Made available in DSpace on 2017-07-21T18:53:18Z (GMT). No. of bitstreams: 1 Lara Tatiane Geremias Ferreira Brites.pdf: 2802840 bytes, checksum: c22d0a4cc841b761b048479e54280f53 (MD5) Previous issue date: 2013-02-20 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Native starches have characteristics that limit their application by industries. Among commercial starches, that extracted from cassava is considered abundant and economical and several studies considering its modification has been carried out with the aim of improving and enhancing industrial application.The oxidation is a form of modification that provides starches with low paste viscosity and increased expansion property. The use of metal ions has been reported by some authors to increase the efficiency of the oxidation process, but the incorporation of ions in starch granules also seems to occur. Another form of modification that is being studied is the acid-alcohol, due to the fact that alcoholic reaction medium allows the use of lower concentrations of acids. In order to improve and enhance the oxidation of starches, this study aimed to investigate the interference of pH, hydrogen peroxide concentration, reaction time and also the interaction of the starch granule with metal ions in the oxidation process. Preliminary tests were conducted for understanding the influence of Cu (II) and Fe (II) in starch oxidation, and their residues in the final product, through qualitative and quantitative instrumental analyses, besides being investigated contribution of pH and the concentration of hydrogen peroxide during the oxidation. From the preliminary tests a central composite rotatable design (CCRD) with 17 treatments and three central points was used to verify the influence of variables pH (2.30 to 5.70), H2O2 concentration (0.5 to 5.5 %, v/w, dry basis) and reaction time (28 to 62 min). Two methods were used for the oxidation, one using water and the other using anhydrous methanol as reaction medium in order to verify the behavior of the oxidation reaction. The effect of variables on the physicochemical properties was evaluated with use of Response Surface Method (RSM). The samples oxidized with the use of metal ions presented residues in the oxidized starch and the results with the use of Fe (II) showed a greater expansion and lower peak viscosity, being used for the entire planning. It was found by the RSM, that the pH, the concentration of hydrogen peroxide and the reaction time influenced the two methods of oxidation and the physicochemical properties of cassava starch. The cassava starch oxidized in aqueous media showed better results, regarding the physicochemical analyses, than those found in the oxidation in anhydrous medium. The best conditions found for oxidation in aqueous media were those of the central point (treatments 15,16 and 17) for the expansion property, carboxyl content and reducing power; for soluble solids at 50 and 80 ° C the best treatments were 4 and 13; for swelling power at 50 and 80 °C treatments 9 and 6, whereas for cycles of freezing and thawing, the treatment 5; in the case of paste property, the most pronounced change occurred in the treatment 7.For anhydrous methanol oxidation due to lack of fit of different models, it is difficult to establish which were the best conditions for the experiment and this methodology should be studied considering other variables in different alcohols 9 and starches, so it can be directly compared with the traditional oxidation is aqueous medium. / O amido nativo possui características que limitam sua aplicação pelas indústrias. Dentre os amidos comerciais, o de mandioca é considerado abundante e econômico, por isso muitos estudos sobre a modificação deste vem sendo realizados, com o intuito de melhorar e aumentar sua aplicação. A oxidação é uma forma de modificação que proporciona amidos com baixa viscosidade de pasta e aumento da propriedade de expansão. A utilização de íons metálicos tem sido reportada por alguns autores para aumentar a eficiência do processo de oxidação, no entanto, a incorporação dos íons nos grânulos de amido também parece ocorrer. Outra forma de modificação que vem sendo estudada é a álcool-ácida, que pela utilização de álcool possibilita que menores concentrações de ácidos sejam utilizadas para se obter amidos com características diferenciadas. Visando melhorar e aperfeiçoar a oxidação de amidos, este estudo teve como objetivo principal investigar a interferência do pH, concentração de peróxido de hidrogênio, tempo de reação e averiguar a interação do grânulo de amido com íons metálicos no processo de oxidação.Testes preliminares foram realizados com o intuito de observar a influência