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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.
291

Polymérisation en émulsion et en miniémulsion. Influence de la combinaison de stabilisants moléculaires et macromoléculaires et suivi en situ par spectroscopie Raman / Emulsion and miniemulsion polymerization. Influence of the combination of molecular and macromolecular stabilizers and in situ monitoring by Raman spectroscopy

Youssef, Itab 06 December 2012 (has links)
Cette thèse a pour objet la comparaison des procèdes de polymérisation en émulsion et en miniémulsion. L'influence de la combinaison de stabilisants moléculaires et macromoléculaires sur la cinétique réactionnelle et la distribution de tailles de particules sont les critères pertinents dans notre étude. Un stabilisant polymère, le poly (alcool vinylique-co-acétate de vinyle) (PVA), a été synthétisé avec différents taux d'hydrolyse par saponification directe du polyacétate de vinyle. Le taux d'hydrolyse de ce copolymère a été caractérisé par la Résonance Magnétique Nucléaire du proton (RMN 1H). Puis, nous avons étudié l'influence de la composition d'un mélange stabilisant [copolymères poly (alcool vinylique-co-acétate de vinyle) (PVA)/laurylsulfate de sodium (SDS)] et en particulier le taux d'hydrolyse du PVA. La présence de complexe (PVA/SDS) influence légèrement la cinétique de polymérisation. Par contre la capacité des complexes à stabiliser les particules de latex final dépend du taux d'hydrolyse du PVA, plus ce dernier est faible, plus l'agrégation est importante. Enfin, nous avons suivi en ligne par spectroscopie Raman des polymérisations en émulsion et en miniémulsion du styrène. Une exploitation du spectre a été réalisée et a permis d'attribuer les différents pics aux vibrations de certaines liaisons. La consommation du monomère et l'apparition du polymère a pu être suivi tout au long de la polymérisation / The aim of this work is to compare processes of emulsion and miniemulsion polymerization. The influence of the combination of molecular and macromolecular stabilizers on the reaction kinetics and particle size distribution are relevant factors in our study. A stabilizer polymer, poly (vinyl alcohol-co-vinyl acetate) (PVA), was synthesized with different degrees of hydrolysis by a direct saponification of polyvinyl acetate. The degree of hydrolysis of this copolymer was characterized by Nuclear Magnetic Resonance (1H NMR). Then, we studied the influence of the composition of a mixture stabilizer [poly (vinyl alcohol-co-vinyl acetate) (PVA)/sodium lauryl sulfate (SDS)], and particulary the degree of hydrolysis of PVA. The presence of complex (PVA/SDS) influences slightly the kinetic of polymerization. The ability of the complexes to stabilize the particles of latex depends on the degree of hydrolysis of PVA, the lower it is, the more the aggregation is important. Finally, we followed in situ emulsion and miniemulsion polymerizations of styrene by Raman spectroscopy. The exploitation of the spectrum allowed us to assign the different peaks to vibrations of certain bands. The consumption of the monomer and the appearance of the polymer could be followed throughout the polymerization
292

A poluição atmosférica por material particulado na mineração a céu aberto. / Atmospheric pollution by particulate matter in the open pit mining.

