Dissertations / Theses: 'Cement hydrates'

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Rheinheimer, Vanessa. "A nanoscale study of dissolution and growth processes in cement hydrates." Doctoral thesis, Universitat Politècnica de Catalunya, 2012. http://hdl.handle.net/10803/285965.

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This thesis aims at providing new knowledge on the, otherwise poorly known, molecular-scale mechanisms that operate during hydration of cement phases and dissolution of their hydrates. In order to pursue this objective, a novel approach has been followed, including the development of a new procedure to synthesize thin films of calcium silicates, real time characterization of grain growth and dissolution with liquid-cell atomic force microscopy, and monitoring of their chemical evolution by X-ray photoelectron spectroscopy of thin films hydrated in-situ, avoiding atmospheric contamination. Nanometer-sized films of clinker phases have been prepared using electron-beam evaporation methods. After deposition on silicon substrates, film thicknesses and mineralogical composition were characterized by atomic force microscopy (AFM) or mechanical profilometry and grazing-angle X-ray diffraction (GAXRD), respectively. Chemical composition was determined by X-ray photoelectron spectroscopy (XPS). Results from the GAXRD and XPS analysis show that aluminates phases are not suitable to be evaporated by electron beam technique. However quantitative analysis of calcium silicates samples shows that the Ca:Si ratio of the deposited film is the same as in the bulk starting material, confirming the suitability of the technique for the synthesis of these materials. Calcium silicate thin films with different thicknesses were submitted to hydration in different ways. XPS results describe clear chemical changes when samples are exposed to water vapor by shifts on the silicon peak, broadening on the calcium peak and decreasing on the Ca:Si ratio, related to the silicon polymerization due to the C-S-H formation. In situ hydration in fluid cell followed by AFM in water and calcium hydroxide saturated solution allows observing the formation of C-S-H particles, that happens very fast in C3S, which is dissolved later, and slower in C2S. Finally, Scanning transmission X-ray microscopy (STXM) of samples hydrated in situ with water allows observing the formation of particles with different concentration of calcium and silicon, and different chemical state at some point. The development of this technique of synthesis and the results obtained on the hydration allow improving the knowledge of early stage clinker phase hydration at the molecular level and to better understand the behavior of these materials, shedding some additional light on the complex problem of the hydration mechanisms of cementitious materials.
Aquesta tesi té per objectiu proporcionar nous coneixements sobre els mecanismes, abans poc coneguts, que operen durant la hidratació de les fases de ciment i la dissolució dels seus hidrats a escala molecular. Per tal d'aconseguir aquest objectiu, un nou enfocament ha estat seguit amb l'elaboració d'un nou procediment per sintetitzar pel·lícules primes de silicats de calci, la seva caracterització en temps real del creixement del gra i de la dissolució amb les cel·les de líquid al microscopi de forces atòmiques i el seguiment de l'evolució de la seva composició química per espectroscòpia de fotoelectrons de raigs X de pel·lícules primes hidratades in-situ, evitant la seva contaminació atmosfèrica. S'han preparat pel·lícules nanomètriques de les fases del clínquer utilitzant l'evaporació per feix d'electrons. Després de la deposició en substrats de silici, es van caracteritzar el gruix mitjançant la microscòpia de forces atòmiques (AFM) i la perfilometria mecànica i la composició mineralògica amb la difracció de raigs X d'angle rasant (GAXRD). La composició química es va determinar per espectroscòpia fotoelectrònica de raigs X (XPS). Els resultats del GAXRD i d'XPS mostren que els aluminats no són adequats per a ser evaporats utilitzant l'evaporació assistida amb feix d'electrons. No obstant això, anàlisis quantitatives de les mostres de silicats de calci mostren que la relació Ca:Si de la pel·lícula dipositada és la mateixa que en el material de partida, el que confirma la idoneïtat de la tècnica per a la síntesi d'aquests materials. Les pel·lícules primes de silicat càlcic de gruixos diferents van ser sotmeses a hidratació de diferents maneres. Els resultats d`XPS descriuen canvis químics clars quan les mostres estan exposades al vapor d'aigua com s'infereix dels canvis en el pic del silici, l'eixamplament del pic del calci i la disminució en la relació Ca:Si, que es relaciona amb la polimerització del silici degut ala formació de C-S-H. La hidratació in situ en aigua o solució saturada d'hidròxid de calci a la cel·la de fluid de l'AFM permet observar la formació de partícules de C-S-H. La hidratació ocorre molt ràpidament en el C3S, que després es dissol, i és més lenta en el C2S. Finalment, la microscòpia de transmissió i escaneig de raigs X (STXM) de les mostres hidratades in situ amb aigua permet observar la formació de partícules amb diferents concentracions de calci i silici i, en alguns casos, la variació de l'estat químic . El desenvolupament d'aquesta tècnica de síntesi i els resultats obtinguts en la hidratació permeten millorar el coneixement de la hidratació de les fases del clínquer en estadis inicials a nivell molecular i entendre millor el comportament d'aquests materials, ajudant a aclarir el complex problema dels mecanismes d'hidratació dels materials del ciment

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Acher, Loren. "Etude du comportement sous irradiation γ et électronique de matrices cimentaires et de leurs hydrates constitutifs." Thesis, Université Paris-Saclay (ComUE), 2017. http://www.theses.fr/2017SACLX045/document.

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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

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Constantinides, Georgios 1978. "Invariant mechanical properties of calcium-silicate-hydrates (C-H-S) in cement-based materials : instrumented nanoindentation and microporomechanical modeling." Thesis, Massachusetts Institute of Technology, 2006. http://hdl.handle.net/1721.1/34377.

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Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Civil and Environmental Engineering, 2006.
Includes bibliographical references (p. 455-478).
Random porous solids such as bone and geomaterials exhibit a multiphase composite nature, characterized by water-filled pores of nm- to m-scale diameter. The natural synthesis and operating environments of such materials significantly alters phase composition and multiscale structural heterogeneities throughout the material lifetime, defining significant changes in macroscopic mechanical performance for applications ranging from multispan bridges to calcium-phosphate bone replacement cements. However, the nanoscale phases formed within the unique chemical environment of pores cannot be recapitulated ex situ in bulk form, and imaging of the composite microstructure is obfuscated by the size, environmental fragility, and nonconductive nature of such geomaterials and natural composites. Thus, there is an increasing drive to develop new approaches to image, quantify the mechanical contributions of, and understand the chemomechanical coupling of distinct phases in such composites. In this thesis, we utilize recent advances in experimentation namely instrumented indentation, and micromechanical modeling namely homogenization techniques, in an attempt to quantify the mutli-phase, multi-scale heterogeneity observed in all cement-based materials. We report a systematic framework for mechanically enabled imaging, measuring and modeling of structural evolution for cement based materials (CBM), porous geocomposites, at length scales on the order of constituent phase diameters (10-8 - 10-6 m), and thus identify two structurally distinct but compositionally similar phases heretofore hypothesized to exist.
(cont.) The presented experimental and modeling results culminated in micromechanical models for elasticity and strength that can predict the macroscopic mechanical behavior for a range of CBM systems. The models directly correlate the changes in chemical and mechanical state to predict the experimentally observed range of macroscopic mechanical properties. This general framework is equally applicable to other man-made and natural composites, and enables accurate prediction of natural composite microstructure and mechanical performance directly from knowledge of material composition.
by Georgios Constantinides
Ph.D.

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Nguyen, Dan-Tam. "Microindentation Creep of Calcium-Silicate-Hydrate and Secondary Hydrated Cement Systems." Thesis, Université d'Ottawa / University of Ottawa, 2014. http://hdl.handle.net/10393/31519.

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The nanostructure, physical properties and mechanical performance of C-S-H, 1.4 nm tobermorite, jennite, and ettringite were studied. C-S-H of variable stoichiometries was examined as a model system in comparison with that produced in the hydration of Portland cement. The current Master’s thesis is comprised of four research papers designed to improve the current understanding of the nanostructure and engineering properties of C-S-H systems and modified C-S-H systems. Many of the controversial issues in cement science were identified and were addressed in a comprehensive research study, which examined the key features of the C-S-H systems at the nano-structure level. In Chapter 4, each paper presented new evidence for a number of mechanical aspects of C-S-H materials. Numerous advanced analytical tools were used in order to verify the observations made in each section. The major achievements of the current work are mentioned briefly as follows: 1. It was determined that microindentation is a useful method for determining the creep behavior of C-S-H of various stoichiometries, 1.4 tobermorite, jennite, and ettringite. 2. Microindentation parameters i.e. creep modulus, indentation modulus and indentation hardness are porosity dependent. 3. Microindentation creep measurements on C-S-H (C/S = 0.80 and 1.20) demonstrated that creep modulus, indentation modulus, and indentation hardness are all dependent on mass-loss from the 11%RH condition. 4. Evidence was presented that the nanostructural role of interlayer water in C-S-H has a significant influence on the creep process.

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Bordy, Arthur. "Influence des conditions thermo-hydriques de conservation sur l'hydratation de matériaux cimentaires à base d’une fine recyclée." Thesis, Cergy-Pontoise, 2016. http://www.theses.fr/2016CERG0876/document.

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La valorisation, comme granulats, des matériaux issus du recyclage du béton de démolition contribueà diminuer les surfaces dédiées au stockage des déchets et à limiter le recours systématique auxressources naturelles. L’emploi de fines recyclées à partir de béton de déconstruction s’inscrit danscette démarche et permet par ailleurs, quand la fine est utilisée en substitution partielle du cimentlors de la fabrication de nouveaux matériaux cimentaires, de réduire l’impact sur l’environnement deces matériaux.Cet usage conduit à mettre en présence dans la pâte à l’état frais du ciment anhydre et du cimenthydraté, ce qui pose la question de l’impact de cette situation sur le matériau. Pour y répondre enpartie, les travaux de recherche présentés dans cette thèse ont pour objectifs principaux d’étudier leprocessus d’hydratation d’une phase anhydre en présence d’autres phases hydratées, et d’analyserl’influence des conditions thermo-hydriques de conservation (HR et T°) sur les cinétiquesd’hydratation des matériaux cimentaires.Pour ce faire, une campagne expérimentale a été menée sur des mortiers et leurs pâtes de cimentéquivalentes fabriqués en remplaçant une partie de leur ciment Portland par une fine issue durecyclage d’une pâte de ciment durcie et bien hydratée. Un suivi au cours du temps des teneurs enPortlandite, de la porosité totale, de la résistance à la compression ainsi que de la résistance à lacarbonatation accélérée des matériaux a été réalisé. Les résultats obtenus montrent qu’il est possiblede fabriquer des mortiers en substituant le ciment par une fine obtenue uniquement par concassageet broyage d’une pâte de ciment durcie. Cependant, l’augmentation du taux de substitution massiquedu ciment par la fine recyclée s’accompagne d’une altération des propriétés et performances desmortiers. Les résultats du suivi d’hydratation couplés aux résultats d’analyse de la microstructure ontmontré que l’effet des conditions thermo-hydriques de conservation sur les cinétiques d’hydratationdes différentes pâtes de ciment dépend de leurs propriétés intrinsèques (microstructure). Celapourrait expliquer l’absence de consensus dans la littérature sur la valeur de l’humidité relativeambiante conduisant à l’arrêt de l’hydratation.En parallèle à l’étude expérimentale, une étude numérique de l’influence des conditions thermohydriquesde conservation sur l’hydratation des pâtes de ciment a été menée. Pour les besoins del’étude, une réadaptation du code de calcul utilisé, CEMHYD3D, a été nécessaire. Les résultatsobtenus montrent que, lors de l’hydratation, la Portlandite initialement présente dans le matériau(apportée par la fine recyclée) se dissout au contact de l’eau alors que la phase encore anhydre enproduit. Cette étude a également permis de conforter les résultats expérimentaux quant à l’influencede l’humidité relative ambiante sur l’hydratation
The use, as aggregates, of recycled materials from demolished concrete contributes to limit landfill and the systematic use of natural resources. Using recycled fines from the deconstruction concrete is an extension of this approach. When used as a partial substitution for cement in cementitious materials, it may also be a solution to reduce the environmental impact of these materials.This specific use induces the presence of anhydrous cement particles and hydrated cement phases in the fresh material. This raises the question whether and how it can impact the hydration process. With the aim to answer, at least partially, to this question, the thesis presents a study of the hydration process of an anhydrous phase in the presence of other hydrated phases, and analyzes the influence of the conservation conditions (RH and T°) on the hydration kinetics of cementitious materials.An experimental campaign was conducted on mortars and their equivalent cement pastes designed by replacing a part of their Portland cement by a recycled cement paste fine. The monitoring of the Portlandite content, the total porosity, the compressive strength and the accelerated carbonation of the materials was achieved. The obtained results show that it is possible to design mortars by substituting their cement by a fine obtained only from crushing and grinding of a hardened cement paste. However, increasing the substitution ratio of the cement by the recycled fine was find to be accompanied by a deterioration of the mortars properties and performances. The results of the hydration monitoring coupled to investigations of the microstructure showed that the effect of conservation conditions on the hydration kinetics of the different cement pastes depends on their intrinsic properties (microstructure). This could explain the lack of consensus in the literature on the drying conditions under which hydration kinetics are strongly affected.In parallel to the experimental study, a numerical study of the influence of the conservation conditions on the hydration of cement pastes was conducted. Readjustments of the parameters of the used code (CEMHYD3D) were necessary. The obtained results show that, during hydration, the Portlandite originally present in the material (provided by the recycled fine) dissolves in contact with water, while the anhydrous phase produces new Portlandite. This study consolidated moreover the experimental results on the influence of the ambient relative humidity on hydration

