Motivation: The accurate and reliable measurement of the concentration of coal tar pitch volatiles (CTPVs) in ambient air has proved to be a challenge for occupational hygienists. The challenge must however be confronted due to, amongst others, the carcinogenic properties of some poly–aromatic hydrocarbons (PAHs) contained in CTPVs. Aim: To determine the feasibility of a thermal desorption (TD) technique based method as an alternative method to be used for the measurement of the concentration of CTPVs in ambient air by assessing it along criteria such as ease of use, cost, accuracy and precision by comparing it to NIOSH’s Method 5515 and OSHA’s Method 58 and to determine the level of exposure to CTPVs on the anode paste floor of an electric furnace, used for the smelting of platinum group metals (PGMs) concentrate. Methodology: To satisfy the research objective, two accepted methods the National Institute of Occupational Safety and Health’s (NIOSH) method 5515 and the Occupational Safety and Health Administration’s (OSHA) method 58 were used for the measurement of the concentration of CTPVs with a TD technique based method used as a third, alternative method. All three methods were used concurrently to measure the concentration of CTPVs in ambient air, at the anode paste floor of a platinum group metals (PGMs) concentrate smelter. Results and conclusions: The NIOSH method proved to be the most precise method while the TD technique based method proved to be the most accurate. The TD technique based method proved to measure the widest range of individual CTPVs and were able to measure the highest concentration of Benzo(a)pyrene, an individual CTPV that is classified as a Group 1 (carcinogenic to humans) chemical substance by the International Agency for Research on Cancer (IARC). The OSHA method measured on average almost four times less total CTPVs than either the NIOSH or the TD technique based method and failed to readily measure individual CTPVs with a molecular weight lower than that of Phenanthrene. / Thesis (M.Sc. (Occupational Hygiene))--North-West University, Potchefstroom Campus, 2012.

The growth of ZnO single crystals and ZnO thin films on Si substrates by an open-system vapor phase method was studied in this thesis. The as-grown ZnO single crystals were investigated by means of photoluminescence (PL). Two unique emissions were observed in virgin and hydrogenated crystals. The up-to-now attempts for the p-type doping of ZnO were summarized and our doping studies were performed using nitrogen and antimony. The seed-free and open-system vapor phase method is a simple and low cost approach to grow good quality ZnO single crystals. The growth parameters, including flow rates of N2, H2, O2, and growth temperatures, have various influences on the crystal growth, and also on the optical properties of the as grown crystals. The as-grown crystals are c-axis oriented needle crystals, and the crystals typically have a maximum length of 40 mm and a maximum diameter of 1 mm. The needle-shaped crystals are n-type with main donors due to Al, Ga, and In impurities, as determined from the PL spectra. Two unidentified PL emission lines (P1 at 3.3643 eV and P2 at 3.3462 eV) are observed in our vapor phase grown ZnO single crystals. P1 is attributed to the recombination of an exciton bound to a shallow donor，which has a binding energy of 42.2 meV. Hydrogenation of the as-grown ZnO single crystal leads to the appearance of the P2 line and a great reduction of the P1 line. Subsequent isochronal annealing in the ambient atmosphere leads to gradual reduction of P2 and the reappearance of P1. The PL measurements indicate that hydrogen is involved in the defect origins of the P2 line. ZnO thin films were deposited on Si substrates by the vapor phase method. Three different types of configurations with alternative source materials and oxidizers were employed and compared. It is demonstrated that, methods with lower growth temperatures are easier to deposit homogenous ZnO films on Si substrate. Donor-acceptor-pair (DAP) transition at 3.245 eV and its phonon replicas were observed in the PL spectra of the thin films, which are grown by the hydrogen-free vapor phase method. The appearance of DAP transition indicates the presence of acceptor in the films. The long-standing challenge of p-type doping in ZnO is mainly attributed to the low valence band maximum (VBM) at the absolute energy scale, the spontaneous formation of compensating defects and the lack of appropriate acceptors with small ionization energy. Two attempts for the p-type doping of ZnO were performed by nitrogen diffusion into ZnO single crystals from plasma after the growth or by in-situ doping antimony during the growth of ZnO films. No hole conductivity could however be achieved in our doped samples. / In dieser Arbeit wurde das Wachstum von