Les ciments sulfoalumineux sont des liants hydrauliques qui, jusqu’aujourd’hui ne sont pas normalisés et ne possèdent donc pas une composition fixe. La teneur en ye’elimite – la phase principale de ce ciment- peut varier de 5 à 70 %. Or la composition du ciment sulfoalumineux (la composition du clinker ainsi que le pourcentage de gypse ajouté) est un paramètre critique qui contrôle sa réactivité, ses performances mécaniques, ainsi que sa durabilité. L’objectif principal de cette thèse est donc l’étude de l’influence de la composition des ciments sulfoalumineux sur leurs propriétés techniques, telles que les performances mécaniques et durabilité. Trois axes principaux ont été abordés. Tout d’abord une étude de l’influence de la composition du ciment sulfoalumineux (25-75 % en masse de ye’elimite) sur ses propriétés hydrauliques et mécaniques ainsi que sur la valeur limite en élément trace (Zn) a été menée. Dans ce but trois ciment sulfoalumineux (25, 50 et 75 % en masse de ye’elimite) ont été synthétisés. Ensuite l’effet de la variabilité de ce ciment sur sa durabilité dans l’eau pure et sulfatée a été investigué par rapport à un ciment sulfoalumineux commercial. Enfin, une étude des potentialités du ciment sulfoalumineux commercial à inhiber la réaction alcali silice dans les mortiers, lors de l’utilisation d’un granulat réactif (Silex), a été conduite. Il en résulte de cette étude qu’une augmentation de taux de ye’elimite dans le ciment sulfoalumineux engendre une augmentation des performances mécaniques. La valeur limite en Zn est de 0,3 % indépendamment de la composition du ciment sulfoalumineux. Par contre cette dernière influence la durabilité de ces ciments. Les résultats révèlent que même si la formulation contenant 75 % en ye’elimite confère les meilleures performances mécaniques, sa durabilité était la plus faible due à l’absence de stratlingite dans sa matrice cimentaire. Enfin, l’utilisation du ciment sulfoalumineux présente des bonnes potentialités à inhiber la réaction alcali silice. / Sulfoaluminate cements are hydraulic binders that, until today, are not standardized and therefore do not have a fixed composition. The content of ye'elimite - the main compound of this cement - can vary from 5 to 70 %. However, the composition of sulfoaluminate cement (clinker composition as well as the percentage of added gypsum) is a critical parameter that controls its reactivity, mechanical performance, as well as its durability. The main objective of this thesis is to study the influence of sulfoaluminate cements composition on their technical properties, such as mechanical performances and durability. Three main axes were discussed in this work. First, the influence of the sulfoaluminate cement composition (25-75 wt. % of ye'elimite) on its hydraulic and mechanical properties, as well as on the threshold limit of Zn, was studied. For this purpose three sulfoaluminate cements (25, 50 and 75 wt. % of ye'elimite) were synthesized. Then the effect of the variability of this cement on its durability in pure and sulphated water was investigated compared to a commercial sulfoaluminate cement. Finally, a study of the potentialities of commercial sulfoaluminate cement to inhibit the alkali silica reaction in mortars, when using a reactive aggregate (flint), was conducted. This study reveals that an increase in ye'elimite content in the sulfoaluminate cement increases the mechanical performance. The threshold limit of Zn is 0.3 % independently of the sulfoaluminate cement composition. Contrariwise, the sulfoaluminate cement composition influences the durability of these cements. Although the formulation containing 75 % of ye’elimite gives the best mechanical performances, its durability was lowest due to the absence of stratlingite in its cement matrix. Finally, the use of sulfoaluminate cement has good potential towards the inhibition of the alkali silica reaction.

Gegenstand der Arbeit ist die Untersuchung der kollektiven Diffusion von Wasser und Ionen in wässrigen Elektrolytlösungen. Dabei wird insbesondere die Dynamik der Wassermoleküle innerhalb der Hydratationshüllen der Ionen und der Einfluss poröser Materialien untersucht. Nach einer Einführung zur Dynamik der Hydratationshülle folgen Grundlagen der NMR-Diffusometrie, welche genutzt wurde um die Selbstdiffusionskoefifizienten der Wassermoleküle und der Ionen der Lösungen zu messen. Daraus wurden die dynamischen Hydratationszahlen der Ionen bestimmt, welche die Anzahl an Wassermolekülen angeben, die durch die Diffusion des Ions in ihrer translatorischen Bewegung beeinflusst sind. Der Einfluss poröser Materialien auf die Dynamik wird am Beispiel nanoporöser Glasmonolithe und mikroporöser Li-LSX Kristalle untersucht.

