Pour améliorer la durée de vie des matériaux à haute température et sous atmosphère oxydante, une solution est l’utilisation d’une protection de surface constituée de matériaux ultra réfractaires non oxydes. Un des objectifs principaux de cette thèse est la sélection et la validation expérimentale de nouvelles compositions chimiques de revêtements utilisés en condition oxydante et corrosive à ultra haute température. Les recherches s’appuient sur une démarche expérimentale physico-chimique se basant sur une approche thermodynamique et thermochimique menée au préalable pour choisir les composés. Les revêtements doivent être stables chimiquement, compatibles thermomécaniquement avec le substrat et adhérent de la température ambiante à celle d’utilisation. De plus, Ils doivent jouer le rôle de barrière environnementale et/ou de barrière thermique.Des tests d’oxydation sont réalisés au four solaire sur les systèmes de matériaux non oxydes massifs élaborés par frittage flash. En parallèle, des composites modèles constitués d’une fibre de carbone revêtue par PVD d’un revêtement métallique ultra réfractaire ont été élaborés puis chauffés par effet Joule afin de réaliser des tests d’oxydation. La compréhension des mécanismes entrant en jeu lors de l’oxydation de ces « nouveaux » revêtements est aussi un des challenges de ce manuscrit. Par ailleurs, elle aide à la classification de ces matériaux selon leur résistance à l’oxydation. / In order to improve material’s lifetime used at a temperature above 2500°C and under oxidizing atmosphere, a solution is to use a surfacing protection constituted of non oxide refractory materials. One of the main objectives of this thesis is to select and experimentally validate new chemical coating compositions which will be used under corrosive and oxidizing atmosphere at ultra high temperature (more than 2000°C). A preliminary thermodynamic and thermo-chemical study aims to select compounds. These compounds are then analyzed with physic-chemical tests. Coatings have to be chemically stable, thermo-mechanically compatible with the substrate and have to stick to the substrate from ambient temperature to more than 2000°C. Moreover, coatings have to act as an environmental barrier and/or as a thermal barrier.Two kinds of oxidation tests are made. On one hand, non oxide massive material’s systems are fabricated by spark plasma sintering in order to be tested at the solar furnace. On the other hand, composite models are fabricated by PVD. A carbon fiber is covered with ultra refractory metallic coating by PVD. Then, these composite models are heated by Joule effect in order to realize oxidation tests. Understanding mechanisms at work during the oxidation of these new coatings is another main objective of this thesis. This understanding will be also useful to classify these materials regarding their resistance to oxidation.

Elementos estruturais de Madeira Laminada Colada (MLC) têm sido muito utilizados na América do Norte e na Europa. Entretanto no Brasil há restrições quanto ao uso, principalmente, em razão da insegurança diante de potenciais riscos relacionados a incêndios. Este trabalho investigou o comportamento térmico e mecânico de elementos estruturais de MLC expostos à curva de incêndio-padrão ISO 834, preparados com duas espécies de madeira (Eucalyptus e Pinus) sem adição de tratamentos preservantes. Adicionalmente, elementos tratados com preservante ignífugo a base Borato de Cobre Cromatado (MOQ® OX 50CCBO) ou tratamento retardantes ao fogo (OSMOGUARD® FR100) também foram utilizados para analisar a influência na carbonização. O objetivo principal da pesquisa foi analisar a resistência ao fogo de elementos de MLC, avaliando a influência da espécie de madeira, a influência da densidade, bem como os efeitos dos tratamentos preservantes. O programa experimental foi realizado no forno horizontal a gás instalado no Departamento de Engenhara das Estruturas - EESC/USP, com dimensões internas de 3m x 4m x 1,5m, e as análises numéricas foram implementadas no pacote computacional ABAQUS. O modelo numérico, com vistas ao monitoramento a deflexão no meio do vão e a avaliação da distribuição da temperatura ao longo da profundidade dos elementos, foram desenvolvidos e os resultados obtidos foram comparados com os dados obtidos por meio das análises experimentais. Métodos de cálculo propostos por diferentes autores e regulamentações internacionais foram aplicados para verificação das propostas de dimensionamento em situação de incêndio. A comparação dos resultados mostrou que a utilização dos métodos de dimensionamento (simplificado ou avançado) representa risco à segurança contra incêndio caso utilize valores para a taxa de carbonização das espécies nacionais determinados a partir dos métodos de cálculo ou normas internacionais. / Structural elements of Glued Laminated Timber (glulam) have long been used in North America and Europe, but their use is still restricted in Brazil for safety reasons, especially related to potential risks in face of fire. The present work investigated the thermal and mechanical behavior of structural elements of glulam exposed to fire standard ISO 834. The glued laminated timber was produced from two wood species (Eucalyptus and Pinus) without any treatments. However, elements treated with wood treatments like Copper Chrome Boron (MOQ® OX 50 -CCB-O) or fire retardant treatment (OSMOGUARD® FR100) were also used to investigate their influence on charring. The main objective of this study was to assess the fire resistance of the glulam elements, evaluating the influence of wood species and, consequently, the influence of density, as well as the effects of preservative treatment. The experimental program was carried out in a gas oven, with internal dimensions of 3m x 4m x 1.5m, and the numerical analyses were performed by ABAQUS. The numerical analyses aimed to monitor the deflection in the middle of the span as well as the temperature distribution along the depth of the elements. The results obtained from both the experimental and numerical analyses were compared. Calculation methods proposed by different authors and international regulations have been applied for verification of the proposed design in fire. A comparison of the results show that the use of calculation methods (simplified and advanced) represents a risk to fire safety in case of using the values of char rate for Brazilian wood species determined from the calculation methods.