ZnO-Einkristallen und Dünnfilmschichten auf Si durch chemische Gasphasenabscheidung in einem offenen System untersucht. Die hergestellten ZnO-Einkristalle wurden mit Photolumineszenzmessungen (PL) untersucht. Es konnten sowohl in unbehandelten als auch in mit Wasserstoff behandelten Proben zwei charakteristische Linien beobachtet werden. Sowohl die bisherigen Versuche zur p-Typ Dotierung von ZnO als auch die in dieser Arbeit durchgeführten Versuche mit Stickstoff und Antimon werden zusammengefasst und präsentiert. Die Keimkristall-freie Gasphasenabscheidung (CVD) in offenen Systemen ist eine einfache und kostengünstige Methode zur Herstellung von qualitativ hochwertigen ZnO-Einkristallen. Die Wachstumsparameter, einschließlich der Flussraten von N2, H2 und O2 sowie der Wachstumstemperatur beeinflussen das Kristallwachstum sowie die optischen Eigenschaften der hergestellten Kristalle. Die hergestellten Kristalle wachsen typischerweise als entlang der c-Achse orientierte Nadeln mit Längen von bis zu 40 mm und Durchmessern von bis zu 1 mm. Die nadelförmigen Kristalle besitzen eine n-Typ Dotierung, welche hauptsächlich durch Verunreinigung mit Al, Ga und In verursacht wird. Zwei bisher nicht identifizierte PL-Linien (P1 bei 3,3643 eV und P2 bei 3,3462 eV) wurden in den hergestellten Kristallen beobachtet. P1 wird der Rekombination von Exzitonen an flachen Donatoren mit einer Bindungsenergie von 42,2 meV zugeordnet. Eine Wasserstoffbehandlung der hergestellten Kristalle führt zum Erscheinen der P2-Linie und einer starken Unterdrückung der P1-Linie. Anschließende isochronische Temperung in Luft führt zu einer schrittweisen Reduzierung der Intensität der P2-Linie und zu einer Verstärkung der P1-Linie. Photolumineszenzmessungen weisen auf eine Korrelation von P2 mit Wasserstoff hin. Zusätzlich wurden mit der CVD-Methode dünne ZnO-Schichten auf Si-Substraten abgeschieden. Drei unterschiedliche Konfigurationen mit verschiedenen Ausgangsmaterialien (ZnO-Pulver bw. Zn-Pulver) und verschiedenen Oxidationsmitteln (O2 bzw. Wasser) wurden untersucht und verglichen. Es wird gezeigt, dass mit den Konfigurationen mit geringerer Wachstumstemperatur am einfachsten homogene ZnO-Schichten auf Si abgeschieden werden können. Ein Donator-Akzeptor-Paar-Übergang (DAP) bei 3,245 eV und die dazugehörigen Phononenrepliken wurden in den Schichten beobachtet, welche in einer Wasserstoff-freien Konfiguration abgeschieden wurden. Diese DAP-Übergänge sind ein Hinweis auf die Anwesenheit von Akzeptoren. Die seit langem bestehende Herausforderung der p-Typ-Dotierung von ZnO hat ihre Wurzeln hauptsächlich in dem niedrig liegenden Valenzbandmaximum (VBM) auf der absoluten Energieskala, der spontanen Bildung von kompensierenden Defekten sowie dem Mangel an geeigneten Akzeptoren mit geringer Ionisierungsenergie. Zwei Versuche zur p-Typ-Dotierung von ZnO durch Behandlung der Kristalle mit N-Plasma bzw. durch in-situ Dotierung mit Sb während des Kristallwachstums wurden durchgeführt. Allerdings konnte damit keine nachweisbare Löcherleitung in den behandelten Proben erreicht werden.

To foster the practical development of constructed wetlands used for wastewater treatment in Turkey, a pilot-scale subsurface constructed wetland system (90 m2) was designed to treat the domestic wastewater produced by 60 PE living in the residential area of METU. In summer 2001, two parallel sets of hybrid wetland systems (vertical flow connected with horizontal flow) with identical design configuration, but with different fill media (blast furnace granulated iron slag and gravel) were built on the old sludge-drying bed of the abandoned wastewater treatment plant of METU, which has not been operating since the 1990s. Wetland cells were planted with common reed (Phragmites australis). The main objective of this research was to quantify the effect of different filter media on the removal performance of subsurface flow constructed wetlands in the prevailing climate of Ankara. Thus, slag-filled and gravel-filled vertical flow wetlands were operated identically with pre-settled domestic wastewater (3 m3.d-1) at a hydraulic loading rate of 110 mm.d-1 for 12 months, intermittently. According to the first year results, annual average removal efficiencies for the slag and gravel wetland cells were as follows: TSS (63% &amp / 59%), COD (47% &amp / 44%), NH4+-N (88% &amp / 53%), TN (44% &amp / 39%), PO43--P (44% &amp / 1%) and TP (45% &amp / 4%). The slag-filled vertical flow system removed phosphorus and ammonium efficiently than the gravel-filled system due to the differences in physical structures and chemical compositions of the fill media, and the different aerobic and anaerobic environments within the wetland cells. These results indicated that the well-designed constructed wetlands could also be used for secondary and tertiary treatment in Turkey, successfully.