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Roosz, Cédric. "Propriétés thermodynamiques des phases cimentaires hydratées : C-S-H, C-A-S-H et M-S-H." Thesis, Poitiers, 2016. http://www.theses.fr/2016POIT2264/document.

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Le béton est l'un des matériaux de construction les plus utilisés au monde. Sa durabilité, ses propriétés mécaniques et chimiques en ont fait un matériau de choix dans les concepts de stockage proposés par l'Agence Nationale pour la gestion des Déchets RadioActifs (Andra), notamment pour la réalisation des ouvrages de soutènement, bouchons d'alvéoles, massifs d'appuis ou encore conditionnement des déchets. L'étude de la stabilité des phases constitutives des matériaux cimentaires est donc nécessaire au vu des quantités envisagées et de la pérennité des ouvrages, et doit considérer (i) des gammes de températures adaptées aux matrices cimentaires de confinement en contact avec des déchets exothermiques (25 à 80°C), et (ii) une échelle de temps représentative de la durée de vie d'un stockage.Le projet ThermoChimie de l'Andra vise donc à développer une base de données (BDD) thermodynamiques cohérente, permettant de modéliser l'évolution chimique des matériaux cimentaires dans l'environnement du stockage de déchets radioactifs. Toutefois, dans l'état actuel, la base de données ne propose que des données thermodynamiques sur les phases cimentaires bien cristallisées, ainsi que sur un jeu de données limité à trois compositions chimiques différentes pour les C-S-H nanocristallins, ne permettant pas de reproduire la dégradation des matériaux cimentaires, ni de modéliser la dégradation des nouvelles formulations telles que les bétons "bas-pH".L'objectif est donc d'acquérir un jeu de données thermodynamiques complémentaire, sur les phases telles que les C-S-H (Silicates de Calcium Hydratés), C-A-S-H (Silicates de Calcium Alumineux Hydratés) et M-S-H (Silicates de Magnésium Hydratés), pour les intégrer à la base de données Thermo-Chimie. Cette étude s'appuie sur un travail expérimental, analytique et numérique dans le but d'obtenir un jeu de données thermodynamiques (ΔfG0, ΔfH0, Cp(T), S0) suffisamment représentatif de la variabilité chimiques de ce type de phases. Enfin, cet ensemble de donnée permet le développement d'un modèle de prédiction de données thermodynamiques dans des espaces de compositions et de températures étendues.Le développement de ce modèle de prédiction requiert (i) l'acquisition de propriétés thermodynamiques sur des phases représentatives du système chimique étudié, et (ii) une connaissance précise de la structure et des formules chimiques de ces phases. Trois types d'hydrates ont donc été synthétisés puis caractérisés : les C-S-H, les C-A-S-H et les M-S-H. Des méthodes analytiques telles que la DRX, l’ATG et la RMN du solide (29Si, 27Al) permettent d'établir des similitudes entre la structure des C-(A-)S-H et celle de la tobermorite d'une part, et entre la structure des M-S-H et celle des phyllosilicates Mg-Si 2:1 d'autre part. Les hydrates présentent toutefois une nanocristallinité ainsi que des défauts tant au niveau de la polymérisation du silicium tétraédrique qu'au niveau de l'empilement de leurs feuillets.Une approche multi-techniques est également utilisée, couplant isothermes d'adsorption (eau et azote) et RMN 1H aux résultats de DRX et ATG, pour discriminer les différents types d'eau plus ou moins liés à la structure des C-(A-)S-H. Cette étude a permis de mettre en évidence et de quantifier les différents types d'eau composant la structure des C-(A-)S-H. L'impact des méthodes de préparation a également été mis en évidence sur la quantification des différents types d'eau et notamment l'eau interfoliaire. L'acquisition des paramètres thermodynamiques sur les phases synthétisées est réalisée à partir de l'analyse des solutions d'équilibre pour le calcul des log K et ΔfG0, alors que des acquisitions calorimétriques permettent l'obtention des capacités calorifiques ainsi que le calcul de S0. Enfin, l'enthalpie de formation de ces phases est calculée à partir des enthalpies libres et des entropies. Le modèle de prédiction des données thermodynamiques est développé sur la base des propriétés acquises
Concrete is one of the most widely used building materials in the world. Durability, mechanical and chemical properties have made it a material of choice in storage concepts proposed by the French National Agency for Radioactive Waste Management (Andra), including the achievement of retaining structures, cell plugs, massive supports or conditioning waste. The study of the stability of the constituent phases of cementitious materials is needed in view of the planned quantities and the durability of the structures, andmust consider (i) temperature ranges suitable for cement matrices containment in contact with exothermic waste (25-80°C), and (ii) a representative time scale of the lifetime of the storage.The Andra ThermoChimie project therefore aims to develop a consistent thermodynamic database, to model the chemical evolution of cement materials in the environment of radioactive waste. However, in the present state, the database offers only thermodynamic data of cementitious crystalline phases, as well as a limited data set of three different chemical compositions for nanocrystalline C-S-H. This does not allow to reproduce the degradation of cementitious materials, or model the degradation of the new formulations, such as "Low pH" concretes.The objective is therefore to acquire a thermodynamic complementary data set on phases such as C-S-H (Calcium Silicate Hydrates) C-A-S-H (Calcium Aluminate Silicate Hydrates) and M-S-H (Magnesium Silicate Hydrates), to complete the ThermoChimie database. This study is based on experimental, analytical and digital work, in order to obtain a set of thermodynamic data (ΔfG0, ΔfH0, Cp(T), S0) sufficiently representative of the chemical variability of these phases. Finally, this set of data allows the development of a thermodynamic predictive model in extended spaces of compositions and temperatures.Development of this predictive model requires (i) The acquisition of thermodynamic properties on representative phases of the studied chemical system, and (ii) a precise knowledge of the structure and chemical formulas of these phases. Three types of hydrates were therefore synthesized and characterized: C-S-H, C-A-S-H and M-S-H. Analytical methods such as XRD, TGA and solid state NMR (29Si, 27Al) are used to ascertain similarities between the structure of C-(A-)S-H and that of tobermorite, and between the structure of M-S-H and that of Mg-Si phyllosilicates 2:1. Hydrates, however, have a lower crystallinity, with defects in the polymerization of silica chains, and random stacking faults (turbostratism).A multi-technique approach is also used, combining adsorption isotherm (water and nitrogen) and 1HNMR with XRDand TGA, and allows characterization of different types of water more or less bound to the structure of C-(A-)S-H.This study allowed to highlight and quantify the different types of water in the C-(A-)S-H structure. The impact of the drying process was also highlighted on the quantification of different types of water, including interlayer water. The acquisition of thermodynamic parameters of the synthesized phases is carried out from the analysis of equilibrium solutions for the calculation of log K and ΔfG0, while calorimetric acquisitions permit obtaining heat capacities and the calculation of S0. Finally, enthalpy of formation of these phases is calculated from the Gibbs free energy of formation and entropies.The predictive model is developed fromthe acquired thermodynamic properties.The Gibbs free energy of formation ΔfG0 is predicted from an electronegativity model, while Cp and S0 are predicted through polyhedral decomposition model. Finally, a comparison of data obtained with those published in the literature, and the realization of predominance diagrams generalized to the whole CaO-MgO-Al2O3-SiO2-H2O system assess the reliability of the proposed model

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Okoronkwo, Monday Uchenna. "Phase development in cement hydrate systems." Thesis, University of Aberdeen, 2014. http://digitool.abdn.ac.uk:80/webclient/DeliveryManager?pid=215261.

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Much progress has been made in understanding the physicomechanical properties of blended cement pastes of various formulations. However, unanswered questions abound, particularly as it concerns the long term chemistry of mineral distribution as clinker is diluted with progressively more supplementary cementitious materials (SCM's) and as a greater fraction of blending agent reacts with cement with time. This Thesis describes progress towards elucidating the mineralogical evolution mainly by isothermal equilibrium of known compositions. The evolution of mineralogy of two major systems: the calcium-alumina-silica-water (CASH) system and sodium-calcium-alumina-silica-water (NCASH) systems were studied at 20 – 85 °C, using ~70 compositions. Phase assemblage models have been developed for the systems, demonstrating the mode of occurrence and coexistence of phases with respect to temperature and composition. The coexistence of gels, one based on calcium silicate hydrate (C-S-H), the other based on aluminosilicate hydrate (A-S-H), and crystalline phases such as hydrogarnet solid solution, strätlingite and gismondine-Ca in the CASH system at 20 – 85°C, are illustrated. Transformation of gels to their corresponding crystalline phases has been predicted. Similarly, models are presented showing the mode of occurrence and coexistence of portlandite, alumina hydrate, silica, tobermorite, strätlingite, hydrogarnet solid solution, gismondine- type zeolite (Na,Ca)P solid solution, zeolite A, zeolite X, sodalite, etc., at temperatures 20 – 85 °C for the NCASH system. The stability and properties of the various crystalline CASH phases such as, hydrogarnet solid solution, strätlingite and gismondine, in relation to other phases relevant to cement hydration – such as C-S-H, AFts, AFms, gypsum and calcite – are characterized. The impact of sulfate, carbonate, alkali and solid solution on phase stability in systems relevant to aluminosilicate substituted cement paste are investigated. Concerns on long-term evolution of pH and its consequences to the passivation of cement-steel composite are discussed.

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Rassineux, François. "Altération des mortiers : étude expérimentale et analogues anciens." Poitiers, 1987. http://www.theses.fr/1987POIT2314.

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Etude de l'evolution de matrices cimentes soumise a une lixiviation par des solutions diluees. La stabilite des deux mortiers de compositions mineralogiques differentes depend du ph et de la pression en co::(2). Le mecanisme de dissolution est le processus dominant durant la lixiviation. L'identification du phases sur les liants modernes et ceuxs de l'epoque gallo romaine permet de connaitre la durabilite a long terme. Une simulation thermodynamique du processus ete realisee

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Shahsavari, Rouzbeh. "Hierarchical modeling of structure and mechanics of cement hydrate." Thesis, Massachusetts Institute of Technology, 2011. http://hdl.handle.net/1721.1/64567.

