Pure, MgO doped and B2C3 doped monocalcium, dicalcium, and tricalcium silicates were prepared with different glass contents. Characterization of the anhydrous materials was carried out using optical microscopy, infrared absorption spectroscopy, and X-ray powder diffraction. The hydration of these compounds was studied as a function of the glass contents. The hydration studies were conducted at 25°C. Water/solid ratios of 0.5, 1, 10, and 16 were used for the various experiments. The hydration behavior was monitored through calorimetry, conductometry, pH measurements, morphological developments by scanning electron microscopy, phase development by X-ray powder diffraction, and percent combined water by thermogravimetry. A highly sensitive ten cell pseudo-adiabatic microcalorimeter was designed and constructed for early hydration studies. Conductometry was found to be of great utility in monitoring the hydration of monocalcium silicate and the borate doped dicalcium silicates.

Slag, by itself, shows very little hydraulic activity. However, hydration is greatly accelerated by incorporation of the slag with Portland cement. This phenomenon is due to the activating role of calcium hydroxide released from the hydration of Portland cement. This study was aimed at finding other activators that will increase hydration in both synthetic and commercial slags. The effects of chemical composition and the aggregation state of the slag on the hydration process were also investigated. For the synthetic slags, the aggregation state was altered by different quenching techniques. The chemical composition was varied by synthesizing a series of slags. The degree of hydration was studied by developing a thermogravimetric analysis technique and the glass content was determined using microscopy. Minerals were determined using powder x-ray diffraction analysis.

Dada a considerável parcela de responsabilidade da indústria de produção de cimento no total de emissão mundial de CO2, um dos desafios atuais mais importantes é a adoção de estratégias que reduzam a utilização do cimento, sem prejuízo ao desempenho mecânico e a durabilidade dos materiais cimentícios. Dentre essas estratégias, uma das usualmente empregadas em alguns segmentos industriais é a reutilização de ligante pré-hidratado na produção. O entendimento de como a pré-hidratação altera as propriedades de pastas cimentícias tem também importante implicação científicas, quanto à cinética de reação do cimento Portland, mas sobretudo devido aos impactos nas propriedades reológicas da pasta, tanto após a mistura quanto ao decorrer da hidratação. Sabe-se que a pré-hidratação altera a cinética de hidratação do cimento, impactando as suas propriedades no estado endurecido. Além disso, a pré-hidratação modifica as propriedades físicas do cimento, influenciando diretamente no modo como as partículas se aglomeram. No entanto, boa parte da literatura refere-se à pré-hidratação que ocorre após má estocagem, diferentemente deste trabalho que trata da pré-hidratação em suspensão, mais comum em processos industriais. Assim, neste trabalho foi avaliada a cinética de reação por calorimetria isotérmica enquanto as propriedades reológicas foram avaliadas por reometria rotacional e oscilatória. Para a identificação e quantificação dos hidratos formados, a hidratação foi paralisada e foram realizados testes de TG e DRX. Os resultados mostraram que a adição do pré-hidratado altera a cinética de dissolução/precipitação do cimento anidro. Assim, quanto maior o teor de pré-hidratado e o período de pré-hidratação, menor o tempo de indução, antecipando a formação dos hidratos (silicatos e aluminatos), embora a taxa de reação no período de aceleração não tenha sido afetada de forma significativa. Quanto às propriedades físicas das partículas, forma realizados teste de granulometria, ASE (Área Superficial Específica) e densidade real. A pré-hidratação aumenta a sua ASE, o que acarreta no incremento da tensão de escoamento e da viscosidade das pastas. Inclusive, se esse aumento de ASE for incorporado em determinados modelos (YODEL e Interferência) é possível a predição dessas propriedades reológicas. O aumento de ASE também é responsável pelo maior enrijecimento e menor tempo de pega das suspensões pré-hidratadas. Correlacionando a reação química com a consolidação da pasta, ficou demonstrado que o maior enrijecimento da pasta pré-hidratada tem relação com a maior aproximação entre as partículas, a ASE inicial das pastas e a reatividade do pré-hidratado, otimizando assim a formação da microestrutura pela hidratação. / Given the considerable share of cement industry on overall share of CO2 emissions, one of the most important current challenges is the adoption of strategies that reduce the use of cement without compromising the mechanical performance and durability of cementitious materials. Among these strategies, one of the commonly employed in some industrial segments is the reuse of pre-hydrated binder in production. The understanding of as pre-hydration changes the properties of cementitious pastes also has important scientific implication regarding the reaction kinetics of Portland cement, but mainly due to the impacts on the rheological properties of the paste, both after mixing and along hydration. It is known that pre-hydration alters the hydration kinetics of the cement, impacting its properties in the hardened state. In addition, pre-hydration modifies the physical properties of the cement, directly influencing the way as the particles agglomerates. However, much of the literature refers to the pre-hydration that occurs after bad storage, unlike this work that works with pre-hydration in suspension, more common in industrial applications. Thus, in this work the kinetics of reaction by isothermal calorimetry was evaluated while the rheological properties were evaluated by rotational and oscillatory rheometry. For the identification and quantification of the hydrates formed, the hydration was paralyzed and TG and XRD tests were performed. The results showed that the inclusion of the pre-hydrate alters the dissolution/precipitation kinetics of the anhydrous cement. Thus, the higher the pre-hydration content and the pre-hydration period, the shorter the induction time, anticipating the formation of the hydrates (silicates and aluminates), although the reaction rate in the acceleration period was not significantly affected. As for the physical properties of the particles, there were realized tests of particle size distribution, SSA (Specific Surface Area) and real density. The pre-hydration increases its SSA, which leads to an increase in the yield stress and viscosity of the pastes. Even if this increase of SSA is incorporated in certain models (YODEL and Interference) it is possible to predict these rheological properties. The increase in ASE is also responsible for the greater hardening and quickly setting time of the pre-hydrated suspensions. Correlating the chemical reaction with paste consolidation, it was demonstrated that the higher hardening of the pre-hydrated paste is related to the greater approximation between the particles, the initial ASE of the pastes and the reactivity of the pre-hydrate, optimizing then the formation of the microstructure by hydration.

