Geopolymers are a relatively new class of materials that have many broad applications, including use as substitute for ordinary Portland cement (OPC), use in soil stabilisation, fire resistant panels, refractory cements, and inorganic adhesives. Geopolymers are an alternative binder to Portland cement in the manufacture of mortars and concrete, as its three-dimensional alumino silicate network develops excellent strength properties. Use of geopolymers in place of ordinary Portland cement is also favoured owing to the possible energy and carbon dioxide savings. Geopolymer is typically synthesized by alkali activation of pozzolanas at moderate temperatures (< 1000C). The focus of the thesis is synthesis and characterization of geopolymers as construction materials. In this context, the role of compositional factors, such as, pozzolana type (fly ash, kaolinite, metakaolinite, ground granulated blast furnace slag, red soil), alkali (sodium hydroxide is used in this study) activator concentration, Si/Al (Si= silicon, Al = aluminium) ratio of the pozzolana and environmental factors, namely, curing period and temperature are examined. Besides synthesizing geopolymers that could be an alternate to concrete as construction material, sand-sized aggregates were synthesized using geopolymer reactions. This was done as river sand is becoming scarcer commodity for use as construction material. Several compositional and environmental factors were varied in geopolymer synthesis in order to identify the optimum synthesis conditions that yield geopolymers with maximum compressive strength. Besides varying external (compositional and environmental) factors, the role of internal microstructure in influencing the compressive strength of the geopolymer was examined. Micro-structure examinations were made using X-ray diffraction (XRD), scanning electron microscopy (SEM) and mercury intrusion porosimetry (MIP) studies. The studies on compositional and environmental factors in geopolymer synthesis brought out several interesting results. The results firstly brought out that amongst the pozzolanas studied, ASTM class F fly ash is most suited for maximum compressive strength mobilization upon geopolymer reactions. Moderate temperature (75-1000C) was adequate to mobilize large compressive strengths. Room temperature curing needed more than 7 days before the pozzolana-NaOH paste began to develop strength. Curing period of 56 days was needed for the geopolymer to develop significant strength (19.6MPa). A similar range of compressive strength could be developed by the pozzolana-NaOH paste upon curing for 3 days at 1000C. Likewise curing the pozzolana-NaOH paste at temperatures > 1000C led to reduction in compressive strength from shrinkage and breakage of bonds. A caustic soda (NaOH) concentration of 10 M was adequate to develop maximum compressive strength of the geopolymer. Caustic soda concentrations in excess of 10 M did not result in further improvement of strength. The Si/Al ratio also contributes to strength mobilization. The Si/Al ratio of the geopolymer was enhanced by mixing commercially obtained silica gel with the pozzolana. Maximum strength mobilization was observed at Si/Al ratio = 2.45 corresponding to 6.5 % silica gel addition to the pozzolana (on dry mass basis). Comparing compressive strengths of geopolymers with varying silica gel contents, geopolymer specimens with least water content and largest dry density did not exhibit maximum compressive strength indicating that the physico-chemical (bond strength, micro-structure) played a pivotal role than physical parameters (dry density, water content) in dictating the strength of the geopolymer. MIP results showed that bulk of the porosity in fly ash geopolymer specimens is contributed by macro pores and air voids. Geopolymerization leads to bulk consumption of cenospheres in fly ash and forms polymerized matrix with network of large pores. After geopolymerization, all the main characteristic peaks of Al–Si minerals observed in fly ash persisted, suggesting that no new major crystalline phases were formed. Presence of small amount of inorganic contaminants in fly ash can drastically reduce the strength of the fly ash geopolymer. For example, 5-20 % presence of red soil reduces the strength of fly ash geopolymer by 16 to 59 %. Presence of unreacted clay coupled with less porous