Photoemission core level and satellite study of TixRu1−xoxide layers

Combined photoemission core level and satellite structure investigations of pyrolytic titanium-rich Ti_xRu_1−x-oxide layers (0.90 ≦ x ≦ 0.97) and RuO₂ layers on titanium are used to gain structural and compositional information about these electro-catalytically active surfaces. By means of this method deviations from stoichiometry, the formation of carbon interstitials and the growth of anatase by ruthenium loss could be pointed out.     

Melting Diagrams of the Quaternary Systems Ga–In–As–Ge and Ga–In–As–Sn

Equilibria between quaternary liquid phases Ga–In–As–Ge(–Sn) and the ternary solid phase Ga–In–As have been calculated by application of the KRUPKOWSKI formalism on the excess free enthalpy. Experimental liquidus data were obtained from solubility experiments in a LPE equipment. Results of calculation and experimental liquidus data are compared.     

Liquid chromatography-mass spectrometry identification of imidacloprid photolysis products

Photolysis of imidacloprid by near ultraviolet (UV) radiation was investigated using reversed phase liquid chromatography (RPLC) and liquid chromatography-electrospray ionization/mass spectrometry (LC-ESI/MS) operated in the positive ion mode. The decomposition of imidacloprid by near UV light is first order with a half life of 10.18 h. Photo-degradation products of imidacloprid identified in this study included imidacloprid urea, imidacloprid olefin, and imidacloprid desnitro. A degradation pathway is proposed for imidacloprid from an examination of the product decay curves obtained in this monitoring study which was performed in a batch test mode.     

Surface site dependence to negative ion formation

The processes of electron transfer and dissociative scattering are explored for collisions of hyperthermal NO⁺ on GaAs(110). The experiments reveal a marked angular dependence to O⁻ emergence. A strong correlation between the O⁻ scattering angle and the final atom-surface interaction site provides a map of the lateral dependence to reactivity. The results are modeled by sequential neutralization, dissociation, and electron attachment steps. Classical trajectory calculations, in conjunction with an empirical opacity function, accurately reproduce the experimental results. The opacity function is interpreted as the probability that an electron will attach to a departing O fragment as a function of the last surface site the atom impacts. The experiments indicate that O⁻ emergence occurs predominantly for oxygen atoms which come in close contact with the localized dangling bond states of GaAs(110).     

Annealing dependent far field of GaAs-(Ga,Al)As LEDs

The far field intensity distribution of spontaneously light-emitting diodes with FABRY-PEROT structure and its dependence on different annealing processes during the diode preparation is studied. The electromagnetic field distribution in the far field is considered for a four-layer-stepdiscontinuity of the dielectric constant in a GaAs-(Ga,Al)As heterostructure diode. Even for a symmetrical dielectric constant profile the maximum luminescence intensity is not emitted necessarily in a plane normal to the light emitting surface of the diode. This cross-eyedness can be influenced by annealing. The changed far-field pattern can be evaluated if one knows the doping profile in the vicinity of the p-n junction and its changes during the annealing. Theoretical statements are in qualitative agreement with experimental results.The authors are grateful to Dr. K.Unger for valuable discussions and to Miss B.Russ for assistance with the measurements. The radioanalytical Zn determination by Mrs. G.Hänold from the VEB Halbleiterkombinat Frankfurt/Oder, Werk Stahnsdorf is gratefully acknowledged. This paper incorporates work carried out in the Arbeitsgemeinschaft AIII-BV-Halbleiter.     

Surface Modification of Poly-ε-Caprolactone with an Atmospheric Pressure Plasma Jet

In this work, poly-ε-caprolactone samples are modified by an atmospheric pressure plasma jet in pure argon and argon/water vapour mixtures. In a first part of the paper, the chemical species present in the plasma jet are identified by optical emission spectroscopy and it was found that plasmas generated in argon/0.05 % water vapour mixtures show the highest emission intensity of OH (A–X) at 308 nm. In a subsequent section, plasma jet surface treatments in argon and argon/water vapour mixtures have been investigated using contact angle measurements and X-ray photoelectron spectroscopy. The polymer samples modified with the plasma jet show a significant decrease in water contact angle due to the incorporation of oxygen-containing groups, such as C–O, C=O and O–C=O. The most efficient oxygen inclusion was however found when 0.05 % of water vapour is added to the argon feeding gas, which correlates with the highest intensity of OH (X) radicals. By optimizing the OH (X) radical yield in the plasma jet, the highest polymer modification efficiency can thus be obtained.     

Mass spectrometric methods prove the use of beeswax and ruminant fat in late Roman cooking pots

Lipid extracts of sherds of archaeological late Roman cooking pots were analysed using high temperature-gas chromatography coupled to a mass spectrometer and liquid chromatography with atmospheric pressure chemical ionization mass spectrometer detection (LC-APCI-MS). With these advanced techniques the use of beeswax was shown through identification of the constituting alkanes, mono and diesters. The detection of high amounts of saturated triacylglycerols (TAGs) further indicated that animal fat was processed in these pots. Part of the animal fat was characterised as originating from ruminants due to the presence of trans-fatty acids. The distribution of saturated TAGs and the higher concentration of stearic acid compared to palmitic acid in the transesterified lipid extract indicated that this was sheep fat. The results illustrate how complex mixtures can be unravelled and original contents of ancient ceramic vessels can be determined using specialised analytical equipment.     

Kinetic and spectroscopic study of 1O2 generation from H2O2 catalyzed by LDH-MoO4(2-) (LDH=layered double hydroxide)

Layered double hydroxides (LDHs), exchanged with molybdate, decompose H2O2 to form one molecule of singlet-state dioxygen (1O2) from two molecules of H2O2. The dependence of the kinetics of H2O2 decomposition on Mo and H2O2 concentrations and on temperature has been related to structural characteristics of the material (X-ray diffraction (XRD), scanning electron microscopy (SEM), IR spectroscopy, N2 adsorption, thermogravimetry) and to molybdate speciation as revealed by in-situ studies in the presence of peroxide (FT Raman, diffuse reflectance UV/visible spectroscopy). The H2O2 decomposition rate is linearly correlated with the amount of LDH-exchanged molybdate, except when a considerable fraction of the molybdate occupies less accessible interlayer positions. A maximum in the H2O2 decomposition rate as the H2O2 concentration is increased is due to the successive formation of mono-, di-, tri-, and tetraperoxomolybdates. This behavior was modeled successfully by using the equilibrium constants for formation of the Mo-peroxo complexes, and the rate constants for decay of the peroxomolybdates with 1O2 liberation. Time-resolved diffuse reflectance and Raman observations of the various MoO4(2-)-peroxide adducts are in line with the proposed kinetic scheme. Of all the Mo-peroxo species on the LDH, the triperoxomolybdate has the highest rate for decay to 1O2. Comparison with the kinetics of dissolved molybdate shows that the monomolecular decay of all peroxomolybdate species proceeds much faster at the LDH surface than in solution. Consequently, maximal rates per Mo atom are at least twice as high for the heterogeneous LDH catalyst as for the homogeneous systems.     

Tetrasulphur Tetranitride: Phase Transition and Crystal Structure at Elevated Temperature

Rietveld X‐ray crystal structure investigations on S₄N₄ give evidence for a new orthorhombic high‐temperature phase (Pbcn, a = 883.9(1) pm, b = 875.5(1) pm, c = 725.81(9) pm) very close to the explosion temperature of the solid‐state material. The phase transition can be described using Landau's theory, yielding a critical temperature of 397 K and a critical exponent of 0.50.