Einstein oscillators in thallium filled antimony skutterudites

Inelastic neutron scattering measurements on several Tl filled skutterudites (Tl0.5Co3.5Fe0.5Sb12, Tl0.8Co3FeSb12, and Tl0.8Co4Sb11Sn) all show a sharp peak in the vibrational density of states at 57+/-2 K, which is absent in the unfilled skutterudite CoSb3. Heat capacity measurements on Tl0.8Co4Sb11Sn as compared to CoSb3 are consistent with the presence of a localized vibrational mode associated with the "rattling" thallium atoms in this filled skutterudite compound. Both results are well described by a localized Einstein mode model with an Einstein temperature Theta(E) of 53+/-1 K. These data provide perhaps the clearest example of local mode behavior in a concentrated metallic system.     

Antimony-121 Mössbauer spectral study of the Eu14MnSb11 and Yb14MnSb11 Zintl compounds

The antimony-121 M?ssbauer spectra of the Yb14MnSb11 and Eu14MnSb11 Zintl compounds have been measured between 2 or 5 and 300 K. The resulting three-dimensional arrays of the spectral counts, velocity, and temperature have been simultaneously fit with a minimum number of free parameters. These fits yield a 0 Kelvin transferred hyperfine field of 2.9(2) T, a Curie temperature of 57(3) K, and a M?ssbauer temperature of 182(2) K for Yb14MnSb11; in this case the transferred field arises solely from the ordering of Mn2+. Because Eu14MnSb11 has both Eu2+ and Mn2+ ions that are magnetically ordered, its antimony-121 M?ssbauer spectra are more complex and reveal two magnetic transitions, the first at 92(1) K resulting from the ordering of the Mn2+ ions and the second at 9.5(1.0) K resulting from the ordering of the Eu2+ ions; the corresponding 0 Kelvin transferred hyperfine fields are 1.3(1) and 3.7(1) T. The antimony-121 isomer shifts yield electronic configurations of 5s1.745p4.28 and 5s1.745p4.19 for the average antimony anion in Yb14MnSb11 and Eu14MnSb11, respectively.     

Variable density flow in porous media. A study by means of pore level numerical simulations

This paper is devoted to the modelling of isothermal low Reynolds and Mach numbers transient compressible flow through porous media. Traditionally, this type of flow at the macroscopic level is described by the classical Darcy's law combined with a mass balance that includes the transient term. This model is called the ‘classic model’. The aim of this paper is to explore the validity of this classic model. To this end, the flow of an ideal gas is considered within two‐dimensional model porous media. The flow is due to the imposed pressure variations at the outlet of the fluid domain. At the microscopic level, the flow is computed by solving the full compressible Navier–Stokes equations in two dimensions. Special attention is given to the outlet boundary conditions. The analysis is based on the comparison between the macroscopic data, obtained on the one hand by spatially averaging the microscopic results, and on the other hand by solving the problem directly at the macroscopic level. Situations for which a good agreement is found between the two series of data and situations for which discrepancies are observed are exhibited. These various behaviours are discussed in terms of the various time scales controlling the flow and are explained by analysing the flow structure at pore level. Copyright © 1999 John Wiley & Sons, Ltd.     

Optical properties of ITO/TiO2 single and double layer thin films deposited by RPLAD

