Comparison of contaminant removal effectiveness and air change efficiency as indicator of air diffusion quality.

The ventilation efficiency concept is an attempt to quantify a parameter that can easily distinguish the different options for air diffusion in the building spaces. Thirteen strategies of air diffusion were measured in a test chamber through the application of the tracer gas method, with the objective to validate the calculation by Computational fluid dynamics (CFD). Were compared the Air Change Efficiency (ACE) and the Contaminant Removal Effectiveness (CRE), the two indicators most internationally accepted. The main results from this work shows that the values of the numerical simulations are in good agreement with experimental measurements and also, that the solutions to be adopted for maximizing the ventilation efficiency should be the schemes that operate with low speeds of supply air and small differences between supply air temperature and the room temperature.

Preliminary study of synthesis gas production from water electrolysis, using the ELECTROFUEL (R) concept

This paper describes preliminary work on the generation of synthesis gas from water electrolysis using graphite electrodes without the separation of the generated gases. This is an innovative process, that has no similar work been done earlier. Preliminary tests allowed to establish correlations between the applied current to the electrolyser and flow rate and composition of the generated syngas, as well as a characterisation of generated carbon nanoparticles. The obtained syngas can further be used to produce synthetic liquid fuels, for example, methane, methanol or DME (dimethyl ether) in a catalytic reactor, in further stages of a present ongoing project, using the ELECTROFUEL® concept. The main competitive advantage of this project lies in the built-in of an innovative technology product, from RE (renewable energy) power in remote locations, for example, islands, villages in mountains as an alternative for energy storage for mobility constraints.

Electrospun Polyaniline-Reduced Graphene Oxide Composite Nanofibers Based High Sensitive Ammonia Gas Sensor

Ammonia is an important gas in many power plants and industrial processes so its detection is of extreme importance in environmental monitoring and process control due to its high toxicity. Ammonia’s threshold limit is 25 ppm and the exposure time limit is 8 h, however exposure to 35 ppm is only secure for 10 min. In this work a brief introduction to ammonia aspects are presented, like its physical and chemical properties, the dangers in its manipulation, its ways of production and its sources. The application areas in which ammonia gas detection is important and needed are also referred: environmental gas analysis (e.g. intense farming), automotive-, chemical- and medical industries. In order to monitor ammonia gas in these different areas there are some requirements that must be attended. These requirements determine the choice of sensor and, therefore, several types of sensors with different characteristics were developed, like metal oxides, surface acoustic wave-, catalytic-, and optical sensors, indirect gas analyzers, and conducting polymers. All the sensors types are described, but more attention will be given to polyaniline (PANI), particularly to its characteristics, syntheses, chemical doping processes, deposition methods, transduction modes, and its adhesion to inorganic materials. Besides this, short descriptions of PANI nanostructures, the use of electrospinning in the formation of nanofibers/microfibers, and graphene and its characteristics are included. The created sensor is an instrument that tries to achieve a goal of the medical community in the control of the breath’s ammonia levels being an easy and non-invasive method for diagnostic of kidney malfunction and/or gastric ulcers. For that the device should be capable to detect different levels of ammonia gas concentrations. So, in the present work an ammonia gas sensor was developed using a conductive polymer composite which was immobilized on a carbon transducer surface. The experiments were targeted to ammonia measurements at ppb level. Ammonia gas measurements were carried out in the concentration range from 1 ppb to 500 ppb. A commercial substrate was used; screen-printed carbon electrodes. After adequate surface pre-treatment of the substrate, its electrodes were covered by a nanofibrous polymeric composite. The conducting polyaniline doped with sulfuric acid (H2SO4) was blended with reduced graphene oxide (RGO) obtained by wet chemical synthesis. This composite formed the basis for the formation of nanofibers by electrospinning. Nanofibers will increase the sensitivity of the sensing material. The electrospun PANI-RGO fibers were placed on the substrate and then dried at ambient temperature. Amperometric measurements were performed at different ammonia gas concentrations (1 to 500 ppb). The I-V characteristics were registered and some interfering gases were studied (NO2, ethanol, and acetone). The gas samples were prepared in a custom setup and were diluted with dry nitrogen gas. Electrospun nanofibers of PANI-RGO composite demonstrated an enhancement in NH3 gas detection when comparing with only electrospun PANI nanofibers. Was visible higher range of resistance at concentrations from 1 to 500 ppb. It was also observed that the sensor had stable, reproducible and recoverable properties. Moreover, it had better response and recovery times. The new sensing material of the developed sensor demonstrated to be a good candidate for ammonia gas determination.

Preparation of gas-filled porous microparticles (GPPs) and microbubbles (MBs) by PGSS method

Dissertation to obtain the Master Degree in Biotechnology

Structural, mechanical and piezoelectric properties of polycrystalline AlN films sputtered on titanium bottom electrodes

Polycrystalline AlN coatings deposited on Ti-electrodes films were sputtered by using nitrogen both as reactive gas and sputtering gas, in order to obtain high purity coatings with appropriate properties to be further integrated into wear resistance coatings as a piezoelectric monitoring wear sensor. The chemical composition, the structure and the morphology of the films were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and atomic force microscopy techniques. These measurements show the formation of highly (101), (102) and (103) oriented AlN films with good piezoelectric and mechanical properties suitable for applications in electronic devices. Through the use of lower nitrogen flow a densification of the AlN coating occurs in the microstructure, with an improvement of the crystallinity along with the increase of the hardness. Thermal stability of aluminum nitride coatings at high temperature was also examined. It was found an improvement of the piezoelectric properties of the highly (10x) oriented AlN films which became c-axis (002) oriented after annealing. The mechanical behavior after heat treatment shows an important enhancement of the surface hardness and Young’s modulus, which decrease rapidly with the increase of the indentation depth until approach constant values close to the substrate properties after annealing. Thus, thermal annealing energy promotes not only the rearrangement of Al–N network, but also the occurrence of a nitriding process of unsaturated Al atoms which cause a surface hardening of the film.

Plasma-enhanced chemical vapor deposition of boron nitride thin films from B2H6-H2-NH3 and B2H6-N2 gas mixtures

Highly transparent and stoichiometric boron nitride (BN) films were deposited on both electrodes (anode and cathode) of a radio-frequency parallel-plate plasma reactor by the glow discharge decomposition of two gas mixtures: B2H6-H2-NH3 and B2H6-N2. The chemical, optical, and structural properties of the films, as well as their stability under long exposition to humid atmosphere, were analyzed by x-ray photoelectron, infrared, and Raman spectroscopies; scanning and transmission electron microscopies; and optical transmittance spectrophotometry. It was found that the BN films grown on the anode using the B2H6-H2-NH3 mixture were smooth, dense, adhered well to substrates, and had a textured hexagonal structure with the basal planes perpendicular to the film surface. These films were chemically stable to moisture, even after an exposition period of two years. In contrast, the films grown on the anode from the B2H6-N2 mixture showed tensile stress failure and were very unstable in the presence of moisture. However, the films grown on the cathode from B2H6-H2-NH3 gases suffered from compressive stress failure on exposure to air; whereas with B2H6-N2 gases, adherent and stable cathodic BN films were obtained with the same crystallographic texture as anodic films prepared from the B2H6-H2-NH3 mixture. These results are discussed in terms of the origin of film stress, the effects of ion bombardment on the growing films, and the surface chemical effects of hydrogen atoms present in the gas discharge.

The use of heterogeneous chemistry for the characterization of functional groups at the gas/particle interface of soot and TiO(2) nanoparticles

Six gases (N((CH3)3), NH2OH, CF3COOH, HCl, NO2, O3) were selected to probe the surface of seven combustion aerosol (amorphous carbon, flame soot) and three types of TiO2 nanoparticles using heterogeneous, that is gas-surface reactions. The gas uptake to saturation of the probes was measured under molecular flow conditions in a Knudsen flow reactor and expressed as a density of surface functional groups on a particular aerosol, namely acidic (carboxylic) and basic (conjugated oxides such as pyrones, N-heterocycles) sites, carbonyl (R1-C(O)-R2) and oxidizable (olefinic, -OH) groups. The limit of detection was generally well below 1% of a formal monolayer of adsorbed probe gas. With few exceptions most investigated aerosol samples interacted with all probe gases which points to the coexistence of different functional groups on the same aerosol surface such as acidic and basic groups. Generally, the carbonaceous particles displayed significant differences in surface group density: Printex 60 amorphous carbon had the lowest density of surface functional groups throughout, whereas Diesel soot recovered from a Diesel particulate filter had the largest. The presence of basic oxides on carbonaceous aerosol particles was inferred from the ratio of uptakes of CF3COOH and HCl owing to the larger stability of the acetate compared to the chloride counterion in the resulting pyrylium salt. Both soots generated from a rich and a lean hexane diffusion flame had a large density of oxidizable groups similar to amorphous carbon FS 101. TiO2 15 had the lowest density of functional groups among the three studied TiO2 nanoparticles for all probe gases despite the smallest size of its primary particles. The used technique enabled the measurement of the uptake probability of the probe gases on the various supported aerosol samples. The initial uptake probability, g0, of the probe gas onto the supported nanoparticles differed significantly among the various investigated aerosol samples but was roughly correlated with the density of surface groups, as expected. [Authors]

Methods to test gas tightness of packages

One of the primary goals for food packages is to protect food against harmful environment, especially oxygen and moisture. The gas transmission rate is the total gas transport through the package, both by permeation through the package material and by leakage through pinholes and cracks. The shelf life of a product can be extended, if the food is stored in a gas tight package. Thus there is a need to test gas tightness of packages. There are several tightness testing methods, and they can be broadly divided into destructive and nondestructive methods. One of the most sensitive methods to detect leaks is by using a non destructive tracer gas technique. Carbon dioxide, helium and hydrogen are the most commonly used tracer gases. Hydrogen is the lightest and the smallest of all gases, which allows it to escape rapidly from the leak areas. The low background concentration of H2 in air (0.5 ppm) enables sensitive leak detection. With a hydrogen leak detector it is also possible to locate leaks. That is not possible with many other tightness testing methods. The experimental work has been focused on investigating the factors which affect the measurement results with the H2leak detector. Also reasons for false results were searched to avoid them in upcoming measurements. From the results of these experiments, the appropriate measurement practice was created in order to have correct and repeatable results. The most important thing for good measurement results is to keep the probe of the detector tightly against the leak. Because of its high diffusion rate, the HZ concentration decreases quickly if holding the probe further away from the leak area and thus the measured H2 leaks would be incorrect and small leaks could be undetected. In the experimental part hydrogen, oxygen and water vapour transmissions through laser beam reference holes (diameters 1 100 μm) were also measured and compared. With the H2 leak detector it was possible to detect even a leakage through 1 μm (diameter) within a few seconds. Water vapour did not penetrate even the largest reference hole (100 μm), even at tropical conditions (38 °C, 90 % RH), whereas some O2 transmission occurred through the reference holes larger than 5 μm. Thus water vapour transmission does not have a significant effect on food deterioration, if the diameter of the leak is less than 100 μm, but small leaks (5 100 μm) are more harmful for the food products, which are sensitive to oxidation.

Modelling of hydrogen stratification and gas mixing in containment using the APROS code

Hydrogen stratification and atmosphere mixing is a very important phenomenon in nuclear reactor containments when severe accidents are studied and simulated. Hydrogen generation, distribution and accumulation in certain parts of containment may pose a great risk to pressure increase induced by hydrogen combustion, and thus, challenge the integrity of NPP containment. The accurate prediction of hydrogen distribution is important with respect to the safety design of a NPP. Modelling methods typically used for containment analyses include both lumped parameter and field codes. The lumped parameter method is universally used in the containment codes, because its versatility, flexibility and simplicity. The lumped parameter method allows fast, full-scale simulations, where different containment geometries with relevant engineering safety features can be modelled. Lumped parameter gas stratification and mixing modelling methods are presented and discussed in this master’s thesis. Experimental research is widely used in containment analyses. The HM-2 experiment related to hydrogen stratification and mixing conducted at the THAI facility in Germany is calculated with the APROS lump parameter containment package and the APROS 6-equation thermal hydraulic model. The main purpose was to study, whether the convection term included in the momentum conservation equation of the 6-equation modelling gives some remarkable advantages compared to the simplified lumped parameter approach. Finally, a simple containment test case (high steam release to a narrow steam generator room inside a large dry containment) was calculated with both APROS models. In this case, the aim was to determine the extreme containment conditions, where the effect of convection term was supposed to be possibly high. Calculation results showed that both the APROS containment and the 6-equation model could model the hydrogen stratification in the THAI test well, if the vertical nodalisation was dense enough. However, in more complicated cases, the numerical diffusion may distort the results. Calculation of light gas stratification could be probably improved by applying the second order discretisation scheme for the modelling of gas flows. If the gas flows are relatively high, the convection term of the momentum equation is necessary to model the pressure differences between the adjacent nodes reasonably.