The number of people suffering from neurodegenerative diseases, such as Alzheimer`s disease, increased dramatically over the past centuries and is expected to increase even further within the next years. Based on predictions of the World Health Organization and Alzheimer`s Disease International, 115 million people will suffer from dementia by the year 2050. An additionally increase in other age related neurodegenerative diseases is also forecasted. Quite naturally, neurodegenerative diseases became a focus of attention of governments and health insurances, trying to control the uprising financial burden. Early detection and treatment of neurodegenerative diseases could be an important component in containing this problem. In particular, researchers focused on automatic methods to analyze patients’ imaging data. One way to detect structural changes in magnetic resonance images (MRI) is the voxel-based method approach. It was specifically implemented for various imaging modalities, e.g. T1-weighted images or diffusion tensor imaging (DTI). Voxel-based morphometry (VBM), a method specifically designed to analyze T1-weighted images, has become very popular over the last decade. Investigations using VBM revealed numerous structural brain changes related to, e.g. neurodegeneration, learning induced structural changes or aging. Although voxel-based methods are designed to be robust and reliable structural change detection methods, it is known that they can be influenced by physical and physiological factors. Dehydration, for example, can affect the volume of brain structures and possibly induce a confound in morphometric studies. Therefore, three-dimensional T1-weighted images were acquired of six young and healthy subjects during different states of hydration. Measurements during normal hydration, hyperhydration, and dehydration made it possible to assess consequential volume changes in gray matter (GM), white matter (WM), and cerebrospinal fluid (CSF). The datasets were analyzed using VBM, FreeSurfer and SIENA. A significant decrease of GM and WM volume, associated with dehydration, was found in various brain regions. The most prominent effects were found in temporal and parietal areas, in the left inferior orbito-frontal region, and in the extra-nuclear region. Moreover, we found consistent increases in CSF, an expansion around 6% of the ventricular system affecting both lateral ventricles, i.e. the third and fourth ventricle. Similar degrees of shrinkage in WM volume and increase of the ventricular system have been reported in studies of Alzheimer’s disease during disease progression and in its prestage mild cognitive impairment. Based on these findings, a potential confound in GM and WM or CSF studies due to the subjects’ hydration state cannot be excluded and should be appropriately addressed. These results underline the sensitivity of VBM and might also concern other voxel-based methods, such as Tract-Based Spatial Statistics (TBSS). TBSS was specifically designed for WM analyses and its sensitivity might be helpful for revealing the spatial relation of structural WM changes and related blood serum biomarkers. Two common brain related biomarkers are the glial protein S100B, a plasticity inducing neuro- and gliotrophin, and neuron-specific enolase (NSE), a marker for neuronal damage. However, the spatial specificity of these biomarkers for brain region has not been investigated in vivo until now. Therefore, we acquired two MRI parameters – T1- weighted and DTI - sensitive to changes in GM and WM, and obtained serum S100B and NSE levels of 41 healthy subjects. Additionally, the gene expression of S100B on the whole brain level in a male cohort of three subjects from the Allen Brain Database was analyzed. Furthermore, a female post mortal brain was investigated using double immunofluorescence labeling with oligodendrocyte markers. It could be shown that S100B is specifically related to white matter structures, namely the corpus callosum, anterior forceps and superior longitudinal fasciculus in female subjects. This effect was observed in fractional anisotropy and radial diffusivity – the latest an indicator of myelin changes. Histological data confirmed a co-localization of S100B with oligodendrocyte markers in the human corpus callosum. S100B was most abundantly expressed in the corpus callosum according to the whole genome Allen Human Brain Atlas. In addition, NSE was related to gray matter structures, namely the amygdala. This effect was detected across sexes. The data demonstrates a very high S100B expression in white matter tracts, in particular in human corpus callosum. This was the first in vivo study validating the specificity of the glial marker S100B for the human brain, and supporting the assumption that radial diffusivity represents