structure is responsible for the reduction in compressive strength of fly ash geopolymer subjected to red soil addition. MIP studies with geopolymers also revealed that there is good bearing between compressive strengths and maximum intruded volume (from MIP test) of geopolymers. For example, fly ash geopolymer specimen exhibits highest total intruded volume (0.3908 cc/g) and largest compressive strength of 29.5 MPa, while red soil geopolymer specimen exhibit least intruded volume (0.0416 cc/g) and lowest compressive strength (5.4 MPa). Further, analysis showed that specimens with larger airvoids+macropores volume had larger compressive strength, suggesting that geopolymers with more porous microstructure develop larger compressive strength. All geopolymer specimens exhibited tri-modal nature of pores i.e. macro-pore mode (entrance pore radius: 25-5000 nm), mesopore mode (entrance pore radius: 1.25 to 25 nm) and air void mode (entrance pore radius >5000 nm). The micro pores (entrance pore radius < 1.25 nm) do not contribute to porosity of the geopolymer specimens. Sand particles prepared from geopolymer reactions (FAPS or fly ash geopolymer sand) predominated in medium sized (2mm to 0.425 mm) sand particles. Their particle size distribution characteristics (uniformity coefficient and coefficient of curvature) classified them as poorly graded sand (SP). Dissolution, followed by polymerization reactions led to dense packing of the Si–O–Al–O– units that imparted specific gravity of 2.59 to FAPS particles which is comparable to that of river sand (2.61). Dissolution in strongly alkaline medium imparted strongly alkaline pH (12.5) to the FAPS particles. The river sand is characterized by much lower pH (7.9). Despite being characterized by rounded grains, the FAPS particles mobilized relatively high friction angle of (35.5o) than river sand (∅ = 28.9o). The river sand-mortar (RS-M) and fly ash geopolymer sand-mortar (FAPS-M) specimens developed similar 28-day compressive strengths, 11.6 to 12.2 MPa. Despite its higher water content, FAPS-mortar specimens developed similar compressive strength and initial tangent modulus (ITM) as river sand-mortar specimens. The FAPS-M specimen is more porous (larger intruded volume) with presence of larger fraction of coarser pores. Total porosity is majorly contributed by macro-pores (67.92%) in FAPS-M specimen in comparison to RS-M specimen (macro-pores = 33.1%). Mortar specimens prepared from FAPS and river sand exhibit similar pH of 12.36 and 12.4 respectively. FAPS-mortar specimens have lower TDS (1545 mg/L) than river sand-mortar specimens (TDS = 1889 mg/L). The RS-M and FAPS-M specimens exhibit leachable sodium levels of 0.001 g Na/g RS-M and 0.007 g Na/g-FAPS-M respectively in the water leach tests. The larger leachable sodium of FAPS-M specimen is attributed to residual sodium hydroxide persisting in the FAPS even after washing. The ultra-accelerated mortar bar test (UAMBT) shows that the percentage expansion of FAPS-M and RS-M specimens are comparable and range between 0.07 to 0.08 %.

Ce travail de recherche porte sur la modélisation mathématique des principaux procédés sidérurgiques en suivant une approche systémique. L’objectif est d’élaborer un outil de modélisation de l’ensemble de la filière destiné à l’optimiser du point de vue énergétique et environnemental. Nous avons développé des modèles physico-chimiques du haut fourneau, de la cokerie, de l’agglomération et du convertisseur. Ces modèles ont ensuite été reliés entre eux sous forme d’un diagramme de flux unique en utilisant le logiciel ASPEN Plus. Dans une première partie, nous nous sommes particulièrement intéressés au haut fourneau à recyclage, une variante innovante du haut fourneau dans laquelle les gaz de gueulard sont recyclés et réinjectés aux tuyères après capture du CO2. Nous avons testé une réinjection à un niveau (aux tuyères) et à deux niveaux (tuyères et ventre). Les résultats ont été comparés avec succès à des données expérimentales issues d’un réacteur pilote et montrent que le recyclage permet une baisse de plus de 20 % des émissions de CO2 du haut fourneau. Le recyclage à deux niveaux ne semble pas plus performant que celui à un seul niveau. Dans un deuxième temps, nous avons simulé le fonctionnement d’une usine sidérurgique intégrée dans son ensemble. Différentes configurations ont été testées, pour un haut fourneau classique ou un haut fourneau à recyclage, en considérant un éventuel recyclage du laitier de convertisseur à l’agglomération, et en étudiant l’influence de la teneur en silicium de la fonte sur toute la filière. On montre notamment qu’il est possible de réduire le prix de revient de la tonne d’acier en substituant et recyclant différents sous-produits / This research study deals with mathematical modeling of the main steelmaking processes following a systems approach. The objective was to build a modeling tool of the whole steelmaking route devoted to its energetic and environmental optimization. We developed physical-chemical models for the blast furnace, the coke oven, the sintering plant and the basic oxygen furnace. These models were then linked together in a single flow sheet using the ASPEN Plus software. First, we focused on the top gas recycling blast furnace, a novel variant of the blast furnace in which the top gas is recycled and re-injected into the tuyeres after CO2 removal and capture. We tested both a reinjection at one level (tuyeres only) and at two levels (tuyeres and shaft). The results were successfully compared with experimental data from a pilot reactor and demonstrate that recycling can lower the blast furnace CO2 emissions by more than 20%. Recycling at two levels does not seem more efficient than at a single level. Second, we simulated the operation of an entire integrated steelmaking plant. Different configurations were tested, using a conventional blast furnace or a top gas recycling blast furnace, considering a possible recycling of the converter slag to the sintering plant, and studying the influence of Si content in the hot metal on the entire steelmaking plant operation. We show that it is possible to reduce the cost of producing steel by substituting and recycling various by-products

The process industries span multiple industrial sectors and constitute a substantial part of the entire manufacturing industry. Since companies belonging to this family of industries are often very asset intensive, their ability to respond to changes is often limited in the short term. The adaptation of the capabilities of existing processes, and conversely finding products and market segments to match the production system capabilities, are an important part of product- and market development activities in the process industry. The importance to companies in the process industry of having a well-articulated manufacturing strategy congruent with the business strategy is second to none. However, to facilitate manufacturing strategy developments, it is essential to start with an improved characterization and understanding of the material transformation system. To that end an extensive set of variables was developed and related measures and scales were defined. The resulting configuration model, focusing on company generic process capabilities in the process industries, is to be regarded as a conceptual taxonomy and as a proposition available for further testing. The usability of the model was subsequently assessed using “mini-cases” in the forestry industry, where the respondents confirmed that the company’s overall strategy could benefit from this kind of platform as a possible avenue to follow. The model was deployed as an instrument in the profiling of company material transformation systems to facilitate the further development of companies' functional and business strategies. The use of company-generic production capabilities was studied in three case companies representing the mineral, food and steel industries. The model was found by the respondents to be usable as a knowledge platform to develop production strategies. In the final analysis of the research results, a new concept emerged called “production capability configuration": A process-industrial company’s alignment of its generic production capabilities in the areas of raw materials, process technology and products to improve the consistency among the variable elements that define operations and improve the congruence between operations and its environment. From the perspective of value creation and capture, firms must be able to manufacture products in a competitive cost structure within the framework of a proper business model. By using the configuration model, the relationship between manufacturing and innovation