Exchange and oxidation of CO on O-predosed Rh---Al2O3 and Rh---CeO2 catalysts

Exchange and oxidation of C¹⁶O were investigated at 450°C on ¹⁸O-predosed Rh and Pt catalysts supported on A1₂O₃, CeO₂ and CeO₂-Al₂O₃. In all cases, a rapid exchange of C¹⁶O with the surface can be observed. CO oxidation leads to C¹⁶O₂, C¹⁶O¹⁸O and C¹⁸O₂. Significant formation of C¹⁶O₂ is due to the relatively high ¹⁶O coverage in reaction resulting from the C¹⁶O exchange and from an exchange between O surface species and ¹⁶O internal atoms. Hydrogen is also formed via a water-gas shift reaction (CO + surface OH) in higher proportion on CeO₂-containing catalysts than on A1₂O₃. Chlorine inhibits all the reactions (exchange, oxidation and WGS) and particularly the internal exchange.     

Issues in nonlinear stochastic grey box identification

Grey box identification refers to the practice of identifying dynamical systems in model structures exploiting partial prior information. This contribution reviews a method for stochastic grey box identification and surveys experiences and lessons of applying it to a number of industrial processes. Issues to be addressed include advantages and costs of introducing stochastics into the model, the question of what contribution must be expected from the model designer as opposed to what can be formalized in computer algorithms, and an outlook on future plans to resolve present shortcomings.     

The radiation crosslinking and scission of ethylene-propylene copolymers studied by solid-state nuclear magnetic resonance

Methyl groups from chain scission and H-crosslinks have been identified by solid-state nuclear magnetic resonance in amorphous ethylene-propylene copolymers containing 23 and 36 mole % propylene after γ-irradiation to 10 MGy at 30°C. G (scission) and G (crosslink) values determined from the n.m.r. spectra and by extraction are in agreement, which suggests that the crosslinks are not clustered. This may differ from the situation in polyethylene where there is a substantial crystalline content. G(S). G(X) and the ratio G(S)/G(X) increase with increasing propylene content of the copolymers.     

Stable Oxygen and Carbon Isotopic Compositions of Lates stappersii Otoliths from Lake Tanganyika,East Africa

In this study, we measured growth trends in oxygen and carbon isotopic ratios in whole sagittal otoliths from three adult centropomid fish (Lates stappersii) from each of three sub-basins of Lake Tanganyika, East Africa. Sampling density was 20 to 50 samples per otolith. Both δ¹⁸O and δ¹³C values increase with age. The δ¹⁸O data suggest that otoliths were precipitated near the expected equilibrium with the ambient environment (ca. +3.5‰) and support a migration pattern from surface waters during larval stages to deeper waters (40 to 80 m) for mature fish. Relatively high δ¹⁸O values in the southern sub-basin are consistent with cooler temperatures in the region during seasonal upwelling. The δ13C increase from otolith core to edge is large (up to 4‰) and is interpreted as due to ontogenetic changes in diet and contributions from a decrease in the proportion of respired CO₂ incorporated into otolith carbonate as metabolic rates of the fish dropped with maturity. The data seem to successfully reveal life strategy and migration patterns of L. stappersii, document regional differences in lake conditions, and provide a record of temperature within the water column during which the fish lived. Higher resolution studies and analyses of historical samples could be used to constrain modern and past growth patterns, and to reconstruct past temperature gradients and productivity patterns in the lake.     

The oxidation of two ternary Ni-Cu-10 at.% Al alloys in 1 atm of pure O2 at 800-900 °C

The oxidation of the ternary alloys Ni-45Cu-10Al and Ni-30Cu-10Al has been studied at 800-900 °C under 1 atm O₂. The presence of 10 at.% Al reduces significantly the oxidation rate of the corresponding Cu-Ni alloys during the initial oxidation stages, even before the establishment of a complete Al₂O₃ layer. The weight of individual sample of the two ternary Ni-Cu-10Al alloys at 800 °C increases more rapidly than at 900 °C during the initial oxidation stage. As oxidation proceeds, the weight gain at 800 °C slows down to a degree that the total weight gain after 24 h oxidation at 800 °C is less than that at 900 °C. Due to a faster formation of the Al₂O₃ layer, which suppresses earlier the further oxidation of Cu and Ni, the external region of the scales grown on Ni-45Cu-10Al contain much less Cu and Ni oxides than those grown on Ni-30Cu-10Al. The transition from the internal oxidation to the selective external oxidation of the most reactive component Al in Ni-Cu-Al alloys is favored by higher values of the Al content, of temperature and of the Cu/Ni ratio.     

Influence of Drying Conditions on Ascorbic Acid during Convective Drying of Whole Persimmons

Degradation kinetics of food constituents may be related to the matrix molecular mobility by glass transition temperature. Our objective was to test this approach to describe ascorbic acid degradation during drying of persimmons in an automatically controlled tray dryer with temperatures (40 to 70°C) and air velocities (0.8 to 2.0 m/s) varying according a second order central composite design. The Williams-Landel-Ferry model was satisfactorily adjusted to degradation curves for both control strategies adopted—constant air temperature and temperature fixed inside the fruit. Degradation rates were higher at higher drying temperatures, independent of the necessary time to attain the desired moisture content.     

High resolution XPS characterization of chemical functionalised MWCNTs and SWCNTs

High resolution XPS analysis of chemical functionalised multi-wall carbon nanotubes (MWCNTs) and single wall carbon nanotubes (SWCNT) was done with ESCA300 (overall instrument resolution of 0.35 eV). Information to the degree of functionalisation was ascertained by argon ion bombardment of the samples followed by XPS analysis to detect the functional groups, the percentage atomic concentration of various elements present and whether or not the detected functional groups imposed a chemical shift on the CNT atoms. The results show that true chemical functionalisation was achieved and by argon ion bombardment these functional groups can be altered relative to the C 1s carbon atoms of the CNT. The choice of chemicals used for functionalisation, the techniques employed and the types of nanotubes treated are important factors in chemical characterisation. The carbon atom on the nanotube ring to which the functional group (atom) is bonded, the chirality of the CNT, the electronegativity of the functional group, the bond type and whether the CNT is single-wall or multi-wall, or cut (short) could play a role in determining the chemical shift on the CNTs atoms. These investigations are relevant to chemical functionalisation of carbon nanotubes for various applications for example DNA sensors and other biomedical sensors.     

Scrolls and nested tubes in multiwall carbon nanotubes

Recent high-resolution transmission electron microscopy (HREM) studies of multiwalled carbon nanotubes (MWCNTs) reveal a class of defects analogous to edge dislocations in a crystal. These defects are believed to mark the transition from scrolls on one side to nested tubes on the other. On the tube side, layer spacing becomes irregular. Analysis of the helicity of the tubes shows a strong correlation between diameter and helicity. This suggests that the organizing principle for the tubes is not Van der Waals forces, as in the case of graphite or turbostratic carbon, but preservation of helicity. Based on these observations and total energy calculations, the authors speculate that graphene monolayers initially form scrolls and subsequently transform into multiwall nanotubes through the progression of defects. Scrolls and nested tubes thus coexist within a single MWNT.