a myelin marker. The results open a new perspective for future studies investigating major neuropsychiatric disorders. All above mentioned studies are mainly dependent on the sensitivity and accuracy of soft and hardware parameters. In particular, technical developments have improved acquisition accuracy in the field of MRI. Interestingly, very little is known about the confounding effects of variations due to hardware parameters and their possible impact on reliability and sensitivity of VBM. Recent studies have shown that different acquisition parameters may influence VBM results. Therefore age-related GM changes were investigated with VBM in 36 healthy volunteers grouped into 12 young, 12 middle-aged and 12 elderly subject. Six T1-weighted datasets were acquired per subject with a 12-channel matrix coil, as well as a 32-channel array, MP-RAGE and MP2RAGE, and with isotropic resolutions of 0.8 and 1 mm. DARTEL-VBM was applied on all images and GM, WM and CSF segments were statistically analyzed.. Paired t-tests and statistical interaction tests revealed significant effects of acquisition parameters on the estimated gray-matter-density (GMD) in various cortical and subcortical brain regions. MP2RAGE seemed slightly less prone to false positive results when comparing data acquired with different RF coils and yielded superior segmentation of deep GM structures. With the 12-channel coil, MP-RAGE was superior in detecting age-related changes, especially in cortical structures. Most differences between both sequences became insignificant with the 32-channel coil, indicating that the MP2RAGE images benefited more from the improved signal-to-noise ratio and improved parallel-imaging reconstruction). A possible explanation might be an overestimation of the GM compartment on the MP-RAGE images. In view of substantial effects obtained for all parameters, careful standardization of the acquisition protocol is advocated. While the current investigation focused on aging effects, similar results are expected for other VBM studies, like on plasticity or neurodegenerative diseases. This work has shown that voxel-based methods are sensitive to subtle structural brain changes, independent of imaging modality and scanning parameters. In particular, the studies investigated and discussed the analysis of T1- and diffusion weighted images with VBM and TBSS in the context of dehydration, blood serum sensitive biomarkers and aging were discussed. The major goal of these studies was the investigation of the sensitivity of voxel-based methods. In conclusion, sensitivity and accuracy of voxelbased methods is already high, but it can be increased significantly, using optimal hardand software parameters. It is of note, though, that these optimizations and the concomitant increase of detection sensitivity could also introduce additional confounding factors in the imaging data and interfere with the latter preprocessing and statistical computations. To avoid an interference e.g. originating from physiological parameters, a very careful selection and monitoring of biological parameters of each volunteer throughout the whole study is recommended. A potential impact of scanning parameters can be minimized by strict adherence to the imaging protocol for each study subjectwithin a study. A general increase in detection sensitivity due to optimized parameters selection in hard- and/or can not be concluded by the above mentioned studies. Although the present work addressed some of those issues, the topic of optimal selection of parameters for morphometric studies is still very complex and controversial and has to be individually decided. Further investigations are needed to define more general scanning and preprocessing standards to increase detection sensitivity without the concomitant amplification of confounding factors.

Anhydrit II (AII) wird industriell hauptsächlich als Bindemittel bei der Fußbodenestrich-Herstellung eingesetzt. Zur Beschleunigung der Abbindereaktion und der daraus resultierenden schnelleren Verfestigung des Fußbodens wird Kaliumsulfat als Additiv verwendet. Im Rahmen dieser Arbeit wurden anorganische Salze (Sulfate und Chloride) im Vergleich zu Kaliumsulfat hinsichtlich ihrer beschleunigenden Wirkung auf die Abbindereaktion von AII untersucht, um eine mögliche Alternative und einen Mechanismus für die Wirkungsweise der Additive angeben zu können. Unter den verwendeten Salz-Additiven wurde keine Alternative zu K2SO4 für die industrielle Anwendung gefunden. Als Ursache für die beschleunigende Wirkung von K2SO4 wird die Bildung des Doppelsalzes Syngenit auf der Anhydrit-Oberfläche angenommen. Durch epitaktische Beziehungen von Kristallflächen oder den Zerfall des Syngenits wird die heterogene Gips-Keimbildung begünstigt und die Abbindereaktion beschleunigt.

