Deposition of combustion aerosols in the human respiratory tract : comparison of theoretical predictions with experimental data

Total deposition of petrol, diesel and environmental tobacco smoke (ETS) aerosols in the human respiratory tract for nasal breathing conditions was computed for 14 nonsmoking volunteers, considering the specific anatomical and respiratory parameters of each volunteer and the specific size distribution for each inhalation experiment. Theoretical predictions were 34.6% for petrol, 24.0% for diesel, and 18.5% for ETS particles. Compared to the experimental results, predicted deposition values were consistently smaller than the measured data (41.4% for petrol, 29.6% for diesel, and 36.2% for ETS particles). The apparent discrepancy between experimental data on total deposition and modeling results may be reconciled by considering the non-spherical shape of the test aerosols by diameter-dependent dynamic shape factors to account for differences between mobility-equivalent and volume-equivalent or thermodynamic diameters. While the application of dynamic shape factors is able to explain the observed differences for petrol and diesel particles, additional mechanisms may be required for ETS particle deposition, such as the size reduction upon inspiration by evaporation of volatile compounds and/or condensation-induced restructuring, and, possibly, electrical charge effects.

Experimental and theoretical studies of the redox potentials of cyclic nitroxides

The redox potentials of 25 cyclic nitroxides from four different structural classes (pyrrolidine, piperidine, isoindoline, and azaphenalene) were determined experimentally by cyclic voltammetry in acetonitrile, and also via high-level ab initio molecular orbital calculations. It is shown that the potentials are influenced by the type of ring system, ring substituents and/or groups surrounding the radical moiety. For the pyrrolidine, piperidine, and isoindolines there is excellent agreement (mean absolute deviation of 0.05 V) between the calculated and experimental oxidation potentials; for the azaphenalenes, however, there is an extraordinary discrepancy (mean absolute deviation of 0.60 V), implying that their one-electron oxidation might involve additional processes not considered in the theoretical calculations. This recently developed azaphenalene class of nitroxide represents a new variant of a nitroxide ring fused to an aromatic system and details of the synthesis of five derivatives involving differing aryl substitution are also presented.

Thin film deposition and characterization of pure and iron-doped electron-beam evaporated tungsten oxide for gas sensors

Pure Tungsten Oxide (WO3) and Iron-doped (10 at%) Tungsten Oxide (WO3:Fe) nanostructured thin films were prepared using a dual crucible Electron Beam Evaporation techniques. The films were deposited at room temperature in high vacuum condition on glass substrate and post-heat treated at 300 oC for 1 hour. From the study of X-ray diffraction and Raman the characteristics of the as-deposited WO3 and WO3:Fe films indicated non-crystalline nature. The surface roughness of all the films showed in the order of 2.5 nm as observed using Atomic Force Microscopy (AFM). X-Ray Photoelectron Spectroscopy (XPS) analysis revealed tungsten oxide films with stoichiometry close to WO3. The addition of Fe to WO3 produced a smaller particle size and lower porosity as observed using Transmission Electron Microscopy (TEM). A slight difference in optical band gap energies of 3.22 eV and 3.12 eV were found between the as-deposited WO3 and WO3:Fe films, respectively. However, the difference in the band gap energies of the annealed films were significantly higher having values of 3.12 eV and 2.61 eV for the WO3 and WO3:Fe films, respectively. The heat treated samples were investigated for gas sensing applications using noise spectroscopy and doping of Fe to WO3 reduced the sensitivity to certain gasses. Detailed study of the WO3 and WO3:Fe films gas sensing properties is the subject of another paper.

Accelerated computation of cyclic steady state for simulated-moving-bed processes

Industrial applications of the simulated-moving-bed (SMB) chromatographic technology have brought an emergent demand to improve the SMB process operation for higher efficiency and better robustness. Improved process modelling and more-efficient model computation will pave a path to meet this demand. However, the SMB unit operation exhibits complex dynamics, leading to challenges in SMB process modelling and model computation. One of the significant problems is how to quickly obtain the steady state of an SMB process model, as process metrics at the steady state are critical for process design and real-time control. The conventional computation method, which solves the process model cycle by cycle and takes the solution only when a cyclic steady state is reached after a certain number of switching, is computationally expensive. Adopting the concept of quasi-envelope (QE), this work treats the SMB operation as a pseudo-oscillatory process because of its large number of continuous switching. Then, an innovative QE computation scheme is developed to quickly obtain the steady state solution of an SMB model for any arbitrary initial condition. The QE computation scheme allows larger steps to be taken for predicting the slow change of the starting state within each switching. Incorporating with the wavelet-based technique, this scheme is demonstrated to be effective and efficient for an SMB sugar separation process. Moreover, investigations are also carried out on when the computation scheme should be activated and how the convergence of the scheme is affected by a variable stepsize.