Indium tin oxide (ITO) and titanium dioxide (TiO₂) single layer and double layer ITO/TiO₂ films were prepared using reactive pulsed laser ablation deposition (RPLAD) with an ArF excimer laser for applications in dye-sensitized solar cells (DSSCs). The films were deposited on SiO₂ substrates either at room temperatures (RT) or heated to 200-400 °C. Under optimized conditions, transmission of ITO films in the visible (vis) range was above 89% for films produced at RT and 93% for the ones deposited at higher temperatures. Increasing the substrate temperature from RT to 400 °C enhances the transmission of TiO₂ films in the vis-NIR from about 70% to 92%. High transmission (≈90%) was observed for the double layer ITO/TiO₂ with a transmission cut-off above 900 nm. From the transmission data, the energies gaps (E_g), as well as the refractive indexes (n) for the films were estimated. n ≈ 2.03 and 2.04, respectively for ITO films and TiO₂ film deposited at 400 °C in the visible region. Post-annealing of the TiO₂ films for 3 h at 300 and 500 °C was performed to enhance n. The refractive index of the TiO₂ films increases with the post-annealing temperature. The direct band gap is 3.6, 3.74 and 3.82 eV for ITO films deposited at RT, 200, and 400 °C, respectively. The TiO₂ films present a direct band gap of 3.51 and 3.37 eV for as deposited TiO₂ films and when annealed at 400 °C, respectively. There is a shift of about 0.1 eV between ITO and ITO/TiO₂ films deposited at 200 °C. The shift decreases by half when the TiO₂ film was deposited at 400 °C. Post-annealing was also performed on double layer ITO/TiO₂.     

Characterization of Ethylene methyl methacrylate and Ethylene butylacrylate Copolymers with Interactive Liquid Chromatography

Summary: Copolymers of ethylene with methyl methacrylate (EMMA) and butyl acrylate (EBA), which are of different average chemical composition and block lengths according to NMR analysis, were analyzed by size exclusion chromatography (SEC), differential scanning calorimetry (DSC), Crystallization Analysis Fractionation (CRYSTAF), and high performance liquid chromatography at high temperature (HT-HPLC). With CRYSTAF and DSC crystallizing fractions were detected only in some samples. HT-HPLC fractionated all the samples irrespective of their crystallinity. Homopolymers, PMMA and PE were also found in the copolymer samples of EMMA. EMMA and EBA were separated in HPLC according to the content of polar comonomer. A linear correlation between the MMA content and elution volume could not be established due to the presence of homopolymers as admixtures. In such a case the average chemical composition obtained by NMR does not correspond to the real chemical composition of the copolymers. Unlike EMMA the EBA samples eluted in single peaks, which was used for evaluation of their chemical composition distribution. The comparison of results obtained by fractionation via CRYSTAF and HT-HPLC clearly demonstrates the advantages of the chromatographic approach to study the chemical heterogeneity of olefin based copolymers.     

Structural, electronic, and magnetic properties of UFeS3 and UFeSe3

Black prisms of UFeS(3) and UFeSe(3) have been synthesized by solid-state reactions of U, Fe, and S or Se with CsCl as a flux at 1173 K. The structure of these isostructural compounds consists of layers of edge- and corner-sharing FeS(6) or FeSe(6) octahedra that are separated by layers of face- and edge-sharing US(8) or USe(8) bicapped trigonal prisms. The isomer shifts in the iron-57 M?ssbauer spectra of both UFeS(3) and UFeSe(3) are consistent with the presence of high-spin iron(II) ions octahedrally coordinated to S or Se. The XANES spectra of UFeS(3) and UFeSe(3) are consistent with uranium(IV). Single-crystal magnetic susceptibility measurements along the three crystallographic axes of UFeSe(3) reveal a substantial magnetic anisotropy with a change of easy axis from the a-axis above 40 K to the b-axis below 40 K, a change that results from competition between the iron(II) and uranium(IV) anisotropies. The temperature dependence of the magnetic susceptibility along the three axes is characteristic of two-dimensional magnetism. A small shoulder-like anomaly is observed in the magnetic susceptibilities along the a- and b-axes at 96 and 107 K, respectively. Below 107 K, the iron-57 M?ssbauer spectra of UFeS(3) and UFeSe(3) show that the iron nuclei experience a magnetic hyperfine field that results from long-range magnetic ordering of at least the iron(II) magnetic moments because the field exhibits Brillouin-like behavior. Below 40 K there is no significant change in the M?ssbauer spectra as a result of change in magnetic anisotropy. The complexity of the iron-57 M?ssbauer spectra and the temperature and field dependencies of the magnetic properties point toward a complex long-range magnetic structure of two independent iron(II) and uranium(IV) two-dimensional sublattices. The temperature dependence of the single-crystal resistivity of UFeSe(3) measured along the a-axis reveals semiconducting behavior between 30 and 300 K with an energy gap of about 0.03 eV below the 53 K maximum in susceptibility, of about 0.05 eV between 50 and 107 K, and of 0.03 eV above 107 K; a negative magnetoresistance was observed below 60 K.     