Almeida, Ivo Torres de 20 December 1999 (has links)
Foram abordadas questões relacionadas com a temática da poluição atmosférica provocada pelo material particulado em suspensão. Dois ambientes foram selecionados para estudo: um ambiente de mineração e um ambiente urbano. Com o objetivo de obter uma avaliação preliminar da qualidade do ar nesses ambientes, foi realizado um programa de amostragem para cada área. Dois pontos básicos foram abordados nessa avaliação: a determinação da concentração de partículas totais em suspensão e a caracterização química e física do material particulado. A determinação das concentrações de partículas totais em suspensão foi obtida através do uso de amostradores de grande volume (Hi-vols). O método de referência utilizado foi o método do amostrador de grande volume proposto pela ABNT através da norma NBR 9547: 97. A caracterização física envolveu a determinação da distribuição granulométrica do material particulado em suspensão enquanto que a caracterização química compreendeu a determinação da sua composição. As técnicas analíticas utilizadas na caracterização do material particulado, foram a espectrometria de Fluorescência de Raios-X (XRF) para a caracterização química, e o Espalhamento de Luz Laser de Baixo Angulo (LALLS) para a caracterização física. Com relação às concentrações de partículas totais em suspensão, os resultados indicaram que as áreas de mineração apresentaram valores superiores aos encontrados na área urbana, inclusive com ultrapassagens dos padrões legais, fato este que não ocorreu na área urbana estudada. Para a distribuição granulométrica do material particulado, os resultados demonstraram que as frações mais finas do particulado apresentaram-se em maiores quantidades nas áreas de mineração, enquanto que as frações mais grosseiras apresentaram-se em maior quantidade na área urbana. Quanto à composição química do material particulado em suspensão, podemos concluir que para as áreas de mineração, esta foi muito semelhante à da rocha lavrada. / Atmospheric pollution aspects were analyzed. Two types of ambients were selected for study: a mining ambient and an urban ambient. To obtain a preliminary evaluation of the quality of the air in these ambients a sampling program was accomplished for each area. Two basic points were studied: the concentration of the total suspended particulates and the chemical and physical characterization of the particulate matter. The concentrations of total suspended particulates were obtained through the use of high volume samplers (Hi-vols). The reference method used was the high volume sampler method, proposed by ABNT through the norm NBR 9547: 97. The physical characterization involved the determination of the size distribution of the suspended particulate matter while the chemical characterization involved the determination of its composition. The analytic techniques used for the characterization of the particulate matter were the X-Ray Fluorescence (XRF) for the chemical characterization, and the Low Angle Laser Light Scattering (LALLS) for the physical characterization. Concentration levels for total suspended particulates showed that the mining areas presented higher values than those for urban area. Legal standards were exceeded in the mining area, fact that did not occur in the urban area. Size distributions of the particulate matter demonstrated that the finest fractions were found in larger amounts in the mining areas, while the coarses fractions were present in larger amounts in the urban area. The chemical compositions of the suspended particulate matter in the mining areas were very similar to the compositions of the rocks been mined.
293

Optimisation d’un générateur de microgouttelettes couplé à un appareil de spectrométrie de masse à plasma d’argon à couplage inductif (ICP-MS) pour l’analyse de nanoparticules

Fournel, François 04 1900 (has links)
No description available.
294

Aplicações do método Warren-Averbach de análise de perfis de difração / Applications of the Warren-Averbach method of X-ray diffraction line profile analysis

Rodrigo Uchida Ichikawa 22 November 2013 (has links)
O objetivo deste trabalho foi desenvolver e implementar uma metodologia envolvendo a análise de perfis de difração de raios X (X-ray Line Profile Analysis - XLPA) para o estudo e determinação do tamanho médio de cristalitos e microdeformação em materiais. Para isto houve o desenvolvimento de um programa computacional para facilitar o tratamento dos picos presentes em um difratograma e realizar a deconvolução de perfis através do Método de Stokes para se corrigir a contribuição instrumental nos perfis de difração. Os métodos de XLPA de espaço real estudados e aplicados neste trabalho foram os métodos de Scherrer, Williamson-Hall e Single-Line (ou Linha Única) e o método de Warren-Averbach de espaço de Fourier. Além disso, utilizando-se um modelamento matemático foi possível calcular a distribuição de tamanhos de cristalitos para um caso isotrópico, onde considerou-se a distribuição log-normal e cristalitos com forma esférica. Foi possível demonstrar que a teoria proposta pode ser considerada como uma boa aproximação avaliando-se uma razão de dispersão. As metodologias descritas acima foram aplicadas em dois materiais distintos: na liga metálica Zircaloy-4 e em ZnO. / The objective of this work was to develop and implement a methodology of X-ray Line Profile Analysis (XLPA) for the study and determination of the mean crystallite sizes and microstrains in materials. A computer program was developed to speed up the treatment of diffraction peaks and perform the deconvolution utilizing the Stokes method to correct the instrumental contribution in the X-ray diffraction measurements. The XLPA methods used were the Scherrer, Williamson-Hall and Single-Line methods, which can be called real space methods, and the Fourier space method of Warren-Averbach. Furthermore, considering a mathematical modelling it was possible to calculate the crystallite size distribution, considering the log-normal distribution and spherical crystallites. It was possible to demonstrate the proposed theory can provide reliable results evaluating a dispersion parameter. The methodologies described above were applied in two distinct materials: in the alloy Zircaloy-4 and in ZnO.
295