Made available in DSpace on 2014-07-29T15:18:24Z (GMT). No. of bitstreams: 1 pretextual.pdf: 140883 bytes, checksum: 5d9ee4b9b3884a0032825e604304580f (MD5) Previous issue date: 2009-09-28 / Increasing the durability of concrete structural elements is primordial, especially those related to power generation in eolic areas that are subjected to the phenomenon of reinforcement corrosion. In this context, this study aims to evaluate the overall protection ability of concrete to the phenomenon of reinforcement corrosion induced by chlorides. To this end, it was adopted a statistical program based on a fractional factorial design in which the variables studied were as follows: the water-binder ratio (0.35, 0.45 and 0.55), the type of mineral admixture (silica fume and blast furnace slag at specific levels), the type of corrosion inhibitor (calcium nitrite, sodium nitrite and amine) and the level of corrosion inhibitor (minimum and maximum recommended by each manufacturer). In the concrete investigations, the tests performed were corrosion potential, polarization resistance and electrochemical impedance. Throughout the experiments, it was possible to testify the beneficial effect of reducing the water-binder ratio. It was also possible to prove the very positive effect of the incorporation of mineral admixtures, especially of silica fume. The satisfactory performance of various inhibitors evaluated was also verified, specially when concrete contains mineral admixtures. A parallel study was conducted to make a comparative analysis of inhibitors at the same range of concentrations (at solid levels of 0.76%, 2.21% and 3.66% of the compound on the cement mass), nevertheless this study have demonstrated that fixing contents for all inhibitor is not appropriated, and the recommended dosages by the manufacturer is the best condition. As the levels recommended by manufacturers, it was found that the higher percentages have not worked well for sodium nitrite otherwise, for amine and nitrite calcium, the higher levels implied better results. Regarding the tannin inhibitor also assessed in the parallel study mentioned above (related to specific inhibitors), its good performance related to corrosion inhibition happened just for the content of 0.76% (the lowest levels). For the other contents, it was verified anomalous results. These results demonstrated that each type of corrosion inhibitor has its optimal concentration for use in concrete. Based on a cost-benefit analysis and evaluating the increase in the concrete value for cubic meter (in R$) in the presence of inhibitors at the same contents, it was verified a relative parity prices among the tested nitrites and an extremely high cost of amine. However, when performing the same analysis but using the levels recommended by the manufacturers for each inhibitor independent, it was found that the large disparity in prices between nitrite and amine was reduced considerably. An assessment of technical and economic feasibility was also performed based on the efficiency of corrosion inhibition and cost per cubic meter of concrete mixtures that did not show a typical depassivation of their stell bar up to the attack age evaluated / O aumento da durabilidade é um aspecto primordial para os elementos estruturais de concreto, em especial aqueles constituintes das estruturas de geração de energia em parques eólicos, sujeitos ao fenômeno de corrosão das armaduras. Nesse contexto, este trabalho tem como objetivo geral avaliar a capacidade de proteção de diferentes concretoS frente ao fenômeno da corrosão da armadura induzida por cloretos. Para tanto, foi adotado um planejamento estatístico baseado em um modelo fatorial fracionado em que as variáveis estudadas foram: a relação água/aglomerante (0,35; 0,45 e 0,55), o tipo de adição mineral (sílica ativa e escória de alto-forno, em teores específicos), o tipo de inibidor de corrosão (nitrito de cálcio, nitrito de sódio e amina) e o teor de inibidor de corrosão (mínimo e máximo recomendado por cada fabricante). Na avaliação dos concretos, foram realizados ensaios de potencial de corrosão, resistência de polarização e impedância eletroquímica. Ao longo de todo experimento foi possível constatar o efeito benéfico da redução da relação a/agl. Também foi possível verificar o efeito extremamente positivo da incorporação das adições minerais, em especial da sílica ativa. Constatou-se também o efeito positivo dos diversos inibidores avaliados, em seus teores mínimo e máximo, beneficio que se mostrou mais pronunciado quando da utilização conjunta com as adições minerais. Um estudo paralelo foi realizado para se fazer uma análise comparativa dos inibidores dentro da mesma faixa de teores empregados (teores de 0,76%; 2,21% e 3,66% de sólidos do aditivo em relação à massa de cimento), no qual se verificou que a utilização desses teores fixos para os diferentes tipos de inibidores não se mostrou tão eficiente quanto em relação à utilização dos aditivos na dosagem de recomendação do fabricante. Quanto a estes teores (recomendados pelos fabricantes), verificou-se que os