Synthesis, structure and electrochemical properties of complexes with a (μ-oxo)bis-(μ-carboxylato)diruthenium(III) core

Reaction of [Ru2O(O2CR)2(MeCN)4(PPh3)2](ClO4)2 (1) with 1,2-diaminoethane (em) in MeOH---H2O yielded a mixture of products, from which a purple diamagnetic and 1:2 electrolytic diruthenium(III) complex, [Ru2O(O2CR)2(en)2(PPh3)2](ClO4)2 (2), was isolated along with a trace by-product of [Ru2O(O2CR)2(en)2(PPh3)2](ClO4)(MeCONH) (3) (R = C6H4-p-X : X = H, a; OMe, b; Me, c). Complex 3b has been characterized by X-ray diffraction analysis. The structure shows the presence of a (Ru2(?-O)(?-O2CR)22+)_core, with the metal centre bonded to an unidentate PPh3 and a bidentate chelating en terminal ligand. The Ru�Ru distance and the Ru�O�Ru angle in the core are 3.255(3) Å and 119.1(4)°. The amidate anion, formed presumably by nucleophilic attack of OH? on the MeCN ligand in complex 1, remains uncoordinated to the metal. In MeCN/0.1 M [NBun4]ClO4 complex 2 exhibits a nearly reversible Ru2III,III?Ru2III,IV couple near 0.9 V and an irreversible Ru2III,III?Ru2III,II process at ?0.6 V (vs S.C.E.). The mechanistic aspects of the substitution and nucleophilic reactions in the formation of complexes 2 and 3 are discussed. References

Synthesis, structure and redox properties of (?-oxo)bis(?-carboxylato)diruthenium(III) complexes containing three different terminal ligands

Blue coloured, unstable, essentially diamagnetic and non-electrolytic diruthenium(III) complexes of the formation [Ru2O(O2CR)4(en)2(PPh3)2] were prepared by reacting [Ru2O(O2CR)4(PPh3)2] with 1,2-diaminoethane (en) in CH2Cl2 (R = C6H4-p-X; X = H, Me and OMe). The molecular structure of the complexes is proposed as [{(?1-O2CR)(?1-en)(PPH3)Ru}2(?-O)(?-O2CR)2] based on the 1H NMR spectral data. The electronic spectra of the complexes display a band near 569 nm with a shoulder at 630 nm. In CH2Cl2-0.1 M [Bun4N]ClO4, the complexes exhibit redox couples Ru2III,III/Ru2III,IV and Ru2III,IV/Ru2IV,IV near 0.1 and 1.2 V (vs SCE), respectively. The potentials are the lowest among diruthenium(III) complexes with a similar core structure.

Structural, dielectric and ferroelectric properties of multilayer lithium tantalate thin films prepared by sol-gel technique

Multilayer lithium tantalate thin films were deposited on Pt-Si Si(111)/SiO2/TiO2/Pt(111)]substrates by sol-gel process. The films were annealed at different annealing temperatures (300, 450 and 650 degrees C) for 15 min. The films are polycrystalline at 650 degrees C and at other annealing conditions below 650 degrees C the films are in amorphous state. The films were characterized using X-ray diffraction, atomic force microscopy (AFM) and Raman spectroscopy. The AFM of images show the formation of nanograins of uniform size (50 nm) at 650 degrees C. These polycrystalline films exhibit spontaneous polarization of 1.5 mu C/cm(2) at an application of 100 kV/cm. The dielectric constant of multilayer film is very small (6.4 at 10 kHz) as compared to that of single crystal. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis and photocatalytic properties of AgLi1/3Ru2/3]O-2: A new delafossite oxide

A new delafossite oxide, AgLi1/3Ru2/3]O-2, synthesized by ion-exchanging interlayer-Li+ with Ag+ in layered Li2RuO3, is reported. The transformation of layered Li2RuO3 (monoclinic, space group C2/c) to AgLi1/3Ru2/3]O-2 possessing a delafossite structure (space group R (3) over barm) has been established with powder X-ray diffraction. The successful conversion of LiLi1/3Ru2/3]O-2 to AgLi1/3Ru2/3]O-2 is further confirmed by EDAX analysis. The diffuse reflectance spectrum of AgLi1/3Ru2/3]O-2 shows broad absorption in the UV-visible region suggesting its use as a photocatalyst. The photocatalytic activity of AgLi1/3Ru2/3]O-2 has been investigated by degrading various dyes. It showed significant photocatalytic activity for dye degradation both under UV and solar radiation. (C) 2010 Elsevier B.V. All rights reserved.