dos íons de Cu (II) e Fe (II) na oxidação, bem como seus resíduos no produto final, por intermédio de análises instrumentais qualitativas e quantitativas, além de se investigara contribuição do pH e da concentração de peróxido de hidrogênio durante a oxidação. A partir dos testes preliminares um Delineamento Composto Central Rotacional (DCCR) com 17 tratamentos sendo três pontos centrais foi utilizado para verificar a influência das variáveis pH (2,30 a 5,70),concentrações de H2O2 (0,5 a 5,5 %, v/m) (b.s) e tempos de reação (28 a 62 min). Duas metodologias foram utilizadas para a oxidação, uma utilizando água e outra utilizando metanol anidro como meio reacional, a fim de verificar o comportamento da reação de oxidação. O efeito das variáveis sobre as propriedades físico-químicas foi avaliado com emprego do Método de Superfície de Resposta. As amostras oxidadas com a utilização de íons metálicos apresentaram resíduos no amido oxidado, no entanto os resultados encontrados com a utilização de Fe(II) demonstraram maior propriedade de expansão e menores picos de viscosidade, sendo utilizado para todo o planejamento. Verificou-se, pela metodologia de superfície de resposta, que o pH, a concentração de peróxido de hidrogênio e o tempo de reação tiveram influência nas duas metodologias de oxidação e nas propriedades físicoquímicas do amido de mandioca. Porém o amido de mandioca oxidado em meio aquoso apresentou resultados superiores em relação as características físico-químicas, aos encontrados na oxidação em meio anidro. As melhores condições encontradas para oxidação em meio aquoso foi no ponto central (tratamentos 15,16 e 17) para as análises de propriedade de expansão, conteúdo de carboxilas e poder redutor; para sólidos solúveis 50 e 80 ºC foram nos tratamentos 4 e 13; poder de inchamento 50 e 80 ºC nos tratamentos 9 e 6;nos ciclos de congelamento e descongelamento o tratamento 5; propriedade de 7 pasta no tratamento 7. Para a oxidação em metanol anidro devido a falta de ajuste de diversos modelos, é difícil afirmar quais as melhores condições para o experimento, devendo essa metodologia ser estudada com diferentes variáveis, em diferentes alcoóis e amidos, para poder ser comparada diretamente com a oxidação tradicional que utiliza água.

abstract: Fluorine (F) is a volatile constituent of magmas and hydrous mantle minerals. Compared to other volatile species, F is highly soluble in silicate melts, allowing F to remain in the melt during magma differentiation and rendering F less subject to disturbance during degassing upon magma ascent. Hence, the association between fluorine in basalts and fluorine in the mantle source region is more robust than for other volatile species. The ionic radius of F- is similar to that of OH- and O2-, and F may substitute for hydroxyl and oxygen in silicate minerals and melt. Fluorine is also incorporated at trace levels within nominally anhydrous minerals (NAMs) such as olivine, clinopyroxene, and plagioclase. Investigating the geochemical behavior of F in NAMs provides a means to estimate the pre-eruptive F contents of degassed magmas and to better understand the degassing behavior of H. The partition coefficients of F were determined for clinopyroxene, olivine, plagioclase, and hornblende within melts of olivine-minette, augite-minette, basaltic andesite, and latite compositions. The samples analyzed were run products from previously-published phase-equilibria experiments. Fluorine was measured by secondary ion mass spectrometry (SIMS) using an 16O- primary beam and detection of negative secondary ions (19F-, 18O-, 28Si-). SIMS ion intensities are converted to concentrations by analyzing matrix-matched microanalytical reference materials and constructing calibration curves. For robust F calibration standards, five basaltic glasses (termed Fba glasses) were synthesized in-house using a natural tholeiite mixed with variable amounts of CaF2. The Fba glasses were characterized for F content and homogeneity, using both SIMS and electron-probe microanalysis (EPMA), and used as F standards. The partition coefficients for clinopyroxene (0.04-028) and olivine (0.01-0.16) varied with melt composition such that DF (olivine-minette) < DF (augite-minette) < DF (basaltic andesite) < DF (latite). Crystal chemical controls were found to influence the incorporation of F into clinopyroxene, but none were found that affected olivine. Fluorine partitioning was compared with that of OH within clinopyroxenes, and the alumina content of clinopyroxene was shown to be a strong influence on the incorporation of both anions. Fluorine substitution into both olivine and clinopyroxene was found to be strongly controlled by melt viscosity and degree of melt polymerization. / Dissertation/Thesis / Ph.D. Geological Sciences 2012

