Di- and tri-metallic complexes containing two bridging cyclodiphosphazane ligands: the crystal structure of [MO2(CO)8{µ-cis-[PhNP(OC6H4Me-p)]2}2]

The reactions of the mononuclear cyclodiphosphazane complexes, cis-[Mo(CO)(4){cis-[PhNP(OR)](2)}(2)] with [Mo(CO)(4)(nbd)] (nbd = norbornadiene). [Mo(CO)(4)(NHC5H10)(2)] or [MCl(2)(cod)] (cod = cycloocta-1,5-diene) afforded the homobimetallic complexes; [Mo-2(CO)(8){mu-cis-[PhNP(OR)](2)}(2)] (R = C(5)H(4)Me-p 5 or CH2CF3 6) or the heterobimetallic complexes. [Mo-2(CO)(8){mu-cis-[PhNP(OE)](2)}(2)MCl(2)] (R = C(6)H(4)Me-p; M = Pd 7 or Pt 8). In all the above complexes, the two metal moieties are bridged by two cyclodiphosphazane ligands. The reactions of the mononuclear complexes, cis-[M(CO)(4)(A){cis-[PhNP(OC(6)H(4)Me-p)](2)}] with (M'Cl-2(cod)] afforded the trinuclear complexes, cis-[M'Cl-2[M(CO)(4)(A){cis-[PhNP(OC(6)H(4)Me-p)](2)}](2)] (M' = Pd, M = Mo, A = P(OMe)(3) 10; M' = Pt, M = Mo. A = P(OMe)(3) 11; M' = Pd. M = W. A = NHC5H10 12; M' = Pt, M = W. A = NHC5H10 13). The structure of the complex 5 has been determined by single-crystal X-ray crystallography.

Monte Carlo simulation of ion conduction in silver based glassy electrolytes

A simplified structural model to study the ionic transport in silver based glasses has been formulated. The diffusion of silver ion under the influence of coulombic interactions of mobile cation and anions has been studied. Monte Carlo simulations of silver ion hopping in glass have suggested two different kinds of population of silver ions. We discuss the results of variation in diffusion constant with dopant (AgI) concentration using the diffusion path model. (C) 1997 Elsevier-Science S.A.

Magnetoresistance of the metallic perovskite oxide LaNiO3-delta

We report a study of the magnetoresistance (MR) of the metallic perovskite oxide LaNiO3-delta as a function of the oxygen stoichiometry delta (delta less than or equal to 0.14), magnetic field (H less than or equal to 6 T) and temperature (1.5 K less than or equal to T less than or equal to 25 K). We find a strong dependence of the nature of the MR on the oxygen stoichiometry. The MR at low temperatures changes from positive to negative as the sample becomes more oxygen deficient (i.e. delta increases). Some of the samples, which are more resistive, show resistivity minima at T-min approximate to 20 K. We find that in these samples the MR is positive for T > T-min and negative for T < T-min. We conclude that in the absence of strong magnetic interaction, the negative MR in these oxides can arise from weak-localization effects.

Hidden order in serrated flow of metallic glasses

We report results of statistical and dynamic analysis of the serrated stress-time curves obtained from compressive constant strain-rate tests on two metallic glass samples with different ductility levels in an effort to extract hidden information in the seemingly irregular serrations. Two distinct types of dynamics are detected in these two alloy samples. The stress-strain curve corresponding to the less ductile Zr65Cu15Ni10Al10 alloy is shown to exhibit a finite correlation dimension and a positive Lyapunov exponent, suggesting that the underlying dynamics is chaotic. In contrast, for the more ductile Cu47.5Zr47.5Al5 alloy, the distributions of stress drop magnitudes and their time durations obey a power-law scaling reminiscent of a self-organized critical state. The exponents also satisfy the scaling relation compatible with self-organized criticality. Possible physical mechanisms contributing to the two distinct dynamic regimes are discussed by drawing on the analogy with the serrated yielding of crystalline samples. The analysis, together with some physical reasoning, suggests that plasticity in the less ductile sample can be attributed to stick-slip of a single shear band, while that of the more ductile sample could be attributed to the simultaneous nucleation of a large number of shear bands and their mutual interactions. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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].

The molecular dynamics study of lithium ion conduction in phosphate glasses and the role of non-bridging oxygen

Molecular dynamics (MD) simulation of lithium phosphate (Li2O-P2O5) glasses with varying Li2O content has been carried out. Two different P-O distances corresponding to phosphorus coordination with bridging oxygen (BO) and non-bridging oxygen (NBO) were identified in the simulated glasses. NBO-BO interconversion or bond switching was noted, which results in a dynamic equilibration of the tetrahedral phosphate units (P-n, n = 1,3 indicates the number of bridging oxygen atoms in the coordination of phosphorus). The NBO-BO bond switching is mildly activated with an effective activation barrier of 0.03-0.05 eV. Lithium ion jumps do not appear to be strongly coupled to bond switching. But the number of Li+ ions coordinated to an optimum number of NBOs and the number of Li+ ions jumping out of their sites appear to be correlated. Detailed analysis was made of the dynamics of P-n species and new insights have been obtained regarding ion migration in network-modified phosphate glasses.