Versatility in the binding of 2-pyrazinecarboxylate with iron. Synthesis, structure and magnetic properties of iron(II) and iron(III) complexes

The synthesis and characterization of two new iron(II) complexes, [Fe(pca)2(py)2].py (1) and {[Fe(pca)2(H2O)].H2O}n (2) and one new iron(III) complex, Na2{[Fe(pca)()]2O}.2H2O.2CH3CN (3) (pca- stands for 2-pyrazinecarboxylate), are reported. Complex 1 is obtained from the reaction of iron powder with 2-pyrazinecarboxylic acid. The reaction of Fe(ClO4)3.10H2O with Hpca in the presence of 3 equiv. of Bu4NOH yields 2, whereas the presence of NaOH yields 3. The molecular structure of 1 contains an iron(II) ion with a pseudo-octahedral environment resulting from the coordination of two pca- ligands in a bidentate chelating fashion and two pyridine molecules; pi-pi stacking interactions between pyridine and pyrazine rings lead to a one-dimensional chain. Complex 2 is an iron(II) coordination polymer with an infinite zig-zag motif and an Fe...Fe separation of 7.1 A. In 2, the pi-pi stacking interactions involving the pyrazine rings and the strong hydrogen bonds between the coordinated water molecule and the carboxylate oxygens of two pca- ligands result in a three-dimensional network structure. Complex 3 consists of an anionic micro-oxo-bridged diiron(III) core with two crystallographically distinct iron(iii) ions; the negative charge is compensated by two sodium cations. Complex 3 is assembled in a three dimensional network structure through coordination of Na(I) and hydrogen bond interactions. Temperature dependent magnetic susceptibility and M?ssbauer spectroscopic studies indicate that 1 and 2 have similar magnetic properties. Both complexes are paramagnetic above 12 K, whereas antiferromagnetic ordering is observed below 12 K. The magnetic properties of reveal strong intramolecular antiferromagnetic interactions between the two iron(III) ions with a J value of -221 cm(-1); no long range intermolecular magnetic coupling is observed between 295 and 4.2 K.     

Coarsening of nanodomains by reorganization of polysiloxane segments at high temperature in polyurethane/α,ω-aminopropyl polydimethylsiloxane blends

The reaction in bulk at high temperature of α,ω-aminopropyl oligodimethylsiloxane and thermoplastic polyurethane (TPU) allowed observing interesting behavior. Mixing at 200 °C first involved dissociation of urethanes and splitting of polyurethane chains followed by reaction of the released isocyanates with amino end-groups of the oligosiloxane. At this stage, a copolymer was formed which morphology consisted of a very fine dispersion of the polysiloxane domains at the nanoscale (20 nm) with a narrow size dispersity. The polymer blend was perfectly transparent. Increasing the reaction time resulted in a significant coarsening of the morphology and a consequent loss of transparency. The reason for such a morphology evolution has been elucidated. The progressive formation of alkyl–alkyl urea linkages at the expense of aryl–alkyl bonds obtained earlier in the process caused an increase in the average number of successive polydimethylsiloxane (PDMS) blocks that organized in larger domains. The average number of consecutive polysiloxane segments was found to evolve from ～1.5 in the first 10–15 min to a value of 3–5 at the end of the reactive process.