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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Physics and chemistry of gas in discs

Tilling, Ian January 2013 (has links)
Protoplanetary discs set the initial conditions for planet formation. By combining observations with detailed modelling, it is possible to constrain the physics and chemistry in such discs. I have used the detailed thermo-chemical disc model ProDiMo to explore the characteristics of the gas in protoplanetary discs, particularly in Herbig Ae objects. I have assessed the ability of various observational data to trace the disc properties. This has involved a number of different approaches. Firstly I compute a series of disc models with increasing mass, in order to test the diagnostic powers of various emission lines, in particular as gas mass tracers. This approach is then expanded to a large multiparameter grid of ~ 10 5 disc models. I have helped to develop a tool for analysing and plotting the huge quantity of data presented by such a model grid. Following this approach I move on to a detailed study of the Herbig Ae star HD 163296, attempting to fit the large wealth of available observations simultaneously. These include new Herschel observations of the far-infrared emission lines, as well as interferometric CO observations and a large number of continuum data. This study addresses the topical issues of the disc gas/dust ratio, and the treatment of the disc outer edge. It explores the effects of dust settling, UV variability and stellar X-ray emission on the disc chemistry and line emission. There is possible evidence for gas-depletion in the disc of HD 163296, with the line emission enhanced by dust settling, which would indicate a later evolutionary stage for this disc than suggested by other studies. Finally, I work to improve the treatment of the gas heating/cooling balance in ProDiMo, by introducing a non-LTE treatment of the atomic hydrogen line transitions and bound-free continuum transitions. I explore the effects of this on the disc chemical and thermal structure, and assess its impact in terms of the observable quantities.
2

Desenvolvimento e avaliação de um instrumento para determinação de estabilidade oxidativa baseado em espectroscopia de emissão no infravermelho próximo / Development and evaluation of a near-infrared emission spectroscopy instrument for determination of oxidative stability

