Afin de conditionner les déchets technologiques issus du démantèlement de l’Atelier de Vitrification de Marcoule au Commissariat à l’Energie Atomique et aux énergies alternatives (CEA), leur blocage dans une matrice cimentaire est envisagé. Dans ce contexte, l’effet des rayonnements ionisants issus des déchets nucléaires sur la matrice de confinement doit être examiné afin de garantir d’une part l’intégrité du colis, et d’autre part une production de gaz de radiolyse limitée. Ce travail de thèse s’intéresse au comportement sous irradiation gamma et électronique de trois types de matériaux cimentaires aux constituants différents et se focalise sur la production de gaz de radiolyse et sur l’évaluation de la résistance physique à travers l’observation des modifications structurales. Le sujet est traité par une double approche à la fois sur pâte de ciment et sur phases modèles, c’est-à-dire sur les hydrates constitutifs des pâtes de ciment synthétisés indépendamment. Il apparaît clairement que l’eau porale ainsi que les hydrates constitutifs contribuent à la production d’hydrogène radiolytique, avec une forte variation selon la nature des matériaux cimentaires. Ainsi, les ciments à base d’aluminates de calcium et les ciments phospho-magnésiens présentent un intérêt notable par rapport aux ciments silico-calciques usuels quant à la production d’hydrogène. Aux très fortes doses (plusieurs GGy) la résistance structurale sous irradiation électronique a été évaluée par diffraction de rayons X. Les hydrates constitutifs des trois familles de ciment étudiées présentent une bonne résistance structurale. Malgré la présence de variations dimensionnelles et microstructurales, ils ne s’amorphisent pas sous irradiation, ce qui s’avère positif en vue de l’application industrielle envisagée. / In order to treat the technological waste arising from the dismantling of the Marcoule Vitrification facility of the French Atomic Energy Commission (CEA), conditioning in a cement matrix is being put forward. Within this context, the impact of ionizing radiation produced by the nuclear waste on the confinement matrix ought to be investigated in order to ensure both the integrity of the package and the limitation of the radiolytic gas production. This thesis investigates the behavior of three types of cement compounds with distinct constituents under gamma and electronic radiation. This study deals with both the radiolytic gas production and the physical resistance of the materials using a structural modification examination. A double and complementary approach is used treating cement pastes and synthetic cement compounds together. It clearly appears that the pore water and the hydrates themselves both contribute to the radiolytic hydrogen production, with a significant variation depending on the nature of the materials. As far as radiolysis is concerned, calcium aluminate-based cements and magnesium phosphate cements are of considerable interest in comparison with the usual calcium silicate cements. At very high doses (GGy range), the structural resistance under electron irradiation was evaluated by X-ray diffraction. The constituent hydrates of the three cement types studied exhibit a good structural resistance. Despite the presence of dimensional variations at the unit cell scale as well as microstructural evolution, no amorphization is observed under irradiation, which is an interesting result with respect to the intended industrial application.

FBC-ashes, as a waste product of a relatively new technology of combustion, so-called fluidized bed combustion, cannot be used for building materials production in contrast to fly-ashes. Problem rests in their chemical as well as their mineralogical composition. Thought it can be admitted that FBC-ash may be used for preparation of the hydraulic binder with a similar chemical and mineralogical composition, but only in a certain limit of concentration. The first part of this thesis was focused on the potentialities of fluid fly ashes utilization as hydraulic bonding material in preparation of dry mortar mixtures and the second part of works was engaged in research development of burned hydraulic binder of FBC ash. The thesis explores the conjunction between parameters of burning mode and hydraulic binder characteristics.

No description available.

