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    Mechanisms of bonding effected by nanoparticles in zirconia coatings applied by spraying of suspensions
    (Saarbrücke : Leibniz-Institut für Neue Materialien, 2008) Adam, Jens; Aslan, Mesut; Drumm, Robert; Veith, Michael
    Zirconia coatings consisting of a mixture of coarse and fine grained zirconia powders prepared by spraying of suspensions and subsequent thermal treatment at limited temperatures (up to 500°C) are poor in adherence and in intrinsic mechanical strength. We have shown elsewhere that mechanical properties of these coatings can be improved clearly by adding a small amount of nanoscaled zirconia. Here, the structural and the chemical development of this coating material and of the nanoparticles is examined to gain information about the underlying bonding mechanisms. The applied temperature is relatively low in comparison to the usual onset temperature of accelerated sintering. Nevertheless, the results show that diffusion controlled material transport mechanisms play their role in bonding. The condensation of surface OH groups may participate in bonding, too. These first results confirm the potential of nanoparticles to act as inorganic binder. Additional research effort to clarify the underlying mechanisms in detail is of interest. For the practical side, it can be concluded that the resulting effect of mechanical consolidation of ceramic structures at relatively low temperatures enables new ceramic applications, for example a new type of ceramic coatings on metallic substrates.
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    High-field ESR studies of the quantum spin magnet CaCu2O 3
    (Milton Park : Taylor & Francis, 2006) Goiran, M.; Costes, M.; Broto, J.M.; Chou, F.C.; Klingeler, R.; Arushanov, E.; Drechsler, S.-L.; Büchner, B.; Kataev, V.
    We report an electron spin resonance (ESR) study of the s = 1/2 Heisenberg pseudo-ladder magnet CaCu2O3 in pulsed magnetic fields up to 40 T. At sub-terahertz frequencies we observe an ESR signal originating from a small amount of uncompensated spins residing presumably at the imperfections of the strongly antiferromagnetically correlated host spin lattice. The data give evidence that these few per cent of 'extra' spin states are coupled strongly to the bulk spins and are involved in the antiferromagnetic (AF) ordering at TN = 25 K. By mapping the frequency/resonance field diagram we have determined a small gap for magnetic excitations below TN of the order of ~0.3–0.8 meV. Such a small value of the gap explains the occurrence of the spin-flop transition in CaCu2O3 at weak magnetic fields μ0Hsf ~ 3 T. Qualitative changes of the ESR response with the increasing field strength give indications that strong magnetic fields reduce the AF correlations and may even suppress the long-range magnetic order in CaCu2O3. ESR data support scenarios with a significant role of the 'extra' spin states for the properties of low-dimensional quantum magnets.
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    Emission fluxes and atmospheric degradation of monoterpenes above a boreal forest: Field measurements and modelling
    (Milton Park : Taylor & Francis, 2001) Spanke, Jörg; Rannik, Üllar; Forkel, Renate; Nigge, Walter; Hoffman, Thorsten
    The contribution of monoterpenes to aerosol formation processes within and above forests is not well understood. This is also true for the particle formation events observed during the BIOFOR campaigns in Hyytiälä, Finland. Therefore, the diurnal variation of the concentrations of several biogenic volatile organic compounds (BVOCs) and selected oxidation products in the gas and particle phase were measured on selected days during the campaigns in Hyytiälä, Finland. α-pinene and Δ3-carene were found to represent the most important monoterpenes above the boreal forest. A clear vertical gradient of their concentrations was observed together with a change of the relative monoterpene composition with height. Based on concentration profile measurements of monoterpenes, their fluxes above the forest canopy were calculated using the gradient approach. Most of the time, the BVOC fluxes show a clear diurnal variation with a maximum around noon. The highest fluxes were observed for α-pinene with values up to 20 ng m−2 s−1 in summer time and almost 100 ng m−2 s−1 during the spring campaign. Furthermore, the main oxidation products from α-pinene, pinonaldehyde, and from β-pinene, nopinone, were detected in the atmosphere above the forest. In addition to these more volatile oxidation products, pinic and pinonic acid were identified in the particle phase in a concentration range between 1 and 4 ng m−3. Beside these direct measurement of known oxidation products, the chemical sink term in the flux calculations was used to estimate the amount of product formation of the major terpenes (α-pinene, β-pinene, Δ3-carene). A production rate of very low volatile oxidation products (e.g., multifunctional carboxylic) from ·OH- and O3-reaction of monoterpenes of about 1.3·104 molecules cm−3 s−1 was estimated for daylight conditions during summer time. Additionally, model calculations with the one-dimensional multilayer model CACHE were carried out to investigate the diurnal course of BVOC fluxes and chemical degradation of terpenes.