Alternating current conduction and impedance spectroscopy analysis on pulsed excimer laser ablated (Pb, La)TiO3 thin films

Lanthanum doped lead titanate (PLT) thin films were identified as the most potential candidates for the pyroelectric and memory applications. PLT thin films were deposited on Pt coated Si by excimer laser ablation technique. The polarization behavior of PLT thin films has been studied over a temperature range of 300 K to 550 K. A universal power law relation was brought into picture to explain the frequency dependence of ac conductivity. At higher frequency region ac conductivity of PLT thin films become temperature independent. The temperature dependence of ac conductivity and the relaxation time is analyzed in detail. The activation energy obtained from the ac conductivity was attributed to the shallow trap controlled space charge conduction in the bulk of the sample. The impedance analysis for PLT thin films were also performed to get insight of the microscopic parameters, like grain, grain boundary, and film-electrode interface etc. The imaginary component of impedance Z" exhibited different peak maxima at different temperatures. Different types of mechanisms were analyzed in detail to explain the dielectric relaxation behavior in the PLT thin films.

Embrittlement of a bulk metallic glass due to low-temperature annealing

Embrittlement of a bulk La-based metallic glass due to isothermal and isochronal annealing below the T-g was investigated. Results show that the impact toughness decreases with increasing annealing time or temperature, accompanied by a change in fracture morphology. Reasons for this are discussed in terms of structural relaxation. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Superconductivity of embedded lead nano particles in metallic and amorphous matrices

Nanodispersed lead in metallic and amorphous matrices was synthesized by rapid solidification processing. The optimum microstructure was tailored to avoid percolation of the particles. With these embedded particles it is possible to study quantitatively the effect of size on the superconducting transition temperature by carrying out quantitative microstructural characterization and magnetic measurements. Our results suggest the role of the matrices in enhancement or depression of superconducting transition temperature of lead. The origin of this difference in behavior with respect to different matrices and sizes is discussed.

Structural Relaxation and Crystallization in a Pd40Cu30Ni10P20 Bulk Metallic Glass

The stability of a Pd40Cu30Ni10P20 bulk metallic glass (BMG) against structural relaxation is investigated by isothermal and isochronal annealing heat treatments below and above its glass transition temperature, Tg, for varying periods. Differential scanning calorimetry (DSC) of the annealed samples shows an excess endotherm at Tg, irrespective of the annealing temperature. This recovery peak evolves exponentially with annealing time and is due to the destruction of anneal-induced compositional short range ordering. The alloy exhibits a high resistance to crystallization on annealing below Tg and complex Pd- and Ni-phosphides evolve on annealing above Tg.

Biaxial strain induced electrical inhomogenities and phase separation in the ferromagnetic metallic phase in thin films of La0.7Ca0.3MnO3: A scanning tunneling potentiometry/spectroscopy study

We have investigated the effect of biaxial strain on local electrical/electronic properties in thin films of La0.7Ca0.3MnO3 with varying degrees of biaxial strain in them. The local electrical properties were investigated as a function of temperature by scanning tunneling spectroscopy (STS) and scanning tunneling potentiometry (STP), along with the bulk probe like conductance fluctuations.The results indicate a positive correlation between the lattice mismatch biaxial strain and the local electrical/electronic inhomogenities observed in the strained sample. This is plausible since the crystal structure of the manganites interfere rather strongly with the magnetic/electronic degrees of freedom. Thus even a small imbalance (biaxial strain) can induce significant changes in the electrical properties of the system.

Microstructure and mechanical properties of electron beam weld joints of a Zr41Ti14Cu12Ni10Be23 bulk metallic glass with Zr

The electron beam welding technique was used to join Zr41Ti14Cu12Ni10Be23 bulk metallic glass (BMG) to crystalline pure Zr. Compositional, microstructural, and mechanical property variations across the welded interface were evaluated. It is shown that a crystalline layer develops close to the welding interface. Transmission electron microscopy of this layer indicates the crystalline phase to be tetragonal with lattice parameters close to that reported for Zr2Ni. However, the composition of this phase is different as it contains other alloying additions. The interface layer close to the bulk metallic glass side contains nanocrystalline Zr2Cu phase embedded in the glassy matrix. Nanoindentation experiments indicate that the hardness of the crystalline layer, although less than the bulk metallic glass, is more than the Zr itself. Commensurately, tensile tests indicate that the failure of the welded samples occurs at the Zr side rather than at the weld joint.

Effect of Dilatation on the Elasto-Plastic Response of Bulk Metallic Glasses Under Indentation

Elasto-plastic response of bulk metallic glasses (BMGs) follows closely the response of granular materials through pressure dependent (or normal stress) yield locus and shear stress induced material dilatation. On a micro-structural level, material dilatation is responsible for stress softening and formation of localized shear band, however its influence on the macro-scale flow and deformation is largely unknown. In this work, we systematically analyze the effect of material dilatation on the gross indentation response of Zr-based BMG via finite element simulation. The strengthening/softening effect on the load-depth response and corresponding stress-strain profiles are presented in light of differences in elastic-plastic regimes under common indenters. Through comparison with existing experimental results, we draw conclusions regarding selection of suitable dilatation parameters for accurately predicting the gross response of BMGs

The Drude parameters for metallic PF6 doped polypyrrole

We measured the two components of the complex dielectric function of insulating and metallic PF6 doped polypyrrole up to 4 meV simultaneously. These data are used as an input performed Kramers-Kronig analysis on the higher energy reflection data. This has helped to clarify those results, which were previously deduced from the FIR and UV/VIS data, that could be artifacts.