Betong är ett material som används dagligen och finns i allt från skyskrapor och tunnlar till skulpturer och möbler. Tryckhållfastheten är en av betongens viktigaste egenskaper och med en konstant utvecklande bransch där det byggs mer och mer är det avgörande att betongen som används håller. Normhållfastheten hos cement kontrolleras regelbundet och visar i vissa fall variationer utanför cementens normala spann. Cementillverkare upptäcker dessa avsteg genom att granska varje leverans som produceras samt genom egna produktkontroller på fabriken. Vid upptäckta felmarginaler finns krav på att berörda kunder i branschen måste informeras för att exempelvis få en möjlighet till att kunna korrigera recept inför betongblandningen. Vid en lägre normhållfasthet i cement skapas generellt en lägre hållfasthet i betong och för att justera avvikelsen ökar betongtillverkare mängden cement i recepten för att kunna leverera en produkt med utlovad hållfasthet till kund. Slutresultatet kommer att hjälpa betongtillverkare att förutse hur betongen kan påverkas av en variation i cementens hållfasthet och vara ett hjälpmedel för hur receptet ska hanteras för att täcka upp eventuella variationer så att kunderna inte påverkas i lika stor grad. Arbetet innefattar tre betongrecept med separata vct som testas med cementen Anläggningscement Slite i en grov-, mellan- och finmald version. Gjutningen sker i Cementa Research laboratorium i Liljeholmen och sammanlagt utförs 18 gjutningar med 22 liter betong per gjutning. Totalt gjuts 216 kuber som sedan trycktestas vid 7 respektive 28 dygn i samma lokal. Data har sedan sammanställts för att kunna jämföras mot cementens normhållfasthet som har testats i Cementas lab i Slite. Arbetet har utförts åt Cementa AB och Thomas Concrete Group AB för att kontrollera sambandet mellan normhållfastheten i cement och den färdiga betongens hållfasthet. Sambandet är av stor vikt i den dagliga produktionen och är något som efterfrågats under lång tid. Resultatet från gjutningarna visar att det finns ett samband till en viss grad men på grund av komplikationer under gjutningarna har vissa värden inte blivit som förväntat. / Concrete is one of the world's most important building materials and is used in everything from skyscrapers, tunnels to sculptures and furniture. The strength of concrete is important and with a constantly developing industry where more and more is being built, it is vital that the concrete that is used holds. The work is performed on behalf of Cementa AB and Thomas Concrete Group AB to investigate the relation between the strength of cement and the strength of the concrete. The relation is of great importance in daily production and is something that has been requested for a long time. The standard strength of cement is checked regularly and shows in some cases deviations outside the normal range of the cement. Cementa detects these deviations by controlling shipped cement and by the product controls at the factory. If margins of error are discovered, there are requirements for those involved in the industry that they must inform the customers in order for them to correct their concrete mixes accordingly. At a lower standard strength in cement, a lower strength in concrete is generally created and to correct the deviation, the affected amount of cement in the recipe increases in order to be able to deliver a promised product to the customer. The end result will help concrete manufacturers predict how the concrete can be affected by a deviation of the strength of the cement and be a tool for how the recipe should be handled to cover any deviations so that customers are not affected to the same extent. The work includes three concrete recipes with separate w/c-ratios that were tested with the cement CEM I 42,5 N SR3 MH/LA in a coarse, medium and finely milled version. The casting took place in Cementa Research's laboratory in Liljeholmen and in summary, 18 castings were performed with 22 liters of concrete per casting. A total of 216 cubes were cast and then pressure tested at 7 and 28 days. The data has then been compiled to be able to be compared with the cement's standard strength that has been tested in Cementa's lab in Slite.

