Ce travail concerne l'étude des modifications de nanocharges lamellaires synthétiques (α-ZrP) et de leur influence sur les propriétés mécaniques et barrière aux gaz de nanocomposites à matrice élastomère (SBR). Cette étude s'inscrit dans le cadre de l'amélioration de l'étanchéité des pneumatiques. L'une des originalités de ce travail a résidé dans l'introduction des nanocharges hydrophiles par le biais d'une dispersion aqueuse (slurry), dans la matrice SBR hydrophobe. La première phase de ce travail a consisté à entreprendre plusieurs types de modification des nanocharges afin d'étudier les mécanismes d'intercalation et/ou d'exfoliation des ces dernières dans le slurry. Ces différentes familles de charges modifiées ont été utilisées pour réaliser des nanocomposites selon différentes voies de mise en oeuvre : principalement solvant et latex. Nous avons ensuite étudié l'influence, (i) de la nature des intercalants, (ii) des distances interfoliaires initiales des nanocharges et (iii) des procédés de mise en oeuvre des nanocomposites, sur la morphologie et les propriétés finales des matériaux. Cette étude a montré la synergie de ces trois paramètres et mis en évidence l'importance du contrôle des interactions charges modifiées/matrice sur les propriétés de transport de gaz. Parmi l'ensemble des matériaux synthétisés, nous avons pu mettre en avant une formulation, permettant d'atteindre des propriétés mécaniques et barrière intéressantes. Cette formulation, en voie latex, est basée sur l'utilisation de la charge modifiée aminosilane et de l'agent de couplage Si69

Cette thèse propose l'étude de matériaux composites industriels simplifiés constitués de caoutchouc non réticulé (copolymère styrène-butadiène " SBR ") renforcés par des charges nanométriques de silice hautement dispersible. Afin d'identifier les mécanismes physico-chimiques responsables de ce renforcement et être capable de l'optimiser, nous devons comprendre les corrélations existantes entre les propriétés macroscopiques du matériau et la structure des charges à différentes échelles. Pour cela, une large campagne d'expériences de diffusion des rayons-X aux petits angles (DXPA) ainsi que de nombreux clichés de microscopie électronique ont été réalisés. En couplant ces données avec des simulations Monte-Carlo, il a été notamment possible de mettre en avant la présence d'une organisation à trois niveaux en partant de billes élémentaires d'une dizaine de nanomètres formant des agrégats eux-mêmes arrangés selon un réseau tridimensionnel branché existant à travers tout l'échantillon. L'analyse du renforcement dans les nanocomposites a été effectuée par rhéométrie et analyse dynamique mécanique. D'autres techniques telles que la spectroscopie diélectrique, la résonnance magnétique nucléaire, l'analyse thermogravimétrique ou la spectrométrie infrarouge ont également contribué à une caractérisation complète de ces matériaux, en particulier pour sonder la dynamique des chaînes de SBR à l'interface avec la charge. Afin de déceler les corrélations existantes entre structure et propriétés, nous nous sommes attachés à décrire systématiquement l'influence de paramètres-clés tels que la fraction volumique en silice, le type de polymère employé (greffable sur la silice ou pas) ou leur masse molaire sur la morphologie des charges (par exemple la taille des agrégats) ainsi que sur le comportement mécanique (par exemple leur module d'élasticité) des composites. Ce travail a permis d'identifier la densité de greffage des chaines comme le paramètre définissant la structure des composites et impactant significativement le renforcement. Cette thèse, résolument tournée vers la compréhension fondamentale, est aussi une contribution à la recherche d'une loi de comportement décrivant l'effet de la structure des charges sur les performances des pneumatiques. Cette dernière doit permettre de répondre à des problématiques rencontrées en ingénierie telles que la résistance à l'usure, l'adhérence, ou la résistance au roulement. De plus, dans le but d'atteindre des informations supplémentaires quant aux interactions entre caoutchouc et silice, nous avons mis au point un protocole expérimental permettant de formuler des échantillons dits " modèles " renforcés avec une silice colloïdale. Cette dernière étant beaucoup mieux définie d'un point de vue géométrique, son analyse structurale est grandement facilitée rendant possible l'étude des potentiels mis en jeu pendant la production des nanocomposites.

Els lixiviats d'abocadors urbans són aigües residuals altament contaminades, que es caracteritzen per les elevades concentracions d'amoni i el baix contingut de matèria orgànica biodegradable. El tractament dels lixiviats a través dels processos de nitrificació-desnitrificació convencionals és costós a causa de la seva elevada demanda d'oxigen i la necessitat d'addició d'una font de carboni externa. En els darrers anys, la viabilitat del tractament d'aquest tipus d'afluents per un procés combinat de nitritació parcial-anammox ha estat demostrada. Aquesta tesi es centra en el tractament de lixiviats d'abocador a través d'un procés de nitritació parcial en SBR, com un pas preparatori per a un reactor anammox. Els resultats de l'estudi han demostrat la viabilitat d'aquesta tecnologia per al tractament de lixiviats d'abocador. El treball va evolucionar des d'una escala inicial de laboratori, on el procés va ser testat inicialment, a uns exitosos experiments d'operació a llarg termini a escala pilot. Finalment, la tesi també inclou el desenvolupament, calibració i validació d'un model matemàtic del procés, que té com a objectiu augmentar el coneixement del procés. / Urban landfill leachate are highly contaminated wastewater, usually characterised by high ammonium concentrations and low biodegradable organic matter content. Treating leachate through conventional nitrification-denitrification processes is expensive due to its high oxygen demand and the requirement of a supplementary external carbon source. In recent years, the feasibility of treating such streams with a low C:N ratio by a combined partial nitritation-anammox process has been demonstrated. This thesis deals with the treatment of landfill leachate by a partial nitritation-SBR, as a preparative step for an anammox reactor. The results of the study have demonstrated the feasibility of this technology for the treatment of landfill leachate. The work evolved from initial lab-scale studies, where the process was first tested, to a successful long-term experiment at pilot-scale. In addition, the thesis also includes the development, calibration and validation of a mathematical model of the process, aiming at increasing process knowledge.

Um sistema combinado anaeróbio-aeróbio composto de um filtro anaeróbio ascendente seguido de reator aeróbio de lodos ativados em batelada, foi continuamente alimentado com água residuária sintética da indústria de polpa celulósica não branqueada, durante o período de trezentos e sessenta e três dias, com o objetivo de verificar o desempenho dos reatores operados sob condições termofílicas. Os reatores foram inoculados com lodo mesofílico com gradual adaptação para a condição termofílica e operados em duas fases distintas. A primeira e segunda fases contemplam os períodos em que os reatores foram operados em temperatura termofílica de 55 e 65 graus Celsius, respectivamente. O filtro anaeróbio trabalhou com tempo de detenção hidráulica de 48 horas em fluxo contínuo e o reator aeróbio operado em bateladas seqüenciais (RBS) com tempos de ciclo de 12, 18 e 24 horas. A melhor eficiênica de remoção de DQO do sistema combinado anaeróbio-aeróbio foi de 65%, devida, em maior parte ao reator anaeróbio. O filtro anaeróbio operado em temperatura de 55 e 65 graus demonstrou eficiência na capacidade de retenção de biomassa termofílica, evitando a perda no efluente. O RBS, quando operado em temperatura de 55 graus e tempo de ciclo de 18 horas, demonstrou melhor eficiência para pós-tratamento de água residuária sintética. Os resultados gerais mostram uma melhor eficiência dos reatores operados em temperatura de 55 graus Celsius. / A combined anaerobic-aerobic system, composed of an upflow anaerobic filter followed by an aerobic reactor of activated sludge in batch, was continuously feed with synthetic wastewater from unbleached cellulose pulp plant during a period of three hundred and sixty three days, aiming to verify the performance of the reactors operating under thermophilic conditions. The reactors were inoculated with mesophilic sludge having a gradual adaptation to the thermophilic condition and they were operated in two distinct phases. The first and second phases contemplate the periods in which the reactors were operated in a thermophilic temperature of 55 and 65 Celsius degrees, respectively. The anaerobic filter worked with hydraulic detention time of 48 hours in a continuous flow, and the aerobic reactor was operated in a sequencing batch (SBR) with a cycle time of 12, 18 and 24 hours. The best efficiency of the combined anaerobic-aerobic system to remove DQO was 65% due to, in most part, the anaerobic reactor. The anaerobic filter, operating in temperatures of 55 and 65 degrees, has demonstrated efficiency in the capacity to retain thermophilic biomass, avoiding effluent lost. The SBR reactor, when operated in temperature of 55 degrees and a cycle time of 18 hours, has demonstrated better efficiency in the post-treatment of synthetic wastewater. The general results have showed a better efficiency of the reactors operating in a thermophilic temperature of 55 Celsius degrees.

FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / Os sistemas de lagoas de estabilizaÃÃo, bastante presentes em aterros sanitÃrios normalmente nÃo sÃo suficientes para o atendimento aos padrÃes ambientais de descarte de lixiviado tratado em Ãguas superficiais. Este trabalho avaliou o emprego das tecnologias aerÃbias do tipo reator aerado submerso (RAS) e reator em batelada seqÃencial (RBS) como opÃÃes de pÃs-tratamento para lixiviado antigo prÃ-tratado em lagoas de estabilizaÃÃo. A coleta do lixiviado se deu na saÃda da Ãltima lagoa de estabilizaÃÃo do sistema de tratamento de lixiviado (duas anaerÃbias em sÃrie, seguidas de uma facultativa) localizadas no Aterro SanitÃrio Metropolitano Oeste (ASMOC), municÃpio de Caucaia, RegiÃo Metropolitana de Fortaleza, estado do CearÃ. Inicialmente foi realizada uma caracterizaÃÃo fÃsico-quÃmica do lixiviado efluente e verificaÃÃo do atendimento aos padrÃes de descarte. O RAS foi operado em cinco fases, sendo divididas entre esgoto sintÃtico e lixiviado, este Ãltimo testado com e sem diluiÃÃo. Avaliou-se o efeito da adiÃÃo de fonte externa de carbono, etanol, para a fase em que o reator era alimentado com lixiviado sem diluiÃÃo. O RBS foi confeccionado em acrÃlico, em formato cilÃndrico, com um volume Ãtil de 5,0L, sendo inicialmente estudado o tempo de operaÃÃo de cada ciclo de 24 horas. Posteriormente, foram avaliados no RBS os tempos totais de ciclo de 12 e 48 horas, alÃm do efeito da adiÃÃo de etanol no desempenho do reator. Os reatores foram instalados no LaboratÃrio de Saneamento (Labosan) do Departamento de Engenharia HidrÃulica e Ambiental (DEHA) da Universidade Federal do Cearà (UFC). Eles foram operados na faixa mesofÃlica, com temperatura ambiente prÃxima de 27ÂC. Em relaÃÃo ao lixiviado tratado, os valores encontrados na caracterizaÃÃo fÃsico-quÃmica confirmam a recalcitrÃncia e complexidade do lixiviado, indicando que apenas as lagoas de estabilizaÃÃo, nÃo atendem plenamente os padrÃes de descarte. A presenÃa de compostos recalcitrantes e tÃxicos no lixiviado afluente ao RAS durante um dos perÃodos de investigaÃÃo causou diminuiÃÃo na remoÃÃo de DQO, mostrando efeito inibitÃrio nos microrganismos presentes no inÃculo. Entretanto, em outra fase de investigaÃÃo, tanto o RAS quanto o RBS se mostraram eficientes e estÃveis na remoÃÃo de DQO e nitrogÃnio amoniacal, mesmo tratando lixiviado sem diluiÃÃo. A adiÃÃo de etanol como fonte externa de carbono foi benÃfica para suprir as necessidades metabÃlicas microbianas, fazendo aumentar tanto a eficiÃncia global do RAS e RBS em termos de remoÃÃo de matÃria orgÃnica (DQO), assim como na estabilidade operacional dos mesmos. O RAS e o RBS foram tambÃm bastante eficientes no processo de nitrificaÃÃo. O estudo no RBS com os tempos de ciclo de 12, 24 e 48 h revelaram que nÃo houve diferenÃa entre os tempos em relaÃÃo à remoÃÃo dos constituintes analisados, fazendo com que se considerasse 12 h como tempo Ãtimo de ciclo, de forma a minimizar os custos com volume do reator e tempo de aeraÃÃo. Como conclusÃo geral do experimento pode-se dizer que o tratamento biolÃgico aerÃbio, tanto utilizando reatores aerados submerso (RAS) quanto reatores em batelada seqÃencial (RBS), pode ser considerado uma boa alternativa para o pÃs-tratamento de lixiviado antigos provenientes de sistemas de lagoas de estabilizaÃÃo, mas ainda requer adequaÃÃes operacionais ou associaÃÃes com processos fÃsico-quÃmicos ou de oxidaÃÃo avanÃados para o enquadramento de todos os constituintes. / The system of stabilization ponds, which is often present in landfills, is usually not efficient to meet environmental standards for disposal of treated leachate on surface waters. This study evaluated the use of submerged aerated reactor (SAR) and sequencing batch reactor (SBR) as post-treatment options for old leachate pre-treated in waste stabilization ponds. The leachate collection took place at the outflow of the last stabilization pond of the treatment system (two anaerobic em series, followed by a facultative pond) located in West Metropolitan Landfill (ASMOC), Caucaia municipality, metropolitan region of Fortaleza, Cearà state. A physical-chemical characterization of the leachate effluent was performed to verify the compliance to reach disposal standards. The SAR was operated in five phases, being divided between synthetic wastewater and leachate, the latter tested with and without dilution. We evaluated the effect of adding an external carbon source, ethanol, for the phase in which the reactor was fed with leachate without dilution. SBR was made of acrylic, in a cylindrical shape with a working volume of 5.0 L and the total time cycle of 24 hours was initially studied. The total time cycles of 12 and 48 hours were also evaluated in the SBR performance, as well as the effect of adding ethanol as carbon source. The reactors were installed at the Laboratory of Sanitation (Labosan) of the Department of Hydraulic and Environmental Engineering (DEHA), Federal University of Cearà (UFC). They were operated in the mesophilic range, with temperature near 27  C. Regarding the treated leachate, the physical-chemical characterization confirmed its recalcitrance and complexity, indicating that only the stabilization ponds did not fully meet the standards of disposal. The presence of recalcitrant and toxic compounds in the leachate influent to the SAR during the investigation period decreased COD removal, showing an inhibitory effect on the microorganisms present in the inoculum. However, in another research phase, both the SAR and SBR were stable and efficient on COD and ammonia removals, even when undiluted leachate was used. The addition of ethanol as external carbon source was beneficial to meet the microbial metabolic needs, increasing both the overall efficiency of SAR and SBR in terms of organic matter removal (COD) and operational stability. The SAR and SBR were also quite efficient in the nitrification process. The study with SBR with cycle times of 12, 24 and 48 h showed no considerable difference amongst the constituent removals, so that 12 h was considered as optimal time cycle in order to minimize the costs with reactor volume and aeration time. As a general conclusion of the experiment we can say that the aerobic biological treatment, using either submerged aerated reactor (SAR) or sequencing batch reactors (SBR), can be considered a good alternative for post-treatment of old leachate pre-treated in stabilization ponds, but still requires operational adjustments and associations with physical-chemical or advanced oxidation processes for accomplish all discharge standards.

At present, the current 4G systems provide a universal platform for broadband mobile services; however, mobile traffic is still growing at an unprecedented rate and the need for more sophisticated broadband services is pushing the limits on current standards to provide even tighter integration between wireless technologies and higher speeds. This has led to the need for a new generation of mobile communications: the so-called 5G. Although 5G systems are not expected to penetrate the market until 2020, the evolution towards 5G is widely accepted to be the logical convergence of internet services with existing mobile networking standards leading to the commonly used term “mobile internet” over heterogeneous networks, with several Gbits/s data rate and very high connectivity speeds. Therefore, to support highly increasing traffic capacity and high data rates, the next generation mobile network (5G) should extend the range of frequency spectrum for mobile communication that is yet to be identified by the ITU-R. The mm-wave spectrum is the key enabling feature of the next-generation cellular system, for which the propagation channel models need to be predicted to enhance the design guidance and the practicality of the whole design transceiver system. The present work addresses the main concepts of the propagation channel behaviour using ray tracing software package for simulation and then results were tested and compared against practical analysis in a real-time environment. The characteristics of Indoor-Indoor (LOS and NLOS), and indoor-outdoor (NLOS) propagations channels are intensively investigated at four different frequencies; 5.8 GHz, 26GHz, 28GHz and 60GHz for vertical polarized directional, omnidirectional and isotropic antennas patterns. The computed data achieved from the 3-D Shooting and Bouncing Ray (SBR) Wireless Insite based on the effect of frequency dependent electrical properties of building materials. Ray tracing technique has been utilized to predict multipath propagation characteristics in mm-wave bands at different propagation environments. Finally, the received signal power and delay spread were computed for outdoor-outdoor complex propagation channel model at 26 GHz, 28 GHz and 60GHz frequencies and results were compared to the theoretical models.

Im ersten Teil dieser Arbeit „Metaanalyse vorhandener Ökobilanzen der Siedlungsentwässerung“ wird mit Hilfe einer qualitativen Metaanalyse vorhandener Ökobilanzen der Siedlungsentwässerung untersucht, welche wichtigen Stellschrauben es in der Umweltleistung von Abwasserreinigungsanlagen gibt und welchen Einfluss diese auf den demographischen Wandel haben. Die Ergebnisse zeigen Stromverbrauch, Schlamm und damit verbundene Toxizität sowie Eutrophierung als Indikatoren der Umweltleistung der Abwasserreinigung, die zur Reaktion auf den demographischen Wandel berücksichtigt werden müssen. Im zweiten Tei. „Ökologische Analyse des Gesamtsystems der Siedlungsentwässerung unter Betrachtung des Siedlungsanschlusses“ werden die ökologischen Auswirkungen des Gesamtsystems der Abwasserentsorgung über den gesamten Lebenszyklus analysiert. Die Arbeit kommt zu dem Ergebnis, dass diese Entscheidung für ein zentrales oder ein dezentrales System sowohl von der Siedlungsgröße, als auch von der Entfernung zur bestehenden Kläranlage abhängig ist. Der dritte Teil „Ökologische Analyse von Kleinkläranlagen“ analysiert eine Alternative zur in Deutschland üblichen Methode der Abwassereinigung durch eine zentrale Kläranlage. Die Kleinkläranlage ist eine dezentrale Lösung für die Haushalte, die nicht an das kommunale Abwassernetz angeschlossen werden. In der Arbeit wird eine SBR-Anlage im Hinblick auf ihre ökologischen Auswirkungen mittels einer Ökobilanzierung mit Hilfe der Software SimaPro untersucht.

Call centers have become a preferred and prevalent means for companies to communicate with their customers. As a consequence of this, the call center industry has seen a huge growth in both volume and scope in the last couple of decades. Operations managers are challenged with the fact that personnel costs, especially staffing, account for over 65% of the cost of running the typical call center. The trade-off between service quality (marketing) and efficiency (operations), thus naturally arises, and a central goal of ours is to contribute to its understanding. We present here a server switching policy for routing of calls to Customer Service Representatives (CSR) in a multi-skilled inbound call center utilizing skill-based routing (SBR). We model the system as a queueing network and propose stochastic Petri net based models for the design and performance analysis of call centers. Our models and experimentations help in identifying practices that result in efficient usage of existing personnel in a call center. In our work, we have considered two types of scenarios in which a multi-skilled SBR call center handling inbound calls can function - (i) with specialist agents only, and (ii) with a mix of specialist and flexible agents. We have developed both these models and compared the rewards obtained from each of them. This analysis helped us answer important issues regarding the routing decision of calls to CSRs, identify the hedging point where one obtains the highest rewards and the impact of varying the strategic and tactical level decisions on the overall call center performance.

En aquesta tesis s'ha desenvolupat un sistema de control capaç d'optimitzar el funcionament dels Reactors Discontinus Seqüencials dins el camp de l'eliminació de matèria orgànica i nitrogen de les aigües residuals. El sistema de control permet ajustar en línia la durada de les etapes de reacció a partir de mesures directes o indirectes de sondes. En una primera etapa de la tesis s'ha estudiat la calibració de models matemàtics que permeten realitzar fàcilment provatures de diferents estratègies de control. A partir de l'anàlisis de dades històriques s'han plantejat diferents opcions per controlar l'SBR i les més convenients s'han provat mitjançant simulació. Després d'assegurar l'èxit de l'estratègia de control mitjançant simulacions s'ha implementat en una planta semi-industrial. Finalment es planteja l'estructura d'uns sistema supervisor encarregat de controlar el funcionament de l'SBR no només a nivell de fases sinó també a nivell cicle. / In this Thesis a control system has been developed which permits optimizing the performance of the Sequencing Batch Reactors (SBR) within the field of organic matter and nitrogen removal from the wastewater. This control system is based on the on-line adjustment of the length of the reaction phases using directly or indirectly the data acquired from the sensors. In a first stage of the Thesis the calibration of the activated sludge models is studied what permits obtaining models for testing different operating and control strategies. From the analysis of historical data several options for controlling the SBR are obtained and most suitable is tested using a simulation approach. Afterwards, the control strategy is implemented in a semi-industrial plant obtaining promising results. Finally, a proposal for a supervisory control system is presented which can be in charge of controlling the performance of the SBR not only at a phase level but also at cycle level.

In the last decades, the awareness of environmental issues has increased in society considerably. There is an increasing need to improve the effluent quality of domestic wastewater treatment processes. This thesis describes the application of the Sequencing Batch Reactor (SBR) technology for Biological Nutrient Removal (BNR) from the wastewater. In particular, the work presented evolves from the nitrogen removal to the biological nutrient removal (i.e. nitrogen plus phosphorous removal) with special attention to the operational strategy design, the identification of possible reactor cycle controls or the influent composition related to the process efficiency. In such sense, also the use of ethanol as an external carbon (when low influent Carbon:Phosphorus (C:P) or Carbon:Nitrogen (C:N) ratios are presented) are studied as an alternative to maintain the BNR efficiency.