Applications of Hot Melt Extrusion (HME) in pharmaceuticals have become increasingly popular over the years but nonetheless a few obstacles still remain before wide scale implementation. In many instances these improvements are related to both processing and product performance. It is observed that HME process optimisation is majorly focused on the active pharmaceutical ingredient's (API) properties. Characterising polymeric properties for their suitability in HME should be equally studied since the impact of excipients on both product and process performance is just as vital. In this work, two well-established cellulose ester derivatives: Hydroxy Propyl Methyl Cellulose Acetate Succinate (HPMCAS) and Hydroxy Propyl Methyl Cellulose Phthalate (HPMCP) are studied for their HME suitability. Their thermal, thermodynamic, rheological, thermo-chemical and degradation kinetic properties were evaluated with model plasticisers and APIs. It was found the thermal properties of HPMCP are severely compromised whereas HPMCAS is more stable in the processing zone of 150 to 200 °C. Thermodynamic properties revealed that both polymers share an important solubility parameter range (20-30 MPa P1/2P) where the majority of plasticisers and BCS class II APIs lie. Thus, greater miscibility/solubility can be expected. Further, the processability of these two polymers investigated by rheometric measurements showed HPMCAS possesses better flow properties than HPMCP because HPMCP forms a weak network of chain interactions at a molecular level. However, adding plasticisers such as PEG and TEC the flow properties of HPMCP can be tailored. The study also showed that plasticisers have a major influence on thermo-chemical and kinetic properties of polymers. For instance, PEG reduced polymer degradation with reversal in kinetic parameters whereas blends of CA produced detrimental effects and increased polymer degradation with reduction in onset degradation temperatures. Further, both polymers are observed to be chemically reactive with the APIs containing free -OH, -SOR2RN- and -NH2 groups. Finally, these properties prove that suitability of HPMCP is highly debated for HME and demands great care in use while that of HPMCAS is relatively better than HPMCP in many instances.

No / A systematic identification of the degradation products of hydroxypropyl methylcellulose phthalate (HPMCP) during hot melt extrusion (HME) has been performed. A reverse phase HPLC method was developed for the extrudates of both hydroxypropyl methylcellulose acetate succinate (HPMCAS) and HPMCP polymers to quantify their thermal hydrolytic products: acetic acid (AA), succinic acid (SA) for HPMCAS and phthalic acid (PA) for HPMCP, without hydrolysing the polymers in strong alkaline solutions. The polymers were extruded in the temperature range of 160-190 degrees C at different screw rotation speeds and hydrolytic impurities were analysed. Investigation of extruded HPMCP showed an additional thermal degradation product, who is structural elucidation revealed to be phthalic anhydride (PAH). Moreover, two environmental analytical impurities, dimethyl phthalate and methyl benzoate formed in situ were recorded on GC-MS and their origin was found to be associated with PAH derivatization. Using the experimental data gathered during this study, a degradation mechanism for HPMCP is proposed.

Le présent travail est consacré au développement et à la validation d'un modèle hybride de propagation d'un incendie de végétation à grande échelle prenant en compte les hétérogénéités locales liées à la végétation, à la topographie du terrain et aux conditions météorologiques. Dans un premier temps, on présente différentes méthodes permettant de générer un réseau amorphe, représentatif d'une distribution réaliste de la végétation. Le modèle hybride est un modèle de réseau où les phénomènes qui se produisent à l'échelle macroscopique sont traités de façon déterministe, comme le préchauffage du site végétal provenant du rayonnement de la flamme et des braises et de la convection par les gaz chauds, mais aussi son refroidissement radiatif et son inflammation pilotée. Le rayonnement thermique provenant de la flamme est calculé en combinant le modèle de flamme solide à la méthode de Monte Carlo et en considérant son atténuation par la couche d'air atmosphérique entre la flamme et la végétation réceptive. Le modèle est ensuite appliqué à des configurations simples de propagation sur un terrain plat ou incliné, en présence ou non d'un vent constant. Les résultats obtenus sont en bon accord avec les données de la littérature. Une étude de sensibilité a été également menée permettant d'identifier les paramètres les plus influents du modèle, en termes de vitesse de propagation du feu, et de les hiérarchiser. La phase de validation a portée sur l'analyse comparative des contours de feux calculés par le modèle avec ceux mesurés lors d'un brûlage dirigé réalisé en Australie et d'un feu réel qui a lieu en Corse en 2009, montrant un très bon accord en termes de vitesse de propagation / The present work is devoted to the development of a hybrid model for predicting the rate of spread of wildland fires at a large scale, taking into account the local heterogeneities related to vegetation, topography, and meteorological conditions. Some methods for generating amorphous network, representative of real vegetation landscapes, are proposed. Mechanisms of heat transfer from the flame front to the virgin fuel are modeled: radiative preheating from the flame and embers, convective preheating from hot gases, radiative heat losses and piloted ignition of the receptive vegetation item. Flame radiation is calculated by combining the solid flame model with the Monte Carlo method and by taking into account its attenuation by the atmospheric layer between the flame and the receptive vegetation. The model is applied to simple configurations where the fire spreads on a flat or inclined terrain, with or without a constant wind. Model results are in good agreement with literature data. A sensitivity study is conducted to identify the most influential parameters of the model. Eventually, the model is validated by comparing predicted fire patterns with those obtained from a prescribed burning in Australia and from a historical fire that occurred in Corsica in 2009, showing a very good agreement in terms of fire patterns, rate of spread, and burned area.