activities has been studied in the previously mentioned three case studies. In many cases the gap in capability appears as a limitation in the production system, requiring development efforts and sometimes investments to overcome. This is illustrated with two examples from the steel industry, where development efforts of the production system capabilities are initiated to better match the market demands. One example is the increase the volume- and product flexibility of an existing stainless steel melt shop, resulting in a proposed oblong Argon Oxygen Decarburisation (AOD) converter configuration that was subsequently verified using water modelling. The second example is from a carbon steel mill, where the target was to increase the raw material- and volume flexibility of another melt shop, by modifying the capabilities of the Electric Arc Furnace (EAF). Enabling EAF technologies are further described and evaluated using operational data and engineering type of estimates. / <p>QC 20170116</p>

La compréhension des mécanismes à l’origine de la formation de la porosité et de ses propriétés dans les matériaux cimentaires est un enjeu majeur pour l’évaluation de leur durabilité. L’utilisation des laitiers de haut fourneau comme liant hydraulique modifie les phases formées, leur proportion et la microstructure des mortiers et bétons. Il reste un grand nombre de verrous scientifiques à lever concernant les paramètres modifiant les valeurs de porosité, le rayon des capillaires et, par conséquent, la perméabilité. Des échantillons de mortiers ont été réalisés avec différents mélanges de CEM I et de laitiers de haut-fourneau puis différentes cures ont été utilisées afin d’évaluer l’influence de la baisse de la température ou de l’hygrométrie sur la géométrie de leur porosité. Différentes techniques d’analyses de porosité et de perméabilité ont permis de mettre en évidence principalement une augmentation de la porosité totale et libre, des rayons des capillaires et de la perméabilité avec l’augmentation de la proportion de laitier et la diminution de l’hygrométrie. Des observations au microscope électronique à balayage à pression de vapeur d’eau contrôlée ont permis de montrer le lien entre l’ouverture des capillaires et l’hygrométrie. Ainsi les forces exercées par les pressions de disjonction et les pressions capillaires déforment les hydrates de manière à fermer les capillaires avec l’augmentation de l’hygrométrie. La mise au point d’une méthode originale de cartographie de la porosité à partir de données de conductivité thermique a permis de confirmer la présence d’une peau et de déterminer son étendue. Grâce à cette technique, il est possible d’évaluer la distribution des taux de porosité au travers des échantillons. De plus, une nouvelle approche d’analyse a permis de cartographier à partir du même modèle la distribution des proportions relatives de granulats. / In order to evaluate the sustainability of cementitious materials, it is significant to understand the mechanisms linked to the formation of the porosity and to its properties. The use of ground granulated blast-furnace slag as an eco-friendly hydraulic binder influences the hydration processes therefore the phases formed, their proportion and their microstructure of mortar and concrete. Mortar samples were made to evaluate the influences of the blast-furnace slag, its grinding fineness and the influence of temperature or relative humidity of curing on the porosity. The analysis of the mortar samples with complementary measures of porosity allowed us to highlight the increase of the total and free porosity, of the threshold diameter and the absolute permeability with the increase of slag proportion used and the decrease of relative humidity. We also showed a gradual slowing down of capillary absorption kinetics called self-sealing effect and observed the relationbetween the relative humidity and the capillary aperture with a low vacuum scanning electron microscopy. Thus, the strength of disjunction and capillary pressures applied on the hydrates clog the capillaries with increasing humidity. The development of a novel method for mortar porosity mapping from thermal conductivity data allowed us to confirm the skin presence and its area. This method allows the evaluation of the porosity distribution and the relative proportion of aggregates through the sample.