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Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Civil and Environmental Engineering, February 2011.
"February 2011." Cataloged from PDF version of thesis.
Includes bibliographical references (p. 236-251).
With an annual production of more than 20 billion tons a year, concrete continues to be the world's dominating manufacturing material for a foreseeable future. However, this ubiquity comes with a large ecological price as concrete stands as the third largest culprit to the torrent of CO2 after transportation and electricity generation. Despite several decades of studies, fundamental questions are still unsettled on the structure and properties of the smallest building block of concrete, Calcium- Silicate-Hydrate (C-S-H). Given the variable stoichiometry and morphology of C-S-H, no accurate models were ever developed that could link electronic information at one end to the C-S-H molecular properties at the other end. This thesis develops a new modeling toolbox that enables unraveling the interplay between structure, composition, morphology and mechanical properties of this "liquid stone" gel. First, using ab-initio calculations we characterize the structural and mechanical properties of several mineral analogs of CS- H (tobermorite family and jennite). We show tobermorite as a class of layered materials that unlike the common intuition, is not softest along the interlayer direction. Instead, the mechanically softest directions are two inclined regions forming a hinge mechanism. This feature sheds light on the complex mechanics of the realistic C-S-H layers. It occurs when the electrostatic interlayer interactions become comparable to the iono-covalent intralayer interactions. Next, to pass information to the next hierarchical level, we start by benchmarking the predictive capabilities of two commonly used force field potentials for C-S-H minerals against ab-initio calculations. While both potentials seem to give structural properties in reasonable agreement with the ab-initio results, the higher order properties such as elastic constants are more discriminating in comparing potentials with regards to predicting mechanical properties. Based on this finding, we use ab-initio structural and elasticity data in tandem to develop a new force field potential, CSH-FF, well customized and substantiated for the C-S-H family. This simple, yet efficient force-field is used in conjunction with statistical mechanics to analyze a series of molecular C-S-H models. Our simulation results predict a range of compositions and corresponding mechanical properties of solid C-S-H molecules that are consistent with real cement paste samples. This confirms our bottom-up multiscale approach with the model parameters linked to electronic structure calculations. The combination of these techniques and findings paves a path toward a predictive computational design strategy to improve the core properties of cement hydrate while reducing its negative environmental impact.
by Rouzbeh Shahsavari.
Ph.D.

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Chen, Quanyuan. "Examination of hydrated and accelerated carbonated cement-heavy metal mixtures." Thesis, University of Greenwich, 2003. http://gala.gre.ac.uk/6132/.

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Cement -based solidification/stabilisation (s/s) has been applied to the disposal of heavy metal bearing contaminated soil and wastes for approximately 50 years. This work studies the interactions of cement and heavy metals and provides further insight into encapsulation of heavy metals in cement matrices. The pastes and suspensions of calcium oxide, calcium hydroxide, pure cement phases ( 38, C}A, C4AF, Ci 2A7 and CA) and Portland cement with or without heavy metals (Zn2+ , Pb2+, Cu2+ and Cr3+) were examined by a number of analytical techniques. These techniques were X-ray powder diffraction (XRD), solid state magic angle spinning/nuclear magnetic resonance (MAS/NMR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), differential thermal analysis (DTA) and thermogravimetry (TG). Thermodynamic modelling using a geochemical code, PHREEQC, and the edited database, was carried out to elucidate the chemical reactions occurring in cement/heavy metal systems. Heavy metals acted as accelerators for hydration of CaO, CaS and Portland cement except that Zn2+ retarded the early-age hydration of Cfi and Portland cement. This work confirmed that the precipitation of portlandite was retarded due to the hydrolysis of heavy metals. Calcium ions resulting from the decomposition of cement phases combined with heavy metals to form calcium-heavy metal double hydroxides, including CaZn2(OH)6.2H2O, Ca2(OH)4Cu(OH)2.mH2O and Ca2Cr(OH)7 .3H2O. The carbonation of CaS and Portland cement resulted in the formation of calcium carbonate and the condensation of silicates from single tetrahedra to branching sites and three-dimensional frameworks (low Ca/Si ratio C-S-H gel). The polymerisation of C-S-H gel, and the polymorphism conversion and decomposition temperature of calcium carbonate were influenced by heavy metals. The incorporation of heavy metal cations in C-S-H gel is similar to that seen in glass. Heavy metals acted as network modifiers or network intermediates. In hydrated Portland cement pastes, aluminium was partitioned in ettringite or calcium carboaluminate. After carbonation, this work revealed that aluminium was in the tetrahedral form, forming mixed AlCVSiC^ branching or three-dimensional networks. This thesis presents the new structural models for C-S-H gel and the chemical mechanisms of 38 reactions with water and carbon dioxide in the presence or absence of heavy metals. In the absence of gypsum, the reaction products detected in the pastes of C3A, C4AF, Ci2A? and CA were gehlenite hydrate, calcium carboaluminate, C4AH X and hydrogarnet. Heavy metals, especially Zn 2+ , inhibited the formation of hydrogarnet and promoted the conversion of C-A-H to calcium carboaluminate and calcium carbonate. In the presence of gypsum, the major hydration product of C^A was ettringite. During carbonation, COs'" substituted for SO 4 2 " and formed calcium carboaluminate, and eventually transformed into calcium carbonate and gibbsite. The conversion of metastable calcium carbonate polymorphs (aragonite and vaterite) to calcite through Ostwald ripening occurred very slowly in the carbonated pastes containing gypsum. The reactivity of C 3 A, C^Ay, CA and C4AF during carbonation was much lower than seen during hydration. Heavy metals influenced the rates and products of hydration or carbonation of CsA, Ci2A7, CA and C4 AF and were completely incorporated in the reaction products of these phases. Thermodynamic modelling confirmed that accelerated carbonation could be beneficially employed to cement-based s/s to improve its effectiveness. Calculations of solubility and equilibrium phase assemblage are consistent with the experimental examination obtained in this work.

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Liu, Lu. "Carbon dioxide and water speciation in hydrated cements, a focus on sustainability." Pullman, Wash. : Washington State University, 2009. http://www.dissertations.wsu.edu/Thesis/Spring2009/l_liu_1042009.pdf.

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Thesis (M.S. in environmental engineering)--Washington State University, May 2009.
Title from PDF title page (viewed on May 14, 2009). "Department of Civil and Environmental Engineering." Includes bibliographical references (p. 71-74).

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Khoshnazar, Rahil. "Durability of Novel C-S-H-based Nanocomposites and Secondary Hydrated Cement Phases." Thesis, Université d'Ottawa / University of Ottawa, 2015. http://hdl.handle.net/10393/32117.

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Issues concerning mechanisms of durability of hydrated cement phases in aggressive environments were studied. The possibility of using organic compounds in order to modify the micro- and nanostructure of the calcium-silicate-hydrate (C-S-H) phases was also investigated. Pure cement-based hydrated phases were synthesized and characterized by several analytical techniques such as X-ray diffraction, thermal gravimetric analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. Compacted samples of the synthetic hydrated cement phases were also prepared and used for the assessment of durability and mechanical properties. This doctoral thesis is comprised of several research chapters which can be categorized into two main parts. The first part focuses on the development of novel organically modified C-S-H systems. The second part involves the mechanisms underlying the volume stability of phase pure sulfoaluminate and related phases. A brief description of each part is as follows: - development of novel organically modified C-S-H systems: The mechanisms of interaction of organic compounds with the nanostructure of C-S-H systems were studied. A model for the nanostructure of the resulting composite systems was proposed. In addition, the organically modified systems were tested for length-change, calcium-ion leaching and diffusion of isopropanol. Dynamic mechanical analysis and microindentation techniques were also used to determine the mechanical performance. Evidence of the superior engineering performance of the novel organically modified C S-H systems was provided. - mechanisms of the volume stability of sulfoaluminate and related phases: Volume stability and change in the microstructure of the synthetic ettringite, monosulfate and thaumasite was critically examined in de-ionized water as well as in highly concentrated gypsum- or lime-water. A new dissolution-based mechanism for the expansion of these phases was proposed. The volume stability of multicomponent systems comprised of the C-S-H-based system (prepared in part I) and these sulfate-based hydrated phases was also investigated. It was suggested that the systems containing the modified C-S-H rather than the phase pure C-S-H had better resistance to crack growth and disintegration originating from the presence of ettringite or thaumasite.

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Yates, Malcolm. "The characterization of novel cements." Thesis, Brunel University, 1991. http://bura.brunel.ac.uk/handle/2438/4883.

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The present study deals with the physical characterization of macrodefect free cements produced by ICI. These materials are made through a specialized mixing technique which incorporates an organic polymer into the cement/water system. The high mechanical strength and low porosity of this class of hardened cement paste had been well documented, however, a detailed characterization of the physical nature of the microstructure had not previously been attempted. Two classes of macrodefect free material were studied, based on Ordinary Portland cement and High Alumina cement, respectively. The porosities of these two materials were determined in their original state and after various forms of heat treatment and conditioning. Samples based on Ordinary Portland cement had a well defined narrow pore size distribution, even after heat treatment, while the High Alumina cement samples displayed a very low total pore volume in their original state, but subsequent heat treatment led to the developement of porosity over a wide range of pore sizes. These fundamental differences in the pore size distributions had significant effects on the homogeneity and reproducibility of the microstructures of the samples. The porosity generated by heat treatment was found to be unstable in the presence of water. In general, reductions in the porosities and permeabilities were observed. This was due to the formation of fresh cement hydrate gel within the pore structure, which caused a shift in the pore size distributions towards smaller pores.

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Estrada, Jonathan Bartholomew. "Scaling the rock : a micromechanical model for the elastic properties of hydrated cement pastes." Thesis, Massachusetts Institute of Technology, 2011. http://hdl.handle.net/1721.1/101860.

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Thesis: S.B., Massachusetts Institute of Technology, Department of Materials Science and Engineering, 2011.
Cataloged from PDF version of thesis.
Includes bibliographical references (pages 61-62).
Cement is the most widely produced material worldwide. However, the understanding on how its nanoscale composition affect its microscale mechanical properties is limited. In this thesis, a micromechanical model for the purpose of cement hydration simulation was developed and tested using HYMOSTRUC3D hydration software and a micromechanical particle with interphase model developed by Deng and Van Vliet. It was then tested against empirical micro- and nanoindentation tests done on samples synthesized, cured, and prepared in situ. Preliminary mechanical calculations coupled with the hydration software show good agreement with experimental data. Additionally, predicted ranges of effective particle moduli values were found in nanoindentation testing. These observations support the validity of treating high density C-S-H as an interphase between low density C-S-H and clinker particles.
by Jonathan Bartholomew Estrada.
S.B.

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Abbas, A. M. "The effects of the initial curing temperatures on the properties and the microstructure of hydrated Portland cement pastes." Thesis, University of Strathclyde, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.382294.

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Ghebrab, Tewodros Tekeste. "Development of stucture-property [i.e. structure-property] relationships for hydrated cement paste, mortar and concrete." Diss., Connect to online resource - MSU authorized users, 2008.

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Thesis (Ph.D.)--Michigan State University. Dept. of Civil & Environmental Engineering, 2008.
Title from PDF t.p. (viewed on Apr. 2, 2009) Includes bibliographical references (p. 217-225). Also issued in print.

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Quarcioni, Valdecir Angelo. "Influência da cal hidratada nas idades iniciais da hidratação do cimento Portland - estudo em pasta." Universidade de São Paulo, 2008. http://www.teses.usp.br/teses/disponiveis/3/3146/tde-15092008-153909/.