Vieira, Francisco Senna, 1988- 21 August 2018 (has links)
Orientador: Célio Pasquini / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T15:29:23Z (GMT). No. of bitstreams: 1 Vieira_FranciscoSenna_M.pdf: 2577567 bytes, checksum: 88e8b413d192407a39a0f0d341572223 (MD5) Previous issue date: 2012 / Resumo: A autoxidação de lipídeos é uma das principais causas de degradação de óleos e gorduras. Este processo gera uma série de compostos indesejáveis, tais como, peróxidos, hidroperóxidos e ácidos carboxílicos de cadeia curta. A determinação da estabilidade oxidativa de um óleo, é, portanto, essencial para estimar o tempo de prateleira - um parâmetro importante para a indústria alimentícia. Para quantificar o grau de oxidação de um óleo, uma série de parâmetros pode ser utilizada, como os índices de peróxido e de anisidina, o teor de dienos conjugados, dentre outros. Métodos acelerados foram desenvolvidos para a estabilidade oxidativa - uma medida da variação do grau de oxidação ao longo do tempo -, em particular o método Rancimat. Nele, uma amostra de cerca de 3 g de óleo e aquecida em temperaturas na faixa de 100-130 °C, e um fluxo de ar constante e passado através da amostra e carreado para um recipiente contendo água deionizada. O monitoramento da condutividade elétrica desta solução permite identificar o período de tempo necessário para que a taxa de formação de ácidos carboxílicos de cadeia curta se torne significativa. Este tempo é denominado tempo de indução (TI), e corresponde ao índice de estabilidade oxidativa (OSI - Oxidative Stability Index) do óleo. A espectroscopia de emissão no infravermelho próximo (NIRES), por outro lado, permite o monitoramento de hidroperóxidos, devido ao aumento e alargamento de uma banda em 2900 nm que ocorre ao longo do processo oxidativo. Neste trabalho foi desenvolvido e avaliado um fotômetro NIRES, dedicado para a determinação de estabilidade oxidativa. No método NIRES, uma amostra de 10 mL e aquecida a uma temperatura fixa (140 - 180 °C), sendo mantido um fluxo constante de ar purificado ao redor da amostra. A emissividade do óleo em 2850 e 2675 nm e continuamente monitorada com um detector de PbS, sendo a seleção dos comprimentos de onda realizada por dois filtros de interferência. A formação de hidroperóxidos ocasiona um aumento significativo da emissividade a 2850 nm, permitindo a determinação de TI de forma análoga ao método Rancimat.. O equipamento construído apresenta uma série de vantagens com relação ao método Rancimat, tais como: rapidez na análise, simplicidade operacional, menor consumo de amostra e a possibilidade de determinar a estabilidade oxidativa em temperaturas de fritura (140-180 °C). A precisão do método NIRES encontrada é equivalente à precisão do método Rancimat, e existe uma correlação entre eles (R = 0,90). / Abstract: Lipid autoxidation is the main cause of fats and oils deterioration. This process generates a series of undesirable compounds, such as hydroperoxides and low chain carboxylic acids. Thus, determination of oil fs oxidative stability is essential for estimation of the shelf life - an important parameter for the food industry. Several parameters are used for quantifying the degree of oxidation of an oil sample, such as the peroxide value, anisidine value, and conjugated dienes. Accelerated methods have been developed for measuring oxidative stability - the variation of the degree of oxidation with time -, particularly the Rancimat method. In this method, a constant air flow passes through a 3 g oil sample, heated at 110 - 130°C, and then is collected in a vessel containing deionized water. By monitoring the deionized water fs conductance, an induction time (IT) - which corresponds to the Oil Stability Index (OSI) - can be determined. On the other hand, near infrared emission spectroscopy (NIRES) allows the determination of IT by monitoring the formation of hydroperoxides. As the oil undergoes autoxidation, a band at 2900 nm becomes broader and more intense. In this work, a near infrared emission spectroscopy photometer, dedicated to determination of oxidative stability, has been developed and evaluated. In the NIRES method, a 10 mL oil sample is heated at a constant temperature (140 - 180 °C), and a purified air flow is maintained around the sample. The oil fs emissivity at 2675 and 2850 nm is continually monitored with a PbS detector, and the wavelengths are selected with two interference filters. Formation of hydroperoxides increases significantly the emissivity at 2900 nm, allowing the determination of IT in a way analogous to the Rancimat method. The developed equipment presents several advantages towards the Rancimat, including: faster analysis, lower sample consumption, operational simplicity, and the possibility of measuring oxidative stability at frying temperatures. Also, the method fs precision is equivalent to the Rancimat fs precision, and a correlation between them has been found (R = 0,90). / Mestrado / Quimica Analitica / Mestre em Química
3

High-resolution infrared emission spectroscopy of diatomic and triatomic metal hydrides

