Dissertations / Theses on the topic 'Direct reduction'

La substitution du carbone fossile par du carbone biogénique issu de la biomasse pourrait réduire considérablement la contribution de l'industrie sidérurgique au réchauffement climatique. L'objectif de ce travail de thèse était de poser les bases et d'analyser un procédé innovant d'élaboration du fer, dénommé BIORED (biomass-based iron ore reduction). Dans celui-ci, des boulettes de minerai de fer et de la biomasse granulaire sont chargées au sommet d'un four à cuve vertical. Le minerai est réduit par CO issu de la gazéification in-situ de la biomasse (réaction de Boudouard). Nous avons déterminé les cinétiques de dévolatilisation et de gazéification de la biomasse choisie, du charbon de bois, par thermogravimétrie. Ces cinétiques ont été modélisées par la méthode des réactions indépendantes en parallèle et l'équation de Langmuir-Hinshelwood, respectivement. Nous avons transformé un modèle existant de simulation du procédé de réduction directe du minerai de fer par les gaz pour tenir compte des deux solides et des réactions associées à la biomasse. Les résultats du nouveau modèle montrent que dans le réacteur BIORED, la gazéification prend place en bas du four, tandis que la réduction du minerai de fer s'étage, la réduction de la wustite en fer métallique étant l'étape la plus longue. Le degré de métallisation obtenu est satisfaisant et le mélange de gaz d'échappement (CO-CO₂) pourrait être recyclé pour réutiliser CO et économiser l'énergie. Nous avons développé un protocole expérimental spécifique pour la validation du modèle et les résultats de l'expérience correspondent relativement bien aux résultats numériques. Enfin, les possibilités de développement potentiel du procédé BIORED dans certaines régions du monde ont été quantifiées, et une analyse du cycle de vie de la fabrication d'acier sur la base de ce procédé a montré une diminution considérable des émissions de CO₂ (moins 96 %) et de la plupart des autres impacts sur l'environnement, par rapport à la filière usuelle haut fourneau et convertisseur
Substituting fossil carbon with biogenic carbon from biomass could considerably reduce the contribution of the steel industry to global warming. The objective of this thesis was to introduce and analyse an innovative ironmaking process, called BIORED (biomass-based iron ore reduction). In this process, iron ore pellets and granular biomass are loaded together at the top of a vertical shaft furnace. The ore is reduced by CO produced from the in-situ gasification of the biomass (Boudouard reaction). The devolatilisation and gasification kinetics of the selected biomass, charcoal, were determined from thermogravimetry experiments. These kinetics were modelled by the scheme of independent parallel reactions and the Langmuir-Hinshelwood equation, respectively. We used an existing numerical model of a gas-based direct reduction process to create a new one that considers two solids and the biomass-related reactions. The model results show that the gasification takes place at the bottom of the BIORED reactor, while the reduction of the iron ore occurs step-wisely, with the reduction of wustite to metallic iron being the slowest. The degree of metallisation is satisfactory and the top gas (CO-CO2 mixture) could be recycled to reuse CO and save energy. We developed a specific experimental protocol for the validation of the model. The experimental results satisfactorily agree with the numerical ones. Eventually, the potential industrial development of the BIORED process in different regions of the world was assessed, and a life cycle assessment of a new steelmaking route based on BIORED process showed a considerable reduction in CO2 emissions (96% less) and most other environmental impacts, compared to the conventional Blast Furnace-Basic Oxygen Furnace route

Kyoto University (京都大学)
0048
新制・課程博士
博士(エネルギー科学)
甲第11840号
エネ博第116号
新制||エネ||30(附属図書館)
23600
UT51-2005-K506
京都大学大学院ｴﾈﾙｷﾞｰ科学研究科ｴﾈﾙｷﾞｰ基礎科学専攻
(主査)教授 尾形 幸生, 教授 八尾 健, 教授 萩原 理加
学位規則第4条第1項該当

The demands for increasing the efficiency and lowering the environmental effects in iron and steelmaking industries have given rise to interests in application of direct reduction (DR) processes for production of iron by different gases. These advancements require comprehensive models for better control of the process conditions and the product properties. In the present thesis fundamental aspects in reduction of iron oxide were investigated. The experimental studies on reduction of iron oxide pellets were performed under well-controlled conditions in a setup designed for thermogravimetric investigations. The results indicated that the reaction rates by the applied procedure are higher compared to the procedure similar to conventional thermogravimetric analysis (TGA). This difference was caused by the time required for replacing the inert gas by the reaction gases. Reduction by H2-CO mixtures was accompanied by deposition of carbon and formation of cementite. The variations of cementite contents in the industrial iron ore pellets reduced isothermally for different durations, showed that cementite formation starts from the initial stages of reduction. The experimental conditions such as reaction temperature, carbon activity in the reaction gas and reaction time have a large impact on carbide content of the reduced samples. The kinetics of reduction of iron ore powder by H2 and CO gas mixtures with different compositions were studied using a commercial TGA setup. The results showed that the apparent rates of reaction vary linearly with the H2 and CO contents of the gas. Larger amount of H2 resulted in higher reaction rates. The data were employed in the developed reduction model for pellets. The model was based on the mechanism observed in the commercial iron ore pellets reduced by pure hydrogen. The microstructure of reacted pellets showed that reduction of the examined industrial samples is controlled by both chemical reaction and gaseous diffusion. The reduction model was developed by combining computations for the flow and mass transfer in the gas phase, diffusion of gases in the solid phase and chemical reaction at the reaction sites. The modelling and experimental results were in reasonably good agreement. The present model provides a good foundation for a dynamic multi-particle process model. The results highlighted the importance of considering the reduction mechanisms in different types of pellets prior to modelling. Experiments were undertaken to investigate the selective reduction of iron oxide in zinc ferrite. It was observed that gaseous reduction by hydrogen at temperatures up to 873 K is a potential method for reduction of iron oxide to metallic iron, while the zinc oxide remains in the product and losses of metallic zinc are negligible. Using this primary step in the hydrometallurgical processing of EAFD can overcome the difficulties for leaching of zinc ferrite.

QC 20160823

Due to enhanced properties such as large surface area-to-volume ratio, metal nanoparticles are often employed as catalysts for various applications. However, most studies involving nanoparticle catalysts have been conducted on collections of particles rather than single nanoparticles. Results obtained for ensemble systems can be difficult to interpret due to variations in particle loading and interparticle distance, which are often challenging to control and characterize. In this study, two immobilization strategies for incorporating gold nanoparticles (AuNPs) on carbon fiber ultramicroelectrodes (UMEs) were compared with the goal of extending these techniques to nanoelectrodes for studies of single AuNPs. Both layer-by-layer deposition of AuNPs on natural carbon fiber UMEs and direct reduction of AuNPs on nitrided carbon fiber UMEs were explored. Although both methods proved feasible, the direct reduction method seemed to be more effective and should better enable direct comparisons of bare and capped AuNPs.

This study aims to find how density affects the reduction extent and reduction rate. H2-CO gas mixture is used as reducing agent. Five groups of different density pellets were reduced at four different temperatures. Light optical microscope (LOM) and scanning electron microscope with energy dispersive X-ray spectroscopy (SEM-EDS) used to detect completely and partially reduced pellets to investigate how density affects the reduction mechanisms. Results illustrate that density affects reduction extent and reduction rate a lot. However, when reaction temperature is 1123 K, density has less influenc on reduction extent. The carbon deposition occurred for high density pellets at 973 K and 1023 K. The reduction process cannot be described by a single rate controlling step. Reduced layer is denser compared with unreduced layer. Reaction at initial stages goes much faster than later stages.

>Magister Scientiae - MSc
Fuel cells are widely considered to be efficient and non-polluting power source offering much higher energy density. This study is aimed at developing oxygen reduction reactions (ORR) catalysts with reduced platinum (Pt) loading. In order to achieve this aim, monometallic Pd and Pt nanostructured catalysts were electrodeposited on a substrate (carbon paper) by surface limited redox replacement using electrochemical atomic layer deposition (ECALD) technique. Pd:Pt bimetallic nanocatalysts were also deposited on carbon paper. Pd:Pt ratios were (1:1, 2.1 and 3:1). The prepared mono and bimetallic catalysts were characterized using electrochemical methods for the ORR in acid electrolyte. The electrochemical characterization of these catalysts includes: Cyclic Voltammetry (CV) and linear sweep voltammetry (LSV). The physical characterization includes: scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) for Morphology and elemental composition, respectively. The deposition of copper (Cu) on carbon paper was done by applying a potential of -0.05 V at 60s, 90s and 120s. 8x cycles of Pt or Pd showed better electrochemical activity towards hydrogen oxidation reaction. Multiples of eight were used in this work to deposit Pt: Pd binary catalyst. Cyclic voltammetry showed high electroactive surface area for Pt24Pd24/Carbon-paper while LSV showed high current density and positive onset potential. HRSEM also displayed small particle size compared to other Pt:Pd ratios.

CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO
Foi estudada a determinação de mercúrio em gasolina pela técnica do vapor frio, com redução em meio orgânico e de solução de três componentes (microemulsão). Foram utilizadas várias metodologias empregando a técnica de geração de vapor frio e detecção em espectrômetro de absorção atômica, a saber: determinação direta em gasolina; determinação direta em gasolina estabilizada na forma de microemulsão, com e sem pré-concentração em rede de ouro; e determinação direta em gasolina estabilizada na forma de microemulsão utilizando uma armadilha para vapores de gasolina antes da pré-concentração em rede de ouro. Analisando os resultados, foi verificado que a determinação de mercúrio em gasolina estabilizada na forma de microemulsão fornece medidas mais repetitivas do que em gasolina in natura; além disso, foi observada a necessidade de utilizar pré-concentração em rede de ouro, devido aos baixos níveis de mercúrio em gasolina; entretanto, foi detectado que os vapores de gasolina envenenam o ouro. Dentre as armadilhas estudadas para evitar o envenenamento do ouro, foi escolhida a armadilha com solução de K2Cr2O7/H2SO4, na qual, os vapores rovenientes do frasco de reação foram borbulhados e o Hg0, oxidado; posteriormente, a solução foi reduzida com SnCl2/ H2SO4 e os vapores enviados para a rede de ouro. Assim, os resultados indicaram que o método para determinação de mercúrio total em gasolina, no qual o mercúrio é reduzido diretamente da gasolina como microemulsão, utilizando armadilha de K2Cr2O7/H2SO4 antes da pré-concentração em ouro, com detecção por CV-AAS, é recomendado. Após uma otimização multivariada, curvas analíticas apresentaram coeficientes de correlação de até 0,9999 com uma massa característica correspondente de 2ng de mercúrio. O limite de detecção obtido por este método foi de 0,10 ng/mL (0,14 ng/g).
The mercury determination in gasoline by cold vapor and AAS, with reduction in organic liquids and in solution of three components (microemulsion)was studied. Some methodologies were used, with cold vapor generation and atomic absorption spectrometer, to know: direct determination in gasoline; direct determination in gasoline stabilized as microemulsion, with and without preconcentration in gold; and direct determination in gasoline stabilized as microemulsion using a trap for gasoline vapors before the preconcentration in gold. Analyzing the results, it was verified that the measurements from the gasoline stabilized as microemulsion supplies more repetitive readings than the gasoline in nature; moreover, it was observed that is necessary to use preconcentration in gold, due to the lower mercury levels in gasoline; however, it was detected that the gasoline vapors poison the gold. Amongst the studied traps to prevent the poisoning of the gold, the trap with solution of K2Cr2O7/ H2SO4 was chosen, in which, the vapors proceeding from the reaction bottle had been bubbled and the Hg0, oxidated; later, the solution was reduced with SnCl2/ H2SO4 and vapors sent to the gold. Thus, the results had indicated that the method for total mercury determination in gasoline, in which the mercury is reduced directly from the gasoline as microemulsion, using the K2Cr2O7/H2SO4 trap before the preconcentration in gold, with CV-AAS detection, is recommended. After multivariate optimization analytical curves showed coefficients of correlation as good as 0.9999 with a corresponding characteristic mass of 2ng of mercury. The limit of detection obtained for this method was 0.10 ng/mL (0.14 ng/g).

Non-specific chronic low back pain has serious personal and socio-economic consequences. International guidelines recommend multimodal cognitive behavioural management (CBT). The effectiveness of CBT might be enhanced by directly targeting central nervous system pain processing. Transcranial direct current stimulation (tDCS) is a novel approach aiming to influence pain by altering cortical excitability. An evaluation of existing reviews indicated the need for an up-to-date review of clinical and experimental pain trials. A systematic review including 14 trials (published 2006-2012) evaluating tDCS for the reduction of clinical and experimental pain identified a low level of evidence for its effectiveness. Only 1 trial had a low risk of bias. A meta-analysis of trials on clinical pain identified a small pain reducing effect that just reached clinical importance. To investigate the effectiveness of tDCS alone and in combination with CBT, a double-blind RCT was conducted; preceded by a feasibility study confirming practicability of trial procedures and patient acceptability of tDCS. Results indicated that tDCS alone or in combination with CBT did not significantly influence pain or disability. An updated meta-analysis, including this trial’s results, lowered the pain reducing effect of tDCS below clinical importance, and increased the level of evidence for its effectiveness to "high".

Includes bibliographical references (leaves 110-111).
The focus of this study was the use of powder metallurgy to produce low cost titanium with comparative mechanical properties to wrought titanium. The objectives of this investigation was to produce sintered titanium compacts that represented metal made by the Direct Powder Rolling method. The critical strain (ɛC) required to induce recrystallization following deformation was determined by hot compressing wrought titanium samples. Finally sintered titanium samples were hot compressed at ɛC and the changes to the microstructure, porosity and mechanical properties was assessed.

Around 50 million tones hematite iron ores with high iron content at a grade of 68% were found in Muko area of Uganda. Currently, the iron and steel making industry in the country has not yet developed to meet the demand to process the natural ores. Based on the analysis of its composition and mechanical properties, I infer that the natural iron lump ores can charge directly into reduction furnace without any prior treatment, so that the cost of whole process without additional enrichment and sintering will be reduced quite much. Also direct reduction iron (DRI) process use natural gases instead of coals which can greatly reduce the environmental pollution and lower the processes cost. If the raw materials that fit for requirements of majority plants, the seller´s market can get greater control over prices, terms due to the easy and cheap processing. All lump ores were from Butare area which is one occurrence of Muko and named sample A in this work. This research aims to use the lowest cost method to reduce Butare area iron ores and find out the optimum parameters on reduction reactions of Butare iron lump ores, such as flow rate, temperature, size of samples. Base on experiments with different designed parameters, Butare iron lump ores successfully reduced by DR furnace and microstructure was found to be an important parameter that strongly influent reduction degree of Butare iron lump ores.

Nowadays, clusters of computers are used to solve computation intensive problems. These clusters take advantage of a large number of computing nodes to provide a high degree of parallelization. Interconnection networks are used to connect all these computing nodes. The interconnection network should be able to efficiently handle the traffic generated by this large number of nodes. Interconnection networks have different design parameters that define the behavior of the network. Two of them are the topology and the routing algorithm. The topology of a interconnection network defines how the different network elements are connected, while the routing algorithm determines the path that a packet must take from the source to the destination node. The most commonly used topologies typically follow a regular structure and can be classified into direct and indirect topologies, depending on how the different network elements are interconnected. On the other hand, routing algorithms can also be classified into two categories: deterministic and adaptive algorithms. To evaluate interconnection networks, metrics such as latency or network productivity are often used. Throughput refers to the traffic that the network is capable of accepting the network per time unit. On the other hand, latency is the time that a packet requires to reach its destination. This time can be divided into two parts. The first part is the time taken by the packet to reach its destination in the absence of network traffic. The second part is due to network congestion created by existing traffic. One of the effects of congestion is the so-called Head-of-Line blocking, where the packet at the head of a queue blocks, causing the remaining queued packets can not advance, although they could advance if they were at the head of the queue. Nowadays, there are other important factors to consider when interconnection networks are designed, such as cost and fault tolerance. On the one hand, a high performance is desirable, but without a disproportionate increase in cost. On the other hand, the fact of increasing the size of the network implies an increase in the network components, thus the probability of occurrence of a failure is higher. For this reason, having some fault tolerance mechanism is vital in current interconnection networks of large machines. Putting all in a nutshell, a good performance-cost ratio is required in the network, with a high level of fault-tolerance. This thesis focuses on two main objectives. The first objective is to combine the advantages of the direct and indirect topologies to create a new family of topologies with the best of both worlds. The main goal is the design of the new family of topologies capable of interconnecting a large number of nodes being able to get very good performance with a low cost hardware. The family of topologies proposed, that will be referred to as k-ary n-direct s-indirect, has a n dimensional structure where the k different nodes of a given dimension are interconnected by a small indirect topology of s stages. We will also focus on designing a deterministic and an adaptive routing algorithm for the family of topologies proposed. Finally we will focus on analyzing the fault tolerance in the proposed family of topologies. For this, the existing fault tolerance mechanism for similar topologies will be studied and a mechanism able to exploit the features of this new family will be designed. The second objective is to develop routing algorithms specially deigned to reduce the pernicious effect of Head-of-Line blocking, which may shoot up in systems with a high number of computing nodes. To avoid this effect, routing algorithms able of efficiently classifying the packets in the different available virtual channels are designed, thus preventing that the occurrence of a hot node (Hot-Spot) could saturate the network and affect the remaining network traffic.
Hoy en día, los clústers de computadores son usados para solucionar grandes problemas. Estos clústers aprovechan la gran cantidad de nodos de computación para ofrecer un alto grado de paralelización. Para conectar todos estos nodos de computación, se utilizan redes de interconexión de altas prestaciones capaces de manejar de forma eficiente el tráfico generado. Estas redes tienen diferentes parámetros de diseño que definen su comportamiento, de los cuales podríamos destacar dos: la topología y el algoritmo de encaminamiento. La topología de una red de interconexión define como se conectan sus componentes, mientras que el algoritmo de encaminamiento determina la ruta que un paquete debe tomar desde su origen hasta su destino. Las topologías más utilizadas suelen seguir una estructura regular y pueden ser clasificadas en directas e indirectas, dependiendo de cómo estén interconectados los diferentes elementos de la red. Por otro lado, los algoritmos de encaminamiento también pueden clasificarse en dos categorías: deterministas y adaptativos. Para evaluar estas redes se suelen utilizar medidas tales como la latencia o la productividad de la red. La productividad mide el tráfico que es capaz de aceptar la red por unidad de tiempo. La latencia mide el tiempo que utiliza un paquete para alcanzar su destino. Este tiempo se puede dividir en dos partes. La primera corresponde al tiempo utilizado por el paquete en alcanzar a su destino en ausencia de tráfico en la red. La segunda sería la debida a la congestión de la red creada por el tráfico existente. Uno de los efectos de la congestión es el denominado Head-of-Line blocking, donde el paquete que encabeza una cola se queda bloqueado, por lo que el resto de paquetes de la cola no pueden avanzar, aunque pudieran hacerlo si ellos encabezaran dicha cola. Otros factores a tomar en cuenta son el coste y la tolerancia a fallos. Las prestaciones deben mantenerse conforme aumentamos el tamaño de la red, pero sin un aumento prohibitivo en el coste. Además, el hecho de aumentar el tamaño de la red implica un aumento en el número de elementos de dicha red, aumentando la probabilidad de la aparición de un fallo. Por ello, es vital contar con algún mecanismo de tolerancia a fallos en las redes para los grandes supercomputadores actuales. En otras palabras, es de esperar una buena relación coste-prestaciones con un alto nivel de tolerancia a fallos. Esta tesis tiene dos objetivos principales. El primer objetivo combina las ventajas de las topologías directas e indirectas para crear una nueva familia de topologías con lo mejor de ambas. En concreto, nos centramos en el diseño de una nueva familia de topologías capaz de interconectar una gran cantidad de nodos siendo capaz de obtener muy buenas prestaciones con un bajo coste hardware. La familia de topologías propuesta, que hemos llamado k-ary n-direct s-indirect, tiene una estructura n-dimensional, donde los diferentes k nodos de una dimensión se conectan entre sí mediante una pequeña topología indirecta con s etapas. También diseñaremos un algoritmo de encaminamiento determinista y otro adaptativo para la familia de topologías propuesta. Finalmente, nos centraremos en estudiar la tolerancia a fallos para la familia de topologías propuesta. Para ello se estudiarán los mecanismos de tolerancia a fallos existentes en topologías similares y se diseñará un mecanismo capaz de aprovechar al máximo las características de esta nueva familia. El segundo objetivo consiste en el desarrollo de algoritmos de encaminamiento capaces de evitar el pernicioso efecto Head-of-Line blocking, lo cual puede aumentar rápidamente en sistemas con un gran número de nodos de computación. Para evitar este efecto se diseñarán algoritmos de encaminamiento capaces de clasificar de forma eficiente los paquetes en los diferentes canales virtuales disponibles, evitando así que la aparición de un punto caliente (Hot-Spot) sat
Hui en dia, els clústers de computadors són utilitzats per solucionar grans problemes computacionals. Aquests clústers aprofiten la gran quantitat de nodes de computació per a oferir un alt grau de paral·lelització. Per a connectar tots aquests nodes de computació, s'utilitzen xarxes d'interconnexió d'altes prestacions capaços de manejar de manera eficient el trànsit generat. Aquestes xarxes tenen diferents paràmetres de disseny que defineixen el seu comportament, dels quals podríem destacar dues: la topologia i l'algoritme d'encaminament. La topologia d'una xarxa d'interconnexió ens defineix com es connecten els seus components, mentre que l'algoritme d'encaminament determina la ruta que un paquet ha de prendre des del seu node origen fins al seu node destí. Les topologies més utilitzades solen seguir una estructura regular i poden ser classificades en directes i indirectes, depenent de com estiguen interconnectats els diferents elements de la xarxa. D'altra banda, els algoritmes d'encaminament també poden classificar-se en dues categories: deterministes i adaptatius. Per avaluar estes xarxes es solen utilitzar mesures com ara la latència o la productivitat de la xarxa. La productivitat mesura el trànsit que és capaç d'acceptar la xarxa per unitat de temps. La latència mesura el temps que utilitza un paquet per arribar al seu destí. Aquest temps es pot dividir en dues parts. La primera correspon al temps emprat pel paquet a aconseguir al seu destí en absència de trànsit a la xarxa. La segona part seria la deguda a la congestió de la xarxa creada per el trànsit existent. Un dels efectes de la congestió és l'anomenat Head-of-line blocking, on el paquet que encapçala una cua es queda bloquejat, de manera que la resta de paquets de la cua no poden avançar, encara que poguessen fer-ho si ells encapçalessen la dita cua. Altres factors a tenir en compte són el cost i la tolerància a fallades. Per tant, les prestacions s'han de mantenir d'acord augmentem la mida de la xarxa, però sense un augment prohibitiu en el cost. A més, el fet d'augmentar la mida de la xarxa implica un augment en el número de elements d'aquesta xarxa, de manera que la probabilitat de l'aparició d'una fallada és més gran. Per això, és vital comptar amb algun mecanisme de tolerància a fallades en les xarxes d'interconnexió per als gran supercomputadors actuals. En altres paraules, és d'esperar bona relació cost-prestacions amb una alta tolerància a fallades. Aquesta tesi té dos objectius principals. El primer objectiu combina les avantatges de les topologies directes i indirectes per a crear una nova família de topologies amb el millor dels dos mons. En concret, ens centrem en el disseny de una nova família de topologies capaç d'interconnectar una gran quantitat de nodes sent capaç d'obtenir molt bones prestacions amb un baix cost hardware. La família de topologies proposada, que hem nomenat k-ary n-direct s-indirect, té una estructura n-dimensional, on els diferents k nodes d'una dimensió se connecten entre si mitjançant una petita topologia indirecta amb s etapes. També dissenyarem un algoritme d'encaminament determinista i un altre adaptatiu per a la família de topologies proposta. Finalment, ens centrarem en estudiar la tolerància a fallades per a la família de topologies proposada. Per a això s'estudiaran els mecanismes de tolerància a fallades existents en topologies similars i es dissenyarà un mecanisme capaç d'aprofitar al màxim les característiques d'aquesta nova família. El segon objectiu consisteix en la creació d'algoritmes d'encaminament capaços d'evitar el perniciós efecte Head-of-line blocking que pot créixer ràpidament amb un gran número de nodes de computació. Per a evitar aquest efecte es dissenyaran algoritmes d'encaminament capaços de classificar de forma eficient els paquets en els diferents canals virtuals disponibles, evitant així que l'aparició d'un punt calent (
Peñaranda Cebrián, R. (2017). Improvement of interconnection networks for clusters: direct-indirect hybrid topology and HoL-blocking reduction routing [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/79550
TESIS

Reducing the thermal impedance between power module and heat sink is important for high-power density, low-cost inverter applications. Mounting a power module by directly soldering it onto a heat sink can significantly reduce the thermal impedance at the module / heat sink interface, as compared to the conventional method of bolting the two together with a thermal grease or some other interface materials in between. However, a soldered interface typically contains a large number of voids, which results in local hot spots. This thesis describes approaches taken to reduce voids in the solder layer through surface treatment, solder paste selection, and adjustment in solder-reflow conditions. A 15MHz scanning acoustic microscope (SAM), a non-destructive inspection tool, was used to determine the void content at the module / heat sink interface. The experimental results show that a significant reduction in thermal resistance can be achieved by reducing the void content at the soldered module / heat sink interface. Moreover, a comparison of the thermal resistances in cases using the worst soldering, which contains the largest voided area, ThermstrateTM and thermal grease are presented. Thermal performances of the modules are studied by simulation with Flotherm.
Master of Science

Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 2010.
Cataloged from PDF version of thesis.
Includes bibliographical references (p. 67-69).
Direct Simulation Monte Carlo (DSMC)-the prevalent stochastic particle method for high-speed rarefied gas flows-simulates the Boltzmann equation using distributions of representative particles. Although very efficient in producing samples of the distribution function, the slow convergence associated with statistical sampling makes DSMC simulation of low-signal situations problematic. In this thesis, we present a control-variate-based approach to obtain a variance-reduced DSMC method that dramatically enhances statistical convergence for lowsignal problems. Here we focus on the Bhatnagar-Gross-Krook (BGK) approximation, which as we show, exhibits special stability properties. The BGK collision operator, an approximation common in a variety of fields involving particle mediated transport, drives the system towards a local equilibrium at a prescribed relaxation rate. Variance reduction is achieved by formulating desired (non-equilibrium) simulation results in terms of the difference between a non-equilibrium and a correlated equilibrium simulation. Subtracting the two simulations results in substantial variance reduction, because the two simulations are correlated. Correlation is achieved using likelihood weights which relate the relative probability of occurrence of an equilibrium particle compared to a non-equilibrium particle. The BGK collision operator lends itself naturally to the development of unbiased, stable weight evaluation rules. Our variance-reduced solutions are compared with good agreement to simple analytical solutions, and to solutions obtained using a variance-reduced BGK based particle method that does not resemble DSMC as strongly. A number of algorithmic options are explored and our final simulation method, (VR)2-BGK-DSMC, emerges as a simple and stable version of DSMC that can efficiently resolve arbitrarily low-signal flows.
by Colin Donald Landon.
S.M.

This project examined the reduction and formation of cementite from hematite and titanomagnetite ores and cementite stability. The aim of the project was to develop further understanding of cementite stability under conditions relevant to direct ironmaking and the mechanism of cementite decomposition. The reduction of hematite and ironsand by hydrogen-methane-argon gas mixtures was investigated from 600??C to 1100??C. Iron oxides were reduced by hydrogen to metallic iron, which was carburised by methane to form cementite. The hematite ore was reduced more quickly than the ironsand. Preoxidation of the ironsand accelerated its reduction. Hematite was converted to cementite faster than preoxidised ironsand. The decomposition of cementite formed from hematite was investigated from 500??C to 900??C. This cementite was most stable at temperatures 750-770??C. The decomposition rate increased with decreasing temperature between 750??C and 600??C and with increasing temperature above 770??C. The stability of cementite formed from pre-oxidised titanomagnetite was studied from 300??C to 1100??C. This cementite was most stable in the temperature range 700-900??C. The rate of decomposition of cementite increased with decreasing temperature between 700??C and 400??C and with increasing temperature above 900??C. Cementite formed from ironsand was more stable than cementite formed from hematite

