Le ciment est le matériau le plus utilisé de nos jours pour plusieurs raisons: de bonnes propriétés mécaniques à la compression, un faible coût et une facilité d'utilisation. Cependant, le ciment est fragile lorsqu'il est soumis à des charges élevées et il est susceptible de se dégrader par des agents externes. Pour cette raison, différents additifs sont utilisés pour modifier le processus de prise et ainsi les propriétés finales du ciment. Parmi ces additifs, il y a un type appelé « accélérateurs de prise » qui permet la prise de la matrice de ciment plus rapidement. Il existe un type d'additifs « accélérateurs » qui constituent des points de germination pour la formation de gel C-S-H autour d'eux. L'objet de ce travail a été de développer une nouvelle voie de synthèse, basée sur la technologie eau supercritique, de deux nanoadditifs d'hydrates de silicate de calcium : la xonotlite et la tobermorite.Dans un premier temps, la synthèse a été effectuée dans des conditions souscritiques. Ensuite, il a été développé un réacteur continu supercritique adapté à la synthèse de ces nanoadditifs. Les synthèses ont été réalisées à 400 ° C et 23,5 MPa. La xonotlite et la tobermorite ont toutes deux été obtenues en réduisant drastiquement les temps de réaction d'heures/semaines (dans des conditions souscritiques) à quelques secondes seulement, dans des conditions supercritiques.Le dernier point étudié a été l'effet d'ensemencement par ces deux additifs de la pâte de ciment. Dans tous les cas, il a été observé, une accélération de la réaction et également une amélioration de la résistance du ciment.En conclusion, ce travail présente une nouvelle méthode ultra-rapide pour synthétiser des hydrates de silicate de calcium très cristallins, et prouve également l'effet « accélérateur » de ces particules lorsqu'elles sont utilisées comme germes dans des pâtes de ciment. Cette recherche propose une nouvelle méthodologie pour la synthèse des additifs pour ciments. / Cement is the most used material nowadays due to several reasons: its good mechanical properties to compression, its low cost, and its easy use. However, cement is fragile when submitted to high charges and it is susceptible to degradation by external agents. For this reason different additions are used modify the setting process or the final properties of the cement paste. Among them there are one type called “setting accelerators” that develop the cementitious matrix faster. There is one type of accelerating additions that act as seeds; these are nucleating points for the formation of C-S-H gel around them. The aim of this work is to develop a new synthesis route, based on supercritical water technology, of two calcium silicate hydrates nanoadditions. These products are xonotlite and tobermorite.The first approach to the synthesis was done under subcritical conditions. After that it was developed the supercritical continuous reactor in order to adapt it to the necessities of the synthesis of the nanoadditions. The syntheses were carried out at 400ºC and 22.5 MPa. Both xonotlite and tobermorite were obtained reducing drastically the reaction times from hours/weeks (under subcritical conditions) to just some seconds under supercritical conditions.The last point studied was the seeding effect of both particles into cement paste. In every case it was observed, an acceleration of the reaction and also an improvement of the strength trough mechanical test.As a conclusion this work presents a new ultrafast method to synthesize highly crystalline calcium silicate hydrates, and also proves the accelerating effect of these particles when they are used as seeds in cement pastes. This research proposes a new methodology for the synthesis of additions to cement.

The nature of the calcium-silicate-hydrate phase in hydrated Portland cement has been the subject of considerable debate for decades. Various nanostructural models have been proposed including those constructed from colloidal-based particulate systems and those formulated on the basis of layered calcium-silicate-hydrates. These are examined in detail in the literature review section of the thesis. Relatively recent composition-based models have been proposed by Taylor and Richardson-Groves. These models contain structural elements comprised of 1.4 nm tobermorite and jennite. Details are also provided in the literature review. There is however a paucity of data on the engineering properties of pure calcium-silicate-hydrate phases and virtually none on the mechanical performance of 1.4 nm tobermorite and jennite. The global objective of this thesis was to examine the compatibility of the composition-based models with the engineering behaviour of the pure tobermorite and jennite phases. Pure phases of a variety of layered calcium-silicate-hydrates were synthesized and novel techniques developed to determine their engineering characteristics in a variety of test environments. The silicate phases investigated included high temperature silicates e.g. gyrolite as these layered structures are known to be cross-linked. Investigation of the role of ‘structural’ water in layered silicates was also a part of these studies. The thesis is based on a series of twelve refereed journal papers by the candidate (eight are published or accepted and four have been submitted for publication). The research is reported in four parts with each part comprised of three papers. Each part provides insight into the nanostructure of C-S-H in hydrated cement. The arguments developed evolve from an assessment of various factors including aging and the state of water in the layered silicates. The first part of the thesis focuses on the development and application of dynamic mechanical thermo-analysis methods that are sensitive to phase changes and are useful for assessing the compatibility of engineering behaviour with model composition based on 1.4 nm tobermorite and jennite. The second part represents a study of volume stability and mechanical property-porosity relationships for the pure silicate phases that are germane to these studies. The third part focuses on prolonged aging and role of structural water in cement paste hydrated for 45 years. The fourth and final part attempts to address the role of layer structure e.g. cross-linking of silicate sheets on engineering behaviour. The non-uniqueness of modulus of elasticity with respect to equilibrium moisture content is demonstrated. Structurally related irreversible effects that are dependent on drying history are rationalized. A summary chapter is provided wherein the evidence for a composition-based model with tobermorite and jennite structural units is rationalized in terms of the experimental evidence provided in this study and suggestions for future research are discussed.

AUne étude théorique et expérimentale de la propagation acoustique dans les milieux à double porosité soumis à l’écoulement de liquides turbides est présentée. Deux matériaux à double porosité supposés obéir à l'extension faite par Berryman et Wang (1995) de la théorie de Biot en régime basse fréquence sont examinés : (i) le ROBU® dont les grains poreux individuels, formés de minuscules billes verre de borosilicate 3.3, sont quasi-sphériques et (ii) la Tobermorite 11 Å dont les grains poreux individuels à base de ciment sont de formes très irrégulières. Nous proposons, d’une part une modélisation numérique de la propagation acoustique à travers une maquette de forme parallélépipédique remplie d’un milieu à double porosité, et d’autre part une validation expérimentale en laboratoire. Les caractérisations du milieu à double porosité par la voie mécanique sont également présentées. Les essais de traçage en vue de la caractérisation du transport et du dépôt de particules en suspension dans le liquide turbide, sont effectués. Les interprétations des résultats sont basées entre autres sur le temps de transfert, le taux de restitution, la capacité de rétention, le profil spatial de la rétention et le tri granulométrique des particules transportées. L’objectif de nos travaux de recherche est de développer une méthode d’investigation non destructive permettant une évaluation du degré de colmatage résultant du dépôt des particules fines dans les pores, par exemple. / A theoretical and experimental study of wave propagation in double porosity media submitted to the flowing of turbid liquids is led. Two samples of double porosity materials assumed to obey Berryman and Wang’s extension (1995) of Biot’s theory in the low frequency regime are considered : (i) ROBU® (pure binder-free borosilicate glass 3.3 manufactured to form the individual grains) and (ii) Tobermorite 11 Å ( the individual porous cement grains show irregular shapes). We propose on the one hand a numerical study of wave propagation through a rectangular box filled with a double porosity medium and, on the other an experimental validation in laboratory. The characterizations of the double porosity medium by using mechanical tools are also presented. The tracing tests for characterizing the transport and the deposition of suspended particles contained in saturating liquids, are realized. The interpretations of the results are based on the transfer time, the restitution ratio, the retention capacity, the spatial profile of the retention and the size sorting of transported particles. The aim of our research is to develop a method for non-destructive testing that allows an assessment of the degree of clogging resulting from the deposition of fine particles in the pores, for example.

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.