Aujourd'hui, les problèmes environnementaux sont plus graves que jamais. Des mesures urgentes devraient être prises dans tous les domaines de l'activité humaine, y compris la construction. L'un des principaux contributeurs à l'impact négatif de cette industrie sur l'environnement est la fabrication du ciment Portland ordinaire (OPC) nécessaire à la production de béton et d’autres matériaux cimentaire. Malgré son importance, il présente un inconvénient important: sa production est accompagnée par de grandes quantités de gaz à effet de serre. Ils représentent 5 à 8% des émissions mondiales totales de CO2. Des matériaux cimentaires plus écologiques sont maintenant nécessaires.Des réductions significatives de l’impact sur l’environnement ne peuvent être obtenues que par l’utilisation de liants de nouvelle génération dont la fabrication ne nécessite pas beaucoup de processus et de traitements supplémentaires. L'une d'elles consiste à utiliser des déchets industriels comme liants (différentes laitiers, cendres volantes, cendres de biomasse, etc.). De cette manière, il y a non seulement une réduction de l'impact de processus tels que l'extraction minière ou la calcination, mais également le recyclage des déchets (un principe de l'économie circulaire).Une possibilité consiste à utiliser du laitier de haut fourneau (GGBS) comme base pour ce ciment de nouvelle génération. En raison de sa réactivité relativement faible avec l'eau, des suppléments (également appelés activateurs) doivent être utilisés pour favoriser le processus d'hydratation. Le carbonate de sodium (Na2CO3) est l’un des activateurs les plus prometteurs et en même temps les moins étudiés. Un tel ciment alkali-activé présente des propriétés mécaniques et de durabilité élevées, ainsi qu'une empreinte CO2 très faible. Parmi les principaux problèmes qui entravent son utilisation à l'échelle industrielle, on peut mentionner une évolution de la résistance lente à jeune âge et de rhéologie médiocre.L'objectif de la présente thèse est de développer une nouvelle conception du liant à base de laitier activé par Na2CO3, qui répondrait à toutes les exigences modernes du secteur de la construction, en particulier les propriétés rhéologiques et le développement de la résistance à jeune âge. Ce liant doit toujours répondre à au moins trois critères principaux: faible impact environnemental, faibles risques de danger dans les applications sur le terrain et être économiquement compétitif à l'échelle industrielle.Dans le présent travail, l’influence de différents paramètres tels que le rapport eau/liant, la concentration de Na2CO3, la finesse du laitier et les conditions de durcissement sur les propriétés du mélange à jeune âge et à long terme a été étudiée. Sur la base des résultats du processus d’hydratation, les additifs à base de phosphonate qui permettent de contrôler efficacement la rhéologie de tels liants ont été testé avec succès. Ils permettent non seulement de contrôler le temps de prise, mais fournissent également un effet plastifiant.En ce qui concerne l’amélioration des propriétés de résistance au jeune âge, différentes méthodes ont été utilisées. L’utilisation d’un traitement thermique ou d’une augmentation de la finesse du GGBS s’est avérée efficace. L’exploration des causes d’une longue période d’induction a montré que l’accélération pouvait également être obtenue par l’ajout d’une source de calcium à cinétique de dissolution contrôlée. En conséquence, le liant est devenu plus réactif et plus robuste à certains facteurs (concentration d’activateur, rapport eau/liant, conditions de durcissement, etc.). Pour compenser l'empreinte carbone supplémentaire de la source de calcium ajoutée, le liant a été dilué avec succès par le calcaire sans aucune dégradation des propriétés à un certain pourcentage de dilution. / Today, environmental problems are more acute than ever. Urgent measures should be taken in all spheres of human activity including construction and civil engineering. One of the major contributors of negative environmental impacts from this industry is the manufacturing of ordinary Portland cement (OPC) required for concrete and other cementitious materials production. Although its importance to economical development, it has a significant drawback - its production is accompanied by the emission of large quantities of greenhouse gases. They account for 5-8% of total world CO2 emissions. More environmentally friendly cementitious materials are now required.Significant reductions of the environmental impact can be achieved only through the use of new-generation binders whose manufacture does not require a lot of additional processes and treatments. One route is through the use of industrial wastes as binders (different slags, fly ash, biomass bottom ash, etc.). In this way there is not only a reduction in the impact of processes such as mining or calcination, but also the recycling of waste materials (circular economy principle).One possibility is to use ground granulated blast furnace slag (GGBS) as the basis for such a new generation cement. Due to its rather low reactivity with water, additional supplements (also called activators) should be used to promote the hydration process. One of the most promising, and at the same time least studied, activators is sodium carbonate (Na2CO3). Such alkali-activated cements present high mechanical and durability properties, as well as a very low CO2 footprint. Among the main problems hindering its industrial scale adoption are their poor rheology and too slow strength gain within the first days of hardening.The objective of the present thesis is to develop a new binder based on Na2CO3 activated GGBS that would meet all the modern requirements of the construction industry, in particular regarding the rheological properties and early age strength development. In addition this binder should always respond to at least three main criteria: low environmental impact, low health and safety concerns in field applications, and be economically competitive at industrial scale.In the present work, the influence of different parameters like water/binder ratio, Na2CO3 concentration, slag fineness and curing conditions on both early age and long term properties of the mixture were studied. Based on the results of the hydration process analysis, phosphonate based additives that allow for the effective control of the rheology of such binders were successfully tested. They not only allow control over the setting time, but also provide a plasticizing effect.Regarding the improvement of early age strength properties, various methods have been used. The use of heat treatment or an increase of GGBS fineness turned out to be efficient. Exploring the causes of the long induction period has shown that acceleration can also be achieved by the addition of a calcium source with controlled dissolution kinetics. As a result, the binder became more reactive and robust against certain factors (activator concentration, Water/Binder ratio, curing conditions, etc.). To compensate for the additional carbon footprint from the added calcium source, the binder was successfully diluted by limestone without any degradation of the properties below some dilution percentages.