Shayesteh, Alireza January 2006 (has links)
Several hydrides of Group 2 and 12 elements were generated in the gas phase using an emission source that combines an electrical discharge with a high temperature furnace, and their high-resolution infrared emission spectra were recorded with a Fourier transform spectrometer. Two classes of molecules were studied: <em>a)</em> diatomic metal hydrides BeH, MgH, CaH, SrH, ZnH and CdH; <em>b)</em> linear triatomic metal hydrides BeH<sub>2</sub>, MgH<sub>2</sub>, ZnH<sub>2</sub> and HgH<sub>2</sub>. <br /><br /> Infrared emission spectra of BeH, MgH, CaH, SrH, ZnH and CdH free radicals contained several vibration-rotation bands in their <sup>2</sup>SIGMA<sup>+</sup> ground electronic state. The new data were combined with all the previous ground state data from diode laser infrared spectra and pure rotation spectra available in the literature. Spectroscopic constants, i. e. , vibrational band origins, rotational, centrifugal distortion, and spin-rotation interaction constants, were determined for each observed vibrational level by least-squares fitting of all the data. In addition, the data from all isotopologues were fitted simultaneously using the empirical Dunham-type energy level expression for <sup>2</sup>SIGMA<sup>+</sup> states, and correction parameters due to the breakdown of the Born-Oppenheimer approximation were determined. The equilibrium internuclear distances (<em>r</em><sub>e</sub>) of <sup>9</sup>BeH, <sup>24</sup>MgH, <sup>40</sup>CaH, <sup>88</sup>SrH, <sup>64</sup>ZnH and <sup>114</sup>CdH were determined to be 1. 342424(2), 1. 729721(1), 2. 002360(1), 2. 146057(1), 1. 593478(2) and 1. 760098(3) angstroms, respectively, and the corresponding <em>r</em><sup>e</sup> distances for <sup>9</sup>BeD, <sup>24</sup>MgD, <sup>40</sup>CaD, <sup>88</sup>SrD, <sup>64</sup>ZnD and <sup>114</sup>CdD are 1. 341731(2), 1. 729157(1), 2. 001462(1), 2. 145073(1), 1. 593001(2) and 1. 759695(2) angstroms, respectively. <br /><br /> Gaseous BeH<sup>2</sup>, MgH<sup>2</sup>, ZnH<sup>2</sup> and HgH<sup>2</sup> molecules were discovered and unambiguously identified by their high-resolution infrared emission spectra. The &nu;<sub>3</sub> antisymmetric stretching fundamental band and several hot bands in the &nu;<sub>3</sub> region were rotationally analyzed, and spectroscopic constants were obtained for almost all naturally-occurring isotopologues. The rotational constants of the 000 ground states were used to determine the <em>r</em><sub>0</sub> internuclear distances. For BeH<sub>2</sub>, ZnH<sub>2</sub>, ZnD<sub>2</sub>, HgH<sub>2</sub> and HgD<sub>2</sub> molecules, the rotational constants of the 000, 100, 01<sup>1</sup>0 and 001 levels were used to determine the equilibrium rotational constants (<em>B</em><sub>e</sub>) and the associated equilibrium internuclear distances <em>r</em><sub>e</sub>. The <em>r</em><sub>e</sub> distances of ZnH<sub>2</sub> and ZnD<sub>2</sub> differed by about 0. 01%, and those of HgH<sub>2</sub> and HgD<sub>2</sub> differed by about 0. 005%. These discrepancies were larger than the statistical uncertainties by one order of magnitude, and were attributed to the breakdown of the Born-Oppenheimer approximation.
4

Studies of Charge Transport and Energy Level in Solar Cells Based on Polymer/Fullerene Bulk Heterojunction

Gadisa, Abay January 2006 (has links)
π-Conjugated polymers have attracted considerable attention since they are potential candidates for various opto-electronic devices such as solar cells, light emitting iodes, photodiodes, and transistors. Electronic de vices based on conjugated polymers can be easily processed at low temperature using inexpensive technologies. This leads to cost reduction, a key-deriving factor for choosing conjugated polymers for various types of applications. In particular, polymer based solar cells are of special interest due to the fact that they can play a major role in generating clean and cheap energy in the future. The investigations described in thesis are aimed mainly at understanding charge transport and the role of energy le vels in solar cells based on polymer/acceptor bulk heterojunction (BHJ) active films. Best polymer based solar cells, with efficiency 4 to 5%, rely on polymer/fullerene BHJ active films. These solar cells are in an immature state to be used for energy conversion purposes. In order to enhance their performance, it is quite important to understand the efficiency-limiting factors. Solid films of conjugated polymers compose conjugation segments that are randomly distributed in space and energy. Such distributio n gives rise to the localization of charge carriers and hence broadening of electron density of states. Consequently, electronic wave functions have quite poor overlap resulting into absence of continuous band transport. Charge transport in polymers and organic materials, in general, takes place by hopping among the localized states. This makes a bottleneck to the performance of polymer-based solar cells. In this context, the knowledge of charge transport in the solar cell materials is quite important to develop materials and device architectures that boost the efficiency of such solar cells. Most of the transport studies are based on polyfluorene copolymers and fullerene electron acceptor molecules. Fullerenes are blended with polymers to enhance the dissociation of excited state into free carriers and transport free electrons to the respective electrode. The interaction within the polymer-fullerene complex, therefore, plays a major role in the generation and transport of both electrons and holes. In this thesis, we present and discuss the effect of various polymer/fullerene compositions on hole percolation paths. We mainly focus on hole transport since its mobility is quite small as compared to electron mobility in the fullerenes, leading to creation of spa ce charges within the bulk of the solar cell composite. Changing a polymer band gap may necessitate an appropriate acceptor type in order to fulfill the need for sufficient driving force for dissociation of photogenerated electron-hole pairs. We have observed that different acceptor types give rise to completely different hole mobility in BHJ films. The change of hole transport as a function of acceptor type and concentration is mainly attributed to morphological changes. The effect of the acceptors in connection to hole transport is also discussed. The later is supported by studies of bipolar transport in pure electron acceptor layers. Moreover, the link between charge carrier mobility and photovoltaic parameters has also been studied and presented in this thesis. The efficiency of polymer/fullerene-based solar cells is also significantly limited by its open-circuit voltage (Voc), a parameter that does not obey the metal-insulator-metal principle due to its complicated characteristics. In this thesis, we address the effect of varying polymer oxidation potential on Voc of the polymer/fullerene BHJ based solar cells. Systematic investigations have been performed on solar cells that comprise several polythiophene polymers blended with a fullerene derivative electron acceptor molecule. The Voc of such solar cells was found to have a strong correlation with the oxidation potential of the polymers. The upper limit to Voc of the aforementioned solar cells is thermodynamically limited by the net internal electric filed generated by the difference in energy levels of the two materials in the blend. The cost of polymer-based solar cells can be reduced to a great extent through realization of all-plastic and flexible solar cells. This demands the replacement of the metallic components (electrodes) by highly conducting polymer films. While hole conductor polymers are available, low work function polymer electron conductors are rare. In this thesis, prototype solar cells that utilizes a highly conducting polymer, which has a work function of ~ 4.3 eV, as a cathode are demonstrated. Development of this material may eventually lead to fabrication of large area, flexible and cheap solar cells. The transparent nature of the polymer cathode may also facilitate fabrication of multi-layer and tandem solar cells. In the last chapter of this thesis, we demonstrate generation of red and near infrared polarized light by employing thermally converted thin films of polyfluorene copolymers in light emitting diodes. This study, in particular, aims at fabricating polarized infrared light emitting devices. / On the day of the defence day the status of article III was In press and article VI was Manuscript.
5

High-resolution infrared emission spectroscopy of diatomic and triatomic metal hydrides

Shayesteh, Alireza January 2006 (has links)
Several hydrides of Group 2 and 12 elements were generated in the gas phase using an emission source that combines an electrical discharge with a high temperature furnace, and their high-resolution infrared emission spectra were recorded with a Fourier transform spectrometer. Two classes of molecules were studied: <em>a)</em> diatomic metal hydrides BeH, MgH, CaH, SrH, ZnH and CdH; <em>b)</em> linear triatomic metal hydrides BeH<sub>2</sub>, MgH<sub>2</sub>, ZnH<sub>2</sub> and HgH<sub>2</sub>. <br /><br /> Infrared emission spectra of BeH, MgH, CaH, SrH, ZnH and CdH free radicals contained several vibration-rotation bands in their <sup>2</sup>SIGMA<sup>+</sup> ground electronic state. The new data were combined with all the previous ground state data from diode laser infrared spectra and pure rotation spectra available in the literature. Spectroscopic constants, i. e. , vibrational band origins, rotational, centrifugal distortion, and spin-rotation interaction constants, were determined for each observed vibrational level by least-squares fitting of all the data. In addition, the data from all isotopologues were fitted simultaneously using the empirical Dunham-type energy level expression for <sup>2</sup>SIGMA<sup>+</sup> states, and correction parameters due to the breakdown of the Born-Oppenheimer approximation were determined. The equilibrium internuclear distances (<em>r</em><sub>e</sub>) of <sup>9</sup>BeH, <sup>24</sup>MgH, <sup>40</sup>CaH, <sup>88</sup>SrH, <sup>64</sup>ZnH and <sup>114</sup>CdH were determined to be 1. 342424(2), 1. 729721(1), 2. 002360(1), 2. 146057(1), 1. 593478(2) and 1. 760098(3) angstroms, respectively, and the corresponding <em>r</em><sup>e</sup> distances for <sup>9</sup>BeD, <sup>24</sup>MgD, <sup>40</sup>CaD, <sup>88</sup>SrD, <sup>64</sup>ZnD and <sup>114</sup>CdD are 1. 341731(2), 1. 729157(1), 2. 001462(1), 2. 145073(1), 1. 593001(2) and 1. 759695(2) angstroms, respectively. <br /><br /> Gaseous BeH<sup>2</sup>, MgH<sup>2</sup>, ZnH<sup>2</sup> and HgH<sup>2</sup> molecules were discovered and unambiguously identified by their high-resolution infrared emission spectra. The &nu;<sub>3</sub> antisymmetric stretching fundamental band and several hot bands in the &nu;<sub>3</sub> region were rotationally analyzed, and spectroscopic constants were obtained for almost all naturally-occurring isotopologues. The rotational constants of the 000 ground states were used to determine the <em>r</em><sub>0</sub> internuclear distances. For BeH<sub>2</sub>, ZnH<sub>2</sub>, ZnD<sub>2</sub>, HgH<sub>2</sub> and HgD<sub>2</sub> molecules, the rotational constants of the 000, 100, 01<sup>1</sup>0 and 001 levels were used to determine the equilibrium rotational constants (<em>B</em><sub>e</sub>) and the associated equilibrium internuclear distances <em>r</em><sub>e</sub>. The <em>r</em><sub>e</sub> distances of ZnH<sub>2</sub> and ZnD<sub>2</sub> differed by about 0. 01%, and those of HgH<sub>2</sub> and HgD<sub>2</sub> differed by about 0. 005%. These discrepancies were larger than the statistical uncertainties by one order of magnitude, and were attributed to the breakdown of the Born-Oppenheimer approximation.
6

Synthèses et propriétés de dibenzoBODIPYs : orthogonalité et chiralité / Syntheses and properties of dibenzoBODIPYs : orthogonality and chirality

Khelladi, Mustapha 24 November 2016 (has links)
Lors de ces trois années de thèse, le développement de nouvelles molécules luminescentes, reposant sur la stabilisation d’un squelette dibenzoBODIPY a été réalisé. Dans un premier temps, la modulation des propriétés photophysiques a été effectuée (par introduction de groupement aromatique et/ou donneur soit lors de la formation du dibenzoBODIPY, soit par couplage croisé). Dans un second temps, nous nous sommes intéressés à la synthèse de dibenzoBODIPYs dissymétriques. La dissymétrie des composés a été réalisée soit par condensation mixte de dicétone soit par mono-couplage des dibenzoBODIPYs. L’utilisation de ces derniers a permis d’obtenir des dibenzoBODIPYs chiraux (soit par formation de liaison C-B, soit par formation de liaison B-O). La mono-fonctionnalisation intramoléculaire par le groupement phénol formé in situ est la première à ce jour. Enfin la formation de nouveau BODIPYs β-fusionnés par un hétérocycle a été entrepris. Nous avons synthétisé le premier BODIPY β-fusionné par un benzofurane. / During this PhD, the development of new luminescent molecules based on the stabilization of a dibenzoBODIPY scaffold was performed. Firstly, the modulation of the photophysical properties was carried out by the introduction of an aromatic and/or a donor group, either during the formation of dibenzoBODIPY or by cross-coupling. Secondly, we were interested in the synthesis of asymmetrical dibenzoBODIPYs. The dissymmetry of compounds was done either by mixed condensation of a diketone or by dibenzoBODIPYs mono-coupling. The use of the latters yielded chiral dibenzoBODIPYs either by C-B bond formation, or by B-O bond formation. Intramolecular mono-functionalization phenol formed in situ has never been reported so far. Finally, the synthesis of β‑fused BODIPYs with a heterocycle was undertaken. We synthesized the first β‑fused BODIPYs by a benzofuran
7

Spectroscopic Characterization of Metal Oxide Nanofibers

Bender, Edward Thomas 18 May 2006 (has links)
No description available.
8

SYNTHESIS AND CHARACTERIZATION OF NOVEL EXCITED STATE INTRAMOLECULAR PROTON TRANSFER (ESIPT) CYANINE DYES WITH NEAR INFRARED (NIR) EMISSION FOR BIOLOGICAL APPLICATIONS

Dahal, Dipendra, Dahal 06 September 2019 (has links)
No description available.
9

Molécules et nanoparticules aromatiques du milieu interstellaire : production et caractérisation au laboratoire / Aromatic molecules and nanoparticles in the interstellar medium : production and characterization in the laboratory

Feraud, Géraldine 09 November 2012 (has links)
Ce travail de thèse traite d'expériences d'astrophysique de laboratoire sur des matériaux aromatiques, étudiés pour la plupart dans des conditions proches de celles rencontrées dans les milieux interstellaire et circumstellaire, comprenant rayons cosmiques et irradiations UV. Ces dernières sont à l’origine de bandes d'émission dans l'infrarouge moyen, dont les porteurs supposés sont principalement les Hydrocarbures Aromatiques Polycycliques (PAHs) et les nanoparticules aromatiques. Un nouveau spectromètre, FIREFLY (Fluorescence in the InfraRed from Excited FLYing molecules), contenant une réplique des filtres circulaires variables à bord de l'instrument ISOCAM du satellite ISO, a été mis au point et caractérisé au cours de cette thèse. Cet instrument a permis de mesurer la désexcitation infrarouge dans la région des modes d'élongations CH (3.3 µm, soit 3000 cm-1) des dérivés du benzène et du naphtalène à température ambiante, suite à l’absorption d'un photon UV. Ceci montre, avec l’appui de la modélisation, que la spectroscopie d’émission IR est un outil puissant permettant de comprendre les effets d'anharmonicité liés à l'énergie interne, l’isomérisation voire même la dynamique intramoléculaire non-adiabatique, au travers de la spectroscopie d'excitation de fluorescence infrarouge (une nouvelle technique). Ce travail est préliminaire à la future mesure de fluorescence infrarouge de nanoparticules aromatiques en phase gazeuse et à basse température produites par une flamme basse pression, dans le but de comparer les spectres de laboratoire avec les observations astrophysiques. Le dépôt d'énergie par les rayons cosmiques a été étudié grâce à une autre expérience, l'irradiation ionique d'analogues de poussières interstellaires et circumstellaires (suies produites par la flamme basse pression), mettant en évidence une réorganisation chimique. Les suies sont caractérisées par différents diagnostics complémentaires tels que la Microscopie Electronique en Transmission à Haute Résolution et les spectroscopies infrarouge à Transformée de Fourier et Raman. L'ensemble des informations tirées permet de mieux cerner la nanostructuration des analogues et ainsi mieux identifier les différentes signatures spectrales astrophysiques (interprétation de la bande à 7.7 µm comme une bande de défauts). Grâce à ces expériences, nous espérons améliorer notre compréhension de la structure, croissance et évolution de la poussière, d'un point de vue astrophysique. / The work presented in this thesis deals with laboratory astrophysics experiments of aromatic compounds, mostly studied in conditions similar to those encountered in interstellar and circumstellar environments, including cosmic rays and UV irradiations. These are the source of mid-infrared emission bands whose carriers are supposed to be composed mainly of Polycyclic Aromatic Hydrocarbons (PAHs) and aromatic nanoparticles.A new spectrometer, FIREFLY (Fluorescence in the InfraRed from Excited FLYing molecules), containing a replica of the circular variable filters of the ISOCAM instrument on-board the ISO satellite, was developed and characterized in this thesis. This instrument was used to measure the infrared de-excitation in the CH stretching mode region (3.3 µm or 3000 cm-1) from benzene derivatives and from naphthalene at room temperature, following the absorption of a single UV photon. With the support of modelling, IR emission spectroscopy is a powerful tool for understanding the effects of anharmonicity related to the internal energy, isomerization and also the non-adiabatic intramolecular dynamics through the new technique of IR fluorescence excitation spectroscopy. This work is preliminary to the infrared fluorescence measurement of low-temperature gas phase aromatic nanoparticles produced by a low pressure flame, in order to compare the laboratory spectra with astrophysical observations.Cosmic-ray energy deposition has been studied with another experiment: the ionic irradiation of interstellar and circumstellar dust analogues (soot produced by the low pressure flame) highlights a chemical reorganization. Soot is characterized by complementary diagnostics such as High Resolution Transmission Electron Microscopy, Fourier Transform Infrared spectroscopy and Raman spectroscopy. The results help identify the analogue nanostructures and better identify the astrophysical spectral signatures (interpretation of the 7.7 µm band as a defect band). Through these experiences, we hope to improve our understanding of the structure, growth and evolution of the dust, in the astrophysical context.
10