In these days of economic crisis subsiding, in the civil engineering the attention is pointed especially to the systems, which effectively reduce energy and decrease costs associated with using of residential or industrial premises. Especially the heat-insulating systems are mentioned, because of their characteristics and construction which will be applied economical solutions. It is possible to use the materials based on aerated concrete which excel within construction materials due to its heat-insulating properties. The use of this material for clearly heat-insulations seems to be fully-fledged alternative to standard heat-insulating systems also due to combination of nature character and sufficient strength. This work deals with possibility of preparation non-bearing, heat-insulating material based on autoclaved aerated concrete with volume weight under 200 kg/m3.

Les hydrates de ciment (C-S-H) obtenus par dissolution/précipitation du ciment anhydre, constituent la matrice donnant au matériau ses propriétés mécaniques et sont structurellement analogues de la tobermorite, un calcio-silicate lamellaire naturel. La compréhension de la cohésion du ciment passe donc par la compréhension de la cohésion entre feuillets tobermoritiques. La structure lamellaire de différents échantillons de CSH tobermoritiques synthétisés par "chimie douce" a été mise en évidence ; les échantillons avec un rapport Ca/Si égal à 0.9 étant particulièrement bien cristallisés. L'étude du processus de déshydratation pour ces échantillons a permis d'identifier 3 phases et de montrer la similarité de comportement vis à vis du "vrai" ciment. Nous montrons que la transition 14-11 Å est irréversible. Se pose alors la question du rôle de l'eau interfoliaire dans la cohésion du matériau en relation avec les deux structures possibles décrites dans la littérature pour la tobermorite naturelle 11 Å : la proposition d'Hamid (1981) décrivant un ensemble de feuillets indépendants et celle de Merlino et al (1999) décrivant des feuillets chimiquement liés. La confrontation entre résultats expérimentaux (29Si-RMN et spectroscopie infra-rouge) et numériques (calculs ab-initio et minimisation d'énergie) indique que la structure d'Hamid est un modèle acceptable pour les C-S-H tobermoritiques. La nature des liaisons inter-feuillets est d'origine coulombienne au sens de l'énergie de réseau des solides ioniques.

This doctoral thesis is focused on the study of reactions in the CaO–SiO2–H2O complex system, primarily to the synthesis of crystalline tobermorite. Hydrothermal conditions are necessary for the formation of crystalline tobermorite, whereas the course of the reaction is influenced by several factors. The main studied factor was the choice of the silica sources differing in means of solubility, crystallinity, particle size distribution, specific surface area, and purity. The water-to-solid ratio turned to be also an important factor as the length of the hydrothermal reaction. The influence of the mechanochemical pretreatment of starting materials to the final phase composition of samples was studied as well. The obtained results show that the crystallinity of the silica source is the main factor influencing the reaction rate and the purity of the synthesized tobermorite. While using the crystalline silica source the shorter silicate chains are formed and the formation of tobermorite structure is easier. Using the amorphous silica sources and the mechanochemical pretreatement of starting materials prolong the hydrothermal reaction. The prepared samples are always the mixture of crystalline or semicrystalline calcium hydrosilicates instead of the phase pure tobermorite.