Aplicações do método Warren-Averbach de análise de perfis de difração / Applications of the Warren-Averbach method of X-ray diffraction line profile analysis

Ichikawa, Rodrigo Uchida 22 November 2013 (has links)
O objetivo deste trabalho foi desenvolver e implementar uma metodologia envolvendo a análise de perfis de difração de raios X (X-ray Line Profile Analysis - XLPA) para o estudo e determinação do tamanho médio de cristalitos e microdeformação em materiais. Para isto houve o desenvolvimento de um programa computacional para facilitar o tratamento dos picos presentes em um difratograma e realizar a deconvolução de perfis através do Método de Stokes para se corrigir a contribuição instrumental nos perfis de difração. Os métodos de XLPA de espaço real estudados e aplicados neste trabalho foram os métodos de Scherrer, Williamson-Hall e Single-Line (ou Linha Única) e o método de Warren-Averbach de espaço de Fourier. Além disso, utilizando-se um modelamento matemático foi possível calcular a distribuição de tamanhos de cristalitos para um caso isotrópico, onde considerou-se a distribuição log-normal e cristalitos com forma esférica. Foi possível demonstrar que a teoria proposta pode ser considerada como uma boa aproximação avaliando-se uma razão de dispersão. As metodologias descritas acima foram aplicadas em dois materiais distintos: na liga metálica Zircaloy-4 e em ZnO. / The objective of this work was to develop and implement a methodology of X-ray Line Profile Analysis (XLPA) for the study and determination of the mean crystallite sizes and microstrains in materials. A computer program was developed to speed up the treatment of diffraction peaks and perform the deconvolution utilizing the Stokes method to correct the instrumental contribution in the X-ray diffraction measurements. The XLPA methods used were the Scherrer, Williamson-Hall and Single-Line methods, which can be called real space methods, and the Fourier space method of Warren-Averbach. Furthermore, considering a mathematical modelling it was possible to calculate the crystallite size distribution, considering the log-normal distribution and spherical crystallites. It was possible to demonstrate the proposed theory can provide reliable results evaluating a dispersion parameter. The methodologies described above were applied in two distinct materials: in the alloy Zircaloy-4 and in ZnO.
296

Avalanching on dunes and its effects : size statistics, stratification, & seismic surveys

Arran, Matthew Iain January 2018 (has links)
Geophysical research has long been interdisciplinary, with many phenomena on the Earth's surface involving multiple, linked processes that are best understood using a combination of techniques. This is particularly true in the case of grain flows on sand dunes, in which the sedimentary stratification with which geologists are concerned arises from the granular processes investigated by physicists and engineers, and the water permeation that interests hydrologists and soil scientists determines the seismic velocities of concern to exploration geophysicists. In this dissertation, I describe four projects conducted for the degree of Doctor of Philosophy, using a combination of laboratory experimentation, fieldwork, numerical simulation, and mathematical modelling to link avalanching on dunes to its effects on stratification, on the permeation of water, and on seismic surveys. Firstly, I describe experiments on erodible, unbounded, grain piles in a channel, slowly supplied with additional grains, and I demonstrate that the behaviour of the consequent, discrete avalanches alternates between two regimes, typified by their size statistics. Reconciling the `self-organised criticality' that several authors have predicted for such a system with the hysteretic behaviour that others have observed, the system exhibits quasi-periodic, system-spanning avalanches in one regime, while in the other avalanches pass at irregular intervals and have a power-law size distribution. Secondly, I link this power-law size distribution to the strata emplaced by avalanches on bounded grain piles. A low inflow rate of grains into an experimental channel develops a pile, composed of strata in which blue-dyed, coarser grains overlie finer grains. Associating stopped avalanche fronts with the `trapped kinks' described by previous authors, I show that, in sufficiently large grain piles, mean stratum width increases linearly with distance downslope. This implies the possibility of interpreting paleodune height from the strata of aeolian sandstones, and makes predictions for the structure of avalanche-associated strata within active dunes. Thirdly, I discuss investigations of these strata within active, Qatari barchan dunes, using dye-infiltration to image strata in the field and extracting samples across individual strata with sub-centimetre resolution. Downslope increases in mean stratum width are evident, while measurements of particle size distributions demonstrate preferential permeation of water along substrata composed of finer particles, explaining the strata-associated, localised regions of high water content discovered by other work on the same dunes. Finally, I consider the effect of these within-dune variations in water content on seismic surveys for oil and gas. Having used high performance computing to simulate elastic wave propagation in the vicinity of an isolated, barchan sand dune, I demonstrate that such a dune acts as a resonator, absorbing energy from Rayleigh waves and reemitting it over an extensive period of time. I derive and validate a mathematical framework that uses bulk properties of the dune to predict quantitative properties of the emitted waves, and I demonstrate the importance of internal variations in seismic velocity, resulting from variations in water content.
297