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O progresso científico e tecnológico das últimas décadas registra um avanço significativo no processo de obtenção da cal, porém, há uma lacuna de conhecimento de base referente à sua ação quando empregada em conjunto com o cimento Portland. O uso da cal nas argamassas mistas de acabamento tem sido associado positivamente apenas à plasticidade no estado fresco e à sua deformabilidade no estado endurecido. Maiores informações são necessárias sobre a ação da cal na evolução das propriedades da argamassa no estado fresco, vinculadas à hidratação do cimento. Este conhecimento é importante para o desenvolvimento de formulações que atendam ao desempenho desejado em diferentes aplicações. O entendimento do mecanismo de hidratação do cimento em presença da cal constitui uma plataforma para estudos de adições minerais ativas ao clínquer, com adição de cal hidratada como fonte externa de cálcio, na produção de novos materiais cimentícios sustentáveis. O estudo em pasta realizado teve como foco a interação cimento-cal visando identificar os fenômenos químicos e físicos relevantes que se sucedem à adição de água ao sistema. Foram caracterizadas as idades iniciais de hidratação do cimento por meio de ensaios de calorimetria de condução, termogravimetria (TG/DTG) e difratometria de raios X em material no estado fluido e em regime consecutivo de coleta de dados. Os experimentos envolveram as proporções 1:1 e 1:2 de cimento Portland tipo CP II E com cales hidratadas tipos CH I e CH III de natureza cálcica e dolomítica, respectivamente. A cal CH I incorpora à mistura elevado teor de hidróxido de cálcio com imediata saturação do meio por íons hidroxila e íons cálcio; a cal CH III incorpora também, em maior quantidade, filler carbonático. Por efeito químico, devido à presença da cal, há alteração da velocidade de hidratação, mas com formação dos produtos de reação característicos da hidratação do cimento. Por efeito físico, o filler carbonático e a fração insolúvel do hidróxido de cálcio da cal, presente no meio saturado, atuam como nucleador para precipitação de fases hidratadas. O efeito combinado desses fenômenos promoveu aceleração da hidratação do cimento Portland, principalmente no período de indução, quando prevalecem as reações de formação de etringita e de aluminatos de cálcio hidratados.
In the last decades, scientific and technological progress has shown a significant advance in the process of obtaining lime; however, there is gap knowledge with relation to its action when employed together with Portland cement. The use of lime in finishing mix mortars has only been positively associated to the fresh state plasticity and ability to deformation in the hardened state. It is necessary to collect data about the role of lime in the gradual development of the properties of mortars in the fresh state, linked to cement hydration. Such knowledge is important to develop formulas which can meet the required performance in different uses. The current demand of sustainable materials has favored the addition of minerals to the composition of Portland cement, and hydrated lime as an extern source of calcium, is a feasible alternative to the composition of byproducts and mixtures to be used as alternative binders. This research focused the cement-lime interaction aiming at identifying relevant chemical and physical phenomena which succeed the addition of water to the system. The paste study characterized the early ages of hydration by means of isothermal calorimetric, thermogravimetric, X-ray diffraction in material in the fluid state analysis collecting data in a consecutive basis. The experiments were carried out by using two proportions of Portland cement type CP II E with hydrated lime types CH I and CH III, calcic and dolomitc, respectively. By adding lime CH I to the cement-water system, calcium hydroxide is abundantly incorporated, with immediate saturation by means of hydroxide ions and calcium ions. The addition of lime CH III, also incorporates, in greater amount, finely ground limestone. Due to chemical effect because of the presence of lime, there is alteration in speed of hydration, forming products characteristics to the cement hydration process. Due to physical effect, the filler and the lime insoluble fraction of calcium hydroxide, present in the saturated environment, work as facilitators to the precipitation of the hydrated phases. The combined effect of these two phenomena accelerated hydration of Portland cement, mainly in the induction period, when ettringite and hydrated calcium aluminates formation reactions prevail. The advancement made in terms of knowledge permits to broaden comprehension on the behavior of mixtures in early stages, when hardening and consolidation processes are applied to mortars and help rheologic studies which involve their application. The understanding of the hydration mechanism in the presence of lime sets a base to study additions of active minerals to the clinker and produce new sustainable cementious compounds.

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Balonis, Magdalena. "The influence of inorganic chemical accelerators and corrosion inhibitors on the mineralogy of hydrated Portland Cement Systems." Thesis, University of Aberdeen, 2010. http://digitool.abdn.ac.uk:80/webclient/DeliveryManager?pid=153269.

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The thermodynamic properties of chloride, nitrate and nitrite AFm hydrates have been determined. Investigations of solid solutions and thermodynamic calculations on the influence of these anions on mineralogical changes in cement paste were performed and compared with experiments. To calculate volume changes, densities of principal crystalline phases occurring in cement were critically assessed and tabulated, in some cases with addition of new data. Database was obtained by calculating densities from crystallographic data and unit cell contents. In hydrated cements, anion sites in AFm phase are potentially occupied by OH, SO₄ and CO₃ ions. C1, NO₃ or NO₂ ions readily displace hydroxide, sulfate and carbonate in the AFm structures. Nitrates and nitrites do not have ability to displace chloride from the Friedel’s salt (C1-AFm) though. The binding power of AFm for nitrite/nitrate/chloride was calculated and confirmed experimentally at 25°C. It was observed that presence of chloride, nitrate or nitrite alters the AFm/Aft balance and thereby affect the specific volume of paste solids. It was found that the success of nitrite as a corrosion inhibitor for protection of embedded steel arises from its “smart” behaviour. AFm normally stores and sequesters nitrite. If chloride ingress occurs in service, the AFm undergoes ion exchange, gaining chloride and forming Friedel’s salt, while releasing soluble nitrite ions to the pore fluid. As a result, the aqueous ratio of [NO₂^-]/[C1^-] increases and remains within the passivation range for steel.

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Rodin, Victor V., Peter J. McDonald, and Sahar Zamani. "A Nuclear Magnetic Resonance Pulsed Field Gradient study of self-diffusion of water in hydrated cement pastes." Universitätsbibliothek Leipzig, 2015. http://nbn-resolving.de/urn:nbn:de:bsz:15-qucosa-184215.

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The results of one- and two-dimensional 1H nuclear magnetic resonance (NMR) pulsed field gradient (PFG) diffusometry studies of water in white cement paste with a water-tocement ratio 0.4 and aged from 1 day to 1 year are reported. The study shows that the NMRPFG method is primarily sensitive to the capillary porosity. Data is fit on the basis of a lognormal pore size distribution with pore size dependent relaxation times. The volume mean capillary pore size is 4.2 μm in mature paste, similar to 1 week suggesting that hydrates and gel porosity do not form in the capillary porosity once the latter has been substantially created. No evidence is found of capillary pore anisotropy in cement paste.

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Rodin, Victor V., Peter J. McDonald, and Sahar Zamani. "A Nuclear Magnetic Resonance Pulsed Field Gradient study of self-diffusion of water in hydrated cement pastes." Diffusion fundamentals 18 (2013) 3, S. 1-7, 2013. https://ul.qucosa.de/id/qucosa%3A13709.

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The results of one- and two-dimensional 1H nuclear magnetic resonance (NMR) pulsed field gradient (PFG) diffusometry studies of water in white cement paste with a water-tocement ratio 0.4 and aged from 1 day to 1 year are reported. The study shows that the NMRPFG method is primarily sensitive to the capillary porosity. Data is fit on the basis of a lognormal pore size distribution with pore size dependent relaxation times. The volume mean capillary pore size is 4.2 μm in mature paste, similar to 1 week suggesting that hydrates and gel porosity do not form in the capillary porosity once the latter has been substantially created. No evidence is found of capillary pore anisotropy in cement paste.

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Androniuk, Iuliia. "Effects of cement organic additives on the adsorption of uranyl ions on calcium silicate hydrate phases : experimental determination and computational molecular modelling." Thesis, Ecole nationale supérieure Mines-Télécom Atlantique Bretagne Pays de la Loire, 2017. http://www.theses.fr/2017IMTA0007/document.

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Les matériaux cimentaires sont largement utilisés dans la conception et la construction des sites de stockage de déchets radioactifs. Une des manières d’améliorer leur performance est d’introduire des adjuvants organiques dans la structure. La présence de matière organique dans l’eau porale peut affecter la mobilité des radionucléides : les molécules organiques forment des complexes solubles et peuvent être en compétition avec les radionucléides au niveau des sites de sorption. Ce travail avait pour but de comprendre les mécanismes de telles interactions au niveau moléculaire. Le système modèle a trois composantes. D’abord, des phases C-S-H ont été choisies en tant que modèles du ciment.Ensuite, le gluconate est sélectionné en tant que modèle d’additif organique pour sonder les mécanismes d’interaction à l’échelle moléculaire. Un système plus complexe impliquant un superplastifiant (PCE) a été testé. La troisième espèce, U(VI), est représentative d’un radionucléide de la série des actinides. Le développement de la description des effets de postproduction des espèces organiques pour les applications de stockage des déchets radioactifs était l’objectif principal de ce travail. L’étude des systèmes binaires fournit des données de référence pour l’investigation de systèmes ternaires C-S-H/matière organique/U(VI) plus complexes. Des cinétiques et des isothermes de sorption/désorption pour les espèces sur les C-S-H sont mesurés. En parallèle, des modèles atomiques ont été développés pour les interfaces d’intérêt. Les aspects structuraux, énergétiques et dynamiques des processus de sorption sur les surfaces de ciment sont modélisés par la technique de la dynamique moléculaire
Cementitious materials are extensively used in the design and construction of radioactive waste repositories. One of the ways to enhance their performance is to introduce organic admixtures into the cement structure. However, the presence of organics in the pore water may affect the radionuclide mobility: organic molecules can form water-soluble complexes and compete for sorption sites. This work was designed to get detailed understanding of the mechanisms of such interactions on the molecular level. The model system has three components. First, pure C-S-H phases with different Ca/Si ratios were chosen as a cement model. Secondly, gluconate (a simple well-described molecule) is selected as a good starting organic additive model to probe the interaction mechanisms on the molecular scale. A more complex system involving polycarboxylate superplasticizer (PCE) was also tested. The third, U (VI), is a representative of the actinide radionuclide series. The development of description of the effects of organics for radioactive waste disposal applications was the primary objective of this work. The study of binary systems provides reference data for the investigation of more complex ternary (C-S-H/organic/U(VI)). The interactions are studied by means of both experimental and computational molecular modelling techniques. Data on sorption and desorption kinetics and isotherms for additives and for U (VI) on C-S-H are acquired in this work. In parallel, atomistic models are developed for the interfaces of interest. Structural, energetic, and dynamic aspects of the sorption processes on surface of cement are quantitatively modeled by molecular dynamics technique

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Perron, Stacey. "The application of A.C. impedance spectroscopy on the durability of hydrated cement paste subjected to various environmental conditions." Thesis, University of Ottawa (Canada), 2002. http://hdl.handle.net/10393/6313.

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Harsh Canadian winters cause many problems in reinforced concrete structures due to damaging freezing-thawing cycles which is exacerbated by the heavy use of de-icing salts on roadways. Evaluation of concrete durability with current ASTM methods may give unreliable results and are destructive to the structure. A relatively new and novel approach to evaluating the durability of concrete uses A. C. Impedance Spectroscopy (ACIS). Hydrated cement paste (hcp), mortar, brick and vycor glass were evaluated using ACIS during drying-rewetting and freezing-thawing cycles. Thermal mechanical analysis (TMA), and differential scanning calorimetry (DSC) tests were also conducted and used as references. Results indicate that ACIS can be used to successfully evaluate the pore structure of hcp. The results from the drying-rewetting cycles are consistent with the pore coarsening theory. ACIS revealed pore structure changes consistent with the mechanical strains and pore solution chemistry. Increased pore continuity with each drying-rewetting cycle was indicated by a reduction in sample resistance. Unique tests were conducted on hydrated cement paste, mortar, brick and vycor glass that measured the ACIS and mechanical strains simultaneously while undergoing temperature changes. The temperature was lowered from 5°C to -80°C and then raised to +20°C. The ACIS results indicate that durability of the material can be assessed using the parameters R, material resistance, and phi, indicative of the frequency dispersion angle. The resistance on freezing values correlates with the amount of pore water freezing. The phi values on freezing are representative of the pore size distribution of the test sample. Resistance and phi data from freezing-thawing tests can be analyzed to assess durability of the sample. A material that is durable to freezing-thawing cycles can be described as having a high resistance at room temperature, a low freezing resistance and small changes in phi. Results were consistent among all the materials tested. Freezing-thawing tests were also conducted on specimens resaturated with salt solutions (5%, 10%, 15%). The results of these tests indicated a lower incipient freezing temperature, increase in pore blockage temperatures, and increased mobility of the pore water during freezing (increase in the change to phi). A series of test were conducted to evaluate the electrode polarization effects associated with the permittivity values at low frequencies. Teflon sheets were used to minimize the electrode polarization effects. It is shown that electrode polarization effects dominate over bulk polarization effects. Effects vary with the porosity of the material.