Orientador: Prof. Dr. Caetano Rodrigues Miranda / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, Santo André, 2018. / A pasta de cimento 'e um material complexo, heterog¿eneo e poroso com excelentes propriedades que o tornam um aglutinante adequado para aplica¸c¿oes em constru¸c¿oes. A qualidade e a durabilidade do cimento t¿em uma forte rela¸c¿ao com a 'agua contida nele. Embora uma boa compreens¿ao das intera¸c¿oes complexas entre os poros do cimento e os flu'ýdos confinados 'e necess'aria para resolver os atuais problemas de durabilidade, at'e ent¿ao nenhum modelo foi bem sucedido na captura de todos os processos e o papel da 'agua no cimento continua a ser uma 'area de pesquisa ativa. Com o intuito de contribuir para a compreens¿ao atual da estrutura do cimento, este trabalho se concentrou no estudo dos processos din¿amicos que acontecem na nanoescala da 'agua confinada em poros de cimento. Utilizamos simula¸c¿oes atom'ýsticas que v¿ao desde primeiros princ'ýpios at'e din¿amica molecular para estudar a principal fase de hidrata¸c¿ao, ou seja, hidrato de silicato de c'alcio (C¿S¿H), modelado por uma estrutura de tobermorita com defeitos. A partir de primeiros princ'ýpios, investigamos a morfologia da superf'ýcie da tobermorita a qual rege as intera¸c¿oes da 'agua com o modelo C-S-H. Demonstramos que a tobermorita forma cristais pseudo-hexagonais e a faceta mais est'avel 'e a (004). A fim de explorar sistemas maiores, checamos a transferabilidade do potencial cl'assico CLAYFF na descri¸c¿ao dos componentes do cimento atrav'es de um estudo comparativo entre simula¸c¿oes de mec¿anica molecular e DFT. Embora as frequ¿encias calculadas com DFT e CLAYFF sejam diferentes, as propriedades estruturais e termodinâmicas apresentam grande concord¿ancia, indicando que o potencial CLAYFF 'e adequado para nossos c'alculos. Um par¿ametro importante para quantificar a din¿amica da 'agua no nanoconfinamento 'e o tempo de relaxa¸c¿ao T2. Para validar a metodologia implementada na determina¸c¿ao te'orica do tempo de relaxa¸c¿ao T2, realizamos simula¸c¿oes para a 'agua confinado dentro de nanoporos de calcita (1¿6 nm). Observamos que a din¿amica translacional 'e a principal respons'avel pela relaxa¸c¿ao de spin das mol'eculas de 'agua pr'oximas 'a superf'ýcie. O tempo de relaxa¸c¿ao T2 para mol'eculas de 'agua adsorvidas na superf'ýcie 'e menor e independente do tamanho de poro, no entanto, uma relaxa¸c¿ao de spin do tipo bulk 'e observada no centro dos poros maiores que 3 nm. Buscando elucidar as diversas propriedades da 'agua nanoconfinada em poros C¿S¿H, dividimos nosso estudo em tr¿es partes. Inicialmente, nos dedicamos a compreender os efeitos de confinamento da 'agua entre camadas (< 1 nm) e poros de gel (1¿5 nm) do modelo C-S-H, assim como suas influ¿encias nas intera¸c¿oes de superf'ýcie. A natureza hidrof'ýlica da superf'ýcie C¿ S¿H 'e evidenciada pela din¿amica lenta da 'agua que interage diretamente com a superf'ýcie. Entre as camadas, a 'agua se encontra praticamente im'ovel e exibe propriedades similares aquelas observadas em 'agua super-resfriada. Na sequ¿encia, investigamos o transporte da 'agua dentro da pasta de cimento implementando a relaxa¸c¿ao de troca do tipo 2D T2¿T2 RMN entre poros de gel com 1 nm e 4 nm conectados entre si. Nossos resultados mostraram que h'a trocas de mol'eculas de 'agua entre poros com um tempo caracter'ýstico de troca de 18 ns. Finalmente, conclu'ýmos nossos estudos considerando a natureza particulada do C¿S¿H a fim de estabelecer uma conex¿ao entre os fen¿omenos observados nas escalas nano e meso. Demonstramos que a 'agua confinada dentro do ambiente C¿S¿H edge-edge apresenta uma din¿amica semelhante ao caso das superf'ýcies planares. / Cement paste is a complex, heterogeneous and porous material with outstanding properties that make it a suitable binder for construction applications. The quality and durability of cement have a strong relationship with the water contained in it. While a good understanding of the complex interactions between the cement pores and the confined fluids is necessary to solve the current durability issues, no single model has been successful in capturing all the processes so far and the role of water in cement still remains an area of active research. To contribute to the current understanding of cement structure, this work has focused on studying the dynamical processes happening at the nanoscale of water confined in cement pores. We employ atomistic simulations ranging from first principles to molecular dynamics to study the main hydration phase, i.e calcium silicate hydrate (C¿S¿H), modeled by a defected tobermorite structure. Starting from first principles, the surface morphology of tobermorite which governs the interactions of water with the C¿S¿H model was investigated. It was shown that tobermorite forms pseudohexagonal crystals and the most stable facet is the (004). To upscale the calculations, the transferability of CLAYFF in the description of cementitious materials was tested through a comparative molecular mechanics and DFT study. Although the frequencies calculated with DFT and CLAYFF differ, the structures and thermodynamic quantities agree quite well, making CLAYFF a reasonable potential for our cement calculations. An important parameter to quantify water dynamics in nanoconfinement is NMR T2 relaxation time. To underpin the implemented methodology for theoretical determination of T2 relaxation time, simulations were performed for water confined within calcite nanopores (1¿6 nm). It was revealed that translational dynamics are the main contribution to spin relaxation of near surface water molecules. The T2 relaxation time for water molecules directly adsorbed on the surface is short and pore size independent, however a bulk¿like spin relaxation is observed at center of pores larger than 3 nm. To disentangle the diverse properties of water nanoconfined in C¿S¿H pores, the study of water within C¿S¿H was subdivided into three parts. The first part was dedicated to understanding the relative effect of the C¿S¿H surface and progressive confinement to water confined in the interlayer (< 1 nm) and gel pores (1¿5 nm) of C¿S¿H model. The hydrophilic nature of the C¿S¿H surface is evidenced by the slow dynamics for the water interacting directly with the surface. Within the interlayer, water is highly immobile and exhibits similar properties as those observed in supercooled water. Next, transport within cement paste was investigated by implementing 2D T2¿T2 NMR exchange relaxation between a 1 nm and 4 nm gel connected pores. We showed that there is water exchange in gel pores quantified by an exchange time of 18 ns. Lastly, the particulate nature of C¿S¿H is taken into consideration to facilitate bridging the gap between the atomistic and the mesoscale cement understanding. It was shown that water confined within the C¿S¿H edge¿edge environment portrays similar dynamics as in the C¿S¿H planar surfaces.

