Sintering is an important processing step for obtaining the necessary mechanical stability and rigidity of ceramic bulk materials. Both mass and heat transfer are essential in the sintering process. The importance of radiation heat transfer is significantly enhanced at high temperatures according to the well-known Stefan-Boltzmann’s law. In this thesis, we modified the pressure-less spark plasma sintering set-up to generate intense thermal radiation, aiming at rapid consolidation of ceramic bulk materials. This approach was named as “Sintering by Intense Thermal Radiation (SITR)” as only thermal radiation contributed. Firstly, the heat and mass transfer mechanisms during the SITR process were studied by choosing zirconia ceramics as references. The results revealed that the multiple scattering and absorption of radiation by the materials contributed to the heat diffusion. The observed enhanced densification and grain growth can be explained by a multiple ordered coalescence of zirconia nanocrystals using high heating rates. Secondly, the temperature distribution during the SITR process was investigated by both numerical simulation and experimental verifications. It showed that the radiator geometry, sample geometry and radiating area were influencing factors. Besides, the change of material and geometry of the radiators resulted in an asymmetric temperature distribution that favored the formation of SiC foams. The foams had gradient structures with different open porosity levels and pore sizes and size distributions. Finally, ceramic bulk materials were successfully fabricated by the SITR method within minutes. These materials included dense and strong ZrO2 ceramics, Si3N4 foams decorated with one-dimensional nanostructures, and nasal cavity-like SiC-Si3N4 foams with hierarchical heterogeneities. Sufficient densification or formed strong necks were used for tailoring these unique microstructures. The SITR approach is well applicable for fast manufacture of ceramic bulk materials because it is clean and requires low energy consumption and properties can be controlled and tuned by selective heating, heating speed or temperature distribution. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 4: Manuscript.</p><p> </p>

Les routes sont le moyen de transport le plus utilisé dans le monde et le développement d'un pays est souvent mesuré en termes de kilométrage total des routes revêtues. Les chaussées sont essentielles à notre réseau social et l’enrobé bitumineux est le matériau le plus utilisé pour leur fabrication. À l'heure actuelle, le réseau routier européen n’est plus en forte croissance et nécessite surtout un entretien. Dans un contexte de développement durable de plus en plus exigeant,la route pourrait donc représenter sa propre source d’approvisionnement en tirant parti du recyclage. Elle doit aussi limiter les quantités d’énergies et de ressources naturelles nécessaires à sa propre maintenance.La combinaison des techniques d’enrobés tièdes (WMA) et de taux de recyclage élevés d’agrégats d’enrobés (RAP) apparaît comme une solution permettant d’économiser à la fois l’énergie et les ressources naturelles. Mais sa durabilité doit être éprouvée. Un programme expérimental a donc été mis en place pour montrer l'évolution des performances de ces enrobés bitumineux avec le temps, mettant en évidence la notion de vieillissement essentiellement lié à la fraction bitumineuse. A l'échelle du bitume, l'évaluation à long terme est effectuée notamment en appliquant la δ-méthode et en comparant avec les mesures de masses moléculaires par GPC à la fois sur des échantillons modèles à teneur en asphaltènes controllée et sur des échantillons de laboratoire. A l’échelle de l’enrobé bitumineux, une étude comparative a été réalisée entre un enrobé à chaud traditionnel et des WMAs incluant 0% ou 50% de RAP soumis à une procédure de vieillissement en laboratoire. Les performances à long terme des mélanges sont comparées au moyen d’essais de module complexe et de fatigue.Les résultats montrent une relation entre l’évolution de la structure des bitumes par vieillissement et les performances mécaniques. Le vieillissement à court terme au moment de la fabrication est beaucoup moins marqué pour les procédés tièdes. Après vieillissement à long terme, les tendances générales sont similaires pour tous les procédés. / Roads are the most widely used mode of transportation in the world, and a country’s development is often measured in terms of its total paved roads mile age. Pavements are an essential part of our social network and asphalt concrete is the main material used for manufacturing them. Currently, the European road network is not much growing anymore and mostly needs only maintenance. In a context of increasing demand of performance and durability of asphalt mixtures, a sustainable, durable and economical conceptionis required. Indeed it could be oriented towards a self sufficient road providing its own raw materials through recycling while limiting the use of energy and other natural resources for its maintenance.The combination of warm mix asphalts (WMA) technologies and high rates of reclaimed asphalt pavements (RAP)appears as a solution to achieve both energy and natural resources savings. But it is still ambiguous in terms of durability. Therefore, an experimental program is set up to show the evolution of the performances of such asphalt concretes with time, highlighting the notion of ageing mostly related to the bituminous fraction. At the bitumen scale, the long term assessment is carried out in particular by applying the δ-method compare with GPC measurements both on model samples with controlled asphaltene content and laboratory aged ones. At the asphalt mixture scale, a comparison studyis carried out between a reference HMA and WMAs with 0%- 50% of RAP submitted to a laboratory ageing procedure. The long term performances of the mixtures are compared by means of complex modulus and fatigue testing. Results show a relation between the evolution of the structure of the bitumen with ageing and the mechanical performances. Short term ageing is less important for warm processes. After ageing, the overall tendencies are similar for all processes.

