Molecular weight characteristics of humic substances from different environments as determined by size exclusion chromatography and their statistical evaluation

Recorded molecular weights (MWs) for humic substances (HS) range from a few hundred to millions of daltons. For purposes of defining HS as a specific class of chemical compounds, it is of particular importance to ascertain if this broad range of MWs can be attributed to actual variability in molecular properties or is simply an artifact of the analytical techniques used to characterize HS. The main objectives of this study were (1)to establish if a preferential range of MWs exists for HS and (2) to determine any consistent MW properties of HS. To reach the goal, we have undertaken an approach to measure under standardized conditions the MW characteristics of a large set of HS from different natural environments. Seventy-seven humic materials were isolated from freshwater, soil, peat, and coal, such that each possessed a different fractional composition: humic acid (HA), fulvic acid (FA), and a nonfractionated mixture of HA and FA (HF). Size exclusion chromatography (SEC) was used as the analytical technique to determine molecular weight characteristics. The MW distributions were characterized by number (Mn) and weight (Mw) average MW, and by polydispersity. The complete range of Mw values varied within 4.7-30.4 kDa. The maximum Mw values were observed for peat HF and soil HA, whereas the smallest weights were measured for river water HF. Maximum values of polydispersity (3.5-4.4) were seen for peat HF and soil HA, while much lower values (1.6-3.1) were found for all preparations isolated with XAD-resins. Statistical evaluation showed consistent Mw and Mn variations with the HS source, while polydispersity was mostly a function of the isolation procedure used. A conclusion was made that HS have a preferential range of MW values that could characterize them as a specific class of chemical compounds.     

Electron-beam treatment of aromatic hydrocarbons that can be air-stripped from contaminated groundwater. 2. Gas-phase studies

The electron-beam (EB) degradation of volatile aromatics (benzene, toluene, ethylbenzene, xylenes: BTEX) in groundwater strip gas, which in the present work has been modeled by the introduction of the desired aromatic(s) to a stream of air or another gas, such as oxygen, is initiated essentially by the addition of *OH radicals to the aromatic ring, giving rise to hydroxycyclohexadienyl radicals, which form the corresponding peroxyl radicals upon addition of oxygen. As studied in some detail with benzene as a BTEX representative, various reactions of these lead to numerous oxidation products in a cascade of reactions, including the decomposition of products under the prevailing conditions of high turnover of the initial aromatic. Importantly, hydroxycyclohexadienylperoxyl radical formation is partly reversible, and the reactions of the hydroxycyclohexadienyl radicals, which thus have a significant presence in these systems, must therefore also be taken into consideration. In the gas phase, in contrast to the aqueous phase (see Part 1), the reactions of the hydroxycyclohexadienyl radicals lead to oligomeric products that appear to contribute, in addition to ionic clusters, to nucleation for the aerosols observed. Various nitrated products, among them nitrophenols, are observed when air is used for the stripping. However, these studies did not clear the pilot plant stage, since BTEX degradation using a bioreactor carried out in parallel was so successful that the EB technology was judged to be noncompetitive. As for the latter, expensive equipment consisting of a stripper, the EB machine, and an aerosol precipitator would be required. The condensed aerosols are biorefractory and would require further treatment for detoxification.     

A cantilever array-based artificial nose

We present quantitative and qualitative detection of analyte vapors using a microfabricated silicon cantilever array. To observe transduction of physical and chemical processes into nanomechanical motion of the cantilever, swelling of a polymer layer on the cantilever is monitored during exposure to the analyte. This motion is tracked by a beam-deflection technique using a time multiplexing scheme. The response pattern of eight cantilevers is analyzed via principal component analysis (PCA) and artificial neural network (ANN) techniques, which facilitates the application of the device as an artificial chemical nose. Analytes tested comprise chemical solvents, a homologous series of primary alcohols, and natural flavors. First differential measurements of surface stress change due to protein adsorption on a cantilever array are shown using a liquid cell.     