Analysis of the physical and chemical properties of atmospheric aerosol at the Puy de Dôme station / Analyse des propriétés physiques et chimiques de l’aérosol atmosphérique à la station du Puy de Dôme

Farah, Antoine 19 December 2018 (has links)
Les particules d'aérosol sont importantes en raison de leurs impacts directs et indirects sur le climat. Dans la couche limite (CL), ces particules ont une durée de vie relativement courte en raison de leur élimination fréquente par dépôt humide. En revanche, lorsque les aérosols sont transportés dans la troposphère libre (TL), leur durée de vie dans l'atmosphère augmente de manière significative, ce qui les rend représentatifs de vastes zones spatiales. Dans le cadre de ces travaux de thèse, nous avons utilisé une combinaison de mesures in situ effectuées à la station PUY (Puy de Dôme, 45 ° 46 'N, 2 ° 57'E, 1465 m d'altitude), ainsi que des profils LIDAR obtenus depuis Clermont-Ferrand pour identifier les conditions de TL et caractériser davantage les propriétés physiques et chimiques des aérosols dans cette zone de l'atmosphère peu documentée. Dans un premier temps, une combinaison de quatre critères a été utilisée pour déterminer le positionnement de la station PUY en TL ou en CL. Les résultats montrent que la station est située en CL avec des fréquences allant de 50% en hiver à 97% en été. Cette classification a ensuite été utilisée pour évaluer, sur un an de mesures, les différences qui existent entre la TL et la CL en termes de caractéristiques physique (distribution en taille) et chimique (fraction non réfractaire) de l’aérosol, et vis-à-vis des concentrations en carbone suie (BC). Sur la base de cette ségrégation, nous avons observé pour la plupart des saisons que les concentrations en particules des modes Aitken et accumulation ainsi que la concentration en BC sont plus élevées dans la CL que dans la TL. Cette observation est cohérente avec le fait que la majorité des sources d’aérosol sont situées dans la CL. Au contraire, des concentrations plus élevées en particules dans les modes Aitken et accumulation (notamment organiques) et en BC sont observées en TL au printemps. Ces aérosols organiques ont été identifiés comme étant âgés / moins âgés ; ils coïncident avec la présence de fortes concentrations en sulfate et en BC et sont probablement originaires de processus de combustion de biomasse, à la suite desquels ils sont directement injectés en TL sous l’effet d’une convection thermique intense. Aucune différence significative entre les concentrations de CL et de TL n'a été observée pour les particules du mode nucléation, et ce quelle que soit la saison, ce qui suggère une source supplémentaire continue de particules du mode nucléation dans la TL en hiver et en automne. Les concentrations en particules du mode grossier sont en revanche plus élevées dans la TL que dans la CL pour toutes les saisons, et en particulier en été. Cela indique un transport longue distance efficace des grosses particules dans la TL depuis des sources lointaines (marines et désertiques), probablement favorisé par les vitesses de vent accrues dans la TL par rapport à la CL. Nous avons ensuite calculé les rétro-trajectoires des masses d'air que nous avons combinées aux estimations de hauteur de couche limite du modèle ECMWF ERA-Interim pour estimer le temps passé par les masses d’air dans la TL depuis leur dernier contact avec la CL, et pour évaluer l'impact de ce paramètre sur les propriétés des aérosols. Nous avons observé que même après 75 heures sans aucun contact avec la CL, les aérosols de la TL conservent les propriétés spécifiques du type de masse d'air auquel ils appartiennent. Ce manuscrit présente également une étude des mesures simultanées au PUY et à une station urbaine à basse