[pt] O presente trabalho tem como objetivo investigar os efeitos químicos, físicos e mecânicos de altas dosagens de escória granulada de alto forno (85 por cento) como adição em cimentos Portland. Foram feitas quatro amostras, sendo uma do cimento padrão referência conhecido como CP IND e com as dosagens de adição de escória, com 60 por cento de adição de escória (usual do mercado), 85 por cento de escória sem aditivo (branco) e 85 por cento de escória com 7,5 por cento de aditivo ativador (Metassilicato de Sódio Anidro). Os materiais foram caracterizados quanto sua composição química, área superficial e granulometria por ensaios de Fluorescência, Blaine e granulometria laser. Para investigar a formação das fases foram realizadas análises de difratometria de raios-x (DRX) e calorimetria. Finalmente, os cimentos hidratados foram ensaiados em compressão uniaxial para as idades de 1, 3, 7, 28 e 91 dias para medir a resistência à compressão na argamassa padrão de cimento pelo método de argamassa padrão, e em 1, 7 e 28 dias em concreto. O uso desse ativador garantiu a reserva alcalina, elevando a precipitação de produtos de hidratação. As misturas ativadas com 85 por cento de escória apresentaram resultados de resistência à compressão satisfatórios para cimentos Portland Classe de resistência 25 MPa. O cimento com 85 por cento de adição de escória ativado com metassilicato de sódio anidro apresentou um desempenho, na argamassa padrão de cimento, na idade de 1 dia, mais de 4 vezes superior quando comparado ao cimento com 85 por cento de adição de escória sem ativador. Esse desempenho foi diminuindo à medida que hidratação evolui, quando se esperava ao contrário, demonstrando que o percentual utilizado e a granulometria do ativador podem não ter sido a mais adequada, havendo a necessidade de um estudo mais aprofundado tanto nessa relação quanto na verificação da porosidade das misturas. / [en] The present work investigates the chemical, physical and mechanical effects of high dosages of granulated blast furnace slag (85 percent) as an addition to Portland cements. Four samples were made, one of the reference standard cement known as CP IND and with the slag addition dosages, with 60 percent slag addition (usual on the market), 85 percent slag without additive (white) and 85 percent slag with 7.5 percent activating additive (Anhydrous Sodium Metasilicate). The materials were characterized regarding their chemical composition, surface area and particle size by Fluorescence, Blaine and laser particle size tests. To investigate the formation of the phases, x-ray diffractometry (XRD) and calorimetry analyzes were carried out. Finally, the hydrated cements were tested in uniaxial compression at ages of 1, 3, 7, 28 and 91 days to measure the compressive strength in the cement paste, and at 1, 7 and 28 days in concrete. The use of this activator guaranteed the alkaline reserve, increasing the precipitation of hydration products. The mixtures activated with 85 percent slag presented satisfactory compressive strength results for Portland cements Strength Class 25 MPa. The cement with 85 percent addition of slag activated with anhydrous sodium metasilicate presented a performance, in the cement paste, at the age of 1 day, more than 4 times higher when compared to cement with 85 percents lag addition without activator. This performance decreased as hydration progressed, when the opposite was expected, demonstrating that the percentage used and the granulometry of the activator may not have been the most appropriate, with the need for a more in-depth study both in this relationship and in the verification of the porosity of the mixtures.

3D printing in construction offers significant advantages in cost, material, and time efficiency, but material-related challenges need to be overcome for accelerated adoption. One of these challenges is understanding the rheological properties of cement paste, the primary fluid component of concrete, and how they are related to its microstructure. Moreover, the change in these properties over time must be monitored as the paste is a dynamic system in the fresh state, the period most relevant for the 3D printing process. The dissertation primarily explores and emphasizes the viability of small amplitude oscillatory shear techniques for understanding and differentiating between the microstructural evolution of cement pastes without and with printability-enhancing additives. Understanding the rheology of cement pastes, especially the time-evolution of viscoelastic properties, is crucial for 3D printing as they affect the flow of the material and structural stability throughout the printing process. Viscoelastic properties can be measured using oscillatory rheological experiments, which have been found suitable for cementitious materials and provide key properties like storage modulus and loss modulus, among others. There has been a growing interest in using such rheological techniques as there still exist many unanswered questions regarding rheological-microstructure and microstructure-printability relationships. The mixture of cement and water by itself is not printable; additives are generally required. Additives like nanoclays, calcium carbonate whiskers, and viscosity-modifying agents can enhance the printability of concrete by improving structural buildup and flow behavior. However, their microstructure-printability relationship remains unexplored, and this investigation has tried to shed some light on it. The dissertation is structured into chapters that discuss rheological measurements, the impact of