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Made available in DSpace on 2014-12-17T14:09:14Z (GMT). No. of bitstreams: 1 AnaADP_TESE.pdf: 2810011 bytes, checksum: 6f11363dfc6e540fe688b7737b77893b (MD5) Previous issue date: 2012-11-04 / Aiming to reduce and reuse waste oil from oily sludge generated in large volumes by the oil industry, types of nanostructured materials Al-MCM-41 and Al-SBA-15, with ratios of Si / Al = 50, were synthesized , and calcined solids used as catalysts in the degradation of oily sludge thermocatalytic oil from oilfield Canto do Amaro, in the state of Rio Grande do Norte. Samples of nanostructured materials were characterized by thermogravimetric analysis (TG / DTG), X-ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). The characterization showed that the synthesized materials resulted in a catalyst nanostructure, and ordered pore diameter and surface area according to existing literature. The oily sludge sample was characterized by determining the API gravity and sulfur content and SARA analysis (saturates, aromatics, resins and asphaltenes). The results showed a material equivalent to the average oil with API gravity of 26.1, a low sulfur content and considerable amount of resins and asphaltenes, presented above in the literature. The thermal and catalytic degradation of the oily sludge oil was performed from room temperature to 870 ? C in the ratios of heating of 5, 10 and 20 ? C min-1. The curves generated by TG / DTG showed a more accelerated degradation of oily sludge when it introduced the nanostructured materials. These results were confirmed by activation energy calculated by the method of Flynn-Wall, in the presence of catalysts reduced energy, in particular in the range of cracking, showing the process efficiency, mainly for extraction of lightweight materials of composition of oily sludge, such as diesel and gasoline / Com o objetivo de reduzir e reutilizar o res?duo de borra oleosa de petr?leo, gerado em grandes volumes pela ind?stria petrol?fera, materiais nanoestruturados dos tipos Al-MCM-41 e Al-SBA-15, com raz?es de Si/Al = 50, foram sintetizados, calcinados e utilizados como s?lidos catal?ticos na degrada??o termocatal?tica da borra oleosa de petr?leo, proveniente do campo petrol?fero Canto do Amaro, no estado do Rio Grande do Norte. As amostras dos materiais nanoestruturados foram caracterizadas por an?lise termogravim?trica (TG/DTG), difra??o de raios X (DRX), microscopia eletr?nica de varredura (MEV), espectroscopia de absor??o na regi?o do infravermelho com transformada de Fourier (FT-IR) e adsor??o de nitrog?nio (BET). A caracteriza??o mostrou que os materiais sintetizados resultaram em um catalisador nanoestruturado, ordenado e com di?metro de poros e ?rea superficial de acordo com a literatura existente. A amostra de borra oleosa foi caracterizada atrav?s da determina??o do grau API e do teor de enxofre e da an?lise do SARA (saturados, arom?ticos, resinas e asfaltenos). Os resultados mostraram um material equivalente ao petr?leo m?dio, com grau API de 26,1, baixo teor de enxofre e com quantidade consider?vel de resinas e asfaltenos, acima da apresentada na literatura. A degrada??o t?rmica e catal?tica da borra oleosa de petr?leo foi realizada da temperatura ambiente at? 870?C, nas raz?es de aquecimento de 5, 10 e 20oC min-1. As curvas geradas pela TG/DTG apresentaram uma degrada??o mais acelerada da borra oleosa quando se introduziram os materiais nanoestruturados. Esses resultados foram ratificados pela energia de ativa??o, calculada atrav?s do m?todo de Flynn-Wall, em que a presen?a dos catalisadores reduziu a energia, em especial na faixa de craqueamento, mostrando a efici?ncia do processo, principalmente para a extra??o de materiais leves da composi??o da borra oleosa, como diesel e gasolina