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-19T17:03:38Z No. of bitstreams: 1 WAGNER BRANDÃO RAMOS - TESE PPGEQ 2016..pdf: 17733872 bytes, checksum: 5e6f59ac00a4f15f43c3f335dc3b2075 (MD5) / Made available in DSpace on 2018-03-19T17:03:39Z (GMT). No. of bitstreams: 1 WAGNER BRANDÃO RAMOS - TESE PPGEQ 2016..pdf: 17733872 bytes, checksum: 5e6f59ac00a4f15f43c3f335dc3b2075 (MD5) Previous issue date: 2016-08-22 / Capes / A destilação extrativa é um método bastante utilizado em indústrias alcooleiras para se obter etanol anidro, cujo processo é composto por duas colunas de destilação, onde a primeira coluna (coluna de destilação extrativa) tem como função desidratar o etanol e a segunda coluna (coluna de recuperação) recuperar o solvente utilizado no processo. Colunas de destilação são responsáveis por um consumo bastante elevado de energia em uma planta e, por isso, diversos métodos de otimização têm sido publicados na literatura, cujos resultados propõem mudanças nas condições operacionais e design do sistema. Além da necessidade de que este sistema opere em condições ótimas, também é necessário se obter um sistema de controle eficiente e que seja capaz de manter o etanol anidro produzido dentro da especificação desejada, mesmo diante distúrbios que ocorrem normalmente neste processo. Sendo assim, o tema deste trabalho surgiu da união destes dois pontos importantes, otimização e controle, no qual o objetivo é estudar o comportamento dinâmico e o controle do processo de destilação extrativa para obtenção de etanol anidro, utilizando etileno glicol como solvente e com integração térmica entre correntes do processo. Sob este escopo, traçou-se objetivos específicos inexistentes na literatura consultada, que são as influências da integração térmica, do teor de solvente e do grau de pureza de etanol anidro que se deseja obter sobre o controle de sistemas de destilação extrativa. Os resultados mostram que o teor de solvente e a presença da integração térmica causam desvios na composição do produto de interesse (etanol anidro), em comparação com o processo sem integração térmica, quando ocorrem distúrbios na alimentação para o mesmo sistema de controle. O grau de pureza de etanol anidro que se deseja obter também causa influência no controle da pureza. De maneira geral, estes efeitos se apresentaram de forma mais acentuada nos casos em que o sistema opera com alto teor de solvente (condição que representa menor consumo energético). Sendo assim, foram propostas modificações no esquema de controle, proporcionando melhores resultados para estes casos. / Extractive distillation is a method widely used in the alcohol industry to obtain anhydrous ethanol, which process consists of two distillation columns where the first column (extractive distillation column) has the function to dehydrate ethanol and the second column (recovery column) recovers the solvent used in the process. Distillation columns are responsible for a very high energy consumption in a plant and thus various methods of optimization, which results suggest changes in operating conditions and system design, have been published in the literature. In addition to the need for this system to operate in optimum conditions, it is also necessary to provide an efficient control system that is able to maintain anhydrous ethanol produced within the desired specification even after the disturbances that normally occur in this process. Thus, the theme of this work arose from the union of these two important points, optimization and control, in which the goal is to study the dynamic behavior and the control of the extractive distillation process for obtaining anhydrous ethanol, using ethylene glycol as a solvent and thermal integration between process streams. Under this scope, specific objectives nonexistent in the literature were drawn, which are the influences of thermal integration, solvent content and the degree of purity of anhydrous ethanol to be obtained on the control of extractive distillation systems. The results show that the solvent content and the presence of thermal integration causes deviations in the product composition of interest (anhydrous ethanol) compared to the process without heat integration, when disturbances occur in the feed for the same control system. The degree of purity of anhydrous ethanol to be obtained also causes influence over controllability. Generally, these effects are exhibited more markedly when the system operates with high solvent content (optimum operating point). So changes were proposed for the control scheme, providing better results for these cases.