additives, and various testing methods to support hypotheses about microstructure-rheology relationships and 3D printability. Chapter 1 involved the use of small amplitude oscillatory sweep techniques to study ordinary Portland and Portland limestone cements. Yield stress and viscosity are commonly measured rheological properties for printability, but these tests may provide little information about the microstructure as they are destructive in nature. Oscillatory sweep tests can be non-destructive and provide information about the microstructure before structural breakdown, which is important for the material that is already extruded. This material is at rest but is also undergoing hydration, which necessitates monitoring the evolution of material properties over time. The relatively few studies that exist that have studied this time-evolution have focused primarily on the evolution of storage modulus, while the change in the critical strain parameter, which is itself important for measuring the storage modulus, has remained unexplored. In this chapter, an ordinary Portland cement (OPC) and a Portland limestone cement (PLC), mixed at different w/c ratios, were subjected to amplitude sweeps to observe the time-evolution of critical strain during the induction period. A Python algorithm was developed for extracting several different rheological properties along with critical strain. As hydration progressed, critical strains were found to increase exponentially and had an inverse correlation with the w/c ratio. The increase was quantified by an equation with a good fit using w/c ratio and time as the dependent variables. It was also shown that critical strain and storage modulus have different growth profiles, which could mean that the underlying microstructural factors for those properties are different. It was also shown that the choice of criterium for locating critical strain significantly affected the calculated critical strain and highlighted the importance of standardization of such criteria. Chapter 2 extended the application of the oscillatory techniques and hypotheses toward cement pastes with additives that could improve 3D printability. Chemical admixtures and mineral additives are generally added to cement-based materials to achieve adequate printability. This investigation employed additives with different physical and chemical properties to observe their impacts on printability and hydration kinetics. Amplitude sweeps were used to measure changes in various rheological properties during the dissolution and induction periods in plain and additive-modified pastes. This chapter shows that amplitude sweeps can be effective methods for differentiating between cement pastes with different additives. The chapter also showed the importance of monitoring properties other than critical strain and storage modulus, specifically the yielding strain, for facilitating an understanding of microstructure-rheological property relationships when combined with other characterization techniques. Establishing these relationships can eventually help explain why printability-enhancing additives that are already used are effective and can provide a tool to explore more additives in the future. Chapter 3 explored the use of in-situ characterization tests to help support the claims made in previous chapters. pH testing on various cement pastes highlighted the correlation between pH and storage modulus. Electrical impedance measurements were conducted to monitor cement hydration and microstructural development. The resistance of the pastes increased over time, with an initial slow rate followed by a rapid exponential increase, correlating with critical strain. The pH and resistance results showed they could be promising in-situ measurement techniques for monitoring prints on-site. The chapter also includes a discussion on the properties of methylcellulose, specifically its foaming capability and polymeric behavior, which potentially affected the rheological results and printability. Chapter 4 discussed the methodologies and results of frequency and time sweeps in rheological tests, focusing on the storage modulus. It examined how different factors, such as amplitude, frequency, and additives, affect continuous measurement. Amplitude and frequency sweeps are interconnected, requiring both to be performed in tandem to determine the best combination of amplitude and frequency for time sweep tests. Frequency sweeps on different cement pastes showed that storage modulus curves change over time, with smoother curves at different frequencies depending on the age of the paste. Additives affect the frequency sweep results, leading to different ranges of ideal frequencies and storage modulus values. Time sweeps were conducted by varying the oscillation amplitude and frequency, and it was found that varying them during the time sweep can improve the quality of storage modulus evolution curves. The results also suggested that the minimum strain rate required varies over time, and can be achieved by changing either the strain amplitude or the frequency. The chapter also included a preliminary investigation on structural rebuilding, which showed that all rheological properties that were monitored recovered fully, at a more rapid rate during rebuilding. The results and hypotheses presented in Chapters 1, 2, and 4 can serve as foundations for improving measurement protocols for oscillatory tests and, combined with Chapter 3, can guide further explorations of viable techniques to study microstructure evolution during the induction period of cement pastes.