A Passive Mid-infrared Sensor to Measure Real-time Particle Emissivity and Gas Temperature in Coal-fired Boilers and Steelmaking Furnaces

Rego Barcena, Salvador 01 August 2008 (has links)
A novel technique for measuring gas temperature and spectral particle emissivity in high-temperature gas-particle streams is presented. The main application of this optical sensor is to improve the process control of batch unit operations, such as steelmaking furnaces. The spectral emission profile of CO and CO2 and the continuous particle emission in the 3.5 to 5 μm wavelength region was recorded and analyzed in real time with a low-resolution passive sensor. The sensor consisted of light collecting optics, a dispersion element (grating spectrometer) and a 64-pixel pyroelectric array. Wavelength and radiance calibrations were performed. The temperature of the gas-particle medium (Tg+p) followed from the least-squares minimization of the difference between the measured radiance in the 4.56-4.7 μm region –which saturates due to the large CO2 concentrations and path lengths in industrial furnaces– and the corresponding blackbody radiance. Particle emissivity (εp) was calculated at 3.95 μm from an asymptotic approximation of the Radiative Transfer Equation that yields the emerging radiance from a semi-infinite particle cloud. The major source of error in the magnitude of Tg+p and εp could come from particle scattering. Through the method of embedded invariance an expression was developed to estimate the lowering effect of particle size and volume fraction on the saturation of the 4.56-4.7 μm CO2 emission region. An iterative procedure for correcting the values of the gas-particle temperature and particle emissivity was applied to the datasets from the two industrial tests. Results from the measurement campaigns with the infrared sensor prototype at two full-scale furnaces are presented. A proof-of-concept test at a coal-fired boiler for electricity production was followed by more extensive measurements at a Basic Oxygen Furnace (BOF) for steelmaking. The second test provided temperature and particle emissivity profiles for eight heats, which highlighted the simplicity of the technique in obtaining in-situ measurements for modeling studies. Through the analysis of the particle emissivity profile in the BOF and the definition of a new variable –the minimum carbon time– a novel end-point strategy to stop the injection of high-purity oxygen during low-carbon heats in BOF converters was proposed.

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