The process of laser-induced brazing constitutes a potential option for connecting several ceramic components (n- and p-type ceramic bars and ceramic substrate) of a thermoelectric generator (TEG) unit. For the construction of the TEGs, TiOₓ and BₓC were used as thermoelectric bars and AlN was used as substrate material. The required process time for joining is well below that of conventional furnace brazing processes and, furthermore, establishes the possibility of using a uniform filler system for all contacting points within the thermoelectric unit. In the work reported here, the application-specific optimization of the laser-joining process is presented as well as the adapted design of the thermoelectric modules. The properties of the produced bonding were characterized by using fatigue strength and microstructural investigations. Furthermore, the operational reliability of the modules was verified.

The diploma thesis deals with design of gas steam boiler with given parameters of steam. Blast furnace and coke oven gas are used as fuel. At the beginning of this work, both co-fired fuels are presented to us, their chemical analysis and stoichiometry are performed. The main part of the diploma thesis deals with the dimensioning of individual heat exchange surfaces such as steam superheaters, evaporators, economizers and air heaters. All heat exchange surfaces meet recommended parameters such as recommended steam rates, flue gas, etc. At the end, the total heat balance of the boiler is performed. Part of the work is also drawing documentation showing the main dimensions of the boiler. It is also indicated the connection of individual heat exchange surfaces.

This diploma thesis describes research and following development of lightweight cement mortars with alternative raw materials. Attention was focused on study of the effects of extreme influences such as high temperature (up to 1200 °C), freeze-thaw and agressive sulfur dioxide. Verification of durability of developed mortars was realized using physical and mechanical tests (density and strength), physical and chemical methods (computed tomography) and scanning electron microscopy. Assessment of durability was realized in a longer period of time (90 days).

Ordinary concrete is the most commonly used building material, but nowadays the requirements for low energy consumption, durability of structures together with their easy diagnostics as well as ecological production raises. This thesis deals with cement and aluminosilicate composites with content of conductive fillers, which allows to monitor the change in electrical properties, most commonly electrical resistance in dependence on mechanical stress. In the experimental part of the thesis, test beams were produced based on alkali-activated slag with content of carbon nanotubes, graphite powder, carbon black and carbon fibre. The beams were subjected to flexural loading in a three-point bending configuration and the shift in electrical resistance was monitored.

This diploma thesis is about an influence of technical gases CO2 and N2, that are present in a fuel, over overall combustion process and a flue gas emissions. The first part of this thesis discussed issues like heat transfer, basic process combustion utilities, used technical gases in experimental part and finally description of observed pollutants. Second part of thesis describes the experiments themselves. Experiments were trying to find how selected parameters were influenced by adding 40 mN3/h or 80 mN3/h of inert gases to a flow of natural gas. Observed parameters were namely emission volumes, flame parameters and maximal heat duty. Experiments took place in horizontal water-cooled combustion chamber and were performed on two different types of burners. Evaluation of results confirmed clear connection of inert gases on temperature of flame; the biggest temperature drop was observed while inert gas CO2 was present in fuel. Lowering of temperature spikes also highly influenced presence of NOx in hot flue gas during all performed trials.