La matière grasse laitière anhydre (MGLA) est composée à plus de 98 % de triglycérides. Leur diversité, liée à la nature des acides gras estérifiés, induit un comportement complexe de la MGLA lors de sa cristallisation. Par ailleurs, d’autres composés, dits mineurs, présents de manière endogène ou formés lors de procédés de transformation peuvent moduler le processus de cristallisation. Néanmoins, leurs modes d’action sont encore mal connus, rendant la maitrise du processus de cristallisation délicat. La mise en oeuvre de méthodes de caractérisation à différentes échelles (RMN, diffraction des rayons X, microscopie optique, analyse thermique différentielle, rhéologie) et à différentes températures permet de discriminer les mécanismes d’action des composés mineurs sur la cristallisation de la MGLA en phase continue ou dispersée. Ainsi, les composés mineurs modifient la cinétique de cristallisation de la MGLA, en agissant sur ses deux étapes, la nucléation et la croissance. En accélérant ou en ralentissant la vitesse de cristallisation, ils modifient la nature et/ou la structure du réseau cristallin et, éventuellement, les propriétés macroscopiques de la matière grasse. Les mécanismes d’action des composés mineurs sur la cristallisation de la MGLA dépendent de leur nature chimique (longueur de la chaine carbonée, degré d’insaturation, estérification) et de leur concentration. Lorsque la matière grasse est émulsionnée, son confinement et la création d’interfaces complexifient le processus de cristallisation : les composés mineurs modulent la cristallisation via l’interface ou la phase grasse selon leur affinité préférentielle pour l’une ou l’autre des deux phases de l’émulsion et induisent des propriétés thermiques et structurales spécifiques. Ce travail permet, donc, de mieux comprendre les facteurs qui modulent la cristallisation de la matière grasse et ainsi de mieux maitriser l’un des processus déterminants dans l’élaboration de la structure et de la fonctionnalité des produits laitiers. / Anhydrous Milk Fat (AMF) comprises more than 98% triglycerides. The diversity of the esterified fatty acids induces a complex behavior of AMF during crystallization. In addition, other minor components, either endogenously present or added upon processing modulate AMF crystallization. Nevertheless, the mechanisms underlying their mode of action are still poorly understood, making the mastery of fat crystallization difficult. Several characterization methods (NMR, X-ray diffraction, optical microscopy, differential scanning calorimetry, rheology) were implemented to screen a large set of minor components at different scales and temperatures. The approach enabled to gain knowledge about the involved mechanisms, both in bulk and in the emulsified state. Minor components modify the kinetics of AMF crystallization through their impact on the two main stages of the process, nucleation and growth. By accelerating or slowing down the rate of crystallization, they modify the nature and/or the structure of the crystal lattice and, possibly, the macroscopic properties of AMF. The impact of minor components on AMF crystallization depend on their chemical nature (length of the carbon chain, degree of unsaturation, esterification) and on their concentration. When fat is emulsified, confinement and interfacial effects come into play. Minor components modulate crystallization via the oil/water interface or via the fat phase depending on their preferential solubility, which may induce specific thermal and structural properties. On the whole, this study enables a better understanding of the factors that modulate milk fat crystallization and provides useful guidances for a better control of this key process controlling the structure and function of dairy products.

Submitted by Clebson Anjos (clebson.leandro54@gmail.com) on 2016-03-04T20:58:30Z No. of bitstreams: 1 arquivototal.pdf: 4279867 bytes, checksum: cc6bcf7dbfdbba66c85512e2c1a25a45 (MD5) / Made available in DSpace on 2016-03-04T20:58:31Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 4279867 bytes, checksum: cc6bcf7dbfdbba66c85512e2c1a25a45 (MD5) Previous issue date: 2015-11-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / “Manteiga da terra” is a traditional product in the northeast of Brazil that consists of a form of anhydrous cow’s milk fat. This product is susceptible to hydrolytic and oxidative rancidity, responsible for undesirable sensory changes, decreases in nutritional quality and economic impact for the industry. In this study, thermal stability and changes in the physicochemical and sensory profiles were evaluated during storage temperatures of 5, 30, 45 and 60°C at 0, 14, 28, 42 and 56 days. Physicochemical analyses were carried out to evaluate chemical composition and fatty acids profile in the initial time and the storage effects on acidity, peroxide value, TBARS value and objective color. From these results, the activation energy and the induction period were estimated. Microbiological analyses were performed for total and fecal coliforms. Quantitative Descriptive Analysis (QDA) was used to the sensory evaluation of appearance (yellow color, opacity, uniformity and visual viscosity), odor (characteