[pt] A qualidade dos óleos vegetais utilizados na produção de biocombustíveis está diretamente relacionada à qualidade do produto final. Como metais desempenham um papel significativo na oxidação do óleo vegetal, a sua presença é indesejável, mesmo em baixas concentrações. No presente trabalho, investigou se como a presença de cobre, em diferentes estados de oxidação, cobre(0) ou cobre(II), afeta a estabilidade dos óleos de canola e girassol, auxiliando, assim, na compreensão dos mecanismos de oxidação dos mesmos. Óxido cúprico ou cobre metálico foram adicionados a amostras de óleo gerando suspensões contendo um teor de cobre equivalente a 2000 mg kg 1. As amostras foram mantidas a 90 graus celsius durante catorze dias. Periodicamente, foram retiradas alíquotas, que foram avaliadas quanto à estabilidade oxidativa através da determinação do índice de acidez, índice de iodo, espectroscopias de absorção nas regiões do UV Vis e do infravermelho (FT IR), espectroscopia Raman e do teste Rancimat. Os resultados confirmam que o cobre (não importa a espécie) participa ativamente do processo de degradação dos óleos vegetais, sugerindo que as espécies de metal não apenas influenciam a taxa de oxidação, mas também a extensão dos processos de degradação. Os espectros FT IR das amostras derivadas do óleo de canola mostraram um aumento na razão (I2856/I1747)tx/(I2856/I1747)t0, ou seja, uma diminuição dos grupos éster nas amostras de óleo contaminado com cobre. No entanto, não ocorreram alterações nas bandas com máximo em 1120 e 1098 cm 1, indicando que este metal atua como um catalisador no processo de hidrólise das ligações éster. Além disso, as razões (I2856/I3009)tx/(I2856/I3009)t0 e (I2856/I3010)tx/(I2856/I3010)t0 medidas por espectroscopia no FT IR para o óleo de canola e para o óleo de girassol, respectivamente, e a razão (I2856/I3012)tx/(I2856/I3012)t0 medida por espectroscopia Raman apresentaram um aumento mais pronunciado nas amostras contendo cobre. Contudo, os resultados obtidos sugerem que, durante a oxidação dos triglicerídeos, não ocorreu a quebra de ligações olefínicas, pois, embora tenha sido observado tanto por FT IR como por Raman que a banda relacionada ao v(C-H)cis diminuiu com o progresso da oxidação, não foi verificada significativa diminuição do índice de iodo, indicando que uma grande parte da oxidação nos óleos contaminados com cobre não envolveu diretamente a perda de duplas ligações, e sim a isomerização das duplas ligações cis direcionando a formação de produtos contendo ligações trans. Os dados deste trabalho indicam que o estado de oxidação +2 exerce um maior efeito catalítico do que o cobre na forma de partículas metálicas, uma vez que a diminuição no tempo de indução, assim como o aumento na formação de produtos secundários derivados de oxidação, acompanhada pela medição da absorvância a 270 nm, foi mais pronunciada nas amostras contaminadas com cobre(II). A extensão da isomerização das duplas ligações, acompanhada por FT IR e espectroscopia Raman, apontam neste mesmo sentido. Além disso, a influência de um antioxidante natural, curcumina, também foi avaliada. Verificou se que a sua adição às amostras de óleo contendo cobre(II) elevou a estabilidade frente aos ensaios realizados. / [en] The quality of vegetable oils used in biofuel production is directly related to the quality of the final product. As metals play a significant role in vegetable oil oxidation and degradation, their presence is undesirable, even at low concentrations. The present study investigated how the presence of copper, in different oxidation states, copper(0) or copper(II), affects the stability of canola and sunflower oil, thus aiding in the understanding of oil oxidation mechanisms. Cupric oxide or metallic copper were added to the oil samples generating suspensions containing overall copper amounts equivalent to 2000 mg kg 1. The samples were maintained at 90 celsius degrees for fourteen days. Aliquots were taken periodically and evaluated with regard to oxidative stability, by determining the acid value, iodine value, by absorption UV Vis and Infrared (FT IR) spectroscopy, Raman spectroscopy and the Rancimat test. The results confirm that copper, no matter in what oxidation state, participates actively in vegetable oil degradation, suggesting that the metal species do not only influence the oxidation rate, but also the extent of the degradation processes. The FT IR spectra of samples derived from copper contaminated canola oil showed an increase in the (I2856/I1747)tx/(I2856/I1747)t0 ratio, i.e., a decrease of the ester groups. However, no changes in the bands with maximums at 1120 and 1098 cm 1 were observed, indicating that this metal acts as a catalyst in the hydrolysis process of ester bonds. Furthermore, the (I2856/I3009)tx/(I2856/I3009)t0 and (I2856/I3010)tx/(I2856/I3010)t0 ratios measured by FT IR spectroscopy, for canola and sunflower oil, respectively, and the (I2856/I3012)tx/(I2856 /I3012)t0 ratio measured by Raman spectroscopy showed a more pronounced increase in the copper containing samples. However, the results also suggest that olefinic bonds did not rupture during triglyceride oxidation, since, despite the fact that a decrease in the band related to cis C-H vibration was observed by both FT IR and Raman during the oxidation progress, no reductions in the iodine value were observed, indicating that the majority of the oxidation in the copper containing oils did not involve the loss of double bonds, but the isomerization of cis double bonds, directing the formation of products containing trans bonds. The results reported in this study indicate that copper in the (II) oxidation state exerts a greater catalytic effect than Cu in the form of metal particles, since the decrease in the induction time, as well as the increase in the production of secondary oxidation products, verified by measuring the absorption intensity at 270 nm, was more pronounced in samples contaminated with copper(II). The influence of a natural antioxidant, curcumin, on the oxidation stability of vegetable oils was also evaluated, and its addition to the oil samples containing copper(II) increased oil stability.

This thesis discusses the experimental verification of sorption and mechanical properties of fir wood from the 17th to 21th century. The wood of different ages is thermally treated with temperature of 60°C, 120°C and 180°C for a 17 hours. The effect of thermal treatment of wood on the isothermal sorption characteristics and compressive strength in fiber direction is evaluated.

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This thesis examines the manufacturing process of a novel flax fibre polypropylene composite material, focusing on understanding the process and its influencing factors. The composite was manufactured using pre-impregnated twill-woven flax fibre sheets (AmpliTex 5040 – PP) as outer layers and two core layers of pre-impregnated polypropylene sheets reinforced with short, randomly oriented natural fibres (NfPP). The manufacturing process involved preheating the material to core temperatures of 180°C, 190°C, or 200°C, followed by compression moulding with tool gaps of 3.0 mm, 3.2 mm, and 3.4 mm. The study found that the core temperature after preheating did not significantly affect the composite's thickness or layer compaction. However, the tool gap exhibited a significant effect, with an increase in thickness with larger tool gaps. The lowest deviation from the tool gap size was observed at 3.2 mm. The compaction of the AmpliTex 5040 – PP layers demonstrated no dependency on the tool gap, while the NfPP layers exhibited the highest compaction at a gap size of 3.0 mm. Thermal degradation analysis indicated that flax fibre is the most critical component, with higher core temperatures reducing the ultimate tensile strength and fracture strain of the composite material. The maximum tensile properties were observed for materials preheated to 180°C during manufacturing. The manufacturing process demonstrated an improvement in reproducibility compared to previous methods, although substantial variance in thickness remained.

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.

No description available.

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.