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Krautwurst, Nina [Verfasser]. "Nucleation of calcium silicate hydrate in aqueous solution and the influence of biomolecules on cement hydration / Nina Krautwurst." Mainz : Universitätsbibliothek Mainz, 2017. http://d-nb.info/1138732915/34.

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Zhang, Tingting. "Development of novel low pH Magnesium Silicate Hydrate (M-S-H) cement systems for encapsulation of problematic nuclear wastes." Thesis, Imperial College London, 2012. http://hdl.handle.net/10044/1/17873.

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There are more than 100,000 tonnes of nuclear waste currently stored in the UK, waiting for final disposal. Composite cements consisting of Portland cement (PC) and blast furnace slag (BFS) have a good track record in encapsulation of a range of nuclear wastes. However, the pH of this system is relatively high (~13.3) for encapsulating wastes that containing trace levels of aluminium, as this can react under high pH conditions. The aim of this research was to develop novel cement systems with lower pH (~10) for encapsulating wastes containing aluminium metal and Magnox swarf. The hydration of magnesium oxide to form brucite produces a pH around 10 and this is a favourable pH for aluminium passivation. A range of reactive fillers were investigated and silica fume (SF) found to be the most suitable to achieve the desired pH. Identification of the hydrated phases in MgO/SF samples showed that magnesium silicate hydrate (M-S-H) gel is the main hydration product. Brucite (Mg(OH)2) also forms in the early stages of hydration but then reacts with SF to produce additional M-S-H gel. The system has been improved by addition of sodium hexameta-phosphate (Na-HMP) as a dispersant, magnesium carbonate to control the early pH and sand to minimise the drying shrinkage. The physical, chemical and mechanical properties of the improved MgO/ SF system have been investigated and compared with the control PC/BFS system. Magnox swarf and aluminium 1050 (Al) supplied by National Nuclear Laboratory (NNL) were used as metal wastes. These metals were encapsulated in the control PC/ BFS system and the optimised MgO/ SF system. The interaction between the metals and the two cement systems has been investigated by monitoring H2 generation, studying the microstructure by SEM and the crystalline phases by XRD. Al strips were firmly bound into the optimised MgO/ SF system and no H2 gas was detected during the test period. The corrosion of Al is very limited in the optimised MgO/SF system compared to the control system. Magnox swarf was found to show similar corrosion behaviour when encapsulated in both the control system and the optimised MgO/SF system. The M-S-H gel forming cement system developed in this research is novel and may have potential for encapsulating certain types of problematic legacy wastes generated from the nuclear industry.

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Dirsė, Liudvikas. "Ceolitų panaudojimo hidrotechninėse cementinėse sistemose tyrimas." Master's thesis, Lithuanian Academic Libraries Network (LABT), 2011. http://vddb.laba.lt/obj/LT-eLABa-0001:E.02~2011~D_20110607_115033-46321.

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Statybos pramonėje, mišiniuose vis plačiau naudojamas įvairus tiek natūralių tiek sintetinių ceolitų spektras. Atliktuose tyrimuose buvo naudojamas sintetinis ceolitas – hidrosodalitas (Na6+x(SiAlO4)6(OH)x•nH2O), modifikuotas hidrosodalitas ir fero silicio gamybos atlieka - SiO2 mikrodulkės. Su pastaraisiais pucolaniniais priedais tiriama sąveika su cementu, nustatyta kaip keičiasi cemento stiprio, tankio ir įgėrio savybės. Tyrimai atlikti ruošiant bandinius su 2%, 5%, 10% ir 15% pucolaninių priedų masės santykiais. Atlikus tyrimus nustatyta, kokia daroma įtaka cementinės masės hidratacijos temperatūrai. Nustatytas bandinių stiprumas, tankis po 3, 7 ir 28 parų. Nustatytas bandinių įgėris po 28 parų. Cementinio akmens gniuždomasis stipris nenaudojant priedo ir ilginant hidratacijos trukmę nuo 3 iki 28 parų didėja nuo 59 iki 80 MPa. Panaši priklausomybė stebima ir cementiniuose bandiniuose su pucolaniniais priedais. Ilgėjant hidratacijos trukmei stipriai gniuždant didėja. Tirtose sąlygose didžiausią stiprį gniuždant turėjo bandiniai su 10 % modifikuoto hidrosodalito priedo po 28 parų, gniuždomasis stipris padidėja iki 101 MPa. Galima daryti prielaidą, kad hidrosodalito, modifikuoto hidrosodalito ir SiO2 mikrodulkių pucolaninės savybės pasireiškia ne iš karto, bet išryškėja po ilgesnes hidratacijos trukmės, t. y. po 28 parų. Vykstant hidratacijai nuo 16 iki 28 parų, įgėris sumažėja nuo 13,41% iki 9,04% (esant 2% hidrosodalito kiekiui). Naudojant 5% SiO2 mikrodulkių kiekį... [toliau žr. visą tekstą]
Construction industry is increasingly being used in combination and variety of natural and synthetic zeolites spectrum. A study carried out using synthetic zeolite - hydrasodalite (Na6 + x (SiAlO4) 6 (OH) x • nH2O) modified hydrasodalite silicon production and Fair play - fume SiO2. With the recent pozzolanic additives investigated the interaction with cement, concrete changes in the strength, density and retention properties. Studies carried out in the preparation of the samples with 2%, 5%, 10% and 15% by weight of pozzolanic additives relations. It was determined, which affect the weight of cement hydration temperature. Fixed specimens the strength and the density of 3, 7 and 28 days. Set of samples absorption after 28 days. Compressive strength of cement stone without the use of additive and longer duration of hydration from three to 28 days increased from 59 to 80 MPa. A similar dependence is observed in samples with cement and pozzolanic additives. Hydration with increasing duration of the compressive strength increases. To examine the conditions had the highest compressive strength of samples with 10% modified hydrasodalite additives after 28 days, compressive strength increases to 101 MPa. It can be assumed that hydrasodalite, and SiO2 modified hydrasodalite fume pozzolanic properties are not immediate, but come on after a longer duration of hydration, etc. Y. after 28 days. During the hydration from 16 to 28 days, absorption decreases from 13.41% to 9.04% (at 2%... [to full text]

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26

Bernard, Ellina. "Magnesium silicate hydrate (M-S-H) characterization : temperature, calcium, aluminium and alkali." Thesis, Bourgogne Franche-Comté, 2017. http://www.theses.fr/2017UBFCK025/document.

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Les différentes options envisagées par la France et la Suisse pour le stockage de déchets radioactifs en couches géologiques profondes argileuses prévoient l’utilisation d’importants volumes de matériaux cimentaires. Les liants dits bas-pH ont été développés afin de limiter la perturbation de la roche encaissante par le panache alcalin. Les études expérimentales menées sur les interfaces béton bas-pH-argile mettent systématiquement en évidence la formation de phases silico-magnésiennes, potentiellement de silicate de magnésium hydraté (M-S-H), mal modélisées à cause de données thermodynamiques limitées. Cette étude a pour objectif de caractériser ces phases en température, en présence d’aluminium, calcium et d’alcalins pour alimenter les bases de données thermodynamiques et améliorer les calculs sur les évolutions physico-chimiques des bétons bas pH et éventuellement des bétons de Portland. Des suspensions de M-S-H ont été synthétisées à partir d'oxyde de magnésium et de fumée de silice à différentes températures, à différents temps de réaction et différents rapports Mg/Si. Un panel de techniques d’analyses de chimie du solide et des mesures en suspensions couplées à des analyses des phases liquides a été utilisé pour caractériser les phases synthétisées. Initialement, et quel que soit le Mg/Si total choisi pour la synthèse, un M-S-H avec un rapport Mg/Si ~1 précipite en présence de brucite et de silice amorphe. Lorsque l’équilibre du système est atteint, 2 à 3 ans à 20 °C ou 1 an à 50 et 70 °C, le Mg/Si varie de ~0,8 à ~1,4. La température a peu d'influence sur le M-S-H formé même si le M-S-H se forme plus rapidement et qu’il est légèrement moins stable thermodynamiquement lorsque la température augmente. A l'équilibre, sa structure mal définie est comparable à des nano-cristallites de phyllosilicates hydratés avec une surface spécifique supérieure à 200 m2/g. Un modèle de solution solide pour le M-S-H a été calculé et ajouté à la base de données.Dans un second temps, les travaux ont été focalisés sur la formation de M-S-H à partir de silicate de calcium hydraté (C-S-H) avec un faible Ca/Si (= 0,8) et de magnésium. Le C-S-H n’est pas stable à des pH avoisinant un pH = 10, ce qui favorise la précipitation de M-S-H. Des recherches détaillées montrent que du calcium peut être faiblement incorporé dans le M-S-H (Ca/Si ≤ 0,10), et des solutions solides contenant du calcium ont été ajoutés à la base de données. Pour des pH supérieurs à 10-10,5, les C-S-H et M-S-H coexistent. L’observation par MEB-EDS d’une interface en cellule de diffusion entre C-S-H (Ca/Si=0,8 représentant un liant bas pH) et M-S-H (Mg/Si=0,8), couplée à la modélisation de celle-ci en transport réactif, sur la base des nouvelles données thermodynamiques dérivées des expériences précédentes, montrent la détérioration rapide du C-S-H et la précipitation de M-S-H dans le disque C-S-H, ainsi qu’une absorption homogène du calcium dans le disque de M-S-H.L’augmentation du pH en solution favorise la sorption de cations. Des M-S-H présentant une sorption de sodium jusqu'à Na/Si ~ 0,20 en absence de brucite ont été observés à des pH avoisinants 12,5. La sorption sur le M-S-H est favorisée dans l'ordre Na+ < Mg2+ < Ca2+. Enfin, l'aluminium s’incorpore dans le M-S-H pour former du M-A-S-H. Un rapport Al/Si jusqu’à 0,2 est observé dans des suspensions synthétisées en présence d’aluminate de sodium ou de métakaolin. Les données de RMN de l’aluminium ont montré que celui-ci est présent dans les sites tétraédriques et octaédriques du M-A-S-H. La phase formée a une structure similaire à celle du M-S-H avec un degré de polymérisation des silicates et une charge effective de surface comparables
The various options to store radioactive wastes in deep geological strata considered in France or Switzerland include the use of large volumes of cementitious materials for infrastructure in contact with argillaceous rocks. So-called low-pH binders were developed to minimize disruption to the surrounding rock by the alkaline plume. Studies conducted on the interaction zone between concrete and clay systematically highlighted the formation of magnesium silicate phases including magnesium silicate hydrate (M-S-H) at the interfaces, which can presently be modeled only partially due to incomplete thermodynamic data. The purpose of this study was to characterize these phases in temperature, aluminum, calcium, and alkali conditions in order to provide the thermodynamic data and improve the calculations on physicochemical evolutions of low-pH concretes and possibly Portland concretes.M-S-H phases were synthesized from magnesium oxide and silica fume in batch experiments at different temperatures, for various times and varying Mg/Si. A large number of different techniques such as chemical solid characterizations coupled with suspension investigations and liquid analyses were used to characterize the phases synthesized. Initially a M-S-H phase with Mg/Si equal to 1 was precipitated in addition to amorphous silica and brucite whatever the total Mg/Si used for the synthesis. After long equilibration times, 2 to 3 years at 20°C or 1 year at 50 and 70°C, the Mg/Si in M-S-H ranged from ~0.8 to ~1.4. The temperature had little influence on the M-S-H formed even if the M-S-H formation occurred faster and M-S-H was thermodynamically slightly less stable when the temperature was increased. At or near to equilibrium, M-S-H phases were characterized with ill-defined structure comparable to nano-crystallite, hydrated phyllosilicates with a surface area greater than 200 m2/g. A M-S-H solid-solution model was calculated and implemented in the thermodynamic database.It was observed that M-S-H also form from calcium silicate hydrate (C-S-H) with a Ca/Si = 0.8 in the presence of additional magnesium. In batch experiments, a low pH of the suspensions (pH ≤ 10) destabilized C-S-H or prevented its formation and favored the precipitation of M-S-H. Detailed investigations showed that small amounts of calcium could be incorporated in M-S-H (Ca/Si ≤0.10), such that also calcium containing end-members were added to the M-S-H solid-solution. At pH ≥ 10-10.5, two separate silicate phases coexist: C-S-H and M-S-H. The interface between a simplified “low-pH” binder mimicked by C-S-H with Ca/Si = 0.8 and a magnesium-rich environment mimicked by M-S-H with Mg/Si = 0.8 confirmed these phenomena. SEM-EDS observations and reactive transport modelling using the thermodynamic data derived in the batch experiments showed the fast deterioration of the C-S-H and the precipitation of M-S-H in the C-S-H disk at the interface and a homogeneous uptake of calcium in the M-S-H disk.The increase of pH favors the sorption. M-S-H with a sodium uptake up to Na/Si ~ 0.20 and without brucite formation were observed at high pH (12.5). The sorption on M-S-H was favored in the order Na+ < Mg2+ < Ca2+. Finally, aluminum was incorporated into M-S-H to form magnesium alumino-silicate hydrate (M-A-S-H). An Al/Si ratio up to 0.2 was observed in presence of sodium aluminate or metakaolin. 27Al MAS NMR data showed that aluminum was present in both tetrahedral and octahedral sites of M-(A-)S-H. The M-(A-)S-H formed had a similar structure as M-S-H with a comparable polymerization degree of the tetrahedral silicates and a similar surface charge