In recent years, scientific studies are carried out to find new refractory material. Having good mechanical properties under very high temperatures, refractories are widely used in industries like iron, steel, glass, cement and pottery. Researches are focused on monolithic refractory making because of their superior properties comparing to conventional firebrick refractories. Providing a mono-block body, having no joints makes the monolithic refractories more durable at elevated temperatures. Easier production and installation are two main points that people are choosing monolithic refractories, thus an economy is made. In this study, for monolithic refractory production, high alumina cement was used as binding material. It is known that the increase in alumina (Al2O3) content increases the high temperature resistance, so that crushed firebrick, having 85% Al2O3 was used as aggregate. Pozzolanic materials, which are silica fume, fly ash, ground granulated firebrick and ground granulated blast furnace slag, were added to improve physical and mechanical properties of mortar. With the addition of steel fibres, change in compressive strength and flexural strength was observed.Superplasticizer was used to understand its behaviour under high temperatures. Portland cement containing mortars were also prepared to make comparison with high alumina cement containing specimens. Specimens were prepared in 5x5x5 cm and 4x4x16 cm prisms. They were cured for one day at curing room, then heated to 105&deg / C and then heated to 1100&deg / C. Weight, size and ultrasound velocity change, compressive strength and flexural strength tests were done to determine physical and mechanical properties of the monolithic refractories, before and after heating. Heated and non-heated specimens were pulverized for microstructural investigation with X-Ray diffraction (XRD) method. Using high alumina cement with 50 &ndash / 60 % granulated blast furnace slag or granulated firebrick, by the weight of cement, and crushed firebrick as aggregate, a satisfactory monolithic refractory material was made. It was observed that, mechanical properties were decreased at the Portland cement used mortars after several times of heating and cooling cycles. Also, it was determined that the microstructure of the high alumina cement containing mortars did not deteriorate much at 1100&deg / C, as long as there was no change observed from the results.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / The study of concrete structures durability necessarily passes by the study of covercrete and by the understanding of the factors that affect the features of this superficial layer. The use of high contents of mineral addictions on the concrete influences meaningfully the resistance of the covering layer to the chemical attack and on the pores structure. This dissertation aimed to analyze, through the obtained results in the tests of capillary water absorption, according to the RILEM TC 116 PCD Recommendation, and to the diffusion of water held following the directives DAN et al (1988) presented by Isaia (1995), based on publications of CSTB, the percolation of water on concrete covering layer, besides co-relating with the resistance to 50 MPa, the total volume of intruding mercury and the critical diameter of the pores. To these analysis perform, prototypes specimens of 75 cm x 20cm x 15cm have been molded with high contents of mineral additions, 70 % of slag and 20% of fly ash, in replacement to the cement mass, with or without addition of 20% of hydrated lime, in mass, and w/cm relationships 0,3 ; 0,4 ; 0,5 besides the reference mix proportion, only with cement and w/cm relationships 0,4; 0,6 e 0,8. The tests of capillary absorption and water diffusion were held, on the 91 and 300 days to execute the comparative study between these two ages, extracted specimens of 10 cm x 20 cm, from the prototypes had been accomplished, being closed to 0, 2,5 e 5,0cm of depth from the surface. After performing the analysis, it has been noticed that the replacement of cement by mineral additions causes a strength reduction to the compression, being it more accentuated in the initial ages and eased as the time passes by. In relation to the coefficients of water absorption and diffusion of the concretes with mineral additions compared to the reference concretes in equality of w/cm and ages, being analyzed the use of additions, meaningful reductions that get to 79% in the absorption and 69% in the diffusion, on the 300 day. When analyzed considering the depth (in equality of w/cm) the layer reduction 3 (5cm) in relation to 1(0,5cm) gets to 55% in the absorption and 31% in the diffusion, on the 300 day, and in the mix proportion with addition of hydrated lime, justifiable by the fact of the hydrated lime stored water helping in the hydrating process producing a more compact matrix. In equality of 50 Mpa compressive strength, the reductions are 86% to the absorption and 70% to the diffusion. It s been noticed, as to the absorption as to the diffusion, a strong co-relation with the intruding total volume and the pores diameter on the 300 day. / O estudo da durabilidade das estruturas de concreto passa, necessariamente, pelo estudo do concreto de cobrimento e pelo entendimento dos fatores que afetam as características dessa camada superficial. O uso de altos teores de adições minerais no concreto influencia significativamente a resistência da camada de cobrimento ao ataque químico e a estrutura dos poros. Esta dissertação tem por objetivo analisar, através dos resultados obtidos nos ensaios de absorção capilar de água, conforme a norma RILEM TC-116 PCD, e de difusão de água, realizado seguindo as diretrizes de Dan et al (1988), apresentadas por Isaia (1995), baseadas em publicações de CSTB, a percolação de água na camada de cobrimento do concreto, além de correlacionar com a resistência a 50 MPa , o volume total de mercúrio intrudido e o diâmetro crítico dos poros. Para realização dessas análises, foram moldadas peças protótipos de 75 cm x 20 cm x 15 cm, que permaneceram em exposição ambiental até a data de realização dos ensaios. Os protótipos foram moldados com altos teores de escória, 70% e cinza volante 20%, em substituição à massa de cimento, com e sem adição de 20% de cal hidratada, em massa, e uma relação a/mc 0,3, 0,4, 0,5, além do traço de referência, somente com cimento e relação a/c 0,4; 0,6 e 0,8. Os ensaios de absorção capilar e de difusão de água foram realizados aos 91 e 300 dias. Para executar o estudo comparativo entre essas duas idades, foram extraídos testemunhos 10 cm x 20 cm dos protótipos sendo cerrados a 0, 2,5 e 5,0 cm de profundidade a partir da superfície. Após a realização das análises, observou-se que a substituição de cimento por adições minerais acarreta uma diminuição na resistência à compressão, sendo mais acentuada nas idades iniciais e amenizada com o passar do tempo. Em relação aos coeficientes de absorção e de difusão de água dos concretos com adições minerais, comparados com os concretos de referência, em igualdade de a/mc e idades analisadas, o uso de adições resultou em significativas reduções nesses coeficientes, que chegam a 79% na absorção e de 69% na difusão, aos 300 dias. Quando analisados em função da profundidade (em igualdade de a/mc), as reduções da camada 3 em relação à camada 1 chegam a 55% na absorção e 31% na difusão, aos 300 dias e nos traços com adição de cal hidratada. Esse comportamento é justificável pelo fato de a cal hidratada armazenar água auxiliando nos processos de hidratação, produzindo uma matriz mais compacta. Em igualdade de resistência, as reduções são de 86% para a absorção e de 70% para a difusão. Observa-se, tanto para a absorção como para a difusão, uma forte correlação com o volume total intrudido e o diâmetro dos poros aos 300 dias.

Le rejet des nutriments (phosphates et nitrates) issues des eaux usées domestiques entraînent la dégradation des écosystèmes (74 % du territoire français concerné en 2006). Compte tenu de la situation, l’Etat français a promulgué la Loi sur l’Eau et les Milieux Aquatiques le 30décembre 2006 qui vise à atteindre le « bon état écologique des eaux et des milieux aquatiques » d’ici 2015. Cette notion bien que difficilement intégrable a généré des normes plus strictes pour les stations d’épuration en termes de rejet de nutriments vers le milieu récepteur (jusque 15 mg NTOT.L-1 et 2 mg PTOT.L-1). Depuis la fin des années 1990, la technologie des filtres plantés de roseaux (FPR) est de plus en plus employée(> 2500 unités en 2012) pour le traitement des eaux usées domestiques des petites collectivités inférieures à 2000 Equivalent-Habitants. Cependant, des limites de traitement existent sur les concentrations résiduelles en azote (rejet de 70-80 mg NTOT.L-1) et en phosphore (rejet> 10 mg PTOT.L-1), en vue de répondre à la réglementation future. Ce travail a eu pour objectif de mettre en oeuvre des améliorations telles que la recirculation sur un étage de traitement pour le