[EN] This research work presents the study of a low pressure EGR loop influence on a SI gasoline turbocharged direct injection engine in steady and transient testing conditions, with an optimization process of the original engine calibration in order to minimize the engine fuel consumption when cooled EGR is introduced in steady testing conditions. The cooled EGR strategy was also evaluated operating in synergy with other fuel consumption reduction strategies, such as: lean burn, multi-injection, higher coolant temperature and in-cylinder induced swirl motion. To fulfill the main objectives of this research work, firstly, a methodical process was followed, where a global methodology was first developed in order to obtain high accuracy engine tests, based on the experimental tools chosen that could comply with the requirements of the testing conditions, and the appropriate theoretical tools and procedure to post-process the tests performed. Secondly, a specific methodology was developed for each stage of the study and testing conditions, taking into account optimization processes or parametric tests in order to study the effect of a single parameter on engine's outputs or optimize an engine parameter in order to minimize the engine fuel consumption. As a first stage of the study, a basic analysis of the impact of cooled EGR on the engine combustion, performance, air management and exhaust emissions is presented. Afterwards, an optimization of the combustion phasing in order to minimize the fuel consumption was performed, and therefore the potential of cooled EGR in order to reduce the engine fuel consumption was observed for low load, part load and full load engine conditions, for two different engine speeds. In addition, a study in transient conditions of the engine operating with cooled EGR was performed. NEDC cycles were performed with different EGR valve openings and therefore a comparison of different cooled EGR rates influence on the engine performance, air management and accumulated exhaust emissions was presented. The second stage, consisted in a methodology developed to optimize the VVT setting and injection timing, for part load engine conditions, in order to maximize the cooled EGR potential to reduce engine fuel consumption. After this optimization, a synergy analysis of the optimum engine condition operating with cooled EGR and three other engine fuel consumption reduction strategies was performed. These strategies were tested to investigate and evaluate the potential of increasing the cooled EGR operational range to further decrease the engine fuel consumption. Furthermore, a basic study of the potential to reduce the engine fuel consumption and impact on combustion, air management and exhaust emissions of a lean burn strategy, in part load engine conditions, was presented as introduction of the final study of the cooled EGR strategy operating in synergy with the lean burn strategy in order to investigate the potential to control the exhaust emissions and reduce the engine fuel consumption.
[ES] El objetivo de este trabajo de investigación es estudiar la influencia de un lazo de baja presión de EGR en las prestaciones de un motor de gasolina de encendido provocado turbosobrealimentado e inyección directa, en condiciones de ensayos estacionarios y transitorios, con un proceso de optimización de la calibración original del motor para minimizar el consumo de combustible del motor. La estrategia de "cooled EGR" fue también evaluada operando en sinergia con otras estrategias usadas para reducir el consumo de combustible del motor, entre ellas: mezcla pobre, múltiples inyecciones, operación a alta temperatura del fluido refrigerante del motor y movimiento de "swirl" inducido en el cilindro. Para cumplir con los objetivos mencionados, se siguió un proceso metódico donde previamente se desarrolló una metodología global para obtener resultados de indudable calidad, basados en el uso de herramientas experimentales que cumplieran con los requerimientos de las condiciones de ensayo, y las apropiadas herramientas teóricas y procedimiento para post-procesar los ensayos realizados. En segundo lugar, se desarrolló una metodología específica para cada etapa del estudio, teniendo en cuenta los procesos de optimización o estudios paramétricos que se pudieran realizar. Como primera etapa, se presenta un estudio básico del impacto del "cooled EGR" en la combustión, prestaciones, renovación de la carga y emisiones contaminantes del motor. Seguidamente, se procedió a la optimización del centrado de la combustión con la finalidad de minimizar el consumo de combustible del motor y poder analizar el potencial del "cooled EGR" como estrategia de reducción de consumo de combustible. El estudio presentado se realizó para baja, media y alta carga del motor con dos diferentes regímenes de giro del motor. Adicionalmente, se llevó a cabo un estudio del motor operando en condiciones transitorias con "cooled EGR". Se realizaron una serie de ensayos usando el ciclo NEDC como base y se probaron diferentes estrategias sencillas de control de la apertura de la válvula de EGR para analizar la influencia del "cooled EGR" en condiciones transitorias. La segunda etapa consiste en el desarrollo de una metodología para optimizar los parámetros del diagrama de distribución (VVT) y el inicio de inyección, para cargas medias del motor, con la finalidad de maximizar el potencial de reducción de consumo de combustible de la estrategia "cooled EGR". Una vez realizada la optimización, se llevó a cabo un estudio usando la configuración óptima encontrada, operando en sinergia con otras tres estrategias usadas para reducir el consumo de combustible del motor. Estas estrategias fueron evaluadas con la finalidad de incrementar el rango de operación de la estrategia "cooled EGR" para lograr reducir aún más el consumo de combustible del motor. Adicionalmente, se llevó a cabo un estudio básico sobre la influencia de operar con mezcla pobre en la combustión, prestaciones, renovación de la carga y emisiones contaminantes del motor, como introducción al último estudio llevado a cabo sobre la posibilidad de usar la estrategia de mezcla pobre en conjunto con la estrategia de "cooled EGR", con la finalidad de analizar el potencial de controlar las emisiones contaminantes y reducir el consumo de combustible del motor al mismo tiempo.
[CAT] L'objectiu d'este treball d'investigació és estudiar la influència d'un llaç de baixa pressió d'EGR en les prestacions d'un motor de gasolina d'encesa provocat turbosobrealimentat i injecció directa, en condicions d'assajos estacionaris i transitoris, amb un procés d'optimització del calibratge original del motor per a minimitzar el consum de combustible del motor. L'estratègia de "cooled EGR" va ser també avaluada operand en sinergia amb altres estratègies usades per a reduir el consum de combustible del motor, entre elles: mescla pobra, múltiples injeccions, operació a alta temperatura del fluid refrigerant del motor i moviment de `"swirl" induït en el cilindre. Per a complir amb els objectius mencionats, es va seguir un procés metòdic on prèviament es va desenrotllar una metodologia global per a obtindre resultats d'indubtable qualitat, basats en l'ús de ferramentes experimentals que compliren amb els requeriments de les condicions d'assaig, i les apropiades ferramentes teòriques i procediment per a post- processar els assajos realitzats. En segon lloc, es va desenrotllar una metodologia específica per a cada etapa de l'estudi, tenint en compte els processos d'optimització o estudis paramètrics que es pogueren realitzar. Com a primera etapa, es presenta un estudi bàsic de l'impacte del "cooled EGR" en la combustió, prestacions, renovació de la càrrega i emissions contaminants del motor. A continuació, es va procedir a l'optimització del centrat de la combustió amb la finalitat de minimitzar el consum de combustible del motor i poder analitzar el potencial del "cooled EGR" com a estratègia de reducció de consum de combustible. L'estudi presentat es va realitzar per a baixa, mitja i alta càrrega del motor amb dos diferents règims de gir del motor. Addicionalment, es va dur a terme un estudi del motor operand en condicions transitòries amb "cooled EGR". Es van realitzar una sèrie d'assajos usant el cicle NEDC com a base i es van provar diferents estratègies senzilles de control de l'obertura de la vàlvula d'EGR per a analitzar la influència del "cooled EGR" en condicions transitòries. La segona etapa consistix en el desenrotllament d'una metodologia per a optimitzar els paràmetres del diagrama de distribució (VVT) i l'inici d'injecció, per a càrregues mitges del motor, amb la finalitat de maximitzar el potencial de reducció de consum de combustible de l'estratègia "cooled EGR". Una vegada realitzada l'optimització, es va dur a terme un estudi usant la configuració òptima trobada, operant en sinergia amb altres tres estratègies usades per a reduir el consum de combustible del motor. Estes estratègies van ser avaluades amb la finalitat d'incrementar el rang d'operació de l'estratègia "cooled EGR" per a aconseguir reduir encara més el consum de combustible del motor. Addicionalment, es va dur a terme un estudi bàsic sobre la influència d'operar amb mescla pobra en la combustió, prestacions, renovació de la càrrega i emissions contaminants del motor, com a introducció a l'últim estudi dut a terme sobre la possibilitat d'usar l'estratègia de mescla pobra en conjunt amb l'estratègia de "cooled EGR", amb la finalitat d'analitzar el potencial de controlar les emissions contaminants i reduir el consum de combustible del motor al mateix temps.
Rivas Perea, ME. (2016). Assessment of fuel consumption reduction strategies on a gasoline turbocharged direct injection engine with a cooled EGR system [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/68497
TESIS

The objective of this study is to characterize the mechanism of drag reduction by comparing the dynamical eigenfunctions of a turbulent pipe flow against those of two known cases of drag reduced flows. The first is forced drag reduction by spanwise wall oscillation, and the second is natural drag reduction found in relaminarizing flow. The dynamics are examined through a Karhunen-Lo`eve (KL) expansion of the direct numerical simulation flow field results. The direct numerical simulation (DNS) is performed using NEK5000, a spectral element Navier-Stokes solver, the first exponentially convergent investigation of DNS of turbulence in a pipe. The base flow is performed at a Reynolds number of Re = 150, resulting in a KL dimension of D_KL = 2130. As in turbulent channel flow, propagating modes are found, characterized with constant phase speed, and contribute of 80.58% of the total fluctuating energy. Based upon wavenumber characteristics and coherent vorticity visualization, four subclasses of propagating modes and two subclasses of non-propagating modes are discovered, qualitatively similar to the horseshoe (hairpin) vortex structure reported in literature. The drag reduced case is performed at the same Reynolds number with a spanwise velocity A+ = 20, a period of T+ = 50, and is driven by a constant pressure gradient. This results in a increase of flow rate by 27 %, and the KL dimension is reduced to D_KL = 102, a 96% reduction. The propagating modes, in particular the wall modes, are pushed away from the wall, resulting in a 34% increase in their advection speed, and a shift away from the wall of the root-mean-square and Reynolds stress peaks. The relaminarizing case observes the chugging motion of the mean flow rate when the Reynolds number is barely turbulent, at Re = 95. This chugging motion is the relaminarization of the flow, resulting in an increased flow rate, and then before complete relaminarization, the flow regains its turbulent state. This occurs because the lift modes, which are responsible for the majority of the energy in the inertial range of the energy spectra, decrease by two or three orders of magnitude. The chugging ends when the wall modes restart the turbulent cascade, and the lift modes are repopulated with energy. A model for the energy path is developed, with energy going from the pressure gradient to the shear modes, then to the roll modes, then to the wall modes, and then finally to the lift modes. It is concluded that drag reduction in a flow can be achieved by disrupting any leg of this model, thus disrupting the self-sustaining mechanism of turbulence. The spanwise wall oscillation shortened the life span of the wall modes, thus limiting their ability to pass energy to the lift modes. Likewise, the low Reynolds number did not provide enough energy to sustain the lift modes, and so relaminarization began. The contribution of this work is twofold. Firstly, the structure of turbulent pipe flow is examined and visualized for the first time using the Karhunen-Lo`eve method. The second, and perhaps greatest contribution of this work, is that the mechanism of drag reduction has been characterized as the link between the wall modes and the lift modes. This will allow future work on developing real methods of drag reduction, and eventually porting it to high Reynolds number flows, like that of an oil pipeline at Re= 40, 000. To achieve this, certain questions remain to be answered, such as what is the most efficient method of disrupting the wall-lift mechanism? Is there a single structure that can be identified and manipulated that gives a similar eect? Once answered, this will allow for a new generation of pipelines to be developed, and considering the implications in petroleum industry alone, will result in a significant contribution to the economy of the world.
Ph. D.

Due to their small size and large surface area-to-volume ratios, nanoparticles (particles with limiting dimensions smaller than 100 nm) have been widely applied as catalysts. Metal nanoparticles are typically produced in suspensions from metal ion precursors, reducing agents, and organic ligands called capping agents. Capping agents help prevent particle agglomeration, fix nanoparticle size, and promote monodispersity. However, capping agents also affect the morphology and the physico-chemical surface properties of nanoparticles, which can influence catalytic properties in unpredictable ways. While there have been extensive studies focused on examining the relationship between nanoparticle size, shape, composition and catalytic activity, relatively few have investigated the effects of capping agent properties on catalysis, and most studies involving nanoparticle catalysts have been conducted on collections, ensembles, or arrays of particles rather than single nanoparticles. Results obtained for systems composed of multiple nanoparticles dispersed on solid surfaces can be difficult to interpret due to variations in particle loading and interparticle distance, which are often challenging or impossible to control and characterize. The complexity of these unavoidable experimental variables may explain some of the seemingly inconsistent conclusions that have been drawn between nanoparticle properties and catalytic activity in recent reports. Single nanoparticle studies should help overcome limitations associated with investigations based on collections of nanoparticles by helping uncover direct relationships between nanoparticle size, surface properties, and catalytic activity that are unobscured by complex factors such as interparticle distance and particle loading. In this work, we aim to use nitrided carbon fiber ultramicroelectrodes to examine electrocatalytic properties of bare (uncapped) and capped gold nanoparticles at the single nanoparticle level.

O ferro-esponja ou DRI (Direct Reduced Iron) é obtido pelo processo de redução direta onde o minério de ferro é transformado em ferro metálico através de reações químicas envolvendo o estado sólido (minério) e o gasoso (gases redutores). Neste processo o minério de ferro não passa pelo estado líquido como ocorre com o ferro-gusa. Isto confere ao ferro-esponja algumas desvantagens que prejudicam o seu desempenho nas aciarias. Pode-se citar a redução no rendimento metálico e o maior consumo de energia elétrica como principais impactos de sua utilização intensiva. O ferro-esponja apresenta menor quantidade de ferro total (maior quantidade de impurezas) do que o ferro-gusa e também apresenta óxidos de ferro remanescentes em sua estrutura (menor metalização). Para torná-lo mais competitivo, inúmeras melhorias no processo têm sido promovidas para aumento da metalização. No entanto, o limite superior alcançado na prática tem ficado ao redor de 95%. Visando contribuir para melhorar a qualidade do ferro-esponja este trabalho apresenta uma proposta inovadora a partir da técnica de auto-redução. O objetivo é aumentar o grau de metalização do ferro-esponja através de seu aquecimento. Para isso, foram realizadas análises termogravimetrias e aquecimentos em forno mufla; análises químicas por via úmida, difração de raios-x, espectroscopia mössbauer e análise de microssonda de raios-x. As análises estruturais foram realizadas utilizando microscópio eletrônico de varredura para confirmar a efetividade da técnica apresentada. Nesta dissertação pode-se comprovar que, através da técnica de auto-redução, o ferro-esponja alcança metalizações acima de 98% em detrimento da queda do teor de carbono total. Um aumento de 4% na metalização traz um ganho estimado de 5 a 10% no consumo de energia elétrica nos fornos de fusão e um acréscimo proporcional na produção horária das aciarias.
The direct reduced iron is obtained by direct reduction process, where iron ore is transformed in metallic iron via chemical reactions involving solid (ore) and gaseous (reductant gases) states. In this process the iron ore does not pass by liquid state like pig iron. This become to direct reduced iron some disadvantages, which decrease its performance in the steelmaking process. It can be mentioned the reduction of metallic yield and the higher consumption of electric energy as the main impacts of its intensive use. The direct reduced iron presents lower amount of total iron (higher amount of impurities) than pig iron and presents iron oxides remained in its structure (lower metallization). To become more competitive, several improvements in the reduction process have been carried out to increase its metallization. However, the highest level of metallization, which has been reached, is 95%. To improve the direct reduced iron quality, the present work evaluates, in an innovative way, using the technique of self reduction. The objective is increase of metallization of the direct reduced iron through its heating. Thermal, chemical and structural characterization was carried out to check the effectiveness of the investigated technique. The research confirms that the direct reduced iron can reach a metallization higher than 98% with a decrease of total carbon amount using the technique presented in this work. An improvement of 4% in the metallization brings savings of 5 to 10% in the electric energy consumption of the electric arc furnaces and a proportional increase of the production in the steelmaking plants.

The purpose of this thesis was to assess the economic implications of an export promotion policy on poverty reduction and inter-industry growth of Ethiopia. The study was conducted in four steps. The first and the second steps involved simulation scenarios. Scenario 1 simulated the change in the incidence of poverty when FDI capital was selectively introduced into non-coffee export agriculture. Scenario 2 simulated a situation in which the coffee industry received the same policy treatment as other export agriculture in accessing FDI capital. Step three analyzed inter-industry growth under the two scenarios. In the fourth step, sensitivity analysis was conducted to assess the possible outcomes of Scenario 1 and 2 under fluctuations in world coffee prices and changes in substitution parameters. A micro-simulated CGE model was constructed to determine optimum production, income and consumption. A Beta frequency distribution function and FGT poverty measures were used to examine the changes in three household groupsâ income distribution and prevalence of poverty. For these analyses, the National Accounting Matrix and the Household Income and Expenditure Sample Survey data set were used. At the macro level, growth in GDP due to expansion of export agriculture was significant. But at a micro level, the magnitude and dimension of economic changes were different with respect to each policy alternative. In the selective export promotion, for instance, only rural households were able to achieve statistically significant income changes. More particularly, about 10 percent of rural households were drawn out of poverty while only 1.7 and 0.5 percent of small and large urban households overcame poverty. When export promotion was assumed to be implemented across the board of all agricultural activities, the welfare gains were extended beyond rural household groups. In this policy alternative, statistically significant mean income changes were observed for both rural and urban household members. Specifically, about 12 percent of rural, 9 percent of small urban and 5 percent of large urban households were able to escape poverty. These achievements were attributed to higher intensification of coffee production and better linkages with other industries to efficiently allocate factors of production where they provided higher rates of return. The increase in income and consumption of millions of coffee dependent households has also stimulated more agricultural and some non-agricultural productions. Simulation results were observed to deteriorate when export promotion was evaluated under world coffee price fluctuation. The negative effect of a price shock, however, was observed to be minimized under alternative an export promotion approach.
Ph. D.

The aviation environment holds challenging application constraints for efficient hydraulic system noise reduction devices. Besides strong limits on component weight and size, high safety and reliability standards demand simple solutions. Hence, basic silencers like inline expansion chambers and Helmholtz-Resonators are state-of-the-art aboard commercial aircrafts. Unfortunately, they do not meet today’s noise attenuation aims regarding passenger comfort and equipment durability. Significant attenuation performance is expected from active concepts that generate anti-phase noise. However, such concepts remain a long term approach unless related costs, e.g. due to additional power allocation and real-time control equipment can be avoided. In this paper an active fluid borne noise attenuation concept is discussed that accounts for the mentioned constraints. An aircraft hydraulic pump is considered as main noise source. The active attenuator is an in-house rotary valve design. The basic feature is a known direct shaft coupling principle of pump and rotary valve, so no speed/ frequency control of the valve and no separate power supply are required. The common-shaft principle is further simplified here and proposed as integral feature of future “smart pumps”.

The blast furnace is still the dominant form of iron production, but over the years, direct reduction methods have increased due to a number of reasons. Overall, iron production methods have optimal requirements with respect to the feed materials especially iron ore. In this study, tests were carried out on Muko iron ore from Uganda to analyse its suitability to meet the feed requirements of today's dominant iron production methods. More specifically, the Tumbler, Abrasion, and Shatter Indices of the ore were determined. In addition, porosity, thermoanalysis, and reducibility tests were performed. Overall, the Muko ore was found to have good mechanical properties exemplified with tumble and shatter index data >89.0 wt% and <2.5 wt%, respectively. Furthermore, its reducibility at 0.87%/min is within the acceptable range as a natural material feed for blast furnace and direct reduction furnaces. Also, the energy requirement for heating the ore to 1100°C was found to be higher in the samples containing a wider size range of irregular grains and the largest contaminations. In summary, it is concluded that the Muko iron ore has good physical and metallurgical properties to serve as a natural material for the blast furnace and direct reduction furnaces.

QC 20130531

Sustainable Technology Development in the Lake Victoria Region

Magister Scientiae - MSc
Fuel cells convert chemical energy from a fuel into electricity through chemical reaction with oxygen. This possesses some challenges like slow oxygen reduction reaction (ORR), overpotential, and methanol fuel cross over in a direct methanol fuel cell (DMFC). These challenges cause inefficiency and use of higher amounts of the expensive platinum catalyst.Several binary catalysts with better ORR activity have been reported. In this study we investigate the best catalyst with better ORR and MOR performances and lower over-potentials for PEMFC and DMFC applications by comparing the in-house catalysts (10%Pt/C, 20%Pt/C,30%Pt15%Ru/C, 40%Pt20%Ru/C, 30%PtCo/C, 20%Pt20%Cu/C and 20%PtSn/C) with the commercial platinum based catalysts (10%Pt/C, 20%Pt/C, 20%Pt10%Ru/C, 20%PtCo/C,20%PtCu/C and 20%PtSn/C) using the cyclic voltammetry and the rotating disk electrode to determine their oxygen reduction reaction and methanol tolerance. HRTEM and XRD techniques were used to determine their particle size, arrangement and the atomic composition. It was observed that the 20%Pt/C in-house catalyst gave the best ORR activity and higher methanol oxidation current peaks compared to others catalysts followed by 20%Pt10%Ru/C commercial catalyst. The 20%PtCo/C commercial, 30%PtCo/C in-house and 20%PtSn/C in-house catalysts were found to be the most methanol tolerant catalysts making them the best catalysts for ORR in DMFC. It was observed that the ORR activity of 20%PtCo/C commercial and 30%PtCo/C inhouse catalysts were enhanced when heat treated at 350 0C. From XRD and HRTEM studies, the particle sizes were between 2.72nm to 5.02nm with little agglomeration but after the heat treatment, the particles were nicely dispersed on the carbon support.

A direct solution procedure is proposed and developed which exploits the parallelism that exists in current symmetric multiprocessing (SMP) multi-core processors. Several algorithms are proposed and developed to improve the performance of the direct solution of FE problems. A high-performance sparse direct solver is developed which allows experimentation with the newly developed and existing algorithms. The performance of the algorithms is investigated using a large set of FE problems. Furthermore, operation count estimations are developed to further assess various algorithms. An out-of-core version of the solver is developed to reduce the memory requirements for the solution. I/O is performed asynchronously without blocking the thread that makes the I/O request. Asynchronous I/O allows overlapping factorization and triangular solution computations with I/O. The performance of the developed solver is demonstrated on a large number of test problems. A problem with nearly 10 million degree of freedoms is solved on a low price desktop computer using the out-of-core version of the direct solver. Furthermore, the developed solver usually outperforms a commonly used shared memory solver.

La fusion reductrice de cu#2o contenu dans un laitier cu#2o-feo#x-sio#2 est a la base d'un nouveau procede non polluant pour la production du cuivre a partir de minerais a forte teneur en as et s. La physico-chimie de la reaction est analogue a celle des nouveaux procedes de reduction directe des minerais de fer qui servent de reference a la presente etude. Une premiere partie fait le point sur la thermodynamique du systeme cu#2o-cuo-feo-fe#2o#3-sio#2. Des essais montrent qu'une reduction de cu#2o par feo est possible avec production de cuivre metal et des ferrites de cuivre. Le reste est consacre aux mesures de vitesse de reduction par divers montages experimentaux entre 1260 et 1350c. La cinetique de reduction par co est de l'ordre de 10##2 a 10##1 mole cu#2o. M##2. S##1 alors que par le graphite elle est de 1 a 10 mole cu#2o. M##2. S##1. La macrocinetique de reduction par le graphite de laitiers contenant feo ou fe#2o#3 est du premier ordre en concentration de cu#2o avec une constante de l'ordre de 10##4 a 10##3 s##1. La reduction n'est influencee ni par la temperature (autothermicite) ni par le brassage (auto-agitation par les bulles). Le gaz produit est du co#2. Cette production entraine un moussage du laitier avec des bulles millimetriques. Ce phenomene est decrit par un modele existant qui suppose que l'accroissement de la hauteur du bain est proportionnelle au debit de gaz. La constante de proportionnalite , qui est egale au temps de vie de la mousse, est d'environ 1s pour le laitier avec feo et 2s pour celui avec fe#2o#3. Chute en presence de gouttes de cuivre en suspension vers 0,2s. Une partie de la reduction se fait par contact direct entre le laitier et le graphite. La reduction du fer qui se produit alors est reversible et le metal qui decante apres un temps de sejour de 5 minutes environ est en equilibre avec le laitier. Le co produit au contact entre graphite et gaz est oxyde en co#2 dans la mousse.

In this study, which is numerical in nature, direct numerical simulation (DNS) of the pipe flow is performed. For the DNS a solenoidal spectral method is employed, this involves the expansion of the velocity using divergence free functions which also satisfy the prescribed boundary conditions, and a subsequent projection of the N-S equations onto the corresponding dual space. The solenoidal functions are formulated in Legendre polynomial space, which results in more favorable forms for the inner product integrals arising from the Petrov-Galerkin scheme employed. The developed numerical scheme is also used to investigate the effects of spanwise oscillations and phase randomization on turbulence statistics, and drag, in turbulent incompressible pipe flow for low to moderate Reynolds numbers (i.e. $mathrm{Re} sim 5000$) ).

Excessive CO2 emissions can negatively impact society and our planet. Reduction of CO2 is one potential avenue for its abatement. One of the most significant challenges to reducing CO2 is its extremely stable linear form. Experimentally, Cu/TiO2 has shown promise for CO2 photocatalytic reduction. Dispersed atomic catalysts can achieve high catalytic efficiency on a per atom basis. Active sites also typically having lower coordination number, and therefore may be more reactive. Using density functional theory and experimental techniques, we have investigated the role of surface oxygen vacancies (Ov) and photoexcited electrons on supported single atom catalysts and CO2 reduction. Cu atoms with Ov have shown to aid in the process of bent, anionic CO2 formation. In the first step involving CO2 dissociation (CO2* --> CO* + O*), a single Cu atom in Ov lowered the activation barrier to 0.10 - 0.19 eV, which could enable fast reduction of CO2 even at room temperature, in agreement with experimental findings. A photoexcited electron model was shown to readily promote Cu binding to the surface vacancy, and CO2 adsorption and direct dissociation. Finally, we briefly compare our results to calculations of supported single Pt atoms to determine how metals besides Cu may behave as photocatalysts for CO2 reduction, and we found a single Pt with Ov can promote CO2 dissociation. Our results show that tailoring TiO2 surfaces with defects in conjunction with atomic catalysts may lead to useful catalysts in the photoreduction of CO2.

This work has been conducted to study the effect of different types of iron ore pellets on an EAFbased steel production. The study has focused on how the chemical composition of the raw materialsinfluences the slag amount and as a result the EAF operation. It is also shown that the raw materialselection can be optimized for a better slag practice. The advantage of slag former additions that arestrictly adapted to the EAF charge composition is also demonstrated.This work is based on a MgO-saturation model for slag, developed by Dr Roger Selin. The model hasbeen implemented in RAWMATMIX®, a software developed by Kobolde & Partners AB in Stockholm.In this report I discuss the following studies: i) A study and comparison between different basicityindices and MgO-saturation for EAF slags, ii) a comparison between different DR-pellets and mixesbetween them and their corresponding DRI, iii) a parameter study on how different properties for theDR-pellet and DRI influence the EAF process, and iv) a case study of two hypothetical steel plants toillustrate the value of an adaptive slag former addition based on the raw material input. Overall,these studies describe the value of using DRI based on DR-pellets, containing low amount of acidicoxides and balanced amounts of MgO, for an EAF based steel production.

Thesis (MA)--Stellenbosch University, 2015
ENGLISH ABSTRACT : The contact hypothesis (Allport, 1954) provides an established theoretical framework for pursuing positive intergroup relationships (Hewstone & Swart, 2011; Pettigrew & Tropp, 2006) and stipulates certain optimal conditions under which contact reduces prejudice. The secondary transfer effect of contact describes a process whereby attitudes towards outgroups not encountered in the original intergroup encounter might also be improved (Pettigrew, 2009; Pettigrew & Tropp, 2006). A three-wave longitudinal experimental study amongst white South African students at Stellenbosch University (N = 58) was undertaken, using two experimental groups (direct and extended) and a control group. The present study investigated whether direct and extended contact with a black (African) confederate would not only improve attitudes towards black (African) South Africans in general, but also improve attitudes towards Indian South Africans, not involved in the contact situation (i.e., the secondary transfer effect). Findings show that the experimentally manipulated contact reduced intergroup anxiety (from baseline levels measured one week earlier) towards black (African) South Africans. These effects were, however, non-significant, and suggest the present study may have been under-powered. Moreover, the findings showed that experimentally manipulated contact significantly improved outgroup attitudes and outgroup trust (from baseline levels measured one week earlier) towards black (African) South Africans in the direct contact condition, as well as the extended contact condition (outgroup attitudes only). Finally, the present study found significant evidence for the operation of the secondary transfer effect via attitude generalisation. Positive intergroup contact with the black (African) South African confederate predicted a significant change in outgroup attitudes towards black (African) South Africans in general from Time 1 (baseline) to Time 2 (post-task), which in turn predicted more positive attitudes towards Indian South Africans in general at Time 2, controlling for prior quantity and quality of contact with Indian South Africans. The secondary transfer effect was not observed for outgroup trust. The present study contributes to the existing literature on the secondary transfer effect and replicates international findings within the South African context.
AFRIKAANSE OPSOMMING : Die kontak hipotese (Allport, 1954) bied ʼn gevestigde teoretiese raamwerk vir die voortsetting van positiewe intergroep verhoudings (Hewstone & Swart, 2011; Pettigrew & Tropp, 2006) en bepaal sekere optimale toestande waaronder kontak vooroordeel verminder. Die sekondȇre oordrag effek van kontak beskryf ʼn proses waardeur houdings teenoor buitegroepe wat nie gedurende die oorspronklike intergroep kontak teёgekom is nie, ook verbeter word (Pettigrew, 2009; Pettigrew & Tropp, 2006). ʼn Drie-golf longitudinale eksperimentele studie onder wit Suid-Afrikaanse studente verbonde aan die Universiteit van Stellenbosch (N = 58) is onderneem, met behulp van twee eksperimentele groepe (direkte en uitgebreide) en ʼn kontrole groep (N = 16). Die huidige studie het ondersoek of direkte en uitgebreide kontak met ʼn swart (Afrikaan) Suid-Afrikaner nie net houdings teenoor swart (Afrikaan) Suid-Afrikaners in die algemeen verbeter nie, maar ook houdings teenoor Indiёr Suid-Afrikaners, wie nie by die oorspronklike kontak situasie betrokke was nie ook verbeter (d.w.s. die sekondȇre oordrag effek). Resultate toon dat die eksperimenteel gemanipuleerde kontak intergroep angs teenoor swart (Afrikaan) Suid-Afrikaners verminder (vanaf basislyn vlakke gemeet een week tevore). Hierdie effek is egter nie beduidend nie, moontlik omdat die statistiese kragdoeltreffendheid van die studie onvoldoende was. Die resultate toon verder dat eksperimenteel gemanipuleerde kontak buitegroep houdings en buitegroep vertroue (vanaf basislyn vlakke gemeet een week tevore) teenoor swart (Afrikaan) Suid-Afrikaners beduidend verbeter in die direkte kontak groep, sowel as die uitgebreide kontak groep (slegs vir buitegroep houdings). Ten slotte, die huidige studie het beduidende bewyse gevind vir die werking van die sekondȇre oordrag effek via houding veralgemening. Positiewe intergroep kontak met die swart (Afrikaan) Suid-Afrikaner voorspel ʼn beduidende verbetering in die buitegroep houding teenoor swart (Afrikaan) Suid-Afrikaners in die algemeen van Tyd 1 (basislyn) tot Tyd 2 (na die eksperimentele manipulasie), wat op sy beurt meer positiewe houdings teenoor Indiёr Suid-Afrikaners in die algemeen teen Tyd 2 voorspel, nadat daar vir beide kwaliteit en kwantiteit van vorige kontak met Indiёr Suid-Afrikaners beheer is. Die sekondȇre oordrag effek is nie vir buitegroep vertroue waargeneem nie. Die huidige studie dra by tot die bestaande literatuur oor die sekondȇre effek van kontak en ondersteun soortgelyke internasionale bevindinge binne die Suid-Afrikaanse konteks. Stellenbosch University.

PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO
Pelo presente trabalho, buscou-se desenvolver uma ferramenta capaz de analisar e otimizar o uso de pelotas de minério de ferro em processos tradicionais de redução direta do tipo forno cuba. A criação de um modelo termoquímico do processo MIDREX foi proposta e elaborada dentro da PUC-Rio, levando-se também em conta alguns aspectos cinéticos relativos à redução dos minérios e à carburização do ferro-esponja, bem como alguns parâmetros operacionais. Este modelo foi subseqüentemente adaptado para interagir com um segundo modelo termoquímico de forno elétrico a arco da RS Consultants, representando assim a cadeia de fabricação de aço líquido primário pela rota redução direta - forno elétrico a arco. Para o gerenciamento computacional do processo de otimização e interação com os dois modelos acima citados, desenvolveu-se, adicionalmente, um terceiro modelo, o qual foi designado neste trabalho como modelo GESTOR. Um máximo uso de ferro-esponja ― e de pelotas, conseqüentemente ― é objetivado sempre que possível, sob determinadas condições operacionais pré-estabelecidas. A avaliação econômica destes processos foi embasada em conceitos de valor de uso. Alguns resultados são apresentados neste trabalho, para demonstrar a efetividade e o poder de análise da ferramenta e espera-se que os profissionais da Samarco possam fazer uso deste instrumento de trabalho, dando o devido suporte à tomada de decisão à comercialização e ao desenvolvimento de produtos existentes ou novos.
The study at issue searched for developing an innovative tool able to effectively analyze and optimize the industrial usage of iron ore pellets undergoing traditional gas-based direct reduction processes. The creation of a thermochemical model for MIDREX process was proposed and carried out by PUC-Rio, taking into account relevant characteristics related to DRI carburization and reduction kinetics, as well as some important operating parameters. Subsequently, this model was adapted in order to interact with a second thermo-chemical model owned by RS Consultants and able to represent an electric arc furnace operation. In this sense, it has been possible to represent thereby the iron and steelmaking route based on direct reduction and electric arc furnace. For the computational management of the optimization methodology and interaction involving the two models above-mentioned, a third model was developed and referred to as GESTOR model. It was built to maximize the DRI usage ¯ and pellets utilization, consequently ¯ respecting certain operating conditions previously established. Economic assessments shall be made premised upon value in use concepts. Some results are shown in this study, based on a hypothetical scenario, aiming at proving the effectiveness of this tool. Its adoption by Samarco´s experts is expected as an important supportive methodology to help them to make decisions properly concerning both marketing strategies and product development activities.

COORDENAÇÃO DE APERFEIÇOAMENTO DO PESSOAL DE ENSINO SUPERIOR
PROGRAMA DE SUPORTE À PÓS-GRADUAÇÃO DE INSTS. DE ENSINO
As pelotas de minério de ferro têm suas propriedades fortemente dependentes da natureza das fases escorificadas que se formam durante o processo de queima. Neste trabalho são apresentados os resultados de uma das pesquisas que compõem o projeto cooperativo entre a Samarco e o Grupo de Siderurgia do DEMa / PUC-Rio, envolvendo a possibilidade de utilização de minérios de ferro portadores de fósforo (pellet feed), na produção de pelotas para redução direta. Com este objetivo foram geradas amostras de escórias sintéticas de mesma composição que as das pelotas RD comerciais, as quais foram submetidas a condições experimentais análogas as do processo industrial. Inicialmente a ciclos térmicos em forno tipo pot-grate e, posteriormente, em escala laboratorial, usando forno de mufla, seguido de etapas de resfriamento em velocidades distintas. Foi possível então constatar que velocidades mais altas de resfriamento, aplicadas na etapa final dos ciclos térmicos, produziam escórias sintéticas sensivelmente amorfas, o que levou a conclusão que as fases escorificadas das pelotas RD também se apresentariam como estruturas não cristalinas. Finalmente, por meio de teste especificamente desenvolvido para a análise seletiva de fósforo em fases oxídicas, conseguiu-se obter uma maior eficiencia na mensuração deste elemento quando dissolvido em escórias amorfas, o que viabilizou a medida das quantidades de fósforo que efetivamente migraram para as mesmas, quando se submetiam as amostras de pellet feed a diferentes temperaturas, variados tempos de residencia e distintas basicidades. Por fim, foi possivel concluir ser o incremento de basicidade do pellet feed um fator de significativa melhoria para o transporte e a dissolução do fósforo pelas escórias, em particular quando submetidos a temperaturas superiores a 900 graus Celsius.
Iron ore pellets have their properties strongly dependent on the nature of the phases present in the slags formed during pelletization. In this work are presented the first results of a research program involving the utilization of phosphorous bearing iron ores in the production of DR pellets (Direct Reduction pellets). Aiming at this, synthetic slags, produced with same composition of the gangue of a commercial DR pellet, were submitted to operational conditions similar to those of the industrial pelletizing process, but performed in a pot-grate reactor and in a laboratory furnace. The obtained slags samples were cooled at different rates, permitting to observe that at high cooling rates the slags obtained were amorphous, suggesting the occurrence of a similar amorphous structure for the slags present in the DR pellets. Finally, tests developed for a selective analysis of phosphorous in oxide phases, showed better efficiency when applied to amorphous slags than in crystalline ones. Further, the behavior of the phosphor dissolution in the obtained slags during the heating of pellet feed samples was evaluated. In this phase different temperatures, resident times and basicities were tested using a laboratory furnace. The results indicated improvements in the phosphor dissolution with the basicity increase when temperatures above 900 Celsius degrees were applied.

Payments for ecosystem services (PES) are widely being applied in the conservation of biodiversity and management of ecosystem services. In developing countries, particularly in Africa, PES mechanisms are expected to generate co-benefits of poverty reduction and improved livelihoods in rural areas. However, there are very few such schemes in the Arid and Semi-Arid Lands (ASAL) that involve pastoral and semi-nomadic communities. Furthermore, there is little empirical evidence of the impact of PES on poverty. This thesis assesses the changes in biodiversity (using wildlife populations as a proxy), ecosystem services (provisioning, habitat and cultural and amenity services), human population and climatic variability in Kenyan ASAL at the national, sub-national and local levels. It further examines the potential and actual implications of PES on poverty and ecosystem based adaptation (EBA) to climate change among two pastoral Maasai communities living adjacent to wildlife protected areas in southern Kenya. It generates evidence of the positive effects of PES on the livelihoods of participating families, particularly during a period of extreme drought when PES serves as a critical safety-net against high livestock mortality and loss of cash income derived from livestock. In addition, PES is found to be an invaluable source of income diversification and is the most equitable of all income sources among participating households. Despite some of its positive attributes, there is need to assess and mitigate the potential negative implications of PES impact on the non-participating households and the landless families. Concerns also arise with regard to the equity implications, leakages and the lack of financial sustainability in the PES programs analysed.
Les payements pour les services d'écosystème (PSE) sont largement utilisés pour la conservation de la biodiversité et le management des services environnementaux. Particulièrement en Afrique, les PSE sont supposés générer des revenus complémentaires pour la réduction de la pauvreté et l'amélioration des moyens de subsistance dans les zones rurales. Cependant, il y a très peu de PSE dans les zones arides et semi-arides (ZASA) qui impliquent les communautés pastorales et semi-nomades. Il y a peu d'évidences empiriques de l'impact des PSE sur la pauvreté. Cette thèse évalue les changements en biodiversité, les services environnementaux, la population humaine et la variation climatique dans les ZASA au Kenya. L'étude examine aussi les implications potentielles et réelles des PSE sur la pauvreté et les adaptations au changement climatique fondées sur les écosystèmes de deux communautés pastorales Maasai vivant à proximité des zones protégées de la faune sauvage dans le sud du Kenya. L'étude génère l'évidence des effets positifs des PSE sur les moyens de subsistance des familles participantes, particulièrement pendant une période d'extrême sécheresse quand les PSE servent comme un moyen de sécurité contre la mortalité élevée du bétail et la perte de revenus de l'élevage. Les PSE sont comme une source précieuse de diversification des revenus avec un effet de réduction de l'inégalité des revenus. Malgré ses aspects positifs, il est nécessaire d'évaluer et de contrôler les conséquences négatives potentielles de l'impact des PSE les non-participants et les familles sans terre. Les inquiétudes se posent sur les implications d'équité, et le manque de financement durable des programmes.

La première partie de cette thèse traite du développement du code de simulation numérique directe YWC, principalement du développement des conditions aux limites. En effet, une forte contribution scientifique a été apportée aux conditions aux limites appelées "Three dimensional Navier-Stokes characteristic boundary condtions" (3D-NSCBC). Premièrement, la formulation de ces conditions aux arêtes et coins a été complétée, ensuite une extension de la formulation a été proposée pour supprimer les déformations observées en sortie dans le cas d'écoulements non-perpendiculaires à la frontière.

De plus, ces conditions ont été étendues au cas des gaz réels et une nouvelle définition du facteur de relaxation pour la pression a été proposée. Ce nouveau facteur de relaxation permet de supprimer les déformations observées en sortie pour des écoulements transcritiques.

Les résultats obtenus avec le code YWC ont ensuite été utilisés dans la seconde partie de la thèse pour développer une nouvelle méthode de tabulation basée sur l'analyse en composantes principales. Par rapport aux méthodes existante telles que FPI ou SLFM, la technique proposée, permet une identification automatique des variables à transporter et n'est, de plus, pas lié à un régime de combustion spécifique. Cette technique a permis d'effectuer des calculs d'interaction flamme-vortex en ne transportant que 5 espèces à la place des 9 requises pour le calcul en chimie détaillée complète, sans pour autant perdre en précision.

Finalement, dans le but de réduire encore le nombre d'espèces transportées, les techniques T-BAKED et HT-BAKED PCA ont été introduites. En utilisant une pondération des points sous-représentés, ces deux techniques permettent d'augmenter la précision de l'analyse par composantes principales dans le cadre des phénomènes de combustion.