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Schönlein, Markus Philipp [Verfasser], Johann P. [Akademischer Betreuer] Plank, Johann P. [Gutachter] Plank, and Anton [Gutachter] Lerf. "Investigations on the very first nucleation and growth of early cement hydrate phases / Markus Philipp Schönlein ; Gutachter: Johann P. Plank, Anton Lerf ; Betreuer: Johann P. Plank." München : Universitätsbibliothek der TU München, 2019. http://d-nb.info/119291158X/34.

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28

Chen, Zhao, and Zhao Chen. "Multiscale characterization and modeling of the viscoelasticity of the cement paste and the alike calcium-silicate-hydrate (C-S-H) at different levels of relative humidity." Doctoral thesis, Université Laval, 2019. http://hdl.handle.net/20.500.11794/37369.

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Le phénomène de fluage, qui est défini comme la déformation dessous une charge constante, a un effet à long terme sur la déformation des structures en béton armé. Récentes recherches montrent que la déformabilité de structures en béton armé du au fluage après quelques décades est largement sous-estimée par les normes. Plusieurs recherchent montrent que le fluage à long terme du béton suit une loi logarithmique dans le temps. Le fluage du béton provient de la microstructure du silicate de calcium (C-S-H) hydratée. Bien que de nombreux travaux expérimentaux et théoriques aient été réalisés, les mécanismes de fluage du C-S-H demeurent mal connus. Parmi les facteurs qui influent sur le comportement au fluage du CS- H, l’humidité relative (HR) est le principal. En fait, la teneur en eau dans les microspores joue un rôle important dans la rigidité, la résistance et la viscosité de la microstructure C-SH. La technique d'indentation permet de caractériser les propriétés mécaniques de la pâte de ciment à l'échelle microscopique et nanométrique à laquelle les mécanismes de fluage agissent. Par rapport aux expériences de fluage traditionnelles qui durent des mois et des années, le test d'indentation présente l'avantage d'évaluer les propriétés de fluage des matériaux à base de ciment en quelques minutes. De plus, il est plus facile pour l’échantillon d’atteindre l’équilibre humidité en raison du petit volume sondé. Pour extraire correctement les propriétés de fluage, la première étape consiste à établir une méthode d’essai d'indentation viscoélastique. Pour cette étude, la microindentation viscoélastique est analysée respectivement par une pointe sphérique et une pointe de Berkovich. Les propriétés de fluage à long terme sont bien décrites par le paramètre module de fluage de contact (C) de la complaisance au fluage logarithmique. Les propriétés mécaniques de structures C-S-H semblables à celles de Jennite et de Tobermorite à 1.4 nm sont ensuite caractérisées par une microindentation à différents niveaux d’HR. À différents niveaux d’HR, le comportement de fluage et de relaxation des C-S-H est étudié par la nanoindentation statistique sur une pâte de ciment. Le rôle de l'eau sur le comportement au fluage de C-S-H est réexaminé. De nouvelles découvertes concernant le mécanisme de fluage de C-S-H sont présentées et discutées.
Le phénomène de fluage, qui est défini comme la déformation dessous une charge constante, a un effet à long terme sur la déformation des structures en béton armé. Récentes recherches montrent que la déformabilité de structures en béton armé du au fluage après quelques décades est largement sous-estimée par les normes. Plusieurs recherchent montrent que le fluage à long terme du béton suit une loi logarithmique dans le temps. Le fluage du béton provient de la microstructure du silicate de calcium (C-S-H) hydratée. Bien que de nombreux travaux expérimentaux et théoriques aient été réalisés, les mécanismes de fluage du C-S-H demeurent mal connus. Parmi les facteurs qui influent sur le comportement au fluage du CS- H, l’humidité relative (HR) est le principal. En fait, la teneur en eau dans les microspores joue un rôle important dans la rigidité, la résistance et la viscosité de la microstructure C-SH. La technique d'indentation permet de caractériser les propriétés mécaniques de la pâte de ciment à l'échelle microscopique et nanométrique à laquelle les mécanismes de fluage agissent. Par rapport aux expériences de fluage traditionnelles qui durent des mois et des années, le test d'indentation présente l'avantage d'évaluer les propriétés de fluage des matériaux à base de ciment en quelques minutes. De plus, il est plus facile pour l’échantillon d’atteindre l’équilibre humidité en raison du petit volume sondé. Pour extraire correctement les propriétés de fluage, la première étape consiste à établir une méthode d’essai d'indentation viscoélastique. Pour cette étude, la microindentation viscoélastique est analysée respectivement par une pointe sphérique et une pointe de Berkovich. Les propriétés de fluage à long terme sont bien décrites par le paramètre module de fluage de contact (C) de la complaisance au fluage logarithmique. Les propriétés mécaniques de structures C-S-H semblables à celles de Jennite et de Tobermorite à 1.4 nm sont ensuite caractérisées par une microindentation à différents niveaux d’HR. À différents niveaux d’HR, le comportement de fluage et de relaxation des C-S-H est étudié par la nanoindentation statistique sur une pâte de ciment. Le rôle de l'eau sur le comportement au fluage de C-S-H est réexaminé. De nouvelles découvertes concernant le mécanisme de fluage de C-S-H sont présentées et discutées.
The phenomenon of creep has a long-term effect on the durability of the concrete structures. It has been widely agreed that concrete creep originates from the microstructure of calciumsilicate- hydrates (C-S-H). Being a formidable problem, the creep mechanism of C-S-H is still an enigma although numerous experimental and theoretical works have been done. Among the factors affecting the creep behavior of C-S-H, relative humidity (RH) is the primary one. The water content in the micropores plays an important role in the stiffness, the strength, and the viscosity of the microstructure C-S-H. The indentation technique allows characterizing the mechanical properties of the cement paste at the microscale and the nanoscale. Notably, the phenomenon of creep can be observed during the indentation holding phase. Compared with the traditional creep experiments lasting for months and years, indentation testing has the advantage of assessing the creep properties of the cement-based materials in minutes. In addition, it is easier for the specimen to reach the moisture equilibrium because of the small volume probed. To properly extract the creep properties, the first step is to establish the scheme of viscoelastic indentation. For this study, viscoelastic microindentation is analyzed by a spherical and a Berkovich indenter tip, respectively. The long term creep properties are well captured by the parameter of contact creep modulus (C) from logarithmic creep compliance. The mechanical properties of alike C-S-H structures of jennite and 1.4 nm tobermorite are then characterized by microindentation at various levels of RH. At the two levels of RH, the creep and the relaxation behavior of C-S-H is finally investigated by the statistical nanoindentation on a cement paste. The role of the water on the creep behavior of C-S-H is re-examined. The new findings for the creep mechanism of C-S-H are presented and discussed.
The phenomenon of creep has a long-term effect on the durability of the concrete structures. It has been widely agreed that concrete creep originates from the microstructure of calciumsilicate- hydrates (C-S-H). Being a formidable problem, the creep mechanism of C-S-H is still an enigma although numerous experimental and theoretical works have been done. Among the factors affecting the creep behavior of C-S-H, relative humidity (RH) is the primary one. The water content in the micropores plays an important role in the stiffness, the strength, and the viscosity of the microstructure C-S-H. The indentation technique allows characterizing the mechanical properties of the cement paste at the microscale and the nanoscale. Notably, the phenomenon of creep can be observed during the indentation holding phase. Compared with the traditional creep experiments lasting for months and years, indentation testing has the advantage of assessing the creep properties of the cement-based materials in minutes. In addition, it is easier for the specimen to reach the moisture equilibrium because of the small volume probed. To properly extract the creep properties, the first step is to establish the scheme of viscoelastic indentation. For this study, viscoelastic microindentation is analyzed by a spherical and a Berkovich indenter tip, respectively. The long term creep properties are well captured by the parameter of contact creep modulus (C) from logarithmic creep compliance. The mechanical properties of alike C-S-H structures of jennite and 1.4 nm tobermorite are then characterized by microindentation at various levels of RH. At the two levels of RH, the creep and the relaxation behavior of C-S-H is finally investigated by the statistical nanoindentation on a cement paste. The role of the water on the creep behavior of C-S-H is re-examined. The new findings for the creep mechanism of C-S-H are presented and discussed.

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Filho, Juarez Hoppe. "Sistemas cimento, cinza volante e cal hidratada: mecanismo de hidratação, microestrutura e carbonatação de concreto." Universidade de São Paulo, 2008. http://www.teses.usp.br/teses/disponiveis/3/3146/tde-19082008-172648/.

