Gas permeation in silicon-oxide/polymer (SiOx/PET) barrier films: role of the oxide lattice, nano-defects and macro-defects

We propose a model for permeation in oxide coated gas barrier films. The model accounts for diffusion through the amorphous oxide lattice, nano-defects within the lattice, and macro-defects. The presence of nano-defects indicate the oxide layer is more similar to a nano-porous solid (such as zeolite) than silica glass with respect to permeation properties. This explains why the permeability of oxide coated polymers is much greater, and the activation energy of permeation much lower, than values expected for polymers coated with glass. We have used the model to interpret permeability and activation energies measured for the inert gases (He, Ne and Ar) in evaporated SiOx films of varying thickness (13-70 nm) coated on a polymer substrate. Atomic force and scanning electron microscopy were used to study the structure of the oxide layer. Although no defects could be detected by microscopy, the permeation data indicate that macro-defects (>1 nm), nano-defects (0.3-0.4 nm) and the lattice interstices (<0.3 nm) all contribute to the total permeation. (C) 2002 Elsevier Science B.V. All rights reserved.

Development of a novel titration and off-gas analysis (TOGA) sensor for study of biological processes in wastewater treatment systems

The development of the new TOGA (titration and off-gas analysis) sensor for the detailed study of biological processes in wastewater treatment systems is outlined. The main innovation of the sensor is the amalgamation of titrimetric and off-gas measurement techniques. The resulting measured signals are: hydrogen ion production rate (HPR), oxygen transfer rate (OTR), nitrogen transfer rate (NTR), and carbon dioxide transfer rate (CTR). While OTR and NTR are applicable to aerobic and anoxic conditions, respectively, HPR and CTR are useful signals under all of the conditions found in biological wastewater treatment systems, namely, aerobic, anoxic and anaerobic. The sensor is therefore a powerful tool for studying the key biological processes under all these conditions. A major benefit from the integration of the titrimetric and off-gas analysis methods is that the acid/base buffering systems, in particular the bicarbonate system, are properly accounted for. Experimental data resulting from the TOGA sensor in aerobic, anoxic, and anaerobic conditions demonstrates the strength of the new sensor. In the aerobic environment, carbon oxidation (using acetate as an example carbon source) and nitrification are studied. Both the carbon and ammonia removal rates measured by the sensor compare very well with those obtained from off-line chemical analysis. Further, the aerobic acetate removal process is examined at a fundamental level using the metabolic pathway and stoichiometry established in the literature, whereby the rate of formation of storage products is identified. Under anoxic conditions, the denitrification process is monitored and, again, the measured rate of nitrogen gas transfer (NTR) matches well with the removal of the oxidised nitrogen compounds (measured chemically). In the anaerobic environment, the enhanced biological phosphorus process was investigated. In this case, the measured sensor signals (HPR and CTR) resulting from acetate uptake were used to determine the ratio of the rates of carbon dioxide production by competing groups of microorganisms, which consequently is a measure of the activity of these organisms. The sensor involves the use of expensive equipment such as a mass spectrometer and requires special gases to operate, thus incurring significant capital and operational costs. This makes the sensor more an advanced laboratory tool than an on-line sensor. (C) 2003 Wiley Periodicals, Inc.

Vertical fluxes of sediment in oscillatory sheet flow

Time series of vertical sediment fluxes are derived from concentration time series in sheet flow under waves. While the concentrations C(z,t) vary very little with time for \z\ < 10d(50), the measured vertical sediment fluxes Q(zs)(z,t) vary strongly with time in this vertical band and their time variation follows, to some extent, the variation of the grain roughness Shields parameter 02,5(t). Thus, sediment distribution models based on the pickup function boundary condition are in some qualitative agreement with the measurements. However, the pickup function models are only able to model the upward bursts of sediment during the accelerating phases of the flow. They are, so far, unable to model the following strong downward sediment fluxes, which are observed during the periods of flow deceleration. Classical pickup functions, which essentially depend on the Shields parameter, are also incapable of modelling the secondary entrainment fluxes, which sometimes occur at free stream velocity reversal. The measured vertical fluxes indicate that the effective sediment settling velocity in the high [(0.3 < C(z,t) < 0.4] concentration area is typically only a few percent of the clear water settling velocity, while the measurements of Richardson and Jeronimo [Chem. Eng. Sci. 34 (1979) 1419], from a different physical setting, lead to estimates of the order 20%. The data does not support gradient diffusion as a model for sediment entrainment from the bed. That is, detailed modelling of the observed near-bed fluxes would require diffusivities that go negative during periods of flow deceleration. An observed general trend for concentration variability to increase with elevation close to the bed is also irreconcilable with diffusion models driven by a bottom boundary condition. (C) 2002 Published by Elsevier Science B.V.