Doctorat en Sciences de l'ingénieur
info:eu-repo/semantics/nonPublished

Submitted by Pedro Silva Filho (pfsilva@ipen.br) on 2017-11-22T17:28:55Z No. of bitstreams: 0
Made available in DSpace on 2017-11-22T17:28:56Z (GMT). No. of bitstreams: 0
Neste trabalho os diferentes sistemas eletrocatalíticos PtIn/C, PtRu/C, PtRuIn/C e suas diferentes proporções mássicas foram sintetizados pelo método de redução por Borohidreto de Sódio, a fim de serem utilizados como ânodo na célula a combustível alcalina de metanol direto (DMFC). Os materiais obtidos foram caracterizados pelas técnicas de EDX, DRX e MET. O método de redução aplicado na síntese se mostrou efetivo, uma vez que as partículas apresentaram boa dispersão no suporte de carbono Vulcan XC72, de acordo com as analises de EDX e MET. Os resultados obtidos por DRX evidenciaram em todos os difratogramas apresentados a estrutura CFC da platina e um relativo deslocamento do pico equivalente ao plano (220) para valores maiores e menores que 2θ. O tamanho médio do cristalito e os parâmetros de rede calculados indicaram a inserção de átomos de Índio e Rutênio à estrutura da Platina, supondo a formação de ligas. A oxidação eletroquímica do metanol foi estudada por voltametria cíclica, cronoamperometria e curvas de polarização. Os experimentos eletroquímicos demonstraram que nos eletrocatalisadores binários com maior composição de Índio e Rutênio a eficiência catalítica frente a oxidação do combustível foi melhor e para os ternários, o eletrocatalisador que possuía maior composição de Rutênio se mostrou mais eficiente. Nos experimentos práticos em células a combustível, as curvas de polarização mostraram divergências de resultados com os obtidos por voltametria cíclica e cronoamperometria, justificadas por problemas de prensagem e descolamento de MEA\'s em sistemas que apresentaram maior quantidade de cocatalisador como Índio e Rutênio.
Dissertação (Mestrado em Tecnologia Nuclear)
IPEN/D
Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

With code division multiple access (CDMA) systems being the prominent multiple access scheme for the air interface for 3G cellular systems, most standardisation bodies have based their terrestrial cellular systems on DS-CDMA (W-CDMA, UMTS, cdma2000). With 4G systems fast approaching, bringing with them improved services and quality of service standards, there is growing interest in further investigating and developing more efficient multiple access techniques such as multicarrier CDMA (MC-CDMA) systems. MC-CDMA combines multicarrier modulation (MCM), namely OFDM, with CDMA profiting from the benefits of both multiplexing techniques; as such, MC-CDMA is emerging as a possible candidate for the air interface multiple access scheme for 4G cellular systems. Multiple access interference (MAI) is a limiting factor of CDMA systems in terms of system capacity as orthogonally designed spreading sequences lose their orthogonality in the presence of timing misalignments amongst mobile subscribers in a cell; such is the case over the uplink channel. Ensuring orthogonal code properties minimises the MAI over synchronous environments, however, it is when the users are allowed to transmit asynchronously, as is the case over the uplink channel, that MAI inflicts significant performance degradation. In CDMA systems, all subscribers are active on the same frequency band simultaneously and signal separation is facilitated upon reception via the properties of the assigned spreading codes. Under asynchronous conditions the code properties alone do not provide the necessary separation and an additive MAI term remains in the detection process. In addition to the separation abilities of the spreading codes, a further method of deciphering the desired subscriber signal from the interfering subscriber signals is sought. In this thesis we propose a statistical model for both the probability density function (pdf) of the total MAI power and the corresponding bit-error rate (BER) observed during asynchronous CDMA transmission. The modelling offers the full statistic the MAI power and resulting BER, not just the first and second order statistics. In addition to statistically quantifying the MAI power, the thesis also proposes a technique for the successful reduction of MAI caused by asynchronous transmission. This interference reduction technique is derived from an ambiguity domain analysis of the asynchronous CDMA detection problem and its application to both the DS-CDMA and MC-CDMA multiplexing techniques is presented and the results show significant MAI reduction, and thus an improved the BER. A methodology for the approximation of the total MAI power pdf and the resulting BER pdf is proposed for the asynchronous DS-CDMA and MC-CDMA techniques. This methodology is derived for the use of Walsh-Hadamard (WH) and Gold spreading sequences, however, it is applicable to any given set of deterministic spreading sequences. The total MAI power pdfs of both systems are statistically modelled as being Nakagamim distributed and the corresponding BER modelling is derived from the Nakagami-m formulation offering the full statistic of both the incurred MAI power and the achievable BER. The proposed pdf acquisition methodology and statistical models can be used as analysis tools to assess the relative performances of the DS-CDMA and MC-CDMA techniques for a variety of communications environments. Here the asynchronous uplink channel is considered in the absence of fading and the results show a clear distinction between the BER performances of the MC-CDMA and DS-CDMA systems, for which the MC-CDMA system offers a superior performance for the purely asynchronous channel considered. The results suggest a higher resistance to MAI in the MC-CDMA technique in comparison to the DS-CDMA system for the considered transmission scenario. Following ambiguity function analysis of the asynchronous CDMA detection problem, the concept of dual-frequency switching is introduced to the existing DS-CDMA and MC-CDMA techniques giving rise to the proposed dual-frequency DS-CDMA (DF/DSCDMA) and dual-frequency MC-CDMA (DF/MC-CDMA) schemes. Periodically switching the carrier frequency between dual frequency bands at consecutive symbol boundaries facilitates partial CDMA signal separation upon asynchronous reception. Such switching of the carrier frequency induces a separation in frequency between offset interference signals and the reference signal; this is equivalent to shifting the energy concentration of the interference signals away form the ambiguity domain origin (representing the decision variable of the matched filter). Further MAI reduction is demonstrated through careful design of the dual carrier frequencies. The newly proposed DF systems clearly outperform the standard DS-CDMA and MC-CDMA systems when adopting equivalent spreading factors. The DF/DS-CDMA technique in particular achieves the most MAI reduction and in doing so, surpasses all other considered techniques to offer the best BER performance for the purely asynchronous channel considered. In terms of bandwidth usage, the DF/DS-CDMA band width is 1.5 times that of the DF/MC-CDMA system and from the BER results presented, one may argue that DF/MC-CDMA offers the better BER given the bandwidth usage. The multicarrier systems presented, MC-CDMA and DF/MC-CDMA, offer attractive BER performances for the bandwidth used and it is concluded that MC-CDMA is a genuine candidate for the uplink air interface multiple access scheme for future mobile cellular technologies.

With code division multiple access (CDMA) systems being the prominent multiple access scheme for the air interface for 3G cellular systems, most standardisation bodies have based their terrestrial cellular systems on DS-CDMA (W-CDMA, UMTS, cdma2000). With 4G systems fast approaching, bringing with them improved services and quality of service standards, there is growing interest in further investigating and developing more efficient multiple access techniques such as multicarrier CDMA (MC-CDMA) systems. MC-CDMA combines multicarrier modulation (MCM), namely OFDM, with CDMA profiting from the benefits of both multiplexing techniques; as such, MC-CDMA is emerging as a possible candidate for the air interface multiple access scheme for 4G cellular systems. Multiple access interference (MAI) is a limiting factor of CDMA systems in terms of system capacity as orthogonally designed spreading sequences lose their orthogonality in the presence of timing misalignments amongst mobile subscribers in a cell; such is the case over the uplink channel. Ensuring orthogonal code properties minimises the MAI over synchronous environments, however, it is when the users are allowed to transmit asynchronously, as is the case over the uplink channel, that MAI inflicts significant performance degradation. In CDMA systems, all subscribers are active on the same frequency band simultaneously and signal separation is facilitated upon reception via the properties of the assigned spreading codes. Under asynchronous conditions the code properties alone do not provide the necessary separation and an additive MAI term remains in the detection process. In addition to the separation abilities of the spreading codes, a further method of deciphering the desired subscriber signal from the interfering subscriber signals is sought. In this thesis we propose a statistical model for both the probability density function (pdf) of the total MAI power and the corresponding bit-error rate (BER) observed during asynchronous CDMA transmission. The modelling offers the full statistic the MAI power and resulting BER, not just the first and second order statistics. In addition to statistically quantifying the MAI power, the thesis also proposes a technique for the successful reduction of MAI caused by asynchronous transmission. This interference reduction technique is derived from an ambiguity domain analysis of the asynchronous CDMA detection problem and its application to both the DS-CDMA and MC-CDMA multiplexing techniques is presented and the results show significant MAI reduction, and thus an improved the BER. A methodology for the approximation of the total MAI power pdf and the resulting BER pdf is proposed for the asynchronous DS-CDMA and MC-CDMA techniques. This methodology is derived for the use of Walsh-Hadamard (WH) and Gold spreading sequences, however, it is applicable to any given set of deterministic spreading sequences. The total MAI power pdfs of both systems are statistically modelled as being Nakagamim distributed and the corresponding BER modelling is derived from the Nakagami-m formulation offering the full statistic of both the incurred MAI power and the achievable BER. The proposed pdf acquisition methodology and statistical models can be used as analysis tools to assess the relative performances of the DS-CDMA and MC-CDMA techniques for a variety of communications environments. Here the asynchronous uplink channel is considered in the absence of fading and the results show a clear distinction between the BER performances of the MC-CDMA and DS-CDMA systems, for which the MC-CDMA system offers a superior performance for the purely asynchronous channel considered. The results suggest a higher resistance to MAI in the MC-CDMA technique in comparison to the DS-CDMA system for the considered transmission scenario. Following ambiguity function analysis of the asynchronous CDMA detection problem, the concept of dual-frequency switching is introduced to the existing DS-CDMA and MC-CDMA techniques giving rise to the proposed dual-frequency DS-CDMA (DF/DSCDMA) and dual-frequency MC-CDMA (DF/MC-CDMA) schemes. Periodically switching the carrier frequency between dual frequency bands at consecutive symbol boundaries facilitates partial CDMA signal separation upon asynchronous reception. Such switching of the carrier frequency induces a separation in frequency between offset interference signals and the reference signal; this is equivalent to shifting the energy concentration of the interference signals away form the ambiguity domain origin (representing the decision variable of the matched filter). Further MAI reduction is demonstrated through careful design of the dual carrier frequencies. The newly proposed DF systems clearly outperform the standard DS-CDMA and MC-CDMA systems when adopting equivalent spreading factors. The DF/DS-CDMA technique in particular achieves the most MAI reduction and in doing so, surpasses all other considered techniques to offer the best BER performance for the purely asynchronous channel considered. In terms of bandwidth usage, the DF/DS-CDMA band width is 1.5 times that of the DF/MC-CDMA system and from the BER results presented, one may argue that DF/MC-CDMA offers the better BER given the bandwidth usage. The multicarrier systems presented, MC-CDMA and DF/MC-CDMA, offer attractive BER performances for the bandwidth used and it is concluded that MC-CDMA is a genuine candidate for the uplink air interface multiple access scheme for future mobile cellular technologies.