Made available in DSpace on 2017-07-21T20:42:36Z (GMT). No. of bitstreams: 1 Andre Cesar Bento.pdf: 1732687 bytes, checksum: 53eb9d5eb1ee3aca52e7d78b1169f466 (MD5) Previous issue date: 2012-04-10 / In this work, the effect of sodium hydroxide as a glass foaming agent using glass waste in the foam formulation was performed. During the synthesis process, the variation of temperature, heating rate and sintering time was investigated. Sample density and average pore sizes were estimated using mercury porosimetry. The morphology of the glass foams were evaluated using scanning electron microscopy, phase formation was studied using X-ray diffraction, and chemical composition was estimated using X-ray fluorescence. As a result, glass foam with hierarchical density. / Neste trabalho foi realizado um estudo sobre a ação do hidróxido de sódio como agente formador de espuma vítrea usando resíduos de vidro em sua composição. Para a síntese, investigou-se a variação da temperatura, da taxa de aquecimento e do tempo de sinterização. Utilizando-se a técnica de porosimetria de mercúrio, para estimar a densidade e o tamanho médio de poros. A morfologia das espumas vítreas foi avaliada através da microscopia eletrônica de varredura de alta resolução (FEG) e as fases das espumas vítreas foram caracterizadas pelas técnicas de difração de raios X e a composição química estimada usando fluorescência de raios X.

Made available in DSpace on 2014-12-17T14:25:23Z (GMT). No. of bitstreams: 1 AbdoFN_TESE.pdf: 1739510 bytes, checksum: 7f520b9c4a32fd74e279d017c0bdd143 (MD5) Previous issue date: 2014-03-31 / Foam was developed as a novel vehicle for streptokinase with the purpose of increasing the contact time and area between the fibrinolytic and the target thrombus, which would lead to a greater therapeutic efficacy at lower doses, decreasing the drug s potential to cause bleeding. Fibrinolytic foams were prepared using CO2 and human albumin (at different v:v ratios), as the gas and liquid phases, respectively, and streptokinase at a low total dose (100,000 IU) was used as fibrinolytic agent conveyed in 1 mL of foam and in isotonic saline solution. The foams were characterized as foam stability and apparent viscosity. The thrombolytic effect of the streptokinase foam was determined in vitro as thrombus lysis and the results were compared to those of a fibrinolytic solution (prepared using the same dose of streptokinase) and foam without the fibrinolytic. In vitro tests were conducted using fresh clots were weighed and placed in test tubes kept at 37 ? C. All the samples were injected intrathrombus using a multiperforated catheter. The results showed that both foam stability and apparent viscosity increased with the increase in the CO2:albumin solution ratio and therefore, the ratio of 3:1 was used for the incorporation of streptokinase. The results of thrombus lysis showed that the streptokinase foam presented the highest thrombolytic activity (44.78 ? 9.97%) when compared to those of the streptokinase solution (32.07 ? 3.41%) and the foam without the drug (19.2 ? 7.19%). We conclude that fibrinolytic foam showed statistically significant results regarding the enhancement of the lytic activity of streptokinase compared to the effect of the prepared saline solution, thus it can be a promising alternative in the treatment of thrombosis. However, in vivo studies are needed in order to corroborate the results obtained in vitro / Uma espuma foi desenvolvida como novo ve?culo para a estreptoquinase com vistas a aumentar a ?rea de contato e o tempo de perman?ncia junto ao trombo, de modo a se obter maior efici?ncia terap?utica em doses menores, diminuindo suas potenciais complica??es hemorr?gicas. A espuma fibrinol?tica foi preparada com CO2, albumina humana e estreptoquinase, em dispositivo desenvolvido para tal fim, com diferentes raz?es de fases g?s/l?quido. Ensaios de estabilidade e viscosidade aparente foram realizados para caracteriza??o das espumas e a escolha da mais est?vel. A estreptoquinase em dose total reduzida (100.000 UI) foi utilizada como fibrinol?tico veiculado em 1 mL de espuma e em solu??o salina isot?nica (0,9%). A espuma sem fibrinol?tico tamb?m foi utilizada como comparativo. Testes in vitro foram realizados utilizando-se co?gulos frescos, que foram pesados e colocados em tubos de ensaio mantidos a 37?C. As espumas com e sem fibrinol?tico e a solu??o fibrinol?tica foram testadas por aplica??o intraco?gulo em doses id?nticas atrav?s de cateter multiperfurado e pistola de inje??o. Os resultados in vitro evidenciaram atrav?s da diminui??o dos pesos dos co?gulos, que a espuma trombol?tica apresentou atividade l?tica de 44,78 ? 9,97%, enquanto as mesmas doses da estreptoquinase em solu??o salina isot?nica promoveram 32,07 ?3,41% de lise dos co?gulos. Na espuma sem fibrinol?tico a redu??o do trombo foi de 19,2 ? 7,19%. Conclui-se que a espuma fibrinol?tica apresentou resultados estatisticamente significativos no tocante ? potencializa??o da atividade l?tica da estreptoquinase, quando comparado ao efeito da solu??o preparada com solu??o salina, podendo ser uma alternativa promissora nos tratamentos das tromboses. Os dados obtidos sinalizam para necessidade de estudos in vivo para comprova??o dos obtidos nos in vitro

Submitted by Cláudia Bueno (claudiamoura18@gmail.com) on 2016-04-08T15:04:34Z No. of bitstreams: 2 Tese - Sandra Regina Marcoline Gherardi - 2014.pdf: 1563773 bytes, checksum: 3c2b927eb08946b0b340ab1b4f2018fd (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2016-04-11T11:10:59Z (GMT) No. of bitstreams: 2 Tese - Sandra Regina Marcoline Gherardi - 2014.pdf: 1563773 bytes, checksum: 3c2b927eb08946b0b340ab1b4f2018fd (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2016-04-11T11:10:59Z (GMT). No. of bitstreams: 2 Tese - Sandra Regina Marcoline Gherardi - 2014.pdf: 1563773 bytes, checksum: 3c2b927eb08946b0b340ab1b4f2018fd (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2014-10-14 / In this work we aimed to evaluate the effect of time and temperature of storage on the quality, chemical composition and functional properties of white and brown eggs from commercial hens aged 50 and 30 weeks, respectively. We conducted two experiments, and in each experiment 240 eggs, white (exp. 1) and brown (Exp. 2) eggs were randomly selected, with an average weight between 55 and 65g stored in natural environment and refrigerated for a period of 28 days. A completely randomized design was adopted in a factorial arrangement with two temperatures (ambient and refrigerated)and five storage periods (1, 7, 14, 21 and 28 days) totaling 10 treatments with six replications and four eggs per experimental unit. The quality parameters evaluated were weight of egg, yolk, albumen and shell, yolk index, Haugh Unit, percentage of eggshell, albumen and yolk and pH of albumen and yolk. In the chemical composition analysis of albumen and yolk, we determined moisture, total lipids, protein, total solids and ash contents. The functional properties studied were foaming, foam stability, emulsion formation, time necessary to destabilize the emulsion and yolk color index. The storage time influenced negatively the parameters for both white and brown eggs with more marked influence on eggs stored under ambient condition. In case of changes, they were more intense in the first seven days of storage regardless of storage condition. The refrigerated conditions improved the stability of foams, decreased the amount of oil required to form emulsion and intensified the yolk color index. Storage under refrigeration guarantees the quality, chemical composition and functional properties of white and brown eggs, during 28-day study, extending the shelf life and hence the use by food industries. / Objetivou-se com este trabalho avaliar a influência do tempo e temperatura de estocagem sobre a qualidade, composição química e propriedades funcionais de ovos brancos e marrons oriundos de aves comerciais com 50 e 30 semanas de idade respectivamente. Foram conduzidos dois experimentos e em cada avaliação, foram selecionados 240 ovos, brancos (Exp. 1) e marrons (Exp. 2), ao acaso, com peso médio entre 55 e 65g sendo armazenados em ambiente natural e sob refrigeração por um período de 28 dias. Foi adotado delineamento inteiramente casualizado, em esquema fatorial, composto de duas temperaturas (ambiente e refrigeração) e cinco períodos de estocagem (1, 7, 14, 21 e 28 dias) totalizando 10 tratamentos com seis repetições e quatro ovos por unidade experimental. Os parâmetros de qualidade avaliados foram peso do ovo, gema, albúmen e casca, índice de gema, Unidade Haugh, porcentagem de casca, albúmen e gema e pH de gema e albúmen. Para determinação da composição química foram determinados os teores de umidade, lipídios totais, proteína bruta, sólidos totais e cinzas tanto de albúmen quanto da gema. As propriedades funcionais estudadas foram capacidade de formação de espuma, estabilidade da espuma formada, capacidade de formação de emulsão, determinação do início da desestabilização da emulsão e índice de coloração da gema. O tempo de armazenamento influenciou negativamente sobre os parâmetros avaliados, tanto para ovos brancos quanto marrons, apresentando influência mais marcante sobre ovos mantidos sob condição ambiente. As modificações quando ocorreram, foram mais intensas nos primeiros dias de estocagem independentemente da condição de armazenagem. A refrigeração melhorou a estabilidade das espumas, diminuiu o volume de óleo necessário para formar emulsão e intensificou o índice de coloração das gemas. O armazenamento sob refrigeração garantiu a manutenção da qualidade, composição química e propriedades funcionais durante os 28 dias do estudo para ovos brancos e marrons, ampliando a vida de prateleira e consequentemente o uso pelas indústrias alimentícias.