percentuais mais altos não funcionaram bem para o nitrito de sódio, ao passo que para a amina e para o nitrito de cálcio os teores mais elevados resultaram em melhores resultados. Em relação ao tanino, inibidor que também foi avaliado no estudo paralelo referido anteriormente (específico sobre os inibidores), só houve algum resultado de inibição de corrosão para o teor de 0,76% (mais baixo dos teores), tendo-se obtido resultados anômalos para os outros 2 teores mais altos. Tais resultados permitiram constatar que cada tipo de inibidor de corrosão possui sua concentração ótima de utilização no concreto. Fazendo-se uma análise de custo e avaliando-se o acréscimo em Reais no valor do m3 do concreto proporcionado pelos diversos aditivos inibidores e nos teores de mesma faixa de emprego, verificou-se uma relativa paridade de preços entre os nitritos e um elevadíssimo custo da amina. No entanto, ao se realizar a mesma análise, mas utilizando os teores recomendados pelos fabricantes de cada inibidor, verificou-se que a grande disparidade de preços entre os nitritos e a amina foi reduzida de forma considerável. Uma avaliação da viabilidade técnico-econômica dos concretos também foi realizada, a partir dos dados de eficiência de inibição à corrosão e custo/m3 das misturas que não apresentaram comportamento típico de despassivação de suas armaduras até a idade de ataque considerada

Este trabalho consiste no estudo da obtenção de aglomerados autorredutores na forma de briquetes a frio tratados termicamente, utilizando minério de ferro e carvão fóssil como matérias-primas. Esta promissora tecnologia tem como premissa a utilização da termo-plasticidade do carvão fóssil para conferir resistência e promover a auto-aglomeração. A obtenção de briquetes dá-se através de três etapas: condicionamento da mistura, briquetagem a frio e tratamento térmico. Os finos de carvão e minério são misturados e homogeneizados. A mistura, então, passa por processo de briquetagem a frio para compactação, promove o aumento de contato entre as partículas de carvão e minério. Finalmente tratamento térmico é realizado para obter a forma de um corpo sólido e coeso de auto-aglomerado autorredutor. O objetivo deste trabalho é determinar as melhores condições de obtenção de briquetes através do estudo de variáveis ao longo do processo de fabricação, utilizando a resistência mecânica como parâmetro. As variáveis estudadas são: granulometria do carvão, envelhecimento do carvão, percentual de carvão na mistura, adição de aglomerantes, pressão de compactação na briquetagem e temperatura de tratamento térmico. Os resultados obtidos neste estudo indicam que estas variáveis afetam significativamente a resistência mecânica. Utilizando-se o carvão Chipanga, o melhor resultado de resistência à compressão foi de 19,82 Mpa. Foram consideradas as seguintes condições de fabricação: mistura na proporção de 75:25 (% em massa) de minério para carvão Chipanga, o carvão continha finos inferiores à 0,075 mm, sem a adição de aglomerantes, e o tratamento térmico foi realizado na temperatura de máxima fluidez do carvão. Além disto, foi observado que as partículas de minério de ferro foram concentradas nas regiões periféricas do briquete após tratamento térmico, e que o envelhecimento do carvão afeta negativamente a propriedade de termo-plasticidade. / This work is focused in the study of obtaining self-reducing cold briquettes of agglomerates, by using iron ore and coal as raw materials. This promising technology has its foundation on the thermo plasticity of coal to manage high mechanical resistance when it is compared with self-reducing pellets. Three steps mainly describes how to obtaining briquettes: mixture, cold briquetting and heat treatment. Fines of raw material are mixed and cold briquetting process results in a compact mixture. This might lead to closer contact between particles of iron ore and coal. Finally, heat treatment is performed to achieve a cohesive body and solid shape containing self-reducing agglomerated. The main purpose of this job is to comprehend the fundamentals on how to obtain self-reducing cold briquettes of agglomerated carbon and iron, by understanding the background of it variables along the manufacturing process, and using mechanical resistance as reference. The variables list is: the particle size of the coal, coal aging, percentage of coal in the mixture, adding binders, briquetting pressure and temperature of heat treatment. The results of this study indicate that these variables affect significantly the mechanical strength. Using Chipanga coal, the best compressive strength achieved was 19.82 MPa. It was considered the following manufacturing variables: the mixture ratio of 75:25 (wt% of iron ore and coal), fines of coal containing less than 0.075 mm, without binders, and heat treatment was performed at the temperature of coal´s maximum fluidity. Moreover, it was observed that the particles of iron ore were concentrated in the peripheral regions of the briquette after heat treatment, and that coal´s aging negatively affects the property of thermo-plasticity.

Abstract Pollutant (such as metals and sulphate) contamination exists in the wastewaters of many industries, including mining operations, metal plating facilities, and tanneries. Adsorption is one of the most commonly used processes for the removal of pollutants from waters and wastewaters due to its high efficiency and simple operation. Activated carbon is the most frequently used adsorbent material, although its high cost inhibits its widespread use in wastewater treatment. Therefore, there is a need to develop other adsorbents from alternative inexpensive raw materials such as locally available industrial and mineral waste and by-products. The aim of this thesis was to study the possibility of using industrial waste materials such as carbon residue, metakaolin, blast-furnace slag and analcime as an inexpensive sorbent for iron, copper, nickel, arsenic, antimony and sulphate removal from aqueous solutions. To enhance their adsorption capacity, different chemical treatments (i.e. activation, modification, geopolymerisation) were performed. As a result, the level of removal of iron, copper and nickel by carbon residue and zinc chloride activated carbon residue was higher than that by the commercial activated carbon. Iron chloride modified carbon residue was the most effective sorbent material for sulphate removal when compared to the other studied chemically modified/activated carbon residues. Blast-furnace slag and metakaolin geopolymers as well as their raw materials, were examined for the simultaneous removal of nickel, arsenic and antimony from the spiked mine effluent. In the case of blast-furnace slag, geopolymerisation clearly increased the efficiency of nickel, arsenic and antimony removal to a beneficial level. The barium chloride modified blast-furnace-slag geopolymer was a very efficient sorbent material for sulphate removal and it could thus be a technically feasible sulphate sorbent for wastewater treatment (e.g. in the mining industry in applications in which very low sulphate levels are desired). Barium chloride modified acid washed analcime could also be a potential sorbent for sulphate removal. / Tiivistelmä Teollisuuden jätevedet kuten kaivosvedet ja metalliteollisuuden prosessien jätevedet voivat sisältää monenlaisia haitallisia ja jopa myrkyllisiä aineita kuten metalleja ja sulfaattia. Adsorptiota käytetään yleisesti esimerkiksi metallien ja orgaanisten yhdisteiden poistossa vesiliuoksista, koska se on tehokas ja yksinkertainen menetelmä. Aktiivihiili on yleisimmin käytetty adsorbenttimateriaali vedenpuhdituksessa, mutta sen hinta joissain tapauksissa rajoittaa sen käyttöä. Tämän vuoksi on tarvetta kehittää vaihtoehtoisia adsorbenttimateriaaleja edullisista raaka-aineista. Viime vuosien aikana on raportoitu mm. teollisuus- ja mineraalijätteistä, joita voidaan hyödyntää vesien ja jätevesien puhdistuksessa. Tämän työn tavoitteena oli hyödyntää teollisuudesta muodostuvia jätemateriaaleja (hiilijäännös, metakaoliini, masuunikuona ja analsiimi) raudan, kuparin, nikkelin, arseenin, antimonin tai sulfaatin poistossa malli- ja jätevesistä. Materiaaleja käsiteltiin erilaisilla kemikaaleilla (aktivointi, modifiointi tai geopolymerointi), jotta niiden adsorptiotehokkuudet paranisivivat poistettavia aineita kohtaan. Tulokset osoittivat, että raudan, kuparin ja nikkelin poisto oli sekä käsittelemättömällä että sinkkikloridilla aktivoidulla hiilijäännöksellä korkeampi kuin kaupallisella aktiivihiilellä. Arseenin, nikkelin ja antimonin poistoa kaivosvedestä tutkittiin masuunikuona- ja metakaoliinigeopolymeereillä, joista masuunikuonageopolymeeri osoittautui tehokkaimmaksi metallien poistajaksi. Bariumkloridilla modifioitu masuunikuonageopolymeeri puolestaan poisti erittäin tehokkaasti sulfaattia kaivoksen jätevedestä. Rautakloridilla modifioitu hiilijäännös ja happopesty bariumkloridilla modifioitu analsiimi osoittatuivat myös lupaavaksi materiaaliksi sulfaatin poistossa.

L’objectif de la thèse est de comprendre le comportement géochimique de l’arsenic dans les remblais miniers en pâte cimentés. Cette technique est employée depuis plusieurs années pour remblayer les galeries de mine exploitées à l’aide des rejets de concentrateurs. Pour cette étude, deux types de remblais sont élaborés en laboratoire : des échantillons de remblai minier en pâte synthétiques, fabriqués à partir de silice et enrichis artificiellement en arsenic, et des remblais miniers en pâte élaborés à partir de rejets miniers arséniés. Dans les deux cas, différents liants cimentaires sont testés. Plusieurs types d’investigations sont menés sur les échantillons de remblai en pâte cimentés. Une caractérisation minéralogique est effectuée à l’aide de divers outils. En parallèle, les échantillons de remblais sont soumis à différents tests de lixiviation complémentaires, afin d’évaluer la mobilité/rétention de l’arsenic dans ces matrices. Enfin, une modélisation géochimique est mise en œuvre à partir des résultats issus des deux études précédentes, afin d’affiner les connaissances sur la nature et la stabilité des composés arséniés dans les remblais étudiés. Les résultats obtenus indiquent que l’arsenic est mieux stabilisé dans les matrices à base de ciment Portland et de laitier de haut-fourneau que dans les remblais à base de cendres volantes. Le comportement à la lixiviation variable d’une matrice à l’autre s’explique par des spéciations et des mécanismes de piégeage de l’arsenic variés. L’arsenic peut précipiter sous forme de minéraux arséniés, principalement sous forme d’arséniates de calcium, mais aussi de divers autres composés secondaires variables d’une matrice à l’autre. Un piégeage physique des grains de rejets miniers arséniés par les hydrates cimentaires peut aussi avoir lieu, par formation d’un revêtement limitant l’oxydation des sulfures porteurs d’arsenic. Tous ces mécanismes interviennent dans la stabilisation/solidification de l’arsenic. / The objective of this study is to understand the geochemical behaviour of arsenic in cemented paste backfills. This technique consists in transporting the tailings in the mine openings. Two types of backfills are prepared in the laboratory for this study. First, synthetic cemented paste backfills artificially spiked with arsenic are synthesized, using silica in replacement of the tailings. In parallel, other cemented paste backfill specimens are prepared with arsenic-rich tailings. In the two cases, various types of hydraulic binders are tested. Several types of