traitement de l’azote d’une part et l’emploi de matériaux réactifs pour piéger le phosphore d’autre part. La démarche scientifique expérimentale déployée a consisté à suivre des pilotes sur site réel et en laboratoire pendant 2 années. Le suivi des performances épuratoires et hydrauliques a été réalisé au cours du temps. Pour l’azote, 2 FPR (2,5 m²) garnis de schiste expansé (Mayennite®) ont été alimentés en effluent brut. L’effet de la hauteur de saturation en eau dans la partie drainante ainsi que l’effet de la recirculation ont été étudiés. Les résultats obtenus ont montré : une couche saturée à 38 % (rapporté à la hauteur totale) et un ratio de recirculation de 100 % permettent une meilleure élimination de la matière particulaire-carbonée (Arrêté du22 juin 2007) et de l’azote (< 20 mg NTK.L-1 ; < 45 mgNTOT.L-1). Deux laitiers de four à arc électrique ont été sélectionnés pour le traitement du phosphore. Ceux-ci ont été mis en œuvre dans 5 colonnes (6 L) en laboratoire alimentées en effluent synthétique en phosphore puis secondaire et dans 4 filtres réactifs pilote (0,3 m² ; 34 L) à flux horizontal sous surfacique alimentés en effluent secondaire. Il ressort de ces expériences: (i) des disparités existent entre les deux échelles en termes de performances (< 2 mg P.L-1 pendant 20 mois en colonne et variation saisonnière des performances en pilote) et mécanismes épuratoires (adsorption/précipitation P-Caen colonne ; P-Ca + P-Fe en pilote), (ii) l’augmentation de la température (> 15 °C) et/ou du temps de séjour (48h et plus) améliore la cinétique d’élimination du phosphore à échelle pilote et (iii) l’implantation d’un filtre réactif garni de laitier de four à arc électrique est limité par le degré de traitement souhaité et la distance du futur chantier (coût du transport). / Nutrient (phosphorus and nitrogen) discharges from wastewater lead to water quality degradation (74 % of the total French territory in 2006). According to the actual situation, the French government has adopted a Water Framework on December 30, 2006 to achieve a“good ecological status of water” in 2015. Therefore,more stringent standards on nutrients removal for raw wastewater treatment plants are expected (down to 15mg TN.L-1 and 2 mg TP.L-1). However, standards actually remain under the responsibility of departmental authorities according to the water quality of the receiving environment. Since 1990s, Vertical Flow Constructed Wetlands(VFCWs) have been more and more popular in treating raw domestic wastewater for small collectivities of less than 2000 person equivalent (> 2500 units in 2012). However, nitrogen and phosphorus removal are limited in VFCWs (70-80 mg TN.L-1; > 10 mg TP.L-1) according to the new legislation. The aim of this work was on the one hand to implement a recirculation of treated effluent on a VFCW for better nitrogen removal and on the other to use reactive materials to improve phosphorus removal. The experimental scientific approach consisted in monitoring both laboratory and field pilot scale systems under process conditions during 2 years. Treatment and hydraulic performances were monitored over time. Two VFCWs (2,5 m²) filled with expanded schist (Mayennite®) were fed with raw domestic wastewater. The effect of a saturated layer and of the recirculation of treated effluent were studied. Results showed that 38 % of a saturated layer and 100 % of recirculation enabled to improve nitrogen treatment performances (< 20 mgTKN.L-1; < 45 mg TN.L-1) and to meet the French standard D4. Electric arc furnace slags were selected as reactive materials to improve phosphorus treatment performance of the VFCWs in laboratory and field pilot scale systems. Five laboratory-scale column experiments (6L) were fed with a phosphorus synthetic effluent then with a secondary effluent. Four horizontal subsurface flow active filters (0,3 m²; 34 L) were fed with a secondary effluent. The main results showed : (i)differences exist between laboratory and pilot scale regarding treatment performance (< 2 mg P.L-1 during20 months in the laboratory ; seasonal variations at pilot scale) and removal mechanisms (adsorption/precipitation Ca-P in laboratory ; Ca-P + Fe-P at pilot scale), (ii) an increase of temperature (> 15°C) and/or hydraulic retention time (more than 2 days) improved the kinetics of phosphorus removal at pilot scale, (iii) the active filter implementing is limited by the discharge standard required (> 3 mg PTOT.L-1) and the distance to the steel factory (transport costs).