altitude, AtmoAura. Les résultats montrent que lorsque le PUY est en TL, les concentrations des PM1 (particules de diamètre inférieur à 1 µm) sont plus faibles au PUY qu’à AtmoAura, ce qui confirme notre classification. Lorsque le PUY est en CL, la composition en aérosol est similaire pour les deux sites, ce qui a permis de quantifier la contribution de la pollution urbaine locale issue de la ville de Clermont-Ferrand. / Aerosol particles are important due to their direct and indirect impacts on climate. Within the planetary boundary layer (BL), these particles have a relatively short lifetime due to their frequent removal process by wet deposition. When aerosols are transported into the free troposphere (FT), their atmospheric lifetime increases significantly, making them representative of large spatial areas. In this work, we use a combination of in situ measurements performed at the high altitude PUY (Puy de Dôme, 45°46’ N, 2°57’E, 1465 m asl) station, together with LIDAR profiles at Clermont-Ferrand for characterizing FT conditions, and further characterize the physical and chemical properties of aerosol in this poorly documented area of the atmosphere. First, a combination of four criteria was used to identify whether the PUY station lies within the FT or within the BL. Results show that the PUY station is located in BL with frequencies ranging from 50% during the winter, up to 97% during the summer. Then, the classification is applied to a year-long dataset of particle size distribution and NR-PM1 data’s to study the differences in particle physical and chemical characteristics and BC concentrations between the FT and the BL. Based on this segregation, we observed higher concentrations in the BL compared to FT for BC, Aitken and accumulation mode particle concentrations for most seasons, as expected from larger sources originating from the surface. However, BC, Aitken mode, accumulation mode and organic aerosols concentrations were higher in the FT compared to BL during spring. These organic aerosols were identified as aged/less aged, and were correlated with sulphate and BC and we suspect that the higher concentrations of particles observed in the FT compared to BL during spring originate from direct injection of BB aerosols in the FT through strong heat convection. No significant difference between the BL and the FT concentrations was observed for the nucleation mode particles for all seasons, suggesting a continuous additional source of nucleation mode particles in the FT during winter and autumn. Coarse mode particle concentrations were found higher in the FT than in the BL for all seasons and especially during summer. This indicates an efficient long-range transport of large particles in the FT from distant sources (marine and desert) due to higher wind speeds in the FT compared to BL. For FT air masses, we used 204-h air mass back-trajectories combined with boundary layer height estimations from ECMWF ERA-Interim to assess the time they spent in the FT since their last contact with the BL and to evaluate the impact of this parameter on the aerosol properties. We observed that even after 75 h without any contact with the BL, FT aerosols preserve specific properties of their air mass type. This manuscript is also presenting a study of simultaneous measurements at PUY and an urban low altitude station AtmoAura. Results show that when the PUY is influenced by FT air masses, the PM1 species are lower at the PUY compared to AtmoAura confirming our classification. When the PUY is predicted to lay within the BL, the aerosol composition was similar among the two sites for several species, which allowed for a quantification of the local urban pollution contribution for the species enhanced within the city of Clermont-Ferrand.
298