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    The polycyclic aromatic hydrocarbon concentrations in soils in the Region of Valasske Mezirici, the Czech Republic
    (London : BioMed Central, 2009) Plachá, Daniela; Raclavská, Helena; Rümmeli, Mark H.
    The polycyclic aromatic hydrocarbon (PAH) contamination of urban, agricultural and forest soil samples was investigated from samples obtained in the surroundings of Valasske Mezirici. Valasske Mezirici is a town located in the north-east mountainous part of the Czech Republic, where a coal tar refinery is situated. 16 PAHs listed in the US EPA were investigated. Organic oxidizable carbon was also observed in the forest soils. The PAH concentrations ranged from 0.86-10.84 (with one anomalous value of 35.14) and 7.66-79.39 mg/kg dm in the urban/agricultural and forest soils, respectively. While the PAH levels in the urban/agricultural soils are within the range typically found in industrialized areas, the forest soils showed elevated PAH concentrations compared to other forest soils in Western and Northern Europe. The PAH concentrations and their molecular distribution ratios were studied as functions of the sample location and the meteorological history. The soils from localities at higher altitudes above sea level have the highest PAH concentrations, and the PAH concentrations decrease with increasing distance from the town.
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    Magnetic field-induced twin boundary motion in polycrystalline Ni-Mn-Ga fibres
    (Milton Park : Taylor & Francis, 2008) Scheerbaum, N.; Heczko, O.; Liu, J.; Hinz, D.; Schultz, L.; Gutfleisch, O.
    Magnetic field-induced twin boundary motion leading to large magnetic field-induced strain of ~1.0% was established in polycrystalline Ni50.9Mn27.1Ga22.0 (at.%) fibres at room temperature (~60–100 μm in diameter and ~3 mm in length). The fibres' grains are as large as the fibre diameter and of random orientation. At room temperature, a ferromagnetic 5M martensite is found. Magnetic field-induced twin boundary motion was indicated by magnetic measurements and validated by electron backscatter diffraction (EBSD). The application of a magnetic field shifts the equilibrium temperature of martensite and austenite by ~0.4 K T−1, which agrees with calculations using the Clapeyron–Clausius approach.
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    Optical study of orbital excitations in transition-metal oxides
    (Milton Park : Taylor & Francis, 2005) Rückamp, R.; Benckiser, E.; Haverkort, M.W.; Roth, H.; Lorenz, T.; Freimuth, A.; Jongen, L.; Möller, A.; Meyer, G.; Reutler, P.; Büchner, B.; Revcolevschi, A.; Cheong, S.-W.; Sekar, C.; Krabbes, G.; Grüninger, M.
    The orbital excitations of a series of transition-metal compounds are studied by means of optical spectroscopy. Our aim was to identify signatures of collective orbital excitations by comparison with experimental and theoretical results for predominantly local crystal-field excitations. To this end, we have studied TiOCl, RTiO3 (R = La, Sm and Y), LaMnO3, Y2BaNiO5, CaCu2O3 and K4Cu4OCl10, ranging from early to late transition-metal ions, from t2g to eg systems, and including systems in which the exchange coupling is predominantly three-dimensional, one-dimensional or zero-dimensional. With the exception of LaMnO3, we find orbital excitations in all compounds. We discuss the competition between orbital fluctuations (for dominant exchange coupling) and crystal-field splitting (for dominant coupling to the lattice). Comparison of our experimental results with configuration-interaction cluster calculations in general yields good agreement, demonstrating that the coupling to the lattice is important for a quantitative description of the orbital excitations in these compounds. However, detailed theoretical predictions for the contribution of collective orbital modes to the optical conductivity (e.g. the line shape or the polarization dependence) are required to decide on a possible contribution of orbital fluctuations at low energies, in particular, in case of the orbital excitations at ≈0.25 eV in RTiO3. Further calculations are called for which take into account the exchange interactions between the orbitals and the coupling to the lattice on an equal footing.
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    Work on non photocatalytically active titania particles
    (Saarbrücke : Leibniz-Institut für Neue Materialien, 2009) Müller, Thomas S.; Faller-Schneider, Christine; Moh, Karsten; Shanmugasundaram, Sakthivel; Oliveira, Peter W. de; Veith, Michael
    Titanium dioxide has photocatalytic properties, i.e. under UV irradiation it develops an oxidative potential. In photocatalysis this is very desirable, but not when nano particulate titania is embedded into organic polymer matrices in order to increase the refractive index. UV irradiation would in this case destroy the material in the long run. For deactivation in general the titania is coated by e.g. silica or alumina which leads to other undesired effects like growth of the particle size and enhanced light scattering. The current work focuses on the application of techniques for doping during synthesis of crystallization of nano particulate TiO2. The photocatalysis activity was determined by degradation experiments of 4-chlorophenol using dip coated glass plates under artificial sunlight, where decreases of the photocatalytic effect of up to 90 % were found.