Quantum Properties in Transport Through Nanoscopic Rings:Charge-Spin Separation and Interference Effects

Many of the most intriguing quantum effects are observed or could be measured in transport experiments through nanoscopic systems such as quantum dots, wires and rings formed by large molecules or arrays of quantum dots. In particular, the separation of charge and spin degrees of freedom and interference effects have important consequences in the conductivity through these systems. Charge-spin separation was predicted theoretically in one-dimensional strongly inter-acting systems (Luttinger liquids) and, although observed indirectly in several materials formed by chains of correlated electrons, it still lacks direct observation. We present results on transport properties through Aharonov-Bohmrings (pierced by a magnetic flux) with one or more channels represented by paradigmatic strongly-correlated models. For a wide range of parameters we observe characteristic dips in the conductance as a function of magnetic flux which are a signature of spin and charge separation. Interference effects could also be controlled in certain molecules and interesting properties could be observed. We analyze transport properties of conjugated molecules, benzene in particular, and find that the conductance depends on the lead configuration. In molecules with translational symmetry, the conductance can be controlled by breaking or restoring this symmetry, e.g. by the application of a local external potential. These results open the possibility of observing these peculiar physical properties in anisotropic ladder systems and in real nanoscopic and molecular devices.

Influence of Substrate Temperature and Deposition Rate on Structural and Mechanical Properties of Shape Memory NiTi Films

NiTi thin films deposited by DC magnetron sputtering of an alloy (Ni/Ti:45/55) target at different deposition rates and substrate temperatures were analyzed for their structure and mechanical properties. The crystalline structure, phase-transformation and mechanical response were characterized by X-ray diffraction (XRD), Differential Scanning Calorimetry (DSC) and Nano-indentation techniques, respectively. The films were deposited on silicon substrates maintained at temperatures in the range 300 to 500 degrees C and post-annealed at 600 degrees C for four hours to ensure film crystallinity. Films deposited at 300 degrees C and annealed for 600 degrees C have exhibited crystalline behavior with Austenite phase as the prominent phase. Deposition onto substrates held at higher deposition temperatures (400 and 500 degrees C) resulted in the co-existence of Austenite phase along with Martensite phase. The increase in deposition rates corresponding to increase in cathode current from 250 to 350 mA has also resulted in the appearance of Martensite phase as well as improvement in crystallinity. XRD analysis revealed that the crystalline film structure is strongly influenced by process parameters such as substrate temperature and deposition rate. DSC results indicate that the film deposited at 300 degrees C had its crystallization temperature at 445 degrees C in the first thermal cycle, which is further confirmed by stress temperature response. In the second thermal cycle the Austenite and Martensite transitions were observed at 75 and 60 degrees C respectively. However, the films deposited at 500 degrees C had the Austenite and Martensite transitions at 73 and 58 degrees C, respectively. Elastic modulus and hardness values increased from 93 to 145 GPa and 7.2 to 12.6 GPa, respectively, with increase in deposition rates. These results are explained on the basis of change in film composition and crystallization. (C) 2010 Published by Elsevier Ltd

Tropical Clays .1. Index Properties And Microstructural Aspects

Soils showing changes in plasticity characteristics upon driving form an important group in tropical soils. These changes are attributed to the grouping of particles into aggregates either due to mineralogy or presence of cementing agents and/or pore fluid characteristics. These changes are found to be permanent. In this paper, the effect of these changes leading to changes in index properties is discussed. The coefficient of permeability has been found to be comparable at liquid limit water content for different soils of varying liquid limit values. Permeability is an indirect reflection of microstructure and indicates the flow rate, which depends upon pore geometry. Other mechanical properties like compressibility and shear strength also depend upon pore geometry. These microstructural aspects of liquid limit as a reference state for the analysis of engineering behavior of tropical soils are examined in detail.

