Insight into the key aspects of the regeneration process in the NOx storage reduction (NSR) reaction probed using fast transient kinetics coupled with isotopically labelled (NO)-N-15 over Pt and Rh-containing Ba/Al2O3 catalysts

For the first time, the coupling of fast transient kinetic switching and the use of an isotopically labelled reactant (15NO) has allowed detailed analysis of the evolution of all the products and reactants involved in the regeneration of a NOx storage reduction (NSR) material. Using realistic regeneration times (ca. 1 s) for Pt, Rh and Pt/Rh-containing Ba/Al2O3 catalysts we have revealed an unexpected double peak in the evolution of nitrogen. The first peak occurred immediately on switching from lean to rich conditions, while the second peak started at the point at which the gases switched from rich to lean. The first evolution of nitrogen occurs as a result of the fast reaction between H2 and/or CO and NO on reduced Rh and/or Pt sites. The second N2 peak which occurs upon removal of the rich phase can be explained by reaction of stored ammonia with stored NOx, gas phase NOx or O2. The ammonia can be formed either by hydrolysis of isocyanates or by direct reaction of NO and H2.

The study highlights the importance of the relative rates of regeneration and storage in determining the overall performance of the catalysts. The performance of the monometallic 1.1%Rh/Ba/Al2O3 catalyst at 250 and 350 °C was found to be dependent on the rate of NOx storage, since the rate of regeneration was sufficient to remove the NOx stored in the lean phase. In contrast, for the monometallic 1.6%Pt/Ba/Al2O3 catalyst at 250 °C, the rate of regeneration was the determining factor with the result that the amount of NOx stored on the catalyst deteriorated from cycle to cycle until the amount of NOx stored in the lean phase matched the NOx reduced in the rich phase. On the basis of the ratio of exposed metal surface atoms to total Ba content, the monometallic 1.6%Pt/Ba/Al2O3 catalyst outperformed the Rh-containing catalysts at 250 and 350 °C even when CO was used as a reductant.

Comparison between fluid simulations and experiments in inductively coupled argon/chlorine plasmas

Comparisons of 2D fluid simulations with experimental measurements of Ar/Cl-2 plasmas in a low-pressure inductively coupled reactor are reported. Simulations show that the wall recombination coefficient of Cl atom (gamma) is a crucial parameter of the model and that neutral densities are very sensitive to its variations. The best agreement between model and experiment is obtained for gamma = 0.02, which is much lower than the value predicted for stainless steel walls (gamma = 0.6). This is consistent with reactor wall contaminations classically observed in such discharges. The electron density, negative ion fraction and Cl atom density have been investigated under various conditions of chlorine and argon concentrations, gas pressure and applied rf input power. The plasma electronegativity decreases with rf power and increases with chlorine concentration. At high pressure, the power absorption and distribution of charged particles become more localized below the quartz window. Although the experimental trends are well reproduced by the simulations, the calculated charged particle densities are systematically overestimated by a factor of 3-5. The reasons for this discrepancy are discussed in the paper.

Space and phase resolved optical emission in mode transitions of radio-frequency inductively coupled plasmas

Inductively coupled radio-frequency plasmas can be operated in two distinct modes. At low power and comparatively low plasma densities the plasma is sustained in capacitive mode (E-mode). As the plasma density increases a transition to inductive mode (H-mode) is observed. This transition region is of particular interest and governed by non-linear dynamics, which under certain conditions results in structure formation with strong spatial gradients in light emission. These modes show pronounced differences is various measureable quantities e.g. electron densities, electron energy distribution functions, ion energy distribution functions, dynamics of optical light emission. Here the transition from E- to H- mode in an oxygen containing inductively coupled plasma (ICP) is investigated using space and phase resolved optical emission spectroscopy (PROES). The emission, measured phase resolved, allows investigation of the electron dynamics within the rf cycle, important for understanding the power coupling and ionization mechanisms in the discharge. The temporal variation of the emission reflects the dynamics of relatively high-energy electrons. It is possible to distinguish between E- and H-mode from the intensity and temporal behaviour of the emission.

Argon metastable state densities in inductively coupled plasma in mixtures of Ar and O2

We have measured the densities of 1s5 and 1s3 argon metastables as a function of the abundance of molecular oxygen in an inductively coupled plasma (ICP) in mixtures of Ar and O2. Laser absorption spectroscopy was used to determine the densities of the metastables. It was found that even small abundances of oxygen lead to large increases in metastable density, mostly due to the reduction in the electron number density, since electron-induced quenching determines the metastable density. At abundances higher than 7% to 15% for powers between 50 and 150W, quenching by oxygen molecules begins to dominate and the metastable density drops again.

Compact ridge waveguide filter with parallel and series-coupled resonators

A novel 3rd-order compact E-plane ridge waveguide filter is presented. Miniaturization is achieved upon introducing a configuration of parallel-coupled E-plane ridge waveguide resonators. Furthermore, the proposed filter allows for transmission zeros at finite frequencies. Fabrication simplicity and mass producibility of standard E-plane filters is maintained. The numerical and experimental results are presented to validate the proposed configuration. A miniaturisation factor of 2 and very sharp upper cutoff are achieved. 2005 Wiley Periodicals, Inc.

Coupled heat and moisture transfer in multi-layer building materials

A dynamic mathematical model for simulating the coupled heat and moisture migration through multilayer porous building materials was proposed. Vapor content and temperature were chosen as the principal driving potentials. The discretization of the governing equations was done by the finite difference approach. A new experimental set-up was also developed in this study. The evolution of transient temperature and moisture distributions inside specimens were measured. The method for determining the temperature gradient coefficient was also presented. The moisture diffusion coefficient, temperature gradient coefficient, sorption–desorption isotherms were experimentally evaluated for some building materials (sandstone and lime-cement mortar). The model was validated by comparing with the experimental data with good agreement. Another advantage of the method lies in the fact that the required transport properties for predicting the non-isothermal moisture flow only contain the vapor diffusion coefficient and temperature gradient coefficient. They are relatively simple, and can be easily determined.

Simulation of coupled heat and moisture transfer in air-conditioned buildings

The simultaneous heat and moisture transfer in the building envelope has an important influence on the indoor environment and the overall performance of buildings. In this paper, a model for predicting whole building heat and moisture transfer was presented. Both heat and moisture transfer in the building envelope and indoor air were simultaneously considered; their interactions were modeled. The coupled model takes into account most of the main hygrothermal effects in buildings. The coupled system model was implemented in MATLAB-Simulink, and validated by using a series of published testing tools. The new program was applied to investigate the moisture transfer effect on indoor air humidity and building energy consumption under different climates. The results show that the use of more detailed simulation routines can result in improvements to the building's design for energy optimisation through the choice of proper hygroscopic materials, which would not be indicated by simpler calculation techniques.