Automation of Chemical Spray Pyrolysis Unit and Fabrication of Sprayed CuInS2/In2S3 Solar Cell

Aim of the present work was to automate CSP process, to deposit and characterize CuInS2/In2S3 layers using this system and to fabricate devices using these films.An automated spray system for the deposition of compound semiconductor thin films was designed and developed so as to eliminate the manual labour involved in spraying and facilitate standardization of the method. The system was designed such that parameters like spray rate, movement of spray head, duration of spray, temperature of substrate, pressure of carrier gas and height of the spray head from the substrate could be varied. Using this system, binary, ternary as well as quaternary films could be successfully deposited.The second part of the work deal with deposition and characterization of CuInS2 and In2S3 layers respectively.In the case of CuInS2 absorbers, the effects of different preparation conditions and post deposition treatments on the optoelectronic, morphological and structural properties were investigated. It was observed that preparation conditions and post deposition treatments played crucial role in controlling the properties of the films. The studies in this direction were useful in understanding how the variation in spray parameters tailored the properties of the absorber layer. These results were subsequently made use of in device fabrication process.Effects of copper incorporation in In2S3 films were investigated to find how the diffusion of Cu from CuInS2 to In2S3 will affect the properties at the junction. It was noticed that there was a regular variation in the opto-electronic properties with increase in copper concentration.Devices were fabricated on ITO coated glass using CuInS2 as absorber and In2S3 as buffer layer with silver as the top electrode. Stable devices could be deposited over an area of 0.25 cm2, even though the efficiency obtained was not high. Using manual spray system, we could achieve devices of area 0.01 cm2 only. Thus automation helped in obtaining repeatable results over larger areas than those obtained while using the manual unit. Silver diffusion on the cells before coating the electrodes resulted in better collection of carriers.From this work it was seen CuInS2/In2S3 junction deposited through automated spray process has potential to achieve high efficiencies.

Gas-solid reactions of single crystals: a study of the reaction of bromine with single crystals of trans-cinnamic acid and a range of its derivatives by infrared and Raman microspectroscopy

Single crystals of trans-cinnamic acid and of a range of derivatives of this compound containing halogen substituents on the aromatic ring have been reacted with 165 Torr pressure of bromine vapour in a sealed desiccator at 20 degrees C for 1 week. Infrared and Raman microspectroscopic examination of the crystals shows that bromination of the aliphatic double bond, but not of the aromatic ring, has occurred. It is demonstrated also that the reaction is truly gas-solid in nature. A time-dependent study of these reactions shows that they do not follow a smooth diffusion-controlled pathway. Rather the reactions appear to be inhomogeneous and to occur at defects within the crystal. The reaction products are seen to flake from the surface of the crystal. It is shown, therefore, that these are not single crystal to single crystal transitions, as have been observed previously for the photodimerisation of trans-cinnamic acid and several of its derivatives. It is shown that there are no by-products of the reaction and that finely ground samples react to form the same products as single crystals.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory studies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (carbon-carbon double bonds) can reach chemical lifetimes of many hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (< 10(-10) cm(2) s(-1)). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas–particle interactions (P¨oschl et al., 5 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface 10 concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory stud15 ies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial transport and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (C=C double bonds) can reach chemical lifetimes of 20 multiple hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (10−10 cm2 s−1). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB 25 as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modelled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmo- spheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270 K is close to unity. Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for eðcient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KMGAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KMGAP is based on the PRA model framework (P¨oschl-Rudich- Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system and the computational constraints, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270K is close to unity (Winkler et al., 2006). Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.