Synthesis, characterization and photoluminescence properties of CaSiO3: Eu3+ red phosphor

CaSiO3:Eu3+ (1-5 mol%) red emitting phosphors have been synthesized by a low-temperature solution combustion method. The phosphors have been well characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and optical spectroscopy. PXRD patterns reveal monoclinic CaSiO3 phase can be obtained at 900 degrees C. The SEM micrographs show the crystallites with irregular shape, mostly angular. Upon 254 nm excitation, the phosphor show characteristic fluorescence D-5(0) -> F-7(J) (J = 0, 1, 2, 3, 4) of the Eu3+ ions. The electronic transition located at 614 nm corresponding to D-5(0) -> F-7(2) of Eu3+ ions, which is stronger than the magnetic dipole transition located at 593 nm corresponding to D-5(0) -> F-7(1) of Eu3+ ions. Different pathways involved in emission process have been studied. Concentration quenching has been observed for Eu3+ concentration >4 mol%. UV-visible absorption shows an intense band at 240 nm in undoped and 270 nm in Eu3+ doped CaSiO3 which is attributed to oxygen to silicon (O-Si) ligand-to-metal charge-transfer (LMCT) band in the SiO32- group. The optical energy band gap is widened with increase of Eu3+ ion dopant. (C) 2010 Elsevier B.V. All rights reserved.

Spectroscopic and electrical properties of SiO2 films prepared by simple and cost effective sol-gel process

Amorphous SiO2 thin films were prepared on glass and silicon substrates by cost effective sol-gel method. Tetra ethyl ortho silicate (TEOS) was used as the precursor material, ethanol as solvent and concentrated HCl as a catalyst. The films were characterized at different annealing temperatures. The optical transmittance was slightly increased with increase of annealing temperature. The refractive index was found to be 1.484 at 550 nm. The formation of SiO2 film was analyzed from FT-IR spectra. The MOS capacitors were designed using silicon (1 0 0) substrates. The current-voltage (I-V), capacitance-voltage (C-V) and dissipation-voltage (D-V) measurements were taken for all the annealed films deposited on Si (1 0 0). The variation of current density, resistivity and dielectric constant of SiO2 films with different annealing temperatures was investigated and discussed for its usage in applications like MOS capacitor. The results revealed the decrease of dielectric constant and increase of resistivity of SiO2 films with increasing annealing temperature. (C) 2010 Elsevier B.V. All rights reserved.

(Ba3MTiMO9)-Ti-III-O-V (M-III = Fe, Ga, Y, Lu, M-V = Nb, Ta, Sb) perovskite oxides Synthesis, structure and dielectric properties

We describe the synthesis structures and dielectric properties of new perovskite oxides of the formula (Ba3MTiMO9)-Ti-III-O-V for M-III = Fe Ga Y Lu and M-V = Nb Ta Sb While M-V = Nb and Ta oxides adopt disordered/partially ordered 3C perovskite structures where M-III/Ti/M-V metal-oxygen octahedra are corner connected the M-V = Sb oxides show a distinct preference for the 6H structure where Sb-V/Ti-IV metal-oxygen octahedra share a common face forming (Sb Ti)O-9 dimers that are corner-connected to the (MO6)-O-III octahedra The preference of antimony oxides (Sb-V 4d(10)) for the 6H structure which arises from a special Sb-V-O chemical bonding that tends to avoid linear Sb-O-Sb linkages unlike Nb-V/Ta-V d(0) atoms which prefer similar to 180 degrees Nb/Ta-O-Nb/Ta linkages - is consistent with the crystal chemistry of M-V-O oxides in general The dielectric properties reveal a significant difference among Mill members All the oxides with the 3C structure excepting those with Mill = Fe show a normal low loss dielectric behaviour with epsilon = 20-60 in the temperature range 50-400 degrees C the M-III = Fe members with this structure (M-V = Nb Ta) display a relaxor-like ferroelectric behaviour with large E values at frequencies <= 1 MHz (50-500 degrees C) (C) 2010 Elsevier Masson SAS All rights reserved