investigations are conducted on the cemented paste backfill specimens. A mineralogical characterization is carried out with the help of specific tools. At the same time, cemented paste backfill samples are submitted to several complementary leaching tests, to assess the mobility/immobilization potential of arsenic in these matrices. Finally, geochemical modeling is implemented, based on the results of the two previous studies, in order to refine the understanding of the nature and stability of the arsenic compounds. The results show that arsenic is better immobilized in Portland cement and slag-based matrices, rather than in fly ash-based matrices. The variable leaching behaviour from a given matrix to another is due to different arsenic trapping mechanisms. Arsenic can precipitate and form several arsenic minerals, mainly calcium arsenates, but also various other secondary compounds, which are different from a matrix to another. Physical entrapment of the tailings grains by the cementitious minerals can also occur, by formation of a coating around the grains, limiting the oxidation and dissolution of arsenic-bearing sulfides (passivation). These mechanisms are involved in the stabilization/solidification of arsenic by cemented paste backfills.

L’étude menée s’attache à évaluer le potentiel d’activation du laitier de haut fourneau dans un liant ternaire constitué de ciment alumineux, de sulfate de calcium et de laitier. Dans ce système ternaire, le constituant majoritaire est le sulfate de calcium. Le potentiel d’un tel système n’est pas encore connu mais cette étude vise à renseigner sur les principaux avantages et limites d’utilisation. D’un point de vue des propriétés d’usage de ce liant, la prise, le durcissement rapide et la montée des résistances sont assurés par le liant ettringitique. Ensuite, et uniquement si la dessiccation est évitée, le laitier de haut fourneau réagit et dans ce cas, l’apport du laitier dans de tels systèmes est double. Il contribue à l’augmentation des performances mécaniques à moyen et long terme et à limiter l’expansion sous eau. D’un point de vue de la compréhension des mécanismes d’hydratation, une démarche expérimentale originale est mise en place et dévoile le potentiel du laitier. Elle est basée sur la comparaison des performances obtenues avec différentes cures. Le potentiel d’hydratation du laitier est amplifié lorsque le système subit un séchage puis une réhydratation. Cependant, les techniques utilisées (diffraction des rayons X et calorimétrie différentielle à balayage) ne sont pas adaptées au suivi et à la quantification de laitier consommé. Ainsi, la compréhension de l’hydratation s’appuie sur des techniques dites indirectes. Une semi-quantification par diffraction des rayons X est réalisée pour le suivi et l’évaluation de la mayénite, le sulfate de calcium (anhydre ou dihydraté), la syngénite et l’ettringite, l’analyse thermogravimétrique permet de mesurer le degré d’hydratation du système, et la porosimétrie mercure informe sur les changements microstructuraux. La plus grosse difficulté dans ces travaux a porté sur le suivi et la quantification des phases amorphes (anhydres ou hydratées), telles que le laitier, les gels de C-S-H et d’AH3, et c’est pour cette raison qu’une approche par modélisation a été mise en place afin d’identifier le rôle de chaque constituant du système ternaire [Ciment Alumineux – Sulfate de Calcium – Laitier] et particulièrement du laitier lors de l’essai de réhydratation. L’approche par modélisation permet de mieux identifier les phénomènes chimiques et physiques ayant lieu lors de l’hydratation du liant. Elle est utilisée pour expliquer les observations macroscopiques (comme les performances mécaniques) et aide à déterminer les cinétique d’hydratation dans le milieu poreux. Le modèle utilisé n’est pas encore parfaitement au point mais il a permis d’identifier les différentes séquences d’hydratation (à savoir que le liant ettringitique réagit dans les premiers instants et qu’ensuite, l’hydratation de l’anhydrite entraine la formation de gypse et l’hydratation du laitier est effective à long terme) et de confirmer que la réaction du laitier est lente. / The potential of activation of a Ground Granulated Blast Furnace Slag has been evaluated into a ternary system comprising of a Calcium Sulfate as major component and a Calcium Aluminate Cement. This system is not well known and the main goal of this study is to determine its main advantages and limitations. From the usage properties point of view, fast setting and initial strengths are governed by the ettringitic binder. Then, and only if the dehydration is avoided, slag reacts. In this case, slag contributes to the increase of mechanical performances at medium and long terms and to limit the expansion under water. From an understanding point of view, the original experimental approach reveals the potential of the slag. It is based on a comparison of performances with different types of curing methods. The potential of hydration of the slag is amplified when the system is dehydrated during a few days and then rehydrated. However, slag contribution is complex to establish because analytical methods to follow-up slag consumption (such as X-ray Diffraction and Differential Scanning Calorimetry analysis) are not well adapted. So, to understand the hydration mechanisms, indirect approaches are used. Semi-quantitative methods by X-ray Diffraction to follow-up the mayenite, calcium sulfate, syngenite and ettringite, ThermoGravimetric Analysis to measure degree of hydration and Mercury Intrusion Porosimetry to identify microstructural changes have been carried. The most important difficulty concerns the identification and quantification of amorphous phases such as slag, C-S-H and AH3. That is why a modelling approach is necessary to understand the role of each compound in the ternary mixture and in particular the obvious contribution of slag during rehydration test. This modelling approach increases knowledge of the physical and chemical phenomena in this ternary binder. It is useful to explain the observed macroscopic properties such as strength and helps to determine the kinetics of hydration in porous environment. Even if this model is still under development, it has allowed identifying the sequences of hydration (ettringitic binder reacts at very initial time, then anhydrite transforms into gypsum and slag reacts at long term) and confirms therefore that the reaction of slag is slow.