No / The presence of free water in mortars destined for silo or bagged storage can lead to the degradation of the binder phase. Such water may be present as a result of using wet, as-delivered sand or as a consequence of prior processes such as de-activation of Roman cement. Thus, water must be removed from the system prior to storage. Part 1 of this paper describes the control of a technique by which quicklime is added to the wet system which principally dries it by both slaking the quicklime and evaporation as a consequence of the exothermic slaking reaction. Two examples of mortars are presented in which excess water is removed from the system by the inclusion of quicklime. In the first, the water is present in the as-delivered sand and the binder is a combination of the slaked lime and ggbs. In the second, the water remains after pre-hydration of a Roman cement which is a process to retard its rapid setting characteristics. It is shown that optimally dried mortars are not subject to degradation following storage of both mortar types. (C) 2015 Elsevier Ltd. All rights reserved.

Les mélanges de ciment sulfoalumineux et de ciment Portland sont des liants hydrauliques innovants permettant de moduler les propriétés des bétons, telles que la vitesse de montée en résistance ou la stabilité dimensionnelle. Les performances du liant peuvent ainsi être ajustées pour de nombreuses applications. Au-delà de cet avantage, les émissions de dioxyde de carbone liées à la production du ciment sulfoalumineux sont significativement réduites comparées à celles du ciment Portland traditionnellement utilisé. La diversité des propriétés de ces liants résulte de la variété des mélanges pouvant être réalisés à partir des deux constituants de base. Chaque mélange présente alors une cinétique d'hydratation et des propriétés qui lui sont propres. Par exemple, certains liants sont expansifs mais présentent une montée en résistance progressive, tandis que d'autres sont stables dimensionnellement alors que leur résistance stagne après quelques jours d'hydratation. L'identification et le contrôle des paramètres à l'origine de ces comportements sont donc nécessaires pour garantir des propriétés spécifiques à un usage donné : chape, mortier de réparation, élément préfabriqué, etc. C'est l'objectif de cette étude qui s'attache à déterminer la cinétique, la minéralogie et les propriétés associées à l'hydratation de trois mélanges contenant 85 %, 70 % et 40 % de ciment Portland. Les essais entrepris ont aussi permis d'aboutir à une modélisation thermodynamique des mécanismes d'hydratation. L'impact de la composition du ciment Portland est également étudié. Enfin, il est montré que l'anhydrite et la chaux sont deux leviers qui modifient radicalement le processus d'hydratation et permettent ainsi d'adapter les propriétés d'un mélange aux exigences de son utilisation / Blends of ordinary Portland cement and sulfoaluminate cement are innovative hydraulic binders allowing control of concrete properties such as hardening speed or dimensional stability for specific applications. Moreover, carbon dioxide emissions linked to sulfoaluminate cement are significantly reduced compared to ordinary Portland cement. The binder properties can be adjusted due to the diversity of blends conceivable with these two constituents. Each blend has its own hydration kinetic and properties. For example, some blends are expansive and the hardening is progressive whereas other mixtures are dimensionally stable but their strength stagnates after few days. Identification and control of the parameters responsible of these comportments are necessary in order to guaranty specific properties for each application: screed, repairing mortar, etc. This is the aim of this study which described the hydration kinetic, the properties and composition of three blends containing 85 %, 70 % and 40 % of Portland cement. These experiments are completed by thermodynamic modeling of the hydration mechanisms. The effect of the Portland cement composition has also been tested. Finally, it's shown that anhydrite and calcium hydroxide are two key parameters which modify radically the hydration process and allow the properties adjustment required for the blend used

O cimento ósseo, utilizado para a fixação de componentes protéticos nas cirurgias de substituição articular, mais resistente às forças de compressão do que às forças de tração, tem suas propriedades mecânicas alteradas por vários fatores entre esses a formulação comercial e o método de preparação empregado. É o objetivo deste trabalho avaliar comparativamente as propriedades mecânicas à compressão de duas formulações comerciais de cimento ósseo preparadas manualmente e a vácuo, segundo as instruções do fabricante. Um conjunto de moldagem confeccionado em aço inoxidável permitiu preparar 48 corpos de prova para cada grupo experimental, totalizando 192 corpos de prova, que foram testados na Máquina Universal de Ensaios, tendo as especificações baseadas nas normas ISO 5833 e ASTM F451-86. A elaboração do diagrama tensão x deformação de cada grupo experimental analisou as propriedades mecânicas do cimento