O tratamento de inclusões com cálcio é uma ferramenta poderosa para a produção de aços mais limpos e com melhores propriedades mecânicas. A simulação em laboratório do processo industrial tem sua importância na possibilidade de estudar as reações e interações químicas do tratamento de inclusões no aço líquido. Esse tipo de estudo é possível através do uso de experimentos associados entre fornos a cálculos termodinâmicos. Dessa forma, os objetivos deste trabalho foram: 1) Avaliar - em escala laboratorial - a evolução de inclusões modificadas com a adição de cálcio no banho do aço SAE 8620; 2) Comparar os resultados obtidos com simulações via termodinâmica computacional; 3) Consolidar uma metodologia para estudo de inclusões em escala laboratorial. Para isso, foram executadas corridas em um forno elétrico resistivo de escala de laboratório. As matérias-primas utilizadas foram: ferro com alta pureza e as ferroligas usadas na indústria. Houve injeção de alumínio e cálcio no aço líquido. Na análise química do aço foram considerados os elementos de liga de rotina de produção inclusive os teores de cálcio e oxigênio total. Nas análises de inclusões foram avaliados, via MEV/EDS: composição química, morfologia, distribuição de fases e tamanho.Para calcular o equilíbrio termodinâmico entre aço líquido e inclusões não-metálicas - via termodinâmica computacional - foram utilizados os bancos de dados do software FactSage. Observou-se a modificação química das inclusões com a adição de cálcio, formando diferentes tipos de cálcio-aluminatos, como previsto. Devido à presença de enxofre, verificou-se a formação de sulfetos de cálcio e manganês associados aos cálcio-aluminatos. Também obteve-se uma boa correlação entre os resultados calculados via termodinâmica computacional e a literatura consultada. / The inclusion treatment with calcium is a powerful tool for the production of cleaner steels with improved mechanical properties. The simulation in laboratory of the industrial process has its importance in the possibility of studying the reactions and chemical interactions of the inclusions treatment in the liquid steel. This kind of study is just possible through the use of experiments associated with furnaces and thermodynamics simulations. This way, the aims of this work were: 1) to evaluate - in laboratorial scale - the evolution of inclusions modified with the calcium addition in the SAE 8620 steel bath; 2) to compare the results obtained with computational thermodynamics simulation; 3) to consolidate a methodology for study inclusions in laboratorial scale. Trials in a electrical resistive furnace in laboratory scale were carried out. The raw materials used were: high purity iron and ferroalloys used in the industry. It had also injection of aluminium and calcium in the liquid steel. In the chemical analysis of the steel it was considered the common alloying elements of steel including calcium and total oxygen. In the inclusions analysis were evaluated by SEM/EDS: chemical composition, morphology, phases distribution and size. To calculate the thermodynamic balance between liquid steel and nonmetallic inclusions - by computational thermodynamics simulation - the FactSage data bases software were used. The chemical modification of the inclusions with calcium addition was observed, forming different types of calcium-aluminates, as predicted. Due to sulphur presence it was verified the formation of calcium and manganese sulphides associates with calciumaluminates. Also it was obtained a good correlation between these results, calculated by computational thermodynamics and literature.

Ce travail de thèse est consacré à la modélisation du procédé de réduction directe du minerai de fer, un procédé alternatif intéressant dans le contexte de la réduction des émissions de CO2 de la sidérurgie. Le four à cuve, réacteur central du procédé, est divisé en trois zones (réduction, transition et refroidissement). Le modèle mathématique mis au point pour simuler l’ensemble repose sur une description détaillée et fidèle des principaux phénomènes physico-chimiques et thermiques intervenant. C’est un modèle bidimensionnel, en régime permanent et multi-échelle. Le lit mobile est constitué de boulettes, elles-mêmes supposées composées de grains et de cristallites. Huit réactions chimiques hétérogènes et deux réactions chimiques homogènes sont prises en compte. Les équations de conservation locales de la masse, l'énergie et de la quantité de mouvement ont été résolues numériquement en utilisant la méthode des volumes finis. Ce modèle a été appliqué avec succès pour simuler le four à cuve de deux usines de réduction directe de capacités différentes. Les résultats obtenus renseignent sur le fonctionnement interne du four et mettent en évidence des zones aux performances inégales. Le modèle a ensuite été exploité, après l’ajout et le couplage d’un modèle du reformeur, pour des calculs paramétriques, en particulier lorsque les caractéristiques des gaz réducteurs sont modifiées. Enfin des pistes sont présentées pour optimiser une installation de réduction directe en augmentant la capacité de production et le degré de métallisation du produit / This thesis is dedicated to the modelling of the iron ore direct reduction process, an attractive alternative process for making steel in the context of the reduction in CO2 emissions. The shaft furnace, the core reactor of the process, is divided into three sections (reduction, transition and cooling). The mathematical model developed to simulate this reactor is based on a detailed and faithful description of the main physical-chemical and thermal phenomena involved. The model is a two-dimensional, steady state and multi-scale. The moving bed is comprised of pellets of grains and crystallites. Eight heterogeneous chemical reactions and two homogeneous chemical reactions were taken into account. The local mass, energy and momentum balances were solved numerically using the finite volume method. The model was successfully applied to simulate the shaft furnace of two direct reduction plants of different capacities. The results obtained provide new insights on the internal behaviour of the furnace and highlight zones of uneven performance. After the addition and coupling of a reformer model, the shaft furnace model was used for parametric calculations, in particular when considering changes in the composition of the reducing gases. Finally, new possibilities are presented for optimizing the direct reduction process, e.g. for increasing the production capacity and the degree of metallization of the produced iron