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A utilização de cinza volante na composição de material cimentício o torna mais sustentável, além de conferir à matriz hidratada características peculiares que melhoram o desempenho frente à ação de diferentes agentes deletérios. A principal desvantagem da utilização de pozolana no sistema cimentício é a maior susceptibilidade à carbonatação. A maior taxa de neutralização da solução aquosa dos poros é devida ao teor remanescente menor de portlandita na matriz. O conhecimento das características da cinza volante que influenciam a interação com a cal, é necessário para subsidiar medidas preventivas com relação ao consumo de portlandita. A presente pesquisa objetiva verificar a eficiência da adição de cal hidratada em concreto executado com cimento pozolânico como forma de reduzir a susceptibilidade à carbonatação. As etapas realizadas para cumprir o objetivo abrangem: a caracterização da cinza volante, com ênfase na determinação do teor de fase vítrea; a cinética de reação em sistema de cinza volante e hidróxido de cálcio; a evolução da hidratação, e a decorrente variação microestrutural. Nos sistemas cimentícios de concretos cujas composições são 100% de cimento ou 50% de cimento e 50% cinza volante, com e sem a adição de 20% de cal hidratada, foi caracterizado a microestrutura da camada de cobrimento e o seu desempenho frente à ação do anidrido carbônico, em ensaio acelerado. Na cinza volante estudada, o teor de fase vítrea foi de 57%, e o consumo máximo por atividade pozolânica, função da área específica BET, foi de 0,69 gramas de Ca(OH)2/grama de fase vítrea de cinza volante. No cimento portland pozolânico, este consumo é menor devido à estrutura formada pela hidratação do cimento. A adição de cal hidratada à pasta de cimento e cinza volante, além de aumentar o consumo de cal por atividade pozolânica, restabeleceu, parcialmente, o teor remanescente de portlandita na matriz. A interação da cinza volante com a cal hidratada não interfere no volume total de vazios da matriz hidratada, porém, refina a microestrutura, aumentando o volume de mesoporos. A carbonatação, em concretos com mesma resistência à compressão de 55 MPa, atingiu maior profundidade quando executado com cimento pozolânico. A adição de cal hidratada não foi eficiente em reduzir a susceptibilidade à carbonatação acelerada.
The use of fly ash in the composition of the cementitious material makes it more sustainable, besides conferring to the hydrated matrix peculiar characteristics which improve its performance with relation to the action of different deleterious agents. The main disadvantage of pozzolan utilization in cementious systems is its susceptibility to carbonation. The greatest neutralization rate of the aqueous solution of the cement pore is, generally, attributed to the smallest amount of portlandite remaining in the matrix. It is necessary to widen knowledge about the characteristics of the fly ash which influence the interaction with calcium hydroxide in order to promote preventive measures with regard to portlandite consumption. This current research aims at verifying the efficiency of hydrated lime addition to concrete by using pozzolanic cement as a way of reducing its susceptibility to carbonation. The steps employed to attain this objective include: fly ash characterization with an emphasis on glass content; fly ash and calcium hydroxide systems kinetics; hydration evolution; and the consequent microstructure variation. In cementious systems of concrete whose composition is either 100% cement or 50% cement and 50% fly ash _ with or without 20% addition of hydrated lime _ it was characterized the microstructure of covercrete and its performance with regard to the interaction with carbon dioxide in accelerated testing. In the studied fly ash, glass content was 57% and the maximum consumption per pozzolanic activity, which is function of BET specific surface area, was 0.69 g of Ca(OH)2/g of glass content in the fly ash. As far as pozzolanic Portland cement is concerned, this consumption is smaller due to the structure formed by the cement hydration. The addition of hydrated lime to the cement paste and fly ash, besides increasing the consumption of lime per pozzolanic activity, partially, reestablished the remaining content of portlandite in the matrix. The interaction of the fly ash with the hydrated lime does not interfere in the total volume of void spaces in the hydrated matrix; however, it refines the microstructure by increasing the volume of mesopores. Carbonation in concrete with the same compressive strength of 55 MPa reached its deepest point when performed in pozzolanic cement. The addition of hydrated lime was not efficient at reducing susceptibility to accelerated carbonation.

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30

Nguyen, Tien Dung. "Apport des aluminates de calcium vis-à-vis de la résistance à l'eau des sulfates de calcium hydratés." Thesis, Lyon, INSA, 2012. http://www.theses.fr/2012ISAL0002.

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Les sulfates de calcium sont des matériaux économiques et écologiques. Pourtant leur utilisation dans le domaine de la construction est assez limitée du fait de leur sensibilité à l’eau. La capacité des ciments alumineux (CAC) à diminuer la sensibilité à l’eau des sulfates de calcium ainsi que les mécanismes d’insensibilisation ont été étudiés. L’insensibilisation à l’eau des sulfates de calcium a été réalisée par ajout de faibles quantités de ciment alumineux (≤ 30%). Quatre sulfates de calcium de nature différente : gypse, hémi-hydrate α et β, anhydrite synthétique ont été étudiés. L’étude des mécanismes d’insensibilisation à l’eau des sulfates de calcium par ajout du ciment Fondu, menée à différentes analyses de la microstructure : IR, DRX, ATD-TG, MEB, a mis en évidence deux approches : la formation de l’ettringite insoluble et la formation du gel d’AH3 qui colle les grains de sulfate de calcium soluble. La nature des phases cristallochimiques du ciment alumineux a des influences sur les caractéristiques mécaniques, la sensibilité à l’eau ainsi que la durabilité des mélanges [sulfate de calcium / CAC]. L’étude des mélanges [anhydrite synthétique / laitier / CAC] offrent des perspectives intéressantes notamment concernant le développement des liants à faible empreinte CO2
Calcium sulphate materials are economical and ecological. But their use in the construction is quite limited because of their sensibility to water. The capacity of aluminate cement (CAC) to decrease the water sensibility of calcium sulphate and the mechanisms of insensibilisation were investigated. Waterproofing of gypsum base materials was carried out by addition of small amounts of aluminate cement (≤ 30%). Different nature of calcium sulphates : gypsum, hemihydrate α and β, synthetic anhydrite was studied. The study of mechanisms of insensibilisation to water of calcium sulphate by adding cement Fondu, with different analysis of microstructure : IR, DRX, ATD-TG, MEB, revealed two approaches : formation of ettringite insoluble and formation of gel AH3 that stick soluble grains of calcium sulphate. The nature of phases of aluminate cement has influences on the mechanical properties, sensibility to water and durability of mixtures [calcium sulphate / CAC]. The studies of mixtures [synthetic anhydrite / slag / CAC] offer interesting perspectives for the development of binders with low imprint CO2

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31

Deschner, Florian [Verfasser], Jürgen [Akademischer Betreuer] Neubauer, Christian [Akademischer Betreuer] Kaps, and Frank [Akademischer Betreuer] Winnefeld. "Reaction of siliceous fly ash in blended Portland cement pastes and its effect on the chemistry of hydrate phases and pore solution / Florian Deschner. Gutachter: Jürgen Neubauer ; Christian Kaps ; Frank Winnefeld." Erlangen : Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), 2014. http://d-nb.info/1054731675/34.

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32

Kanchanason, Vipasri [Verfasser], Johann P. [Akademischer Betreuer] Plank, Johann P. [Gutachter] Plank, and Anton [Gutachter] Lerf. "A Comprehensive Study on Calcium Silicate Hydrate – Polycarboxylate Superplasticizer (C-S-H – PCE) Nanocomposites as Accelerating Admixtures in Cement / Vipasri Kanchanason ; Gutachter: Johann P. Plank, Anton Lerf ; Betreuer: Johann P. Plank." München : Universitätsbibliothek der TU München, 2018. http://d-nb.info/1207074845/34.

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33

Plusquellec, Gilles. "Analyse in situ de suspensions de silicate de calcium hydraté : application aux interactions ioniques à la surface des particules." Thesis, Dijon, 2014. http://www.theses.fr/2014DIJOS046/document.

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Cette étude a pour objectif d’étudier expérimentalement les interactions entre différents anions (chlorure, bromure, nitrate et sulfate) et le silicate de calcium hydraté (C-S-H) afin de construire un modèle thermodynamique capable de prédire cette interaction. Des suspensions de C-S-H synthétisées ont été mises en contact avec différents types de sel (sel de calcium ou d’alcalins). L’influence de la température et de l’incorporation d’aluminium au sein de la structure du C-S-H ont également été prises en compte.L’utilisation d’une méthode d’analyse classique de ce type de système (c’est-à-dire séparation des phases liquide et solide puis analyse de la solution) a révélé ses limites avec, entre autres, une mauvaise reproductibilité des résultats. L’étape de séparation des phases s’est trouvée être à l’origine des difficultés rencontrées.Une seconde méthode d’analyse ne nécessitant pas de filtration des suspensions de C-S-H a été mise au point pour cette étude.Les résultats obtenus ont alors démontrés la non-adsorption des chlorures, nitrates ou bromures par les particules de C-S-H : ces anions n’ont qu’un rôle de compensation de charge au sein de la couche diffuse entourant les particules en suspensions.Les ions calcium (dans le cas d’ajout de sel de calcium) ne s’adsorbent que très faiblement à la surface du C-S-H. Ceci n’est pas influencé par la présence d’aluminium dans la structure. Une température plus faible (5°C) ou plus élevée (40°C) conduit à une adsorption plus faible, voire nulle.L’utilisation d’un modèle thermodynamique de simulation de C-S-H (développé dans une autre étude) a permis de reproduire les résultats expérimentaux obtenus, confirmant donc la validité de ces derniers mais également celle du modèle utilisé
This project aims to study the interactions between calcium silicate hydrate (C-S-H) and different anions (chlorides, bromides, nitrates and sulfates) in order to build a thermodynamic model and then be predictable. The simplified system CaO-SiO2-H2O is studied by synthesizing C-S-H suspensions and mixing them with different kind of salts (calcium salt or alkali salt). The influence of the temperature and the presence of aluminum in the structure of the C-S-H is also examined.A classical way to investigate this kind of system is to separate the liquid phase from the solid phase in order to analyze them separately. Nevertheless, this step has a large influence on the system, and the experimental results suffer from a really bad reproducibility.Another analysis method has then been developed in order to avoid the separation of the different phases. The results show that there is no adsorption of chlorides, bromides or nitrate on the surface of the C-S-H. They only have a role as a charge compensator in the diffuse layer around the particles in suspension.The calcium cation (in the case of calcium salt addition) can be adsorbed by C-S-H, but in a small quantity. The substitution of silicon by aluminum in C-S-H doesn’t have any influence on this phenomenon. A higher or lower temperature results in a weaker adsorption, even inexistent.Those experimental results have been reproduced by using a thermodynamic model developed in a previous study. Thus, the validity of the experimental part but also the one of the model are confirmed

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SILVA, José de Arimatéia Almeida e. "Utilização do politereftalato de etileno (PET) em misturas asfálticas." Universidade Federal de Campina Grande, 2015. http://dspace.sti.ufcg.edu.br:8080/jspui/handle/riufcg/878.

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Capes
A adição do resíduo de Politereftalato de Etileno (PET) em Cimentos Asfálticos de Petróleo (CAP), triturados em partículas cujo diâmetro está entre 0,6 e 0,074 mm, pode ser uma alternativa técnica viável para melhorar as propriedades mecânicas e reológicas das misturas asfálticas. Esta adição tem como finalidade proporcionar uma menor susceptibilidade das misturas asfálticas a fadiga e, conseqüentemente aumentar a vida útil de revestimentos asfálticos em regiões com clima tropical e a temperaturas elevadas. Este trabalho tem como objetivo principal a incorporação de um aditivo no Cimento Asfáltico de Petróleo. A adição de PET foi realizada em proporções de 4%, 5% e 6% relativas ao peso do teor de CAP ótimo e mensuradas as propriedades volumétricas e mecânicas. Além disso foram realizados análises físicas e reológicas do CAP puro e modificado. De acordo com os resultados obtidos nesta pesquisa pode -se inferir que o PET micronizado pós consumo corresponde a um polímero melhorador das propriedades reológicas do CAP 50/70, em termos de rigidez, proporcionado a mistura asfáltica um incremento no comportamento mecânico a luz dos ensaios de Resistência à Tração por Compressão Diametral, Módulo de Resiliência, Resistência por Umidade Induzida, Flow Number e Ruptura por Fadiga. É possível aceitar que “o resíduo do PET micronizado, no teor de 5% pode ser utilizado como agente modificador do CAP e, que o mesmo e capaz de promover ganhos nas Propriedades Mecânicas de Revestimentos Asfálticos.
The addition of polyethylene terephthalate (PET) waste in binder, crushed into particles whose diameter is between 0.074 and 0.6 mm, may be a viable alternative technique to improve the mechanical and rheological properties of asphalt mixtures . This addition is intended to provide a lower susceptibility of fatigue in asphalt mixtures and consequently improve the durability of asphalt mixtures in regions with tropical climate and high temperatures. This work has the objective the incorporation of an additive in binder. It was add in proportions of 4% 5% and 6% relative to the weight of the optimum binder content and it was measured volumetric and mechanical properties of asphalt mixtures. Also performed were physical and rheological analysis of pure and modified binder. According to the results obtained in this study can be inferred that the micronized PET improve the performance of binder 50/70. The addition of PET provided an increase in the mechanical behavior in the Indirect Tensile Strength, Resilient Modulus, Moisture susceptibility, Flow Number and Fatigue life. It is possible to accept that the use of 5% micronized PET waste may be used as modifying agent of binder, and that it improve mechanical properties of asphalt mixtures.