Abstract Most of the steel produced in the world is based on the integrated blast furnace-converter route, which is based on the use of virgin raw materials. Large amounts of fossil-based, carbon containing reductants are used in blast furnaces, which results in carbon dioxide emissions into the atmosphere. Fossil carbon dioxide emissions from steel production can be reduced by new technologies or moving from non-renewable to renewable energy sources. Biomass-based reductants could be one way to reduce the specific emissions from blast furnace-based steel production. The aim of this thesis was to examine the techno-economic and CO₂ mitigation potentials of using bioreducers in blast furnace ironmaking. Bioreducer feasibility was analyzed in the Finnish context, but the research methods used can be applied more widely. The metallurgical properties of bioreducers were evaluated and compared to fossil-based reductants. The impact of bioreducers on blast furnace behavior and on other steel plant processes was evaluated, with an emphasis on the reductions achieved in CO₂ emissions at the plant scale. The CO₂ emissions, energy consumption and production costs of bioreducers were evaluated, as was the availability of energy wood for bioreducer production. The results show that solid, liquid and gaseous bioreducers can be produced with thermochemical conversion technologies. However, their suitability for blast furnace use varies greatly. The highest substitution of fossil-based reductants in a blast furnace is achieved with charcoal injection. The carbon footprint of torrefied wood, charcoal and Bio-SNG is moderate compared to fossil-based reducing agents and their production is energetically feasible. The economic feasibility of bioreducers is currently weak in comparison to fossil-based reducing agents, but competitive when compared to other CO₂ emission reduction measures such as carbon capture and storage. The biomass availability assessment revealed that sufficient amount of energy wood could be available for bioreducer production in the areas where Finnish steel plants are situated. The feasibility of bioreducer production could be improved by producing a number of products from the biomass and taking advantage of the process of integration possibilities. / Tiivistelmä Suurin osa maailmassa tuotetusta teräksestä valmistetaan integroidulla masuuni-konvertteri reitillä, joka perustuu neitseellisten raaka-aineiden käyttöön. Masuuniprosessissa käytetään suuri määrä fossiilisia, lähinnä hiilipohjaisia pelkistimiä, jotka aiheuttavat hiilidioksidipäästöjä ilmakehään. Fossiilisia hiilidioksidipäästöjä voidaan teräksenvalmistuksessa vähentää uusilla teknologioilla tai siirtymällä uusiutumattomista energialähteistä uusiutuviin. Biomassasta valmistetut pelkistimet voisivat olla yksi mahdollinen keino alentaa masuunipohjaisen teräksenvalmistuksen ominaispäästöjä. Tämän työn tavoitteena oli tarkastella biopelkistimien käytön teknistaloudellista potentiaalia masuunikäytössä ja aikaansaatavia hiilidioksidipäästövähenemiä eri systeemirajauksilla. Työssä keskityttiin tarkastelemaan biopelkistimien hyödynnettävyyttä lähinnä Suomen tasolla, vaikka käytetyt tutkimusmetodit ovat sovellettavissa myös laajemmin. Työssä arvioitiin biopelkistimien metallurgisia ominaisuuksia, niiden vaikutusta masuuniprosessiin ja laajemmin muihin terästehtaan prosesseihin, pääpainon ollessa saavutettavan CO₂ päästövähenemän tarkastelussa. Työssä tarkasteltiin biopelkistimien valmistuksen CO₂ päästöjä, energiankulutusta ja tuotantokustannuksia sekä energiapuun saatavuutta biopelkistimien tuotantoon. Tulokset osoittavat, että biomassasta voidaan valmistaa kiinteitä, nestemäisiä ja kaasumaisia pelkistimiä termokemiallisilla konversioteknologioilla, joiden soveltuvuus masuunikäyttöön vaihtelee suuresti. Masuuniprosessissa suurin fossiilisten pelkistimien korvaavuus saavutetaan käyttämällä puuhiili-injektiota. Torrefioidun puun, puuhiilen ja Bio-SNG:n hiilijalanjälki on varsin maltillinen verrattuna fossiilisiin pelkistimiin ja niiden tuotanto on energeettisesti järkevää. Biopelkistimien taloudellinen kannattavuus verrattuna fossiilisiin pelkistimiin on tällä hetkellä heikko, mutta kilpailukykyinen verrattuna muihin CO₂ päästöjen vähennyskeinoihin, kuten hiilidioksidin talteenottoon ja -varastointiin. Energiapuun saatavuus biopelkistimien valmistukseen on suurin alueilla, jotka sijaitsevat lähellä Suomen terästehtaita. Biopelkistimien tuotannon kannattavuutta voitaisiin parantaa tuottamalla useita tuotteita ja hyödyntämällä prosessi-integraatiota.