The carbonation phenomenon, reaction between CO2 from the atmosphere in the presence of humidity with the Portland cement hydration products, induces pH reduction to levels that can cause the elimination of steel s protective layer, enabling the corrosion mechanism of the steel structure to start.. This is one of the main pathologies in the reinforced concrete and its occurrence depends on the existence of oxygen, humidity and potential difference between two different locations of the steel bar. This research analyzed the performance of different concrete mixtures produced with Portland cement with high levels of blast furnace slag, with and without the chemical activator sodium sulfate (Na2SO4), in relation to compressive strength, capillary absorption and carbonation. For comparison purposes, gray Portland cement concrete test samples were also cast. For the white Portland cement concrete, slag contents of 0% and 50%, without and with chemical activator at concentrations of 4% and 70% were chosen. With the gray Portland cement it was produced concrete with 0% and 50% of slag addition, with and without chemical activator. For each mixture was adopted water/binder ratios of 0.30, 0.42 and 0.55. The samples cast with white Portland cement, destined to the compressive strength tests were broken at 3, 7, 28 and 91 days and the capillary absorption tests were done 91 days after molding. The samples destined to accelerated carbonation tests, cast with the two kinds of cements, were submitted to an atmosphere with 2% CO2 concentration, temperature of 23±1ºC and relative humidity of 75±2%. The carbonation depths determination was realized in the ages of 0, 3, 6, 9 and 12 weeks, after entrance in the chamber. From results obtained it was noticed that compressive strength reduced as the slag content and water/binder ration increased. In more advanced ages, however, the difference in compressive strength between mixtures with slag and the reference mixture was smaller than in the first ages. The capillary absorption reduced with the slag content increase, as a consequence of the refinement pores. The carbonation depth, for the white and gray concretes, increased with the slag content and the chemical activator utilization. In a comparison between white and gray Portland cement concretes, for the same slag content and water/binder ratio, the higher carbonation depths were reached with the white concrete, and this difference was higher when the water/binder ratio was increased. / O fenômeno da carbonatação, reação entre o CO2 da atmosfera em presença de umidade com os produtos de hidratação do cimento Portland, provoca a redução do pH do concreto a níveis que podem causar a eliminação da película passivadora do aço, podendo ocorrer a instalação do mecanismo de corrosão das armaduras, uma das principais patologias em estruturas de concreto armado, desde que para isto, exista oxigênio, umidade e uma diferença de potencial entre dois pontos distintos da barra de aço. Esta pesquisa analisou o desempenho de diferentes misturas de concretos produzidos com cimento Portland branco com altos teores de escória de alto forno, com e sem ativador químico sulfato de sódio (Na2SO4), frente à resistência à compressão, absorção capilar e carbonatação. Para efeito de comparação da resistência à carbonatação, também foram moldadas amostras com concreto de cimento Portland cinza. Para o concreto de cimento Portland branco foram adotados os teores de adição de escória de 0%, 50% sem e com ativador químico no teor de 4% e 70%. Com o cimento Portland cinza foram produzidos concretos com 0% e 50% de adição de escória sem e com ativador químico. Para cada mistura foram adotadas três relações água/aglomerante, 0,30, 0,42 e 0,55. Os corpos-deprova, moldados com cimento Portland branco, destinados aos ensaios de resistência à compressão foram rompidos aos 3, 7, 28 e 91 dias e os ensaios de absorção capilar foram realizados 91 dias após a moldagem. As amostras destinadas ao ensaio de carbonatação acelerada, moldadas com os dois tipos de cimento, foram submetidas a uma atmosfera com concentração de 2% de CO2, temperatura de 23±1ºC e umidade relativa de 75±2%. A determinação da profundidade carbonatada foi realizada nas idades de 0, 3, 6, 9 e 12 semanas, após a entrada na câmara de carbonatação. Dos resultados obtidos constatou-se redução nos valores de resistência à compressão das misturas com escória com o aumento no teor de adição e da relação água/aglomerante, porém, em idades mais avançadas, a diferença entre as resistências das misturas com adição e aquelas da mistura de referência foi menor que nas primeiras idades. A absorção capilar diminuiu com o aumento no teor de adição de escória, conseqüência do refinamento dos poros. A profundidade de carbonatação, para os concretos branco e cinza, aumentou com o aumento no teor de escória e a utilização de ativador químico. Na comparação entre os concretos de cimento Portland branco e cinza analisados, para mesmo teor de adição e relação água/aglomerante, as maiores profundidades de carbonatação foram atingidas pelo concreto branco, e esta diferença foi maior à medida que aumentou a relação água/aglomerante.