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35

Vyskocilova, R., W. Schwarz, D. Muncha, David C. Hughes, R. Kozlowski, and J. Weber. "Hydration processes in pastes of Roman and American Natural Cements." 2007. http://hdl.handle.net/10454/4003.

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Hydration of five Roman and American natural cements was analyzed using X-ray diffraction, mercury intrusion porosimetry, and scanning electron microscopy of cement pastes. Two cements were prepared in the laboratory by burning marls from geological sources in Poland (Folwark) and Austria (Lilienfeld). The selection of raw materials and burning conditions were optimized so that the hydraulic nature and appearance of the final burnt materials matched as closely as possible historic Roman cements widely used in the 19th and the beginning of the 20th centuries in Europe to decorate buildings. Three other cements are produced commercially: quick setting Prompt cement from Vicat, France, and Rosendale cements from Edison Coatings Inc., USA. The hydration of the cements studied was shown to comprise two distinct stages. The immediate setting and early strength is due to the formation of calcium aluminum oxide carbonate (or sulfate) hydroxide hydrates. The development of long-term strength is brought about by the formation of calcium silicate hydrates. Similarities and differences between the individual cements are discussed.

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36

Νταφαλιάς, Ευστάθιος. "Έλεγχος υδατοπερατότητας τσιμέντου." Thesis, 2009. http://nemertes.lis.upatras.gr/jspui/handle/10889/2469.

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Η ευρύτατη χρήση του τσιμέντου οφείλεται στην χρήση του ως βασικού δομικού υλικού σε σύγχρονες κατασκευές περιλαμβανομένου και του εγκιβωτισμού επικίνδυνων στερεών ή υγρών αποβλήτων. Οι υψηλές τιμές pH και οι πολύπλοκες στερεοχημικές δομές των ένυδρων αλάτων του πυριτικού ασβεστίου (C-S-H gel) στο τσιμέντο, μπορούν να εγκλωβίσουν πολλά χημικά είδη βαρέων μετάλλων στο πλέγμα τους, καθιστώντας τα έτσι ανενεργά. Ο βαθμός σχηματισμού των ένυδρων πυριτικών αλάτων είναι επίσης, ρυθμιστικός παράγων του πορώδους, της σκληρότητας και της αντοχής του σκυροδέματος. Οι κυριότεροι τύποι του C-S-H gel που εντοπίζονται στα συστατικά του τσιμέντου είναι το πυριτικό διασβέστιο Ca2SiO4 και το πυριτικό τριασβέστιο Ca3SiO5. Εύλογα λοιπόν, η μελέτη της θερμοδυναμικής και της κινητικής σχηματισμού των αλάτων αυτών είναι πολύ σημαντική. Στην παρούσα εργασία, πραγματοποιήθηκε μελέτη της κινητικής της καταβύθισης του C-S-H gel σε υπέρκορα υδατικά διαλύματα παρασκευαζόμενα από στόκ διαλύματα Ca(NO3)2 και Na2Si3O7 σε σταθερή θερμοκρασία 25°C. Η επίδραση παραμέτρων, όπως το pH των υπέρκορων διαλυμάτων και του γραμμομοριακού λόγου των συγκεντρώσεων Ca/Si στα διαλύματα, μελετήθηκαν σε συνθήκες σταθερού pH με την προσθήκη διαλύματος NaOH από αυτόματο τιτλοδοτητή. Η κινητική ανάλυση έδειξε ότι ο μηχανισμός της ανάπτυξης των κρυσταλλικών στερεών γίνεται κυρίως με επιφανειακή διάχυση και εξαρτάται από το pH των διαλυμάτων στην περιοχή pH 10-12. Η ταυτοποίηση των ιζημάτων με τεχνικές περίθλασης ακτίνων Χ (ΧRD), υπερύθρου (FTIR) και με θερμοσταθμική ανάλυση, έδειξε τον σχηματισμό C-S-H gel με πιθανή συγκαταβύθιση άμορφης σίλικας. Το γεγονός ότι το καθορίζον την ταχύτητα στάδιο είναι η επιφανειακή διάχυση των δομικών μονάδων οδηγεί στο συμπέρασμα ότι η τροποποίηση της επιφάνειας των κρυστάλλων παρέχει την δυνατότητα ελέγχου του ρυθμού σχηματισμού του C-S-H gel και κατ’ επέκταση των ιδιοτήτων του τσιμέντου κατά την ενυδάτωσή του. Η τροποποίηση της επιφάνειας μπορεί να πραγματοποιηθεί με την βοήθεια υδατοδιαλυτών και μη χημικών ουσιών οι οποίες μπορούν να αλληλεπιδράσουν με την επιφάνεια, αλλοιώνοντας τον αριθμό και την ενεργότητα των κρυσταλλικών κέντρων ανάπτυξης. Βάσει των αποτελεσμάτων της επίδρασης της παρουσίας προσθέτων στην κινητική της καταβύθισης, πραγματοποιήθηκαν δοκιμές σε δοκίμια τσιμέντου στα οποία έγινε και εφαρμογή πολυμερών (υδατοδιαλυτών και μη) και μετρήθηκαν η υδροπερατότητα και η αντοχή τους, ιδιότητες που εξαρτώνται από τον βαθμό σχηματισμού του πυριτικού ασβεστίου.
The widespread use of cement as a building material in modern construction, including use for embedding radioactive wastes makes it a material of paramount importance. The formation of calcium silicate hydrates is of key importance for the determination of the cement characteristic properties including porosity, strength and hardness. The main types of C-S-H gel identified between cement components include di-calcium silicate Ca2SiO4 and tri-calcium silicate Ca3SiO5. Since these silicate salts during the cement hydration interact with water yielding C-S-H gel, the investigation of homogeneous precipitation of this phase is very interesting. In the present work the kinetics of spontaneous C-S-H gel precipitation in aqueous solutions was investigated at constant solution pH from supersaturated solutions at 25°C. The pH range investigated covered the range between 10-12. The effect of the solution pH and of the molar calcium:silicate ratio in the supersaturated solutions was investigated. Plots of the rates of precipitation as a function of the solution supersaturation, showed a high order dependence suggesting that the rate determining step for the precipitation of C-S-H gel was surface diffusion. The rates were found to be pH dependent in the range investigated. The precipitate was identified by powder X-ray diffraction, infrared spectrometry (FTIR) and thermogravimetric analysis as a mixture of calcium silicate hydrate gel and amorphous silica. The fact that the rate determining step was surface diffusion control, suggested that it is possible to control the rate of precipitation through surface modification, possibly treating the surface with compounds which may interact, resulting in poisoning of the active crystal growth sites. It is anticipated that control of kinetics may result in the control of the rate and of the extent of C-S-H gel formation and subsequently of the cement properties during its hydration. On the basis of the results obtained for the precipitation of C-S-H gel in the presence of additives, a series of experiments was done on cement specimens using both water soluble and compounds soluble in organic solvents. In general, the presence of the tested additives resulted in a significant reduction of water uptake suggesting, indirectly, that the formation of C-S-H gel was suppressed. Moreover the resistance to friction was reduced, possibly due to the fact that the compounds tested formed soft but impermeable to water, surface films.

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Hajilar, Shahin. "Nano-Scale Investigation of Mechanical Characteristics of Main Phases of Hydrated Cement Paste." 2015. https://scholarworks.umass.edu/masters_theses_2/151.

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Hydrated cement paste (HCP), which is present in various cement-based materials, includes a number of constituents with distinct nano-structures. The elastic properties of the HCP crystals are calculated using molecular dynamics (MD) methods. The accuracy of estimated values is verified by comparing them with the results from experimental tests and other atomistic simulation methods. The outcome of MD simulations is then extended to predict the elastic properties of the C-S-H gel by rescaling the values calculated for the individual crystals. To take into account the contribution of porosity, a detailed microporomechanics study is conducted on low- and high-density types of C-S-H. The obtained results are verified by comparing the rescaled values with the predictions from nanoindentation tests. Moreover, the mechanical behavior of the HCP crystals is examined under uniaxial tensile strains. From the stress-strain curves obtained in the three orthogonal directions, elastic and plastic responses of the HCP crystals are investigated. A comprehensive chemical bond and structural damage analysis is also performed to characterize the failure mechanisms of the HCP crystals under high tensile strains. The outcome of this study provides detailed information about the nonlinear behavior, plastic deformation, and structural failure of the HCP phases and similar atomic structures.

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Cunha, Diogo Manuel Ferreira da. "Betões eco eficientes com incorporação de cinzas de biomassa." Master's thesis, 2017. http://hdl.handle.net/1822/70630.

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Dissertação de mestrado integrado em Engenharia Civil
A sustentabilidade da construção é um assunto com grande influência e consequências na atualidade. Uma das medidas de modo a contribuir para a sustentabilidade é reduzir a produção e o consequente consumo de cimento que deriva da construção. A produção de cimento Portland origina a libertação de grandes quantidades de CO2 e consome grandes quantidades de energia. Como o betão é utilizado na construção em grandes quantidades, pode ser utilizado de maneira a nele serem incorporados resíduos e subprodutos industriais de forma segura e económica. Um exemplo é a incorporação de cinzas volantes de carvão provenientes de centrais termoelétricas. Betão com um elevado volume de cinzas volantes, possui uma reação pozolânica lenta e, portanto, a resistência mecânica inicial do betão é menor que o betão com cimento como único ligante. O destino de valorização mais comum dos resíduos florestais é a sua valorização térmica através da combustão. As cinzas volantes de biomassa têm características semelhantes às cinzas volantes de carvão, no entanto, são mais alcalinas (maior pH) e possuem um teor de cálcio maior. O principal objetivo deste trabalho consiste em avaliar a possibilidade de produzir betões de desempenho melhorado incorporando elevado volume de cinzas volantes de carvão, bem como utilizar pequenas quantidades de cinzas volantes de biomassa, de forma a mitigar alguns dos inconvenientes dos betões com elevado volume de cinzas volantes de carvão. Com base nos resultados obtidos, a durabilidade das composições com elevado volume de cinzas volantes, revelou-se, em geral, superior à da composição de referência, com exceção relativamente à resistência à carbonatação que, contudo, foi melhorada com a inclusão de uma reduzida quantidade de cinzas de biomassa. A cinza volante de carvão possuiu uma boa sinergia com quantidades reduzidas de cinza de biomassa que resultou numa boa atividade pozolânica.
The sustainability of construction is a subject with great influence and consequences at the present time. One of the measures to contribute to sustainability is to reduce the production and consequent consumption of cement that comes from construction. The production of Portland cement gives rise to the release of large amounts of CO2 and consumes large amounts of energy. As concrete is used in large-scale construction, it can be used to incorporate industrial waste and by-products in a safe and economical way. An example is the incorporation of coal fly ash from thermoelectric power plants. Concrete with a high volume of fly ash has a slow pozzolanic reaction and, therefore, the initial mechanical strength of the concrete is lower than the concrete with cement as the sole binder. The most common destination for forest residues is their thermal recovery through combustion. Biomass fly ash has characteristics similar to coal fly ash, however, they are more alkaline (higher pH) and have a higher calcium content. The main objective of this work is to evaluate the possibility of producing improved performance concrete incorporating a high volume of coal fly ash, as well as to use small amounts of biomass fly ash to mitigate some of the drawbacks of concretes with high volume of coal fly ash. Based on the obtained results, the durability of the compositions with a high volume of fly ash has generally proved to be superior to that of the reference composition, except for the resistance to carbonation which has however been improved by the inclusion of a reduced amount of biomass ash. Coal fly ash had a good synergy with reduced amounts of biomass ash which resulted in good pozzolanic activity.

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Dissertations / Theses on the topic 'Cement hydrates'

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