governing the steady incompressible electrically conducting fluid flow have been solved numerically using a shooting method. This problem is interesting because a solution exists only when the ratio of the wall velocity does not exceed a certain critical value and this critical value depends on the magnetic field and magnetic Prandtl number. Also dual solutions exist for a certain range of wall velocity.

Laser-fused refractory oxides for optical coatings

Laser sintering was carried out using a high power continuous-wave CO2 laser to prepare pellets of zirconia (ZrO2), hafnia (HfO2) and yttria (Y2O3) mixed oxides as starting materials in the deposition of optical coatings. Hardened recrystallized pellets appeared to have been formed during laser treatment. X-ray diffraction analysis revealed a monoclinic-to-tetragonal phase transformation in the binary system while the ternary system was found to have a mixture of two crystalline phases. Cross-sectional scanning electron microscopy showed two isothermal crystalline regions in the ternary system. The optical inhomogeneity was low in the films deposited from the laser-fused pellets, but the absorption at a wavelength of 351 nm increased with increasing HfO2 content. The films deposited from laser-fused pellets were analysed by electron spectroscopy for chemical analysis and found to be stoichiometric and homogeneous.

Nucleation and growth of Al2O3/metal composites by oxidation of aluminum alloys

The nucleation and growth mechanisms during high temperature oxidation of liquid Al-3% Mg and Al-3% Mg-3% Si alloys were studied with the aim of enhancing our understanding of a new composite fabrication process. The typical oxidation sequence consists of an initial event of rapid but brief oxidation, followed by an incubation period of limited oxide growth after which bulk Al2O3/Al composite forms. A duplex oxide layer, MgO (upper) and MgAl2O4 (lower), forms on the alloy surface during initial oxidation and incubation. The spinel layer remains next to the liquid alloy during bulk oxide growth and is the eventual repository for most of the magnesium in the original alloy. Metal microchannels developed during incubation continuously supply alloy through the composite to the reaction interface. During the growth process, a layered structure exists at the upper extremity of the composite, consisting of MgO at the top surface, MgAl2O4 (probably discontinuous), Al alloy, and finally the bulk Al2O3 composite containing microchannels of the alloy. The bulk oxide growth mechanism appears to involve continuous formation and dissolution of the Mg-rich oxides at the surface, diffusion of oxygen through the underlying liquid metal, and epitaxial growth of Al2O3 on the existing composite body. The roles of Mg and Si in the composite growth process are discussed.