Effect of current density and sulfuric acid concentration on persulfuric acid generation by boron-doped diamond film anodes

This research investigated the effects of current density and sulfuric acid concentration on the rates of persulfate generation by boron-doped diamond film anodes. Also investigated was the maximum conversion of sulfate to persulfate that could be achieved from electrolysis of sulfuric acid. Experiments were performed in batch systems using a rotating disk electrode (RDE) and a flow-through reactor with parallel plate electrodes. Both the RDE and flow-through experiments showed that there was a linear relationship between persulfate generation rates and current density. Persulfate generation rates became current limited at sulfuric acid concentrations of 2.25 M and above; however, Faradaic efficiencies under current-limited conditions were only ~60 %, and were only weakly dependent on the current density. Persulfate generation rates in the flow-through reactor showed similar dependencies on current density and sulfuric acid concentration as those in the RDE reactor, but were 20–50 % lower. Acid catalyzed and thermal decomposition of persulfate limited the maximum conversion of sulfate to persulfate. A maximum fractional conversion of 78 % was achieved using an initial sulfuric acid concentration of 0.77 M. Surprisingly, this value was independent of the current density over the range of 100–300 mA cm^?2.     

Al2O3/Cu-O composites fabricated by pressureless infiltration of paper-derived Al2O3 porous preforms

Al₂O₃/Cu-O composites were fabricated from the paper-derived alumina matrix infiltrated with a Cu-3.2?wt% O alloy. Paper-derived alumina preforms with an open porosity ranging from ～ 14 to ～ 25?vol% were prepared by sintering of alumina-loaded preceramic papers at 1600?°C for 4?h. Pressureless infiltration at 1320?°C for 4?h of the preforms with Cu–O alloy resulted in the nearly dense materials with good mechanical and electrical properties, e.g. fracture toughness up to 6?MPa?m^0.5, four-point-bending strength up to 342?MPa, Young's modulus up to 281?GPa and electrical conductivity up to 2?MS/m depending on the volume fraction of copper alloy in the composites. The technological capability of this approach was demonstrated using prototypes in various engineering fields fabricated by lamination, corrugating and Laminated Object Manufacturing (LOM) methods.     

Konstruktion und Test eines Gradientensystems für NMR‐Diffusionsuntersuchungen in Grenzflächensystemen

A z‐gradient system for NMR diffusion measurements with intensive pulsed field gradients was redesigned. The gradient field of an actively screened gradient coil was optimized using finite element analysis. The gradient system was constructed with glass ceramic as coil support material. It does not show any background ¹H NMR signal and has a high current‐to‐gradient conversion factor of 0.37 T m^–1A^–1. The functionality of the system for studying slow diffusion processes in interface systems is demonstrated by observing isotropic and anisotropic diffusion in aqueous solutions of a PEO‐PPO‐PEO triblock copolymer and of methane in two different microporous crystalline absorbencies.     

Development of a model for the sintering of PZT multilayer ceramics and their dielectric properties

Piezoelectric multilayer ceramics are increasingly used in sophisticated applications for high-precision positioning systems. The reproducibility of the piezo-electrical properties is of major importance for the manufacture of high quality products. This study focuses on the variation of the sintering parameters and its effect on the poling behaviour as a contribution to the establishment of an understanding of PZT multilayer processing. To cover the complexity of the sintering process, the experiments were conducted with the design of experiments method. As parameters the sintering temperature, the holding time, the airflow in the furnace and the lead oxide atmosphere were investigated. As target variables the grain size, density and mass loss were investigated. In the following the correlations between the target variables and the sintering parameters were discussed and summarised in a model. The ceramic properties were correlated to the dielectric properties and the influence of the poling process was evaluated.     

Robocasting of alumina hollow filament lattice structures

Robotic controlled deposition (robocasting) of an aqueous colloidal α-Al₂O₃ gel for manufacturing of cellular ceramics with periodical lattice structure was investigated. The colloidal gel was loaded with 50 vol% α-Al₂O₃ and exhibits shear-thinning behavior, a shear modulus of 288 kPa and a yield-stress of ～700 Pa. Tubular filaments of circular and rectangular cross section having an outer diameter of 1.5 mm and a capillary diameter of 0.75 mm were deposited in an oil bath to fabricate lattice truss structures with free spanning filaments. After freeze drying the robocast grids were sintered in air at 1550 °C. X-ray μ-CT revealed continuity of the tubular filaments for long distances (～650 mm). Critical conditions to avoid capillary collapse were discussed by considering bulging stress and pressure distribution within the hollow filament. At short filament length oil infiltration into the capillary driven by capillary suction supports the tubular filament whereas oil flow driven by movement of the tool nozzle causes pressure difference to increase linearly with increasing filament length.     

Production of 1‐Octanol from n‐Octane by Pseudomonas putida KT2440

A two‐phase biotransformation process for selective hydroxylation of n‐octane to 1‐octanol via Pseudomonas putida KT2440 harboring heterologously expressed P450 monooxygenase from Mycobacterium marinum is presented. Maximum cell‐specific conversion rates of 12.7 mg_octanol g_CDWh^–1 were observed not only in shaking flasks but also in 3.7‐L‐bioreactor studies. The bioreactor experiments were performed avoiding explosive gas mixtures by lowering volumetric power input, aeration rates and substrate concentrations. Based on a stoichiometric network of P. putida KT2440 topological studies were carried out. As a conclusion, potential limitations of NAD(P)H and/or ATP supply at production conditions can be excluded. Hence, the great potential of the host for further increasing conversion is outlined.     

Real-Time Chemical Analysis of Organic Aerosols Using a Thermal Desorption Particle Beam Mass Spectrometer

An instrument has been developed for real-time, quantitative chemical analys is of organic particles in laboratory environments. In this apparatus, which we call a Thermal Desorption Particle Beam Mass Spectrometer (TDPBMS), particles are sampled into a differentially-pumped vacuum chamber, focused into a narrow, low-divergence particle beam using aerodynamic lenses, and then transported into a high-vacuum region where they impact on a heated surface, evaporate, and the vapor is mass analyzed in a quadrupole mass spectrometer. The average composition of a continuous stream of particles is thus measured in real time, and size-dependent composition can be obtained by passing the incoming aerosol through a differential mobility analyzer. The TDPBMS can analyze multi component organic particles in the 0.02-0.5mu m size range for compound concentrations 0.1-1mu g m3 without particle matrix effects. By using careful calibration techniques that account for particle shape and transport efficiency, the particulate organic components can be quantified with an estimated uncertainty of 20%. The utility of TDPBMS for laboratory studies of aerosol chemistry is demonstrated by monitoring the tridecanoic acid concentration in secondary organic aerosol formed during a smog chamber reaction of 1-tetradecene and ozone.