La spectroscopie de dissociation par absorption de photons infrarouges (IRPD) permet d’obtenir les signatures vibrationnelles d’espèces chargées en phase gazeuse, telles que de petits peptides ou des ions hydratés dans des agrégats d’eau. L’attribution des modes de vibration pour établir une relation entre le spectre expérimental et une structure moléculaire est une tâche délicate et nécessite le recours à la modélisation moléculaire.Ce manuscrit présente un ensemble d’outils théoriques pour le calcul et l’attribution de spectres vibrationnels, basée principalement sur la dynamique moléculaire classique et le champ de forces polarisable AMOEBA, ainsi que son application à des ions gazeux de tailles diverses. Les ions hydratés dans des agrégats d’eau M(H2O)n (n allant de 6 à 100) sont caractérisés par une dynamique importante, et leur spectre expérimental ne peut pas être décrit par une seule structure. La signature des peptides évolue avec la température et les effets d’anharmonicité dynamique. Ils peuvent également être le siège de mécanismes de transfert de proton, présentant une signature vibrationnelle très caractéristique.La surface d’énergie potentielle de ces systèmes est explorée par la dynamique moléculaire classique en trajectoires individuelles ou avec échange de répliques, afin d’engendrer des structures énergétiquement stables. Pour les plus petits systèmes, les méthodes quantiques DFT et post-HF sont utilisées pour confirmer les structures de plus basse énergie, calculer leurs spectres IR statiques et proposer des attributions des modes de vibration. Pour les plus systèmes de plus grandes tailles, c’est-à-dire les ions dans des gouttes d’eau de plusieurs dizaines de molécules, la simulation des spectres IR à température finie est basée sur la transformée de Fourier de la fonction d’autocorrélation du moment dipolaire (DACF), calculée pour une trajectoire de dynamique moléculaire classique. Cette méthode n’offrant pas d’accès direct aux modes normaux de vibration, nous avons implémenté une méthode d’attribution dynamique, basée sur la Driven Molecular Dynamics (DMD) et couplée au DACF. La combinaison AMOEBA/DACF/DMD a été utilisée pour reproduire et attribuer le spectre du dipeptide Ace-Phe-Ala-NH2, et ceux d’ions hydratés dans des agrégats d’eau.Enfin, la signature vibrationnelle d’un transfert de proton ne peut être décrite, ni par des méthodes statiques quantiques, ni par la dynamique classique. Sa modélisation a nécessité le développement d’un modèle Empirical Valence Bond (EVB) à deux états, couplé au champ de forces polarisable AMOEBA. Le modèle EVB a été implémenté dans la suite logicielle Tinker. Il permet de reproduire le comportement dynamique du transfert de proton au sein de petits peptides et de diacides déprotonés, ainsi que la signature spectroscopique observée expérimentalement.Une partie importante des applications de ces développements concerne des ions simples hydratés dans des nano-gouttelettes, et en particulier l’ion sulfate de grande importance environnementale. Nous avons pu reproduire de façon satisfaisante, pour la première fois, les spectres d’agrégats contenant jusqu’à 100 molécules d’eau. Le principal contributeur à cette spectroscopie expérimentale est l’équipe d’E. Williams à l’université de Californie à Berkeley. Nous avons établi avec eux une collaboration pour compléter ce travail en modélisant les spectres IR d’ions sulfates hydratés [SO4(H2O)n=9-36]2-, dont ils ont obtenu les signatures expérimentales. / Spectroscopy dissociation by absorption of infrared photons (IRPD) provides vibrational signatures of charged species in the gas phase, such as small peptides or hydrated ions in water clusters. The vibrational normal modes assignment to establish a relationship between the experimental spectrum and molecular structure is a delicate task and requires the use of molecular modeling.This manuscript presents a set of theoretical tools for calculation and assignment of vibrational spectra, based mainly on classical molecular dynamics and polarizable AMOEBA force field, and its application to gaseous ions of various sizes. Hydrated ions in water clusters M(H2O)n (n in 6-100 range) are characterized by a dynamic behavior, and their experimental spectrum can not be described by a single structure. The signature of peptides changes with temperature and dynamic anharmonicity effects. They can also be the site of proton transfer mechanisms, with a very characteristic vibrational signature.The potential energy surface of these systems is explored by classical molecular dynamics in individual trajectories or replica exchange to generate energetically stable structures. For smaller systems, quantum methods, as DFT and post-HF, are used to confirm the lowest energy structures, calculate their static IR and propose normal modes assignments. For larger systems, i.e ions in water drops of several tens of molecules, the simulation of IR spectra at finite temperature is based on the Fourier transform of the autocorrelation function of the dipole moment (DACF), calculated during a classical molecular dynamics trajectory. As this method does not allow direct access to the vibrational normal modes, we implemented a method of dynamic assigments, based on the Driven Molecular Dynamics (DMD) and coupled to the DACF. The combination AMOEBA /DACF / DMD was used to reproduce and assign the spectrum of the dipeptide Ace-Phe-Ala-NH2, and those of hydrated ions in water clusters.Finally, the vibrational signature of a proton transfer can not be described by quantum static methods or by classical dynamics. Its modeling required the development of a two states Empirical Valence Bond Model (EVB), coupled with AMOEBA polarizable force field. The two states EVB model was implemented in the software TINKER. It can reproduce the dynamic behavior of proton transfer in small peptides and deprotonated acids, as well as the spectroscopic signatures observed experimentally.An important part of the applications of these developments relates simple hydrated ions in nano-droplets, and in particular the sulfate ion of great environmental importance. We were able to reproduce satisfactorily, for the first time, the spectra of clusters containing up to 100 water molecules. The main contributor to this experimental spectroscopy is the team of E. Williams from the University of California of Berkeley. We have established cooperation with them to complete this work by modeling the IR spectra of hydrated sulfates ions [SO4(H2O) n=9-36]2-, for which they obtained experimental signatures.