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    Electronic properties of LaO1-xFxFeAs in the normal state probed by nmr/nqr
    (Milton Park : Taylor & Francis, 2009) Grafe, H.-J.; Lang, G.; Hammerath, F.; Paar, D.; Manthey, K.; Koch, K.; Rosner, H.; Curro, N.J.; Behr, G.; Werner, J.
    We report 139La, 57Fe and 75As nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements on powders of the new LaO1−xFxFeAs superconductor for x=0 and 0.1 at temperatures up to 480 K, and compare our measured NQR spectra with local density approximation (LDA) calculations. For all three nuclei in the x=0.1 material, it is found that the local Knight shift increases monotonically with an increase in temperature, and scales with the macroscopic susceptibility, suggesting a single magnetic degree of freedom. Surprisingly, the spin lattice relaxation rates for all nuclei also scale with one another, despite the fact that the form factors for each site sample different regions of q-space. This result suggests a lack of any q-space structure in the dynamical spin susceptibility that might be expected in the presence of antiferromagnetic correlations. Rather, our results are more compatible with simple quasi-particle scattering. Furthermore, we find that the increase in the electric field gradient at the As cannot be accounted for by LDA calculations, suggesting that structural changes, in particular the position of the As in the unit cell, dominate the NQR response.
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    Magnetic quantum oscillations of diagonal conductivity in a two-dimensional conductor with a weak square superlattice modulation under conditions of the integer quantum Hall effect
    (Milton Park : Taylor & Francis, 2009) Gvozdikov, V.M.; Taut, M.
    We report on analytical and numerical studies of the magnetic quantum oscillations of the diagonal conductivity σxx in a two-dimensional conductor with a weak square superlattice modulation under conditions of the integer quantum Hall (IQHE) effect. The quantum Hall effect in such a system differs from the conventional IQHE, in which the finite width of the Landau bands is due to disorder only. The superlattice modulation potential yields a fractal splitting of the Landau levels into Hofstadter minibands. For rational flux through a unit cell, the minibands have a finite width and intrinsic dispersion relations. We consider a regime, now accessible experimentally, in which disorder does not wash out the fractal internal gap structure of the Landau bands completely. We found the following distinctions from the conventional IQHE produced by the superlattice: (i) the peaks in diagonal conductivity are split due to the Hofstadter miniband structure of Landau bands; (ii) the number of split peaks in the bunch, their positions and heights depend irregularly on the magnetic field and the Fermi energy; (iii) the gaps between the split Landau bands (and related quantum Hall plateaus) become narrower with the superlattice modulation than without it.
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    Momentum-resolved superconducting gap in the bulk of Ba1-xK xFe2As2 from combined ARPES and μSR measurements
    (Milton Park : Taylor & Francis, 2009) Evtushinsky, D.V.; Inosov, D.S.; Zabolotnyy, V.B.; Viazovska, M.S.; Khasanov, R.; Amato, A.; Klauss, H.-H.; Luetkens, H.; Niedermayer, Ch.; Sun, G.L.; Hinkov, V.; Lin, C.T.; Varykhalov, A.; Koitzsch, A.; Knupfer, M.; Büchner, B.; Kordyuk, A.A.; Borisenko, S.V.
    Here we present a calculation of the temperature-dependent London penetration depth, λ(T), in Ba1-xKxFe 2As2 (BKFA) on the basis of the electronic band structure (Zabolotnyy et al 2009 Nature 457 569, Zabolotnyy et al 2009 Physica C 469 448) and momentum-dependent superconducting gap (Evtushinsky et al 2009 Phys. Rev. B 79 054517) extracted from angleresolved photoemission spectroscopy (ARPES) data. The results are compared to the direct measurements of λ(T) by muon spin rotation (μSR) (Khasanov et al 2009 Phys. Rev. Lett. 102 187005). The value of λ(T = 0), calculated with no adjustable parameters, equals 270 nm, while the directly measured one is 320 nm; the temperature dependence λ(T) is also easily reproduced. Such agreement between the two completely different approaches allows us to conclude that ARPES studies of BKFA are bulk-representative. Our review of the available experimental studies of the superconducting gap in the new ironbased superconductors in general allows us to state that most of them bear two nearly isotropic gaps with coupling constants 2ΔkBTc = 2.5±1.5 and 7±2.