Drying Shrinkage is a phenomenon that occurs in concrete, subjected or not to a load, due to water loss, once exposed to environment and allowed to dry. It is responsible for almost the entire total shrinkage strain in concrete. A concrete element with restrained shrinkage deformation may develop tensions that cause cracks, allowing the ingress of aggressive agents that may cause some damage to the reinforcement, reducing, consequently, its strength and durability. The most common aggressive agent into concrete is the chloride ion, which is considered the great responsible for the early reinforcement corrosion of concrete structures, affecting its stability and durability. Corrosion of reinforcement bars due to the ingress of salts from sea water into concrete is recognized to be the most influent factor in the destructive mechanisms for marine structures. The use of mineral admixtures such as blast furnace slag, the increase of curing duration and the water/binder ratio reduction are measures that may reduce the chloride ion penetration. The aim of this study was to investigate the influence of the cement replacement content by slag, as well as the duration of curing on drying shrinkage, chloride ion penetration and compressive strength of concretes made with high early age strength cement and white Portland cement. Water-binder ratios of 0.30, 0.42 and 0.55, curing duration of 3 and 7 days, besides the cement replacement contents of 0%, 50% and 70% were investigated. In order to analyze the influence of the alkali activation on the properties investigated, a concrete made with 50% white Portland cement replacement content by slag and activated by sodium sulfate (4% in mass of binder) was used. The compressive strength was evaluated in the ages of 3, 7, 28 and 91 days; the drying shrinkage in the ages of 7, 14, 21, 28, 35, 56, 91 and 182 days, and the chloride ion penetration (immersion test in chloride solution) in the ages of 7, 14, 28, 56 and 91 days. Before being immersed in the chloride solution, the specimens were subjected to a drying period of 91 days. The results obtained revealed that an increase in the slag content decreased the compressive strength and the drying shrinkage values, besides the smaller depths of chloride penetration with both cements used. Reducing the curing duration resulted greater drying shrinkage and depth of chloride penetration for both cements, independently the slag content. / A retração hidráulica é um fenômeno que ocorre no concreto, submetido ou não a carregamento, devido à perda de umidade, uma vez exposto ao meio ambiente e permitida sua secagem. Ela é responsável por praticamente toda a deformação total por retração no concreto. Um elemento de concreto com restrição de deformação por retração pode desenvolver tensões que levam à formação de fissuras, através das quais agentes agressivos podem penetrar e causar algum dano à armadura, reduzindo sua resistência e durabilidade. O agente agressivo mais comum é o íon cloreto, o qual é considerado como a maior causa de corrosão prematura das barras de armaduras das estruturas de concreto, afetando sua estabilidade e vida útil. A corrosão de armaduras devido ao ingresso de íons cloretos da água do mar no concreto é universalmente conhecida como o fator de maior influência nos mecanismos destrutivos de estruturas marinhas. A utilização de adições minerais como a escória de alto forno, o aumento no prazo de cura e a redução na relação água/aglomerante são medidas que podem diminuir a penetração desses íons no concreto. Este trabalho teve por objetivo investigar a influência do teor de escória e do período de cura na retração hidráulica, na penetração de íons cloretos e na resistência à compressão axial de concretos compostos de cimento Portland de alta resistência inicial e cimento Portland branco estrutural. Foram adotadas relações água/aglomerante de 0.30, 0.42 e 0.55, teores de escória, em substituição ao cimento Portland, de 0%, 50% e 70%, além de períodos de cura de 3 e 7 dias. Foi empregada uma mistura composta de 50% de escória em substituição ao cimento Portland branco, ativada quimicamente por sulfato de sódio (4% da massa de aglomerante) para analisar a influência do ativador nas propriedades investigadas. As idades avaliadas para o ensaio de resistência à compressão foram de 3, 7, 28 e 91 dias; para retração hidráulica idades de 7, 14, 21, 28, 35, 56, 91 e 182 dias e, para penetração de íons cloretos (imersão em solução salina) as idades de 7, 14, 28, 56 e 91 dias. Antes de serem imersos em solução salina os corpos-de-prova foram submetidos a um período de secagem de 91 dias. Dos resultados obtidos, constatou-se que o aumento do teor de escória resultou em decréscimo nos valores de resistência à compressão, de retração e de penetração de cloretos para os dois cimentos investigados. A diminuição no período de cura resultou em maiores valores de retração e de penetração de cloretos, tanto no concreto branco quanto no cinza, independentemente do teor de escória utilizado.