No description available.

Concrete is one of the most used building materials in the world because of its good properties. However, cement which is one of the main components in concrete, produces a high amount of heat during the hydration process. The generated heat leads to temperature rise inside the structure. This temperature rise becomes an issue for massive concrete structures, such as hydropower plants and dams, since natural cooling is no longer sufficient. In combination with restrained boundary conditions, increasing temperatures result in tensile stresses causing thermal cracking of the structure. Reducing thermal cracking in a restrained massive concrete structure can be done by lowering or controlling the temperature rise. Several methods of cooling can be used to achieve this. These methods may be divided in pre-cooling and post-cooling methods. To pre-cool concrete the cement content can be reduced by replacing it with mineral additions such as limestone, fly ash, silica fume and ground granulated blast furnace slag. Another method is to increase the size of the aggregates or to pre-cool the aggregates. Ice can also be used to reduce the temperature at casting the concrete and reduce the amount of water that is needed in the mix. The main post-cooling method is cooling pipes, with cold water circulating in the pipes to cool the structure. This master thesis project focuses on comparing the possible methods to reduce the temperature in massive concrete structures. Simulations with the computer program HACON were performed to analyse the effect of these methods. The results from this study showed that cooling pipes gave the best reduction of the maximum temperature and the maximum temperature gradient by 42 % and 76 %, respectively. However, if cooling pipes were to be avoided, the best result of the studied mineral additions was with a replacement of 30 % fly ash resulting in almost the same reduction in maximum temperature but less than one third of the reduction in the gradient. The reduction obtained with fly ash was not as efficient as cooling pipes; therefore appropriate combinations of different pre-cooling methods were also studied. The results of the combination of fly ash, ice, and larger aggregates showed even better reduction of the maximum temperature reduction compared to cooling pipes. The results also showed that the obtained temperature reductions were almost independent from the thickness of the structure. This conclusion is however only valid for massive structures, where cases with 1.5 and 3.0 m were analysed. Further study may be on finding suitable combination of pre-cooling methods to avoid the use of cooling pipes, as well as analysing the cost for the different pre-cooling methods. / Betong är ett av de mest använda byggmaterialen i världen, tack vare dess goda egenskaper. Cement, som är en av huvudkomponenterna i betong, genererar en stor värmeutveckling under hydratationen. Värmeutveckling som genereras leder till temperaturhöjningar i strukturen. Denna temperaturhöjning blir således ett problem för massiva betong- konstruktioner, såsom vattenkraftverk och dammar, på grund av att den naturliga avkylningen inte längre är tillräcklig för att avlägsna värmen. I kombination med yttre och inre tvång resulterar högre temperaturer i dragspänningar som orsakar sprickor i strukturen. Minskningen av sprickbildning i en fastgjuten massiv betongstruktur kan ske genom att minska eller reglera temperaturhöjningen. För att göra det kan flera kylmetoder användas. Dessa metoder kan delas in i förberedande kylning och efterkylning. Med förberedande kylning kan cementhalten i betong reduceras genom ersättning med mineraltillsatser såsom kalksten, flygaska, silikastoft eller markgranulerad masugnsslagg. En annan metod är att öka ballastens storlek eller att kyla ballasten. Is kan användas både för att minska temperaturen vid gjutning av betong och reducera mängden vatten som behövs i blandningen. Den vanligaste efterkylningsmetoden är användning av kylrör med cirkulerande kallt vatten för att kyla strukturen, dvs. utan att ändra mängden värme som produceras av cementhydratationen. Denna uppsats ämnar jämföra olika metoder för att reducera temperaturen i massiva betongkonstruktioner. Simuleringar har genomförts med datorprogrammet HACON i syfte att analysera inverkan av olika metoder. Resultaten från studien visade att kylrör gav den bästa minskningen av den maximala temperaturen och den maximala reduktionen av temperaturgradienten med 42 % respektive 76 %. Om kylrör ska undvikas erhålls det bästa resultatet vid användning av 30 % flygaska, vilket resulterade i en snarlik minskning i maximal temperatur med mindre än en tredjedel av reduktionen av gradienten. Då reduceringen med flygaska inte var lika effektiv som med kylrör har lämpliga kombinationer av olika förberedande kylmetoder studerats. Resultatet av kombinationen med flygaska, is och större ballast visade en ännu effektivare minskning av den maximala temperaturreduceringen jämfört med kylrör. Vidare visade resultaten även att de erhållna temperaturreduceringarna nästan var oberoende av konstruktionens tjocklek. Denna slutsats kan endast tillämpas för massiva konstruktioner, där fall med en 1.5 och 3.0 m tjock vägg analyserades. Fortsatta studier kan vara att hitta fler lämpliga kombinationer av förberedande kylmetoder för att undvika användning av kylrör, liksom att analysera kostnaden för de olika förberedande kylmetoderna.