Integrated Simulation of Machine Tool and Process Interaction for Turning

The interaction between process and machine tool behaviour can lead to process instabilities in terms of self‐excited vibrations where the energy of the machine tool oscillation is generated by process excitation. The regenerative chatter effects lead to wavy surfaces on the work‐piece. This effect has been simulated for turning processes with an integrated simulation approach, which couples a time domain simulation model for the machine tool and the workpiece with an analytical turning model. In this paper a procedure is illustrated for coupling an FEA‐based 3‐dimensional turning model with the time domain model for the machine tool under consideration of the resulting workpiece surface. In comparison to an analytical approach for calculating the mechanical tool load, the 3D‐FEA‐model has the potential to determine the resulting cutting forces for even complex‐shaped tool geometries, e.g. a complicated chip breaker or a varying cutting edge radius on the main or minor cutting edge. As a matter of the huge model size the calculation time in particular for 3‐dimensional problems is comparatively long to analytical cutting force models. Therefore, in this paper an approach to reduce the calculation time by using characteristic diagrams for the calculated process forces in the FEA‐model is presented. The research has also been focused on the current major problem in the FEA‐based modelling that the thrust and feed forces are generally underestimated in the simulation.     

Impact of the Nanoscale Gap Morphology on the Plasmon Coupling in Asymmetric Nanoparticle Dimer Antennas

Coupling of plasmon resonances in metallic gap antennas is of interest for a wide range of applications due to the highly localized strong electric fields supported by these structures, and their high sensitivity to alterations of their structure, geometry, and environment. Morphological alterations of asymmetric nanoparticle dimer antennas with (sub)‐nanometer size gaps are assigned to changes of their optical response in correlative dark‐field spectroscopy and high‐resolution transmission electron microscopy (HR‐TEM) investigations. This multimodal approach to investigate individual dimer structures clearly demonstrates that the coupling of the plasmon modes, in addition to well‐known parameters such as the particle geometry and the gap size, is also affected by the relative alignment of both nanoparticles. The investigations corroborate that the alignment of the gap forming facets, and with that the gap area, is crucial for their scattering properties. The impact of a flat versus a rounded gap structure on the optical properties of equivalent dimers becomes stronger with decreasing gap size. These results hint at a higher confinement of the electric field in the gap and possibly a different onset of quantum transport effects for flat and rounded gap antennas in corresponding structures for very narrow gaps.     

Electrical Conduction Behavior of La1+xSr1−xGa3O7–δ Melilite-Type Ceramics

Ceramics of the melilite-type compound La_{1+ x} Sr_{1− x} Ga₃O_7−δ were prepared by conventional ceramic processing. Samples prepared represented the entire homogeneity region of the phase (i.e., x =−0.15 to 0.60). Electrochemical characterization under variable temperature and atmospheric conditions in the vicinity of air entailed four-point direct-current conductivity measurements and electromotive force measurements. La_{1+ x} Sr_{1− x} Ga₃O_7−δ samples exhibited a p -type behavior with generally increased conductivity with increased substitution of lanthanum for strontium, which reached a saturation value of ∼10⁻¹ S·cm⁻¹ at 950°C.     

Electrochemical oxidation analysis for dressing bronze-bonded diamond grinding wheels

Electrochemical dressing of fine-grained metal-bonded diamond grinding wheels enables to grind hard and brittle materials in the ductile mode. Optical surfaces can be manufactured by grinding, which reduces the need for subsequent, time-consuming polishing work. When using metal-bonded grinding wheels, the emerging oxides regulate the electrochemical dissolution. Bronze-bonded grinding wheels are more suitable for grinding cemented carbides and ceramics than iron-bonded grinding wheels, as it is easier to modify their chemical composition to suit a specific grinding task. They can also be sintered at lower temperatures, which reduces the risk of thermal damage to the diamond. In this paper, the dissolution and the oxidation of different bronze alloys are characterized for the electrochemical dressing process. The relevant evaluation criteria are the oxide layer thickness, the electrical behavior and the different emerging bronze alloy oxides. This work is funded by the German Research Association DFG within the Transregional Collaborative Research Center SFB/TR4 “Process Chains for the Replication of Complex Optical Elements”.     

Thermal Annealing and Propagation of Shockley Stacking Faults in 4H-SiC PiN Diodes

Stacking faults within 4H-SiC PiN diodes are known to be detrimental to device operation. Here, we present electroluminescence (EL) images of 4H-SiC PiN diodes providing evidence that electrically and optically stimulated Shockley stacking fault (SSF) propagation is a reversible process at temperatures as low as 210°C. Optical beam induced current (OBIC) images taken following complete optical stressing of a PiN diode and that lead to a small number of completely propagated SSFs provide evidence that such defects propagate across the n–/p+ interface and continue to grow throughout the p+ layer. These observations bring about questions regarding the validity of the currently accepted driving force mechanism for SSF propagation.