Dada a considerável parcela de responsabilidade da indústria de produção de cimento no total de emissão mundial de CO2, um dos desafios atuais mais importantes é a adoção de estratégias que reduzam a utilização do cimento, sem prejuízo ao desempenho mecânico e a durabilidade dos materiais cimentícios. Dentre essas estratégias, uma das usualmente empregadas em alguns segmentos industriais é a reutilização de ligante pré-hidratado na produção. O entendimento de como a pré-hidratação altera as propriedades de pastas cimentícias tem também importante implicação científicas, quanto à cinética de reação do cimento Portland, mas sobretudo devido aos impactos nas propriedades reológicas da pasta, tanto após a mistura quanto ao decorrer da hidratação. Sabe-se que a pré-hidratação altera a cinética de hidratação do cimento, impactando as suas propriedades no estado endurecido. Além disso, a pré-hidratação modifica as propriedades físicas do cimento, influenciando diretamente no modo como as partículas se aglomeram. No entanto, boa parte da literatura refere-se à pré-hidratação que ocorre após má estocagem, diferentemente deste trabalho que trata da pré-hidratação em suspensão, mais comum em processos industriais. Assim, neste trabalho foi avaliada a cinética de reação por calorimetria isotérmica enquanto as propriedades reológicas foram avaliadas por reometria rotacional e oscilatória. Para a identificação e quantificação dos hidratos formados, a hidratação foi paralisada e foram realizados testes de TG e DRX. Os resultados mostraram que a adição do pré-hidratado altera a cinética de dissolução/precipitação do cimento anidro. Assim, quanto maior o teor de pré-hidratado e o período de pré-hidratação, menor o tempo de indução, antecipando a formação dos hidratos (silicatos e aluminatos), embora a taxa de reação no período de aceleração não tenha sido afetada de forma significativa. Quanto às propriedades físicas das partículas, forma realizados teste de granulometria, ASE (Área Superficial Específica) e densidade real. A pré-hidratação aumenta a sua ASE, o que acarreta no incremento da tensão de escoamento e da viscosidade das pastas. Inclusive, se esse aumento de ASE for incorporado em determinados modelos (YODEL e Interferência) é possível a predição dessas propriedades reológicas. O aumento de ASE também é responsável pelo maior enrijecimento e menor tempo de pega das suspensões pré-hidratadas. Correlacionando a reação química com a consolidação da pasta, ficou demonstrado que o maior enrijecimento da pasta pré-hidratada tem relação com a maior aproximação entre as partículas, a ASE inicial das pastas e a reatividade do pré-hidratado, otimizando assim a formação da microestrutura pela hidratação. / Given the considerable share of cement industry on overall share of CO2 emissions, one of the most important current challenges is the adoption of strategies that reduce the use of cement without compromising the mechanical performance and durability of cementitious materials. Among these strategies, one of the commonly employed in some industrial segments is the reuse of pre-hydrated binder in production. The understanding of as pre-hydration changes the properties of cementitious pastes also has important scientific implication regarding the reaction kinetics of Portland cement, but mainly due to the impacts on the rheological properties of the paste, both after mixing and along hydration. It is known that pre-hydration alters the hydration kinetics of the cement, impacting its properties in the hardened state. In addition, pre-hydration modifies the physical properties of the cement, directly influencing the way as the particles agglomerates. However, much of the literature refers to the pre-hydration that occurs after bad storage, unlike this work that works with pre-hydration in suspension, more common in industrial applications. Thus, in this work the kinetics of reaction by isothermal calorimetry was evaluated while the rheological properties were evaluated by rotational and oscillatory rheometry. For the identification and quantification of the hydrates formed, the hydration was paralyzed and TG and XRD tests were performed. The results showed that the inclusion of the pre-hydrate alters the dissolution/precipitation kinetics of the anhydrous cement. Thus, the higher the pre-hydration content and the pre-hydration period, the shorter the induction time, anticipating the formation of the hydrates (silicates and aluminates), although the reaction rate in the acceleration period was not significantly affected. As for the physical properties of the particles, there were realized tests of particle size distribution, SSA (Specific Surface Area) and real density. The pre-hydration increases its SSA, which leads to an increase in the yield stress and viscosity of the pastes. Even if this increase of SSA is incorporated in certain models (YODEL and Interference) it is possible to predict these rheological properties. The increase in ASE is also responsible for the greater hardening and quickly setting time of the pre-hydrated suspensions. Correlating the chemical reaction with paste consolidation, it was demonstrated that the higher hardening of the pre-hydrated paste is related to the greater approximation between the particles, the initial ASE of the pastes and the reactivity of the pre-hydrate, optimizing then the formation of the microstructure by hydration.