Concrete, the second most consumed material on earth after water, is a source of environmental problems due to global urbanization. The production of this construction material requires a large amount of natural resources, and portland cement (PC) is responsible for around 8 % of planet-warming CO2 emissions. Producing 1 ton of PC will release roughly 1 ton of CO2 into the atmosphere. In 2021, around 92 million metric tons of PC were produced in the U.S., and a total of 4.4 billion tons were manufactured worldwide. While there was a yearly increase of around 1.5 % in the direct CO2 intensity of cement production from 2015 to 2021, urgent annual declines of 3 % until 2030 are necessary to be in line with the Net Zero Emissions by 2050 Scenario. This dissertation presents different approaches and technologies to offset the CO2 footprint of the production of cement clinker, concrete, and cementitious materials in general. First, this dissertation investigated the possibility of using end-of-life tire (ELT) rubber powder and its zinc-recovered residual (treated ELT rubber) to partially replace fine aggregates of different construction and infrastructure materials including stabilized soft soil (0 %, 10 %, 30 %, and 50 % ELT rubber added by clay volume), portland cement concrete (0 %, 10 %, 20 %, and 30 % ELT rubber added by sand volume), and asphalt concrete (20 % ELT rubber added by sand volume). This work was discussed through aspects of engineering properties and environmental impacts. The results reveal that the ELT rubber had both negative and positive effects on the engineering properties of the three materials while this waste posed a huge leachability of zinc and total organic carbon (TOC) content when being subjected to aqueous environments. However, the findings indicate that all three materials' matrices could effectively immobilize most leachable zinc from the ELT rubber by more than 90 %. Meanwhile, only stabilized soft soil and asphalt concrete could effectively deal with leachable TOC content from ELT rubber, and portland cement concrete needed the addition of silica fume to reduce TOC concentration in its leachate. Second, while previous studies have shown that steel furnace slag (SFS) can stabilize clay soils, the evidence is not clear if the stabilization mechanism is chemical and/or mechanical. This dissertation used isothermal calorimetry (IC) to quantify the heat of hydration of the mixture to assess the chemical aspects of the stabilization. Specifically, kaolin and bentonite clays were each blended with 40 % SFS by mass at water-to-binder ratios ranging from 1.0 to 1.5. The hydration properties of stabilized mixtures using lime or PC were also tested for comparison at the same experimental conditions. The obtained thermal power and total heat curves of stabilized mixtures confirmed that, for the specific SFS in this study, there is a hydration process taking place in clay stabilized by SFS. Relative to lime and PC, the SFS performed similarly in terms of heat of hydration behavior. When blended into clays, SFS provided a more significant heat of hydration behavior than cement, but that was much milder than lime. X-ray diffraction (XRD) and thermogravimetric analysis (TGA) were also employed to qualitatively analyze the mineralogy of the stabilized mixtures. Finally, this dissertation adopted a Digestion-Titration Method (DTM) for the determination of CO2 content in cementitious materials that has been mineralized in the form of calcium carbonate (CaCO3). This method was modified based on tests that were originally developed in the early 1900s. The method uses hydrochloric acid to digest CaCO3 under vacuum conditions. The CO2 released is captured by a barium hydroxide solution, which is then titrated to quantify the amount of CO2 absorbed. A design of experiments approach was used to optimize the experimental conditions. Samples of known CaCO3 content were first evaluated to establish the baseline test performance, and additional tests were performed on portland cement and various rock samples. The results were also compared to TGA, including a discussion to compare the two test methods. The data suggest that the new test method is feasibly applicable to chemically determine the CO2 captured in cementitious materials, and it can be an alternative