La production d’électricité par voie solaire apparait comme la solution la plus prometteuse pour l’avenir, tant en termes de coûts que de pollution. Cependant, afin d’atteindre le niveau de technologie requis pour envisager l’implémentation de telles centrales à grande échelle, plusieurs verrous technologiques et scientifiques sont encore à lever.Dans cette optique, les récepteurs/absorbeurs volumiques pourraient permettre d’atteindre de plus hautes températures que les récepteurs surfaciques (technologie actuellement utilisée dans les tours solaires à concentration), permettant l’usage de cycles thermodynamiques à haute rendement, tels que les cycles Brayton. Via le projet ANR-OPTISOL, la thèse présentée ici veut répondre en partie à ces problématiques par l’étude des absorbeurs solaires volumiques :- Une étude expérimentale des mousses céramiques utilisées comme absorbeur solaire volumique haute température a été menée au laboratoire CNRS-PROMES (UPR 8521). Une expérience a été conçue afin de tester des échantillons de 5cm de diamètre soumis au flux solaire concentré en conditions quasi-1D au foyer d’un four solaire à axe vertical ;- Un code de calcul des transferts thermiques couplés en milieu poreux a été développé utilisant l’hypothèse de « milieu homogène équivalent », puis validé sur les campagnes expérimentales ;- Finalement, un algorithme d’optimisation par essaim de particules a été utilisé afin de déterminer les propriétés géométriques optimales de mousses céramiques maximisant l’efficacité de conversion thermosolaire. / Solar-to-electricity power plants appear to be the most promises way for large electricity production in the future, in terms of costs as well as environmental impacts. Thus, reaching the required technology level still requires research and innovations in order to implement such power plants at large scale.In this context, volumetric solar receivers/absorbers could allow us to reach higher temperatures in comparison to surface receivers (actual concentrating solar power technology used in solar towers), leading to high efficiency thermodynamical cycles such as Brayton cycles. With the ANR-OPTISOL project, this thesis tends to give new answers on volumetric solar absorbers using ceramic foams:- Experimental studies of open pores ceramic foams used as high temperature volumetric solar absorber have been conducted at CNRS-PROMES laboratory (UPR 8521), with designed of a dedicated experiment for 5cm diameter samples operating under quasi-1D conditions submitted to concentrated solar power at the focal point of a vertical axis solar furnace;- A numerical code has been developed in order to solve coupled heat transfers in porous medium using the “equivalent homogeneous medium” hypothesis, then validated on the experimental campaigns;- Finally, an optimization algorithm has been used (“particle swarm optimization”) aiming the identification of the optimal geometrical characteristics maximizing the solar-to-thermal efficiency of ceramic foams.

Carbon dioxide emissions to the atmosphere today cause problems around the world. In Sweden, the steel production contributes significantly to carbon dioxide emissions. The steel industry challenge is to improve the metallurgical processes to decrease the carbon dioxide emissions. One way to reduce the emissions is to use renewable carbon sources. The blast furnace process is a counter current reduction process for ironmaking. Raw materials such as iron ore agglomerates, coke and slag formers are charged at the top of the furnace while oxygen-rich blast air and powdered coal are injected in the bottom. The gases produced by combustion rise through the burden on the top of the furnace. The combustion of carbon produces carbon monoxide which is the reducing gas used for the reduction of iron oxides to pig iron. The process is the highest producer of CO2 emissions in Sweden; biomass can partially replace fossil carbon in coal blends for cokemaking, coal powder for coal injection and coke in self-reducing briquettes.  The purpose of this project was to maximize the addition of biomass in coal blends for cokemaking and the addition in briquettes produced for the recovery of iron bearing rest products. The challenge with biomass in cokemaking is its low density and high reactivity which decrease the coke yield and coke strength at the same time that it increases the coke reactivity. The coke quality has to be kept at sufficient quality in order to avoid effects on productivity and process stability in the blast furnace. The addition of biomass in briquettes is limited due to the low density of the biomass which may affect the strength of the briquettes. The effect of the addition of sawdust in coke and briquettes has been studied to understand the effect on reaction behaviour of bio-coal. Heat-treatment of sawdust with high volatile coal was performed in order to achieve a coating of coal on the sawdust surface and get less reactive sawdust. Torrefied sawdust contained 23 wt. % fixed carbon while the pre-treatment of sawdust with high volatile coal increased the content to about 60 wt. %. Pre-treated sawdust was added