Fizičke karakteristike zemljišta i distribucija teških metala na gradskom području Novog Sada / Physical properties and the distribution of heavy metals in soils of the urban area of Novi Sad

Mihailović Aleksandra 25 August 2015 (has links)
<p>Uzorci zemlji&scaron;ta iz pov&scaron;inskog sloja dubine 0 - 10 cm<br />prikupljeni su sa 121 lokacije na gradskom području Novog<br />Sada. Ispitivano područje obuhvatilo je povr&scaron;inu (4 x 5)km<sup>2</sup>,<br />koja je podeljena na mrežna polja veličine (400 x 400) m<sup>2&nbsp;</sup>i u&nbsp; &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;<br />svakom polju uzet je po jedan uzorak. Za 121 uzorak<br />gradskog zemlji&scaron;ta Novog Sada ispitana su fizičko-hemijska<br />svojstva zemlji&scaron;ta, ukupni i pristupačni sadržaj metala (As,<br />Co, Cr, Cu, Mn, Ni, Pb, Zn) i njihova prostorna raspodela.<br />Konturne mape prostorne raspodele metala u zemlji&scaron;tu<br />dobijene su kori&scaron;ćenjem interpolacijske metode običnog<br />kriginga. Za pojedine uzorke izvr&scaron;eno je razdvajanje čestica<br />po veličinama frakcionisanjem u vodi pomoću sita različitih<br />veličina i identifikovani su minerali prisutni u frakciji prah +<br />glina. Aktivnosti radionuklida &bdquo;unsupported&rdquo;<sup> 210</sup>Pb i <sup>137</sup>Cs<br />određene su za jedan deo uzoraka zemlji&scaron;ta u Novom Sadu i<br />za uzorke zemlji&scaron;ta pored fabrike akumulatora u Somboru.<br />Ispitana je i vertikalna distribucija stabilnog i radioaktivnog<br />Pb u zemlji&scaron;tu.</p><p>Na 14 lokacija u Novom Sadu prikupljeno je 35 uzoraka<br />snega direktno sa asfaltnih puteva i sa zemljanih povr&scaron;ina u<br />okolini puteva i na pe&scaron;ačkim ostrvima. Raspodela čestica po<br />veličinama i ukupne koncentracije metala (Al, Ca, Cu, Fe, K,<br />Na, Mn, Ni, Pb, Zn) određene su analizom filtriranih uzoraka,<br />a za 4 uzorka ispitana je morfologija čestica i urađena<br />semikvantitativna analiza čestica u suvoj materiji.</p><p>Prilikom obrade rezultata merenja primenjene su metode<br />deskriptivne statistike i multivarijacione statističke analize u<br />cilju identifikacije izvora zagađenja i određivanja povezanosti<br />između samih metala i drugih parametara.</p> / <p>A total of 121 surface soil samples were collected&nbsp;across the central part of Novi Sad covering a surface&nbsp;area (4 km x 5 km). The physicochemical properties,&nbsp;pseudo total and available metal concentrations (As,&nbsp;Co, Cr, Cu,&nbsp; Mn, Ni, Pb, and Zn) were determined.&nbsp;Contour maps of spatial distribution of the investigated&nbsp;metals were obtained using ordinary&nbsp; kriging&nbsp;interpolation method. Separation of different particle&nbsp;<br />size fractions by wet sieving&nbsp; and identification of&nbsp;minerals in the clay and silt fraction for some soil&nbsp;samples were performed.&nbsp; Specific activities of&nbsp;radionuclides &ldquo;unsupported&rdquo; <sup>210</sup>Pb and <sup>137</sup>Cs were&nbsp;measured in forty soil samples collected in urban area&nbsp;of Novi Sad and industrial area of Sombor (near a&nbsp;battery manufacturer).&nbsp; Vertical distribution of stable and&nbsp;radioactive&nbsp; Pb for&nbsp; two samples from the industrial soil&nbsp;was examined.</p><p>Thirty five snow samples were collected at fourteen&nbsp;locations near crossroads in Novi Sad. The samples&nbsp;were taken directly from the road surface and from the&nbsp;ground surface in the vicinity of roads and on&nbsp;pedestrian islands. Particle size distribution and &nbsp;total&nbsp;concentration of the metals (Al, Ca, Cu, Fe, K, Na, Mn,&nbsp;Ni, Pb, Zn) were &nbsp;determined for filtered samples. Semi-quantitative analysis of the particles was &nbsp;conducted and&nbsp;morphology of the particles was examined for dry&nbsp;matter of four snow samples.&nbsp;</p><p>Methods of descriptive and multivariate statistics and&nbsp;geostatistics were carried out for &nbsp;the analysis and&nbsp;interpretation of the data.</p>
299

Contribution aux traitements des incertitudes : application à la métrologie des nanoparticules en phase aérosol. / Contribution to the treatment of uncertainties. : Application to the metrology of nanoparticles under aerosol-phase.