The high temperature microstructure of the solid phases within the electric arc furnace (EAF) slag has a large effect on the process features such as foamability of the slag, chromium recovery, consumption of the ferroalloys and the wear rate of the refractory. The knowledge of the microstructural and compositional evolution of the slag phases during the EAF process stages is necessary for a good slag praxis. In supplement 1, an investigation of the typical characteristics of EAF slags in the production of the AISI 304L stainless steel was carried out. In addition, compositional and microstructural evolution of the slag during the different EAF process stages was also investigated. Computational thermodynamics was also used as a tool to predict the equilibrium phases in the top slag as well as the amount of these phases at the process temperatures. Furthermore, the influence of different parameters (MgO wt%, Cr2O3 wt%, temperature and the top slag basicity) on the amount of the spinel phase in the slag was studied. In supplement 2, a novel study to characterize the electric arc furnace (EAF) slags in the production of duplex stainless steel at the process temperatures was performed. The investigation was focused on determining the microstructural and compositional evolution of the EAF slag during and at the end of the refining period. Slag samples were collected from 14 heats of AISI 304L steel (2 slag samples per heat) and 7 heats of duplex steel (3 slags sample per heat). Simultaneously with each slag sampling, the temperature of the slag was measured. The selected slag samples were studied both using SEM-EDS and LOM. In some cases (supplement 2), X-ray diffraction (XRD) analyses were also performed on fine-powdered samples to confirm the existence of the observed phases. It was observed that at the process temperature and at all process stages, the stainless steel EAF slag consists mainly of liquid oxides, magnesiochromite spinel particles and metallic droplets. Under normal operation and at the final stages of the EAF, 304L steelmaking slag contains 2-6 wt% magnesiochromite spinel crystals. It was also found that, within the compositional range of the slag samples, the only critical parameter affecting the amount of solid spinel particles in the slag is the chromium oxide content. Petrographical investigation of the EAF duplex stainless steelmaking showed that, before FeSi-addition, the slag samples contain large amounts of undissolved particles and the apparent viscosity of the slag is higher, relative to the subsequent stages. In this stage, the slag also includes solid stoichiometric calcium chromite. It was also found that, after FeSi-injection into the EAF and during the refining period, the composition and the basicity of the slag in the EAF duplex steelmaking and EAF stainless steelmaking are fairly similar. This indicates that, during the refining period, the basic condition for the utilization of an EAF foaming-slag praxis, in both austenitic and duplex stainless steel cases, is the same. Depending on the slag basicity, the slag may contain perovskite and/or dicalcium silicate too. More specifically, the duplex stainless steel slag samples with a higher basicity than 1.55 found to contain perovskite crystals. / QC 20110413

Today, a huge part of waste products from pulp and paper industries ends up in landfill which is both economically and environmentally adversely. This report examines the possibilities of using those products as a slag foamer and fuel in different furnaces in the metal industry. The waste products contain valuable elements, especially carbon. Therefore, there is an increased interest in finding possible use for the waste products in the metal industry. The reuse would contribute to preservation of energy as fossil fuel can be replaced. In the report, two waste materials called mixed biosludge and fiber reject are examined. The experiments are performed with the waste products pressed together with a base material and cement forming a briquette. The requirements examined are strength needed for both transportation and use in furnaces and ability to create a foaming slag. The results in strength were ambiguous, no waste material based briquettes met the set criteria. As of now, the briquettes are probably not strong enough to be