Abstract: Oxygen-deficient complex cobalt oxides BaCo1 − xYxO3 − y, = 0.15, 0.25 and 0.33, with a cubic perovskite structure have been synthesized in air at 1100 °C using a citrate route. Cation composition of the compounds was confirmed by energy-dispersed X-ray (EDX) microanalysis while oxygen content was determined by iodometric titration. An electron diffraction (ED) study of the x = 0.25 and 0.33 compositions show the presence of a diffuse intensity, indicating possible short-range ordering of the B cations. It was found that the treatment of BaCo0.75Y0.25O2.55 in a humid atmosphere leads to the absorption of water vapour at the first stage. Oxygen permeation studies of the ceramic membranes of BaCo0.75Y0.25O2.55 and BaCo0.67Y0.33O2.55 with variable thickness showed high oxygen fluxes of 0.170.32 µmol/cm2/s at 950 °C.

Abstract: We study the effects of the rippling of a graphene sheet on quasiparticle dispersion. This is achieved using a generalization to the honeycomb lattice of the momentum average approximation, which is accurate for all coupling strengths and at all energies. We show that even though the position of the Dirac points may move and the Fermi speed can be renormalized significantly, quasiparticles with very long lifetimes survive near the Dirac points even for very strong couplings.

Abstract: We report the high temperature electronic transport properties of SrFeO3 − ä epitaxial thin films obtained by pulsed laser deposition on NdGaO3(110) substrates. The films show total conductivity higher than the bulk material and apparent activation energy of about 0.12 eV in O2, lower than reported values for SrFeO3 − ä films. The conductivity dependence with oxygen partial pressure shows a power dependence with an exponent close to + 1/4, in agreement with expected point defect equilibrium. For a given oxygen partial pressure, the temperature coefficient of resistance (TCR) shows a low positive value of about 1.52.5 10− 3 K− 1, which is still suitable for resistive oxygen sensing applications. The transport properties of the films are discussed in view of their particular microstructure.

Abstract: Hybrid titania films have been prepared using an adapted sol-gel method for obtaining well-dispersed hydrogen plasma-treated multiwall carbon nanotubes in either pure titania or Nb-doped titania. The drop-coating method has been used to fabricate resistive oxygen sensors based on titania or on titania and carbon nanotube hybrids. Morphology and composition studies have revealed that the dispersion of low amounts of carbon nanotubes within the titania matrix does not significantly alter its crystallization behaviour. The gas sensitivity studies performed on the different samples have shown that the hybrid layers based on titania and carbon nanotubes possess an unprecedented responsiveness towards oxygen (i.e. more than four times higher than that shown by optimized Nb-doped TiO(2) films). Furthermore, hybrid sensors containing carbon nanotubes respond at significantly lower operating temperatures than their non-hybrid counterparts. These new hybrid sensors show a strong potential for monitoring traces of oxygen (i.e. <= 10 ppm) in a flow of CO(2), which is of interest for the beverage industry.

Abstract: We illustrate the potential of advanced transmission electron microscopy for the characterization of a new class of soft porous materials: metal@Zn4O(bdc)3 (metal@MOF-5; bdc = 1,4-benzenedicarboxylate). By combining several electron microscopy techniques (transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), electron diffraction (ED), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and electron tomography) and by carefully reducing the electron dose to avoid beam damage, it is possible to simultaneously characterize the MOF-5 framework material and the loaded metal nanoparticles. We also demonstrate that electron tomography can be used to accurately determine the position and distribution of the particles within the MOF-5 framework. To demonstrate the implementation of these microscopy techniques and what kind of results can be expected, measurements on gas-phase-loaded metal−organic framework materials Ru@MOF-5 and Pd@MOF-5 are presented.

Abstract: Quantum confinement of the transverse electron motion is the major effect governing the superconducting properties of high-quality metallic nanofilms, leading to a nonuniform transverse distribution of the superconducting condensate. In this case the order parameter can exhibit significant local enhancements due to these quantum-size effects and, consequently, quasiparticles have lower energies when they avoid the local enhancements of the pair condensate. Such excitations can be considered as new Andreev-type quasiparticles but now induced by quantum confinement. By numerically solving the Bogoliubovde Gennes equations and using Anderson's approximate solution to these equations, we: (a) formulate a criterion for such new Andreev-type states (NATS) and (b) study their effect on the superconducting characteristics in metallic nanofilms. We also argue that nanofilms made of low-carrier-density materials, e.g., of superconducting semiconductors, can be a more optimal choice for the observations of NATS and other quantum-size superconducting effects.