Coquelin, Loïc 04 October 2013 (has links)
Cette thèse a pour objectif de fournir aux utilisateurs de SMPS (Scanning Mobility Particle Sizer) une méthodologie pour calculer les incertitudes associées à l’estimation de la granulométrie en nombre des aérosols. Le résultat de mesure est le comptage des particules de l’aérosol en fonction du temps. Estimer la granulométrie en nombre de l’aérosol à partir des mesures CNC revient à considérer un problème inverse sous incertitudes.Une revue des modèles existants est présentée dans le premier chapitre. Le modèle physique retenu fait consensus dans le domaine d’application.Dans le deuxième chapitre, un critère pour l’estimation de la granulométrie en nombre qui couple les techniques de régularisation et de la décomposition sur une base d’ondelettes est décrit.La nouveauté des travaux présentés réside dans l’estimation de granulométries présentant à la fois des variations lentes et des variations rapides. L’approche multi-échelle que nous proposons pour la définition du nouveau critère de régularisation permet d’ajuster les poids de la régularisation sur chaque échelle du signal. La méthode est alors comparée avec la régularisation classique. Les résultats montrent que les estimations proposées par la nouvelle méthode sont meilleures (au sens du MSE) que les estimations classiques.Le dernier chapitre de cette thèse traite de la propagation de l’incertitude à travers le modèle d’inversiondes données. C’est une première dans le domaine d’application car aucune incertitude n’est associée actuellement au résultat de mesure. Contrairement à l’approche classique qui utilise un modèle fixe pour l’inversion en faisant porter l’incertitude sur les entrées, nous proposons d’utiliser un modèle d’inversion aléatoire (tirage Monte-Carlo) afin d’intégrer les erreurs de modèle. Une estimation moyenne de la granulométrie en nombre de l’aérosol et une incertitude associée sous forme d’une région de confiance à 95 % est finalement présentée sur quelques mesures réelles. / This thesis aims to provide SMPS (Scanning Mobility Particle Sizer) users with a methodology to compute the uncertainties associated with the estimation of aerosol size distributions. Recovering aerosol size distribution yields to consider an inverse problem under uncertainty.The first chapter of his thesis presents a review of physical models and it shows that competitive theories exist to model the physic.A new criterion that couples regularization techniques and decomposition on a wavelet basis is described in chapter 2 to perform the estimation of the size distribution.Main improvement of this work is brought when size distributions to be estimated show both broad and sharp profiles. The multi-scale approach helps to adjust the weights of the regularization on each scale of the signal. The method is then tested against common regularization and shows better estimates (in terms of the mean square error).Last chapter of this thesis deals with the propagation of the uncertainty through the data inversion process.Results from SMPS measurements are not given with any uncertainty at this time so providing end-users with an uncertainty is already a real improvement. Common approach is to consider a fixed physical model and to model the inputs (particle count) as random. We choose to consider both the physical model as well as the inputs as random to account for the model error. The result is expressed as a mean estimate of the size distribution with a 95% coverage region. The all methodology is finally tested on real measurements.
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Mechanistic approaches towards understanding particle formation in biopharmaceutical formations : the role of sufactant type and level on protein conformational stability, as assessed by calorimetry, and on protein size stability as assessed by dynamic light scattering, micro flow imaging and HIAC

Vaidilaite-Pretorius, Agita January 2013 (has links)
Control and analysis of protein aggregation is an increasing challenge to biopharmaceutical research and development. Therefore it is important to understand the interactions, causes and analysis of particles in order to control protein aggregation to enable successful biopharmaceutical formulations. This work investigates the role of different non-ionic surfactants on protein conformational stability, as assessed by HSDSC, and on protein size stability as assessed by Dynamic Light Scattering (DLS), HIAC and MFI. BSA and IgG2 were used as model proteins. Thermal unfolding experiments indicated a very weak surfactant-immunoglobulin IgG2 interaction, compared to much stronger interactions for the BSA surfactant systems. The DLS results showed that BSA and IgG2 with different surfactants and concentration produced different levels of particle size growth. The heat treatment and aging of samples in the presence of Tween 20, Tween 80, Brij 35 and Pluronic F-68 surfactants led to an increase in the populations of larger particles for BSA samples, whereas IgG2 systems did not notably aggregate under storage conditions MFI was shown to be more sensitive than HIAC technique for measuring sub-visible particles in protein surfactant systems. Heat treatment and storage stress showed a significant effect on BSA and IgG2 protein sub-visible particle size stability. This work has demonstrated that both proteins with different Tween 20, Tween 80, Brij 35 and Pluronic F-68 concentrations, have different level of conformational and size stability. Also aging samples and heating stress bears the potential to generate particles, but this depends on surfactant type. Poor predictive correlations between the analytical methods were determined.

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