transported. No foaming occurred during the experiment, but only one experiment was performed. Therefore, further experiments are needed before any conclusions can be drawn. The briquettes can possibly replace coke and coal in applications where strength is not as important. Nevertheless, it is uncertain if the briquettes affect the steel quality. / Idag läggs en stor del av restprodukter från pappers och massaindustrin på deponi, vilket innebär såväl ekonomiska som miljömässiga nackdelar. Den här rapporten undersöker möjligheterna att använda dessa restprodukter som slaggskummare och bränsle i de olika ugnarna inom metallindustrin. Restprodukterna innehåller värdefulla ämnen, framförallt kol. Därför finns det ett ökat intresse för att hitta möjliga användningsområden för restprodukterna inom metallindustrin. Denna återanvändning skulle bidra till energibevarande eftersom fossila bränslen kan ersättas. I den här rapporten undersöks två restmaterial, blandat biologiskt slam och fiberavfall. Experimenten utfördes med dessa restprodukter pressade samman med ett basmaterial och cement till en brikett. Kraven som undersöks är styrka för både transport och användning i ugnarna samt förmågan att skumma en slagg. Resultaten för briketternas styrka var tvetydiga, inga av briketterna innehållande restprodukter satisfierade det uppsatta kriteriet. Styrkan är troligtvis för låg för att transport ska vara möjlig. Ingen skumning skedde under experimentet, men endast ett experiment genomfördes. Därför behöver ytterligare experiment genomföras innan några slutsatser kan dras. Men briketterna tros kunna ersätta koks och kol där styrkan inte är viktig. Men det är osäkert om briketterna påverkar stålkvaliteten.

Dans un contexte de valorisation de molécules issues de la biomasse, de nouvelles architectures moléculaires et polyols ont été développé à partir du sorbitol et divers synthons biosourcés en se basant autant que possible sur les principes de la chimie verte. A partir de réactions d’estérifications contrôlées plusieurs polyols polyesters ont été synthétisés, en l’absence de solvant. Grace à l’utilisation de diols de différentes tailles (C2 à C12) comme monomères, la viscosité et la teneur en fonctions hydroxyles des polyols finaux ont pu être adaptée jusqu’à obtention de propriétés satisfaisantes à l’élaboration de mousses polyuréthanes. Ainsi, des mousses polyuréthanes semi-flexible et des mousses polyisocyanurate rigides ont pu être formulés avec des profils cinétiques de moussage rapide (inférieur à 3 min). Les mousses polyisocyanurates rigides présentent d’excellente propriétés mécaniques et thermiques pouvant pleinement satisfaire à la l’isolation thermique de bâtiment. D’autre part, une voie de transestérification entre le sorbitol et diméthyle carbonate a été étudié afin d’élaborer une nouvelle molécule plateforme bi-fonctionnelle : un bis-cyclocarbonate. A partir de cette molécule plateforme des réactions de polymérisation par ouverture de cycles et d’aminolyses ont été mise en place pour la synthèse de diols, polyéthers réticulés, et de polyuréthanes sans isocyanate (NIPU). Les synthèses de NIPU réalisées à partir de diamines courtes ou longues (issus de dimer d’acide gras) a permis d’étudier les relations existantes entre le choix des monomères et les températures de transitions vitreuses des matériaux polymères résultant. / In a context of renewable molecules valorization, new molecular architectures and polyols have been developed from sorbitol and various biobased building-blocks with respect to the green chemistry principles. Several polyesters polyol have been synthesized from controlled esterification reactions in bulk conditions. Thanks to the used of variable size diols (C2 to C12) monomers, polyols final viscosity and hydroxyls values were tuned until the obtaining of suitable properties for polyurethanes foams elaborations. Thus, semi-flexible polyurethane foams and rigid polyisocyanurate foams were formulated with fast foaming kinetic profiles (less than 3 min). Rigids polyisocyanurates foams exhibit excellent mechanical and thermal properties, in great agreement with building insulating application requirement. Otherwise, transesterifications reaction involving sorbitol and dimethyl carbonate were studied in order to develop a new bi-functional chemical platform, a bis-cyclocarbonate. Ring opening polymerization and aminolysis reactions were investigated from this chemical platform to the elaboration of cross-linked polyether and non-isocyanate polyurethanes (NIPU). NIPU syntheses were performed with short and long diamines in order to study the relationships between monomers choice and the resulting polymer material temperature of glass transition.