Dans ce travail de thèse il a été rapporté que, pour la premiere fois, l'utilisation de TMSCl associée au NaI permet de réduire régiosélectivement divers composés de type benzile dans le chlorure de méthylene. Par ailleurs, nous avons montré que ce couple de réactifs est aussi capable de réduire diverses arylalkylcétones aussi bien que des alpha-cétoesters -cétoacides et hydrazinoesters avec des sélectivités totales. Le mécanisme original de type radicalaire a été étudié au travers de nombreuses expériences. / In this work, we have described that, for the first time the TMSCl - NaI association was used to regioselectively reduce a variety of alpha diketones as benzils in methylene chloride. Moreover, we showed that this association was able to reduce various arylalkylketones as well as alpha ketoesters, ketoacids and hydrazinoesters with total selectivity. The mechanism of action is probably due to radicals was fully studied with many experiments.

This research was designed to investigate the hydration reaction of fly ash when exposed to water. The effects that calcium nitrate and calcium formate have on the hydration reactions were also examined.

Yes / Reactive Powder Concrete (RPC) is a new type of cementitious materials with a complex hydration mechanism, and active admixtures greatly influence the hydration reaction, formation of hydration products, and evolution of microstructure. In order to comprehensively study the quantitative effects of active admixtures contents, namely silica fume, slag and fly ash, on hydration characteristics, hydration products, and microstructure of RPCs, tests of workability, setting time, electrical conductivity, bound water and mechanical properties were conducted. Furthermore, a series of properties including morphology and micro-structure characteristics of RPCs were analyzed by thermogravimetric (TG) analysis, X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), mercury intrusion porosimetry (MIP), Brunauer-Emmet-Teller (BET), and scanning electron microscope (SEM). The results indicate that the initial hydration reaction rate of RPCs is reduced by partly replacing cement with active admixtures. The pozzolanic effect created by the active admixtures enhances hydration and improves RPC's compressive and flexural strength. RPCs made of cement-silica fume mixture exhibit the best macroscopic properties. The adoption of silica fume promotes the production of C-S-H gel during hydration and exerts pozzolanic and crystal nucleation effects to promote cement hydration. RPCs made of pure cement exhibit 15.3% porosity after 28 days of hydration, with the largest proportion of less harmful pores in the microstructure. The porosity is reduced to 5.2% when cement is partially replaced with silica fume, and the microstructure is dominated by harmless pores. When replacement of silica fume is kept at 25%, using slag powder or fly ash substitute part of cement also reduces the number of less harmful pores. It is beneficial to add slag powder to increase the number of gel pores, whereas fly ash reduces the number of gel pores. The investigation presented in this paper would contribute to the production of low cost and environmentally-friendly RPCs, and accelerate the wider applications of ultra-high performance concrete (UHPC) in engineering structures.

ITC/USA 2009 Conference Proceedings / The Forty-Fifth Annual International Telemetering Conference and Technical Exhibition / October 26-29, 2009 / Riviera Hotel & Convention Center, Las Vegas, Nevada / The field of Terahertz (THz) radiation, electromagnetic energy, between 0.3 to 3 THz, has seen intense interest recently, because it combines some of the best properties of IR along with those of RF. For example, THz radiation can penetrate fabrics with less attenuation than IR, while its short wavelength maintains comparable imaging capabilities. We discuss major challenges in the field: designing systems and applications which fully exploit the unique properties of THz radiation. To illustrate, we present our reflective, radar-inspired THz imaging system and results, centered on biomedical burn imaging and skin hydration, and discuss challenges and ongoing research.

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