method for TGA with lower experimental cost and easier access. Overall, it is evident that cement, concrete, and construction materials are essential to the functionality of civilization. Dealing with CO2 emissions and natural resource depletion induced by the production of these construction materials is urgent for sustainable development. Attempts toward construction materials with lower embodied CO2 by using low-carbon aggregates (e.g., waste aggregates, recycled aggregates) and alternative cementitious binders while controlling the environmental effects of the utilized waste materials are currently viable sustainable approaches. In addition, tools or new test methods that can support measuring the effectiveness of these reduced carbon cementitious materials are necessary. This dissertation investigates the feasibility of the use of ELT rubber waste in construction materials to reduce the exploitation of natural resources considering engineering properties and environmental impacts. It also provides a deeper understanding of the hydration behavior of stabilized soil using SFS which is expected to partially or fully replace PC in the material. Experimentally, it develops a chemical test model as an alternative method for TGA with lower experimental cost, less interference, and easier access to determine the CO2 captured in cementitious materials. / Doctor of Philosophy / Concrete, the second most consumed material on earth after water, is a source of environmental problems due to global urbanization. The production of this construction material requires a large amount of natural resources, and portland cement (PC) is responsible for around 8 % of planet-warming CO2 emissions. This dissertation presents different approaches and technologies to offset the CO2 footprint of the production of construction materials (i.e., cement clinker, concrete, and general cementitious materials). First, this dissertation investigated the possibility of using end-of-life tire (ELT) rubber powder in different construction materials including stabilized soft soil, portland cement concrete, and asphalt concrete. This work was discussed through aspects of engineering properties and environmental impacts. The results reveal that the ELT rubber had both negative and positive effects on the engineering properties of the three materials. In return, all three materials' matrices could effectively immobilize most leachable zinc and total organic carbon (TOC) from the ELT rubber, which are detrimental to aquatic animals, plants, and humans. Second, this dissertation used isothermal calorimetry (IC) for the first time to study the heat of hydration of soil stabilized by steel furnace slag (SFS) to assess the chemical aspects of the stabilization. The work compared the hydration behavior of SFS in clayey soil with traditional stabilizers such as lime or portland cement. The results demonstrated that there were chemical reactions taking place during the hydration of stabilized soil using SFS, explaining the improvement in engineering properties of the stabilized soil. Moreover, this dissertation adopted a Digestion-Titration Method (DTM) for the determination of mineralized CO2 content in cementitious materials. The method uses hydrochloric acid to digest CaCO3 under vacuum conditions. The CO2 released is captured by a barium hydroxide solution, which is then titrated to quantify the amount of CO2 absorbed. The data suggest that the new test method is feasibly applicable to chemically determine the CO2 mineralized in cementitious materials, and it can be an alternative method for thermogravimetric analysis with lower experimental cost and easier access. Overall, it is evident that cement, concrete, and construction materials are essential to the functionality of civilization. Dealing with CO2 emissions and natural resource depletion induced by the production of these construction materials is urgent for sustainable development. This dissertation is expected to fill the knowledge gap in carbon neutral construction materials research, including increasing the use of low-carbon aggregates (e.g., waste aggregates, recycled aggregates) and alternative cementitious binders as well as developing new test methods that can support measuring the effectiveness of these reduced carbon cementitious materials.