Cette thèse porte sur la production et l’étude de mousses de polymères micro ou nanoporeux à partir de mélanges nanostructurés à base de PMMA (poly(méthyl méthacrylate)) par dissolution et moussage avec CO2. D’autre part, plusieurs techniques expérimentales ont été améliorées ou adaptées afin de fournir de précieuses informations sur les systèmes étudiés. La nanostructuration de mélanges solides denses à base de PMMA est induite par l’addition d’un copolymère à blocs (MAM, poly(méthyl méthacrylate)-co-poly(butylacrylate)-co-poly(méthyl méthacrylate)). Les structures cellulaires des mousses produites à partir de ces mélanges ont été caractérisées et expliquées ; on a démontré que la nanostructuration agit comme un modèle (un gabarit) pour la structure cellulaire, permettant l’obtention d’un large éventail de structures cellulaires et en particulier des mousses nanocellulaires. De plus il est démontré que les paramètres du procédé, tels que la pression et la température, permettent la différenciation entre les deux voies de moussage utilisées ;ceux-ci ont une influence significative sur les caractéristiques finales des mousses de PMMA seul, mais peu sur celles des mélanges PMMA/MAM. Les mousses dans ces mélanges présentent un mécanisme de nucléation hétérogène contrôlée par la nanostructuration, ce qui permet de limiter l’influence des paramètres de traitement thermique dans la nucléation de la cellule. En outre, certains mélanges de PMMA/MAM présentent également une remarquable stabilité de leur morphologie au cours de la croissance cellulaire, ce qui évite l’effondrement cellulaire et la coalescence.Enfin, on a étudié l’influence de la transition entre les structures micro-cellulaires et les structures nano-cellulaires sur les propriétés : une nette diminution de la conductivité thermique en raison de l’effet de Knudsen que nous avons mis en évidence, une augmentation notable de la température de transition vitreuse en raison de l’isolement des chaînes de polymères dans les parois (les murs) de la cellule ; mais n’avons pas noté d’influence importante de cette transition sur le module de Young. / This dissertation focuses on the production and study of nanocellular foams from PMMA based(poly(methyl methacrylate) materials by CO2 gas dissolution foaming.Due to the novelty of this research field several experimental techniques have been improved or adapted in order to provide valuable information from the systems understudy. Nanostructuration of PMMA-based blends induced by the addition of a block copolymer (MAM, poly(methyl methacrylate)-b-poly(butyl acrylate)-b-poly(methyl methacrylate)) and the cellular structure of the foams produced from these blends have been characterized and related; obtaining that the nanostructuration acts as a pattern for the cellular structure, allowing obtaining a wide range of cellular structures and in particular nanocellular foams. It is demonstrated that processing parameters, such as pressure and temperature, allow differentiating between two foaming routes ; and present a significant influence on the foaming process and final characteristics of neat PMMA foams, but not on PMMA/MAM blends. PMMA/MAM blends present a heterogeneous nucleation mechanism controlled by the nanostructuration that avoid the influence of the processing parameters in the cell nucleation. In addition, some PMMA/MAM blends also present a high stability during the cell growth, avoiding the cellular collapse and coalescence. Finally, it has been studied the influence on the foams properties of the transition between the microcellular and the nanocellular ranges; obtaining that there is a clear influence on the thermal conductivity, which decreases in nanocellular foams due to the Knudsen effect,and the glass transition temperature, which increases in nanocellular foams due to the confinement of the polymer chains in the cell walls, but not on the Young’s modulus. / Esta tesis se centra en la producción y estudio de de espumas poliméricas nanocelulares producidas a partir de materiales basados en PMMA (poli(metil metacrilato)), mediante la técnica de espumado por disolución de gas usando CO2. Debido a la novedad de este campo de investigación ha sido necesario mejorar o adaptar varias técnicas experimentales para obtener la información necesaria de los sistemas bajo estudio. Se han caracterizado y relacionado la nanoestructuración de mezclas basadas en PMMA, inducida por la adición de un copolímero de bloque (MAM, poli(metil metacrilato)-copoli(butil acrilato)-co-poli(metil metacrilato)), y la estructura celular de