Improved mechanical properties of polymer nanocomposites incorporating graphene-like BN: Dependence on the number of BN layers

The mechanical properties of composites of polymethylmethacrylate (PMMA) with two-dimensional graphene-like boron nitride (BN) have been investigated to explore the dependence of the properties on the number of BN layers. This study demonstrates that significantly improved mechanical properties are exhibited by the composite with the fewest number of BN layers. Thus, with incorporation of three BN layers, the hardness and elastic modulus of the composite showed an increase of 125% and 130%, respectively, relative to pure PMMA. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A study of the synthetic methods and properties of graphenes

Graphenes with varying number of layers can be synthesized by using different strategies. Thus, single-layer graphene is prepared by micromechanical cleavage, reduction of single-layer graphene oxide, chemical vapor deposition and other methods. Few-layer graphenes are synthesized by conversion of nanodiamond, arc discharge of graphite and other methods. In this article, we briefly overview the various synthetic methods and the surface, magnetic and electrical properties of the produced graphenes. Few-layer graphenes exhibit ferromagnetic features along with antiferromagnetic properties, independent of the method of preparation. Aside from the data on electrical conductivity of graphenes and graphene-polymer composites, we also present the field-effect transistor characteristics of graphenes. Only single-layer reduced graphene oxide exhibits ambipolar properties. The interaction of electron donor and acceptor molecules with few-layer graphene samples is examined in detail.

Optical properties change in amorphous (As2S3)(0.87)Sb-0.13 thin films by photo and thermal induced process

Exposure with above band gap light and thermal annealing at a temperature near to glass transition temperature, of thermally evaporated amorphous (As2S3)(0.87)Sb-0.13 thin films of 1 mu m thickness, were found to be accompanied by structural effects, which in turn, lead to changes in the optical properties. The optical properties of thin films induced by illumination and annealing were studied by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. Photo darkening or photo bleaching was observed in the film depending upon the conditions of the light exposure or annealing. These changes of the optical properties are assigned to the change of homopolar bond densities. (C) 2010 Elsevier B.V. All rights reserved.

Cement stabilised rammed earth. Part A: compaction characteristics and physical properties of compacted cement stabilised soils

Rammed earth is used for load bearing walls of buildings and there is growing interest in this low carbon building material. This paper is focused on understanding the compaction characteristics and physical properties of compacted cement stabilised soil mixtures and cement stabilised rammed earth (CSRE). This experimental study addresses (a) influence of soil composition, cement content, time lag on compaction characteristics of stabilised soils and CSRE and (b) effect of moulding water content and density on compressive strength and water absorption of compacted cement stabilised soil mixes. Salient conclusions of the study are (a) compaction characteristics of soils are not affected by the addition of cement, (b) there is 50% fall in strength of CSRE for 10 h time lag, (c) compressive strength of compacted cement stabilised soil increases with increase in density irrespective of moulding moisture content and cement content, and (d) compressive strength increases with the increase in moulding water content and compaction of CSRE on the wet side of OMC is beneficial in terms of strength.

Solvent effect on the spectroscopic properties of 6MAMC and 7MAMC

The absorption and emission spectra of two dyes namely 6MAMC and 7MAMC have been recorded at room temperature in solvents of different polarities. The ground-state dipole moments (mu(g)) of these two were determined experimentally by Guggenheim method and were compared with theoretical values obtained using quantum chemical method. The exited state (mu(e))dipole moments were estimated from Lippert's, Bakhshiev's and Chamma-Viallet's equations by using the variation of the Stokes shift with the solvent dielectric constant and refractive index. The ground and excited-state dipole moments were calculated by means of the solvatochromic shift method and also the excited-state dipole moments are determined in combination with ground-state dipole moments. It was observed that dipole moments of excited state were higher than those of the ground state, indicating a substantial redistribution of the pi-electron densities in a more polar excited state for these two dyes. (C) 2010 Elsevier B.V. All rights reserved.