Selection and optimization of piezoelectric polyvinylidene fluoride polymers for adaptive optics in space environments

Various piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest for large aperture space-based telescopes. Dimensional adjustments of adaptive polymer films depend on charge deposition and require a detailed understanding of the piezoelectric material responses which are expected to deteriorate owing to strong vacuum UV, � -, X-ray, energetic particles and atomic oxygen exposure. We have investigated the degradation of PVDF and its copolymers under various stress environments detrimental to reliable operation in space. Initial radiation aging studies have shown complex material changes with lowered Curie temperatures, complex material changes with lowered melting points, morphological transformations and significant crosslinking, but little influence on piezoelectric d33 constants. Complex aging processes have also been observed in accelerated temperature environments inducing annealing phenomena and cyclic stresses. The results suggest that poling and chain orientation are negatively affected by radiation and temperature exposure. A framework for dealing with these complex material qualification issues and overall system survivability predictions in low earth orbit conditions has been established. It allows for improved material selection, feedback for manufacturing and processing, material optimization/stabilization strategies and provides guidance on any alternative materials.

Piezoelectric PVDF materials performance and operation limits in space environments

Piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest for large aperture space-based telescopes. Dimensional adjustments of adaptive polymer films are achieved via charge deposition and require a detailed understanding of the piezoelectric material responses which are expected to suffer due to strong vacuum UV, gamma, X-ray, energetic particles and atomic oxygen under low earth orbit exposure conditions. The degradation of PVDF and its copolymers under various stress environments has been investigated. Initial radiation aging studies using gamma- and e-beam irradiation have shown complex material changes with significant crosslinking, lowered melting and Curie points (where observable), effects on crystallinity, but little influence on overall piezoelectric properties. Surprisingly, complex aging processes have also been observed in elevated temperature environments with annealing phenomena and cyclic stresses resulting in thermal depoling of domains. Overall materials performance appears to be governed by a combination of chemical and physical degradation processes. Molecular changes are primarily induced via radiative damage, and physical damage from temperature and AO exposure is evident as depoling and surface erosion. Major differences between individual copolymers have been observed providing feedback on material selection strategies.

Deposition of hydroxyapatite and calcium oxalate dihydrate on a heat exchanger tube

Most studies on the characterisation of deposits on heat exchangers have been based on bulk analysis, neglecting the fine structural features and the compositional profiles of layered deposits. Attempts have been made to fully characterise a fouled stainless steel tube obtained from a quintuple Roberts evaporator of a sugar factory using X-ray diffraction and scanning electron microscopy techniques. The deposit contains three layers at the bottom of the tube and two layers on the other sections and is composed of hydroxyapatite, calcium oxalate dihydrate and an amorphous material. The proportions of these phases varied along the tube height. Energy-dispersive spectroscopy and XRD analysis on the surfaces of the outermost and innermost layers showed that hydroxyapatite was the major phase attached to the tube wall, while calcium oxalate dihydrate (with pits and voids) was the major phase on the juice side. Elemental mapping of the cross-sections of the deposit revealed the presence of a mineral, Si-Mg-Al-Fe-O, which is probably a silicate mineral. Reasons for the defects in the oxalate crystal surfaces, the differences in the crystal size distribution from bottom to the top of the tube and the composite fouling process have been postulated.

A cyclic porphyrin tetramer linked by azo and butadiyne bridges

A soluble cyclic porphyrin oligomer (CPO) consisting of four 5,10- diarylporphyrins linked by alternating azo and butadiyne bridges has been synthesised via an aminated dinickel(II) butadiyne dimer. This is the first cyclic tetramer that combines both azo and butadiyne bridges and extends the azoporphyrin family, which comprises only a very few examples. The electronic absorption spectrum of the tetramer is more similar to spectra of azoporphyrins than to those of butadiyne-linked dimers or tetramer, exhibiting a two component Soret band with a splitting of 4190 cm-1 and a strongly red-shifted Q band maximum at 735 nm.

Atmospheric deposition as a source of stormwater pollution in Gold Coast, Australia

Atmospheric deposition is one of the most important pollutant pathways for urban stormwater pollution. Atmospheric deposition can be in the form of dry and wet depositions which have distinct characteristics in terms of pollutant types, pollutant sources and influential parameters. This paper discusses the outcomes of a comprehensive study undertaken to identify the characteristics of wet and dry deposition of pollutants. Sample collection was undertaken at eight study sites with distinct characteristics. Four sites were close to road sites with varying traffic characteristics, whilst the other four sites had different land use characteristics. Dry deposition samples were collected for different antecedent dry days and wet deposition samples were collected immediately after rainfall events. The dry deposition was found to increase with the antecedent dry days and consisted of relatively coarser particles (greater than 1 µm) when compared to wet deposition. The wet deposition showed a strong affinity to rainfall depth, but was not related to the antecedent dry period. It was also found that smaller size particles (less than 1 µm) travel much longer distances from the source and deposit mainly with the wet deposition