Autoclaved sand aerated concrete is a modern building material with high thermal insulation properties. Only sand is used as the primary silicate component of aerated concrete in the Czech Republic. For the more favourable economic and ecological properties of aerated concrete, the use of secondary raw materials is used in this work. The secondary raw materials examined included fluidized bed and fly ash, slag and glass recycled. The aerated concrete composite with secondary admixtures was developed under hydrothermal conditions of a laboratory autoclave for 7 and 12 hours at 190°C. From the secondary raw materials tested, a 10% glass recycler additive yielded the highest strength. Other additives that have a positive effect on mechanical properties include SAKO and Oslavany. From the results of the work it is evident that the use of secondary raw materials increases the strength, improves the rheology of the mixture and supports the formation of tobermorite.

Autoclaved aerated concrete is a used building material, especially for its thermal insulating properties. During autoclaving, an aerated concrete microstructure produces crystalline CSH phases, primarily tobermorite. The ingoing substances are calcium oxide and silica. In addition to commonly used raw materials, secondary raw materials rich in silicon dioxide can be used for production. The use of secondary raw materials gives the opportunity for the construction industry to be more environmentally friendly. Another benefit is the reduction of financial costs. The work explores the influence of individual secondary raw materials on the microstructure. High-temperature fly ash, fluid fly ash, cinder, ground glass and zeolite were used The raw materials were mixed with unalloyed lime at a molar ratio of calcium oxide to silicon dioxide of 0.73 and 1.0. Autoclaving capsules were used to synthesize tobermorite under laboratory conditions. Autoclave was performed at 170 °C and 190 °C with hydrothermal durations of 4, 8 and 16 hours. The most important influence on the microstructure was high-temperature fly ash, on the contrary, the greatest influence on the mechanical properties is attributed to the ground glass.