Les pompiers méditerranéens sont confrontés à des embrasements soudains de la végétation (AFF) dont les mécanismes ne sont pas encore bien compris. La végétation étant l'unique combustible, nous nous sommes penchés sur les gaz qui en proviennent. Nous avons d’abord étudié la dégradation thermique de quatre Composés Organiques Volatils biogéniques (COVb) à l'aide d'une pyrolyse flash et d'un four tubulaire. À partir de cette étude et de la littérature, nous avons choisi un mélange d'étude afin expérimenter ses propriétés de combustion. Nous avons ainsi déterminé l'Énergie Minimale d’Inflammation (EMI) et la vitesse fondamentale de flamme de mélanges d'α-pinène/benzène qui sont respectivement les principaux COV détectés dans les plantes et dans les fumées de feux de forêt. Le dernier chapitre concerne l'étude stationnaire de l'accumulation de gaz dans des vallées à partir d'une maquette de forêt 1/400ème disposée dans une soufflerie. / Mediterranean firefighters cope with powerful accelerations of forest fires (AFF) whose mechanisms are not very well understood. Vegetation is the only fuel of forest fire, then we studied the gases coming from them. First, we studied the thermal degradation of four Biogenic Volatil Organic Compounds (BVOCs) thanks to a flash pyrolysis and a tubular oven. From this study and literature, we chose a representative VOC mixture to study its combustion properties. We determined Minimal Ignition Energy (MIE) and its laminar burning speed of mixtures of α-pinene/benzene that are respectively the main VOC detected in vegetation and forest fire smoke. The last chapter experiment the steady-state gas accumulation above a 1/400 V-shaped forest model.

Poptávka ze strany vesmírného výzkumu, zdravotnictví a bezpečnostního průmyslu způsobila v posledních letech zvýšený zájem o vývoj materiálů pro detekci a zobrazování vysokoenergetického záření. CdTe a jeho slitina CdZnTe. jsou polovodiče umožnují detekci záření o energiích v rozsahu 10 keV až 500 keV. Šířka zakázaného pásma u CdTe / CdZnTe je 1.46 -1.6 eV, což umožňuje produkci krystalů o vysoké rezistivitě (10^10-10^11 cm), která je dostačující pro použití CdTe / CdZnTe při pokojové teplotě. V mé práci byly zkoumány detektory CdTe/CdZnTe v různých stádiích jejich poruchovosti. Byly použity velmi kvalitní spektroskopické detektory, materiál s nižší rezistivitou a výraznou polarizací, detektory s asymetrií elektrických parametrů kontaktů a teplotně degenerované vzorky. Z výsledků analýzy nízkofrekvenčního šumu je patrný obecný závěr, že zvýšená koncentrace defektů způsobí změnu povahy původně monotónního spektra typu 1/f na spektrum s výrazným vlivem generačně-rekombinačních procesů. Další výrazná vlastnost degenerovaných detektorů a detektorů nižší kvality je nárůst spektrální hustoty šumu typu 1/f se vzrůstajícím napájecím napětí se směrnicí výrazně vyšší než 2. Strukturální a chemické analýzy poukázaly, že teplotní generace detektorů způsobuje difuzi kovu použitého při kontaktování a stopových prvků hlouběji do objemu krystalu. Část mé práce je věnována modifikaci povrchu svazkem argonových iontů a jejímu vlivu na chemické složení a morfologii povrchu.