[pt] O sulfato de magnésio está presente em diversos rejeitos industriais e de mineração. Ele e seus derivados poderiam ser reaproveitados em várias áreas industriais, deixando de ser um rejeito para se tornar parte de um processo. Seu óxido, MgO, pode ser utilizado em algumas funções, como regulador de pH, dependendo de sua reatividade. Devido a isto sua formação deve ocorrer em temperaturas abaixo das temperaturas de decomposição do MgSO4. Assim sendo este trabalho avaliou aspectos da decomposição do MgSO4 através de dois artigos. O artigo 1 (Thermodynamics Simulations and Kinetics Modeling of the Thermal Decomposition of MgSO4.7H2O: Part 1 – Reducing Agent Effect), avaliou o efeito cinético da utilização do carbono, através de quatro diferentes agentes redutores, na decomposição térmica do MgSO4.7H2O, enquanto que o artigo 2 (Thermodynamics Simulations and Kinetics Modeling of the Thermal Decomposition of MgSO4.7H2O: Part 2 – Hydration Effect) analisou as influências da taxa de aquecimento dos ensaios e do grau de hidratação do sulfato de magnésio utilizado. Os ensaios termogravimétricos realizados ao longo destes artigos, utilizaram amostras com massa de aproximadamente 10 mg de mistura (sulfato + agente redutor) e estas misturas tiveram uma relação estequiométrica de 1:1. Os experimentos realizados no artigo 1, utilizaram como agentes redutores agentes redutores, carvão vegetal, coque verde, coque breeze e grafite. No artigo 2, os sulfatos analisados foram o anidro, o monohidratado e o heptahidratado e as taxas de aquecimento utilizadas foram de 5 K.min(-1) , 10 K.min(-1) , 15 K.min(-1) e 20 K.min(-1) . Todos os dados obtidos dos ensaios termogravimétricos foram processados através de modelagem matemática para se obter os dados cinéticos. No artigo 1 a utilização dos agentes redutores se mostrou eficiente reduzindo a energia de ativação da decomposição do sulfato de magnésio de 22,731 kJ.mol(-1) (sulfato puro) para 340,391 kJ.mol(-1) (coque verde), 196,120 kJ.mol(-1) (grafite), 191,100 kJ.mol(-1) (coque breeze) e 162,302 kJ.mol(-1) (carvão vegetal). No artigo 2, a taxa de aquecimento não se mostrou como um fator determinante para a decomposição do MgSO4, já em relação a hidratação do sulfato de magnésio, os resultados indicaram que uma pequena parcela de H2O no sistema pode influenciar positivamente a decomposição, visto que os valores de Ea médio foram de 404,5 KJ.mol(-1) (mono), 407 KJ.mol(-1) (anidro) e 433,3 KJ.mol(-1) (hepta). / [en] Magnesium sulfate is present in several industrial and mining wastes. It and its derivatives could be reused in various industrial areas, ceasing to be a waste to become part of a process. Its oxide, MgO, can be used in some functions, as a pH regulator, depending on its reactivity. Due to this, its formation must occur at temperatures below the decomposition temperatures of MgSO4. Therefore, this work evaluated aspects of the decomposition of MgSO4 through two articles. Article 1 (Thermodynamics Simulations and Kinetics Modeling of the Thermal Decomposition of MgSO4.7H2O: Part 1 – Reducing Agent Effect), evaluated the kinetic effect of using carbon, through four different reducing agents, on the thermal decomposition of MgSO4.7H2O, while article 2 (Thermodynamics Simulations and Kinetics Modeling of the Thermal Decomposition of MgSO4.7H2O: Part 2 – Hydration Effect) analyzed the influences of the heating rate of the tests and the degree of hydration of the magnesium sulfate used. The thermogravimetric tests carried out throughout these articles used samples with a mass of approximately 10 mg of the mixture (sulfate + reducing agent) and these mixtures had a stoichiometric ratio of 1:1. The experiments carried out in article 1 used reducing agents, charcoal, green coke, breeze coke, and graphite as reducing agents. In article 2, the sulfates analyzed were anhydrous, monohydrate, and heptahydrate and the heating rates used were 5 K.min(-1) , 10 K.min(-1) , 15 K.min(-1) , and 20 K.min(-1). All data obtained from thermogravimetric tests were processed through mathematical modeling to obtain kinetic data. In article 1, the use of reducing agents proved efficient, reducing the activation energy of magnesium sulfate decomposition from 22.731 kJ.mol(-1) (pure sulfate) to 340.391 kJ.mol(-1) (green coke), 196.120 kJ.mol(-1) (graphite), 191,100 kJ.mol(-1) (coke breeze) and 162,302 kJ.mol(-1) (charcoal). In article 2, the heating rate was not shown to be a determining factor for the decomposition of MgSO4, in relation to the hydration of magnesium sulfate, the results indicated that a small portion of H2O in the system can positively influence the decomposition since the average Ea values were 404.5 KJ.mol(-1) (mono), 407 KJ.mol(-1) (anhydrous) and 433.3 KJ.mol(-1) (hepta).

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