to coal blend for coke making and briquettes containing iron oxide. The pre-treated sawdust was added to five coal blends for coke production, the contents were 5, 10 and 20 wt. %, and a base blend was used as reference. Coke reactivity, chemical composition and cold compression strength in coke were studied. This work resulted in an improved bulk density; up to 20 wt. % pre-treated sawdust could be added to the coal blend and still keep a bulk density of 800 kg/m3. The coke yields in cokes with pre-treated sawdust were comparable to the coke reference. The temperature at which carbon in coke began to be consumed was slightly higher in coke containing sawdust treated with 50 wt. % high volatile coal. It was estimated that the CO2 emission from fossil coal could be reduced with 8.6 % per ton hot metal (THM) with the addition of 10 wt. % pre-treated sawdust to coal blends for cokemaking. The addition of 20 wt. % pre-treated sawdust could reduce the CO2 emission with 10% per THM. In addition, two different mixes of briquettes were produced, one with torrefied sawdust and one with pre-treated sawdust. The chemical composition and reduction of iron oxides in briquettes was also studied and evaluated. Briquettes with treated sawdust were more compact, i.e. had a higher density than briquettes containing torrefied sawdust. The amount of hematite that could be added to the briquette mixes was 0.107 moles in briquettes with torrefied sawdust and 0.112 moles in briquettes with pre-treated torrefied sawdust. / Koldioxidutsläppet till atmosfären orsakar idag problem runt om i världen. I Sverige bidrar stålproduktionen avsevärt till koldioxidutsläppet. Stålindustrin har som en utmaning att förbättra de metallurgiska processerna för att sänka utsläppet av koldioxid. Ett sätt att sänka koldioxidutsläppen är att minska påverkan genom att använda förnybara kolkällor. Masugnsprocessen är en kontinuerlig reduktionsprocess för råjärnframställning och en av processerna där det används reduktionsmedel från fossila kolkällor. Råmaterial som järnmalm, koks och slaggformare chargeras på toppen av ugnen medan syrgasberikad blästerluft och pulveriserat kol injiceras i botten av ugnen genom masugnens formor. De gaser som produceras vid förbränning stiger upp genom beskickningen upp till ugnens topp. Vid förgasning av kol bildas kolmonoxid som är den reducerande gasen, den möjliggör reduktionen av järnoxider vid framställning av råjärn. Torrefierad biomassa kan delvis ersätta fossilt kol i kolblandningarna för kokstillverkning, i kolinjektionen och i briketter. Syftet med detta projekt var att maximera mängden tillsatt biomassa i kolblandningarna för kokstillverkning och i briketter för återvinning av järnbärande restprodukter. Utmaningen med biomassa i kokstillverkningen är den höga reaktiviteten och den låga densiteten av kol, vilket resulterar i låg koksutbyte när den tillsätts i kolblandningar. Biomassa innehåller också en högt halt flyktiga ämnen vilket resulterar i koks med låg hållfasthet och hög reaktivitet. Kokskvalitén måste behållas för att undvika processvariationer i masugnen. Tillsatsen av biomassa i briketter, är begränsat då biomassa kan påverka briketternas hållfasthet. Effekten av tillsatsen av biomassa i koks och briketter har studerats för att kunna förstå reaktionsbeteendet i dessa när torrefied sågspån och förbehandlat sågspån med hög fluiditetskol har tillsatts till blandningarna. Värmebehandling av torrifierat sågspån med en hög fluiditeteskol gjordes för att uppnå en mindre reaktiv biomassa. Torrifierat sågspån innehöll 22.9 viktsprocent kol, förbehandlingen av sågspån med hög fluiditetskol ökade halten till cirka 60 viktsprocent. Den behandlade sågspånen tillsattes till fem kolblandningar för koksframställning, 5, 10 och 20 viktprocent tillsattes till en bas blandning som användes referens. Koksreaktiviteten, kemisk sammansättning och hållfasthet i koks studerades. Arbetet resulterade i en förbättrad bulkdensitet då upp till 20 viktprocent förbehandlad biomassa kunde tillsättas i kolblandningen och fortfarande behålla en bulkdensitet på 800 kg/m3. Koksutbytet i alla koks med förbehandlat sågspån var jämförbart med koksreferensen. Temperaturen där kemisk kol i koks började förbrukas, var något högre i koks som innehöll sågspån med 50 viktsprocent hög fluiditetskol. Koldioxidutsläppen från fossilt kol per ton råjärn (THM) uppskattades att vara 8,6 % lägre med tillsatsen av 10 viktprocent förbehandlat sågspån i kolblandningar för kokstillverkning. Tillsatsen av 20 viktprocent skulle innebära en minskning på 10 % per ton råjärn. Briketter med två olika blandningar framställdes, en blandning med torrifierat sågspån och en blandning med behandlat sågspån. Briketterna karakteriserades genom att analysera den kemiska sammansättningen och reduktionen av järnoxider i termisk reducerade briketter. Briketter med behandlat sågspån var mer kompakta, d.v.s. hade en högre densitet än briketter som innehöll torrifierad sågspån. Mängden hematit som kunde tillsättas i mixen med torrifierad sågspån var 0.107 mol, medan i mixen med förbehandlat sågspån 0.112 mol kunde tillsättas. / Bio4metals / CAMM