Abstract: We measured the electrical resistivity R(T) and specific heat C-p(T) between room temperature (RT) and 4.2 K as well as the microstructure by transmission electron microscopy (TEM) of a Ni-52 Ti-48 SMA quenched from 1000degreesC (B2-Phase range) to RT and then annealed for 1h at T=380degreesC, 550degreesC and 650degreesC. In the “as quenched” and the “650degreesC annealed” state no martensitic transformations (MT's) occur. The diffraction patterns show faint reflections originating from coherent Ni4Ti3 precipitates in an early state of formation. Additional reflections of the type 1/2 <110>, 1/2 <111> and 1/3 <110> result from various lattice displacement waves, which are precursors of the MT's to the B19' and R-phase, respectively. Indeed, high resolution TEM micrographs of the [001] zone of the “as quenched” sample reveal transverse 1/2 <110> <110> lattice displacement waves, precursors of the B19' martensite. The coherent Ni4Ti3 precipitates, homogeneously distributed on a small length scale, binder the MT's in the “as quenched” and the “650degreesC annealed” state, and thus only the precursors appear. When annealed at T=380degreesC, however, coherent Ni4Ti3 precipitates with a length of 10nm are clearly visible in TEM. These precipitates trigger the NIT from the B2 to the R-phase on cooling, as evidenced also by anomalies in R(T) and C-p(T). Annealing at T-550degreesC leads to the well known two step MT's from the B2 to the R-phase and then into the B19'-phase. These martensitic transitions are clearly seen as additional peaks in the specific heat and anomalies in the resistance, while the “as quenched” and 650degreesC annealed samples show weak features in R(T) and C-p(T).

Abstract: The time dependence of the resistance RAC of a La0.8Sr0.2MnO3 single crystal has been investigated in the vicinity of the metal-to-insulator transition temperature. We used local probe microscopy to show the existence, at room temperature, of coexisting clusters of micrometer size. Our analysis shows that relaxation effects can be described with a simple exponential contribution using a random resistor-network, based on phase separation between insulating and metallic domains. Our results clearly prove the existence of a percolation threshold over which no percolation path exists. Moreover, these results highlight the significant role of the remanent magnetization.

Abstract: A new oxygen-deficient Ruddlesden−Popper (RP) cobaltite Sm2BaCo2O7−δ (δ ≈ 1.0) has been synthesized and the crystal structure elucidated by Rietveld analysis of X-ray powder diffraction (XRD) data and transmission electron microscopy (TEM). The phase crystallizes in a primitive orthorhombic unit cell, with lattice parameters a = 5.4371(4) Å; b = 5.4405(4) Å and c = 19.8629(6) Å, and space group Pnnm. Contrary to other oxygen-deficient cobalt RP phases, the oxygen vacancies are located in the equatorial positions of the [CoO] layers to give an intralayer structure similar to Sr2Mn2O5, which is not usually observed for cobalt-containing materials. The Sm3+ and Ba2+ cations show a strong preference for distinct sites, with the majority of the larger Ba2+ cations situated in the perovskite block layers and Sm3+ cations predominantly in the rock salt layers. Magnetic susceptibility data demonstrate the strong antiferromagnetic (AFM) character of Sm2BaCo2O7−δ.

Abstract: The highly porous and desolvated (activated) coordination polymer [Zn4O(btb)2] (btb = benzene-1,3,5-tribenzoate; MOF-177) was loaded with the organometallic compounds [Cp2Fe], [Cp*2Zn], [Cu(OCHMeCH2NMe2)2], [CpCuL] (L = PMe3, CNtBu) and [CpPd(3-C3H5)] via solvent-free adsorption from the gas-phase. The inclusion compounds of the type [LnM]a@MOF-177, where [LnM] indicates the respective compound and the parameter a denotes the number of molecules per formula unit of the MOF-177, were characterised by elemental analysis, FT-IR, solid-state NMR spectroscopy and by powder X-ray diffraction (PXRD). Remarkably high effective loadings of up to 11 molecules [Cp2Fe] and 10 molecules [CpPd(3-C3H5)] per cavity were determined. The analytical data prove that the host lattice and the guest molecules interact only by weak van-der-Waals forces without any significant change of the framework or the chemical nature of the included molecules. Cu nanoparticles showing the typical surface plasmon resonance at 580 nm and Pd nanoparticles of about 2.6 nm in size were formed inside the cavities of MOF-177 by the thermally activated hydrogenolysis of the inclusion compounds [CpCuCNtBu]2@MOF-177 and by photolysis of [CpPd(3-C3H5)]10@MOF-177 in an inert atmosphere (Ar). PXRD, FT-IR and NMR studies revealed that the MOF-177 matrix remained unchanged during the decomposition process of the precursors. N2 adsorption studies of the obtained materials Cu@MOF-177 (e.g. 10.6 wt.% Cu, 2309 m2 g-1) and Pd@MOF-177 (e.g. 32.5 wt.%, 1063 m2 g-1) reveal high remaining specific surface areas (Langmuir model).

Abstract: We have studied granular films consisting of nanoscale Ga droplets formed on GaAs films via a method of vacuum annealing to promote As evaporation. For temperatures and magnetic fields below the bulk Ga critical parameters, the samples are very sensitive towards external microwave radiation when two point voltage measurements are performed. Together with the observation of an oscillating magnetic field dependence of the voltage, a scenario in which the samples consist of Josephson-coupled loops seems to be the most likely one for explaining the obtained results.