las espumas producidas a partir de esas mezclas; obteniéndose que la nanoestructuración actúa como patrón para la estructura celular, permitiendo obtener una amplia variedad de estructuras celulares y en particular de estructuras nanocelulares.Se ha demostrado que los parámetros de procesado, como la presión y temperatura,permiten diferenciar entre dos rutas de espumado y presentan una influencia significativa en las características finales de las espumas de PMMA puro, pero no en las mezclas de PMMA/MAM. Estas mezclas presentan un mecanismo de nucleación heterogénea controlado por la nanoestructuración, que evita que los parámetros de procesado influyanen el proceso de nucleación de las celdas. Además, algunas mezclas de PMMA/MAM también presentan una alta estabilidad durante el crecimiento de las celdas, evitando el colapso de la estructura celular y la coalescencia.Finalmente, se ha estudiado la influencia en las propiedades de las espumas de la transición entre el rango microcelular y el rango nanocelular; obteniéndose que hay una clara influencia sobre la conductividad térmica, que decrece en las espumas nanocelulares debido al efecto Knudsen, y sobre la temperatura de transición vítrea, que se incrementa debido al confinamiento de las cadenas poliméricas en las paredes de las celdas, pero no sobre el módulo de Young.

Avec l'augmentation de l'utilisation des mousses polyuréthanes dans l'industrie automobile et la complexité des formes des pièces, plusieurs défauts de production qui influent sur la qualité des produits finaux peuvent apparaître. L'utilisation des outils numériques pour la simulation du procédé de moussage du polyuréthane est une solution pour prédire le comportement de la mousse pendant le remplissage du moule et détecter les défauts à l'avance. Dans ce contexte, les travaux de cette thèse avaient pour objectif de modéliser et de simuler le procédé de moussage du polyuréthane. Des modèles prenant en compte les deux principales réactions chimiques de la formation du polyuréthane, l'effet exothermique de ces réactions ainsi que le couplage thermo-rhéo-cinétique caractérisant ce procédé ont été proposés. Ces modèles ont été implémentés dans le logiciel NOGRID-points basé sur une méthode sans maillage (FPM) qui donne plus de flexibilité en termes de simulation des écoulements à surface libre. Une technique d'identification inverse qui permet de minimiser l'écart entre les résultats numériques et les résultats expérimentaux obtenus suite à un travail expérimental de caractérisation a permis de déterminer les paramètres des modèles utilisés. Les résultats numériques ont été validés en réalisant des incomplets avec un sous-système de forme simple et un moule d'une pièce industrielle de forme complexe. Cette validation a consisté à comparer les positions des fronts de la mousse obtenues expérimentalement avec celles obtenues numériquement. Nous avons également proposé une prédiction de certaines caractéristiques acoustiques de la mousse en se basant sur les résultats de la simulation numérique du moussage et un modèle semi-phénoménologique. / With the increasing use of polyurethane foam in the automotive industry and the complexity of the shapes of the parts, several production defects that affect the quality of the final products may occur. The use of numerical simulation tools is a valuable method to control the mold filling during the foaming process and to detect defects at an early stage. In this context, this work aimed to model and to simulate the polyurethane foaming process. Models taking into account the two main chemical reactions of the formation of polyurethane, the exothermic effect of these reactions as well as the thermo-rheo-kinetic coupling characterizing this process have been proposed. These models have beenimplemented in the software NOGRID-points based on a meshless method (FPM) which gives more flexibility in terms of simulation of free surface flows. The parameters of the used models were identified by an inverse analysis method which minimizes the difference between the numerical and the experimental results obtained by an experimental characterization work. The numerical resultswere validated by carrying out a set of short shot foams using a panel mold cavity and an automotive underlay carpet cavity. The validation was to compare the flow front positions obtained experimentally with the numerical ones. We have also proposed a prediction of some acoustic foam characteristics based on the results of the numerical simulation of the foaming process and a semiphenomenological model.