ósseo quanto ao módulo de elasticidade, tensão e deformação no limite de proporcionalidade, entre grupos de mesma formulação comercial e entre os grupos com mesmo método de mistura. Analisados estatisticamente pelo método de Variança de Kruskal-Wallis (p ≤0,001) e pelo método de Dunn's (p ≤0,05). Quanto ao módulo de elasticidade, o grupo 2M foi o que apresentou maior módulo, 1563 MPa, valor estatisticamente significante (p ≤ 0,05) em relação aos grupos 1M, 1V e 2V. Para a tensão no limite de proporcionalidade os grupos 1M (39,40 MPa) e 2V (39,65 MPa) foram os maiores valores de tensão no limite de proporcionalidade, não havendo diferença estatisticamente significante entre eles, mas essas diferenças foram significativas quando comparadas aos grupos 1V e 2M. A deformação no limite de proporcionalidade de maior valor percentual foi para o grupo 1M, 3,36%, sendo esta diferença estatisticamente significante quando comparado ao grupo 2M. Os testes de resistência à compressão do cimento nacionalizado e importado, preparados manualmente e a vácuo, mostraram não haver diferença importante entre os dois tipos de cimento ósseo, nem entre as duas formas de misturá-los. / The bone cement used for the fixation of the prosthetic components in the surgeries of joint replacement, more resistant to the compression than to the traction, has its mechanical properties altered by several factors among those the commercial formulation and preparation employee's method. It is the objective of this work to evaluate the mechanical properties to the compression of the two commercial formulas of bone cement manually prepared and using vacuum, according to the manufacturer's instructions. A molding set was made in stainless steel and it allowed for the preparation of 48 bodies of proof for each experimental group, adding up to 192 proof bodies total which were tested in the Universal Rehearsal Machine, with the specifications based on the ISO 5833 and the ASTM F451-86 regulations. The elaboration of the diagram "tension vs. deformation" of each of the experimental group analyzed the mechanical properties of the bone cement in relation to the elasticity module, tension and deformation on the proportional limit among the groups with the same commercial formula and among the groups with the same mixture method. Analyzed statistically, by Kruskal-Wallis's method of the variation (p ≤0.001) and by the Dunn’s method (p ≤0.05). Regarding the elasticity, the group 2M was the one with the highest module, 1563 MPa, a statistically significant value (p ≤0.05) in relation to the groups 1M, 1V and 2V to the tension at the limit of the proportionality, there is no significant differences among them, but these differences were relevant when compared to groups 1V and 2M. The deformation at the limit of the proportionality of the highest percentage was to group 1M, 3.36%, being this the relevant statistical difference when compared to group 2M. The resistance tests to the compression of the national and international cement prepared manually and by vacuum show that there is no important difference between the two kind of bone cement, and neither between the two ways of mixing them.

The specific objectives of this research were to quantify the effects of certain environmental factors on the relative strength loss of soil-cement subjected to compaction delay and to develop a numerical tool that can be easily used by engineers and contractors for determining a maximum compaction delay time for a given project. These objectives were addressed through extensive laboratory work and statistical analyses. The laboratory work involved testing an aggregate base material and a subgrade soil, each treated with two levels of cement. Environmental factors included in the experimentation were wind speed, temperature, and relative humidity, and three levels of each were evaluated in combination with varying compaction delay times. The primary response variables in this research were relative compaction and relative strength. The findings indicate that relative strength is sensitive to variability among the selected independent variables within the ranges investigated in this research, while relative compaction is not. Inferring relative strength from relative compaction is therefore not a reliable approach on soil-cement projects. Consistent with theory, higher wind speed, higher air temperature, lower relative humidity, and higher compaction delay time generally result in lower relative strength. With the nomographs developed in this research, the maximum delay time permitted for compaction of either a base or subgrade material similar to those tested in this research can be determined. Knowing in advance how much time is available for working the soil-cement will help contractors schedule their activities more appropriately and ultimately produce higher quality roads. When acceptable compaction delays are not obtainable due to adverse environmental conditions, a contractor may consider using set retarder, mixing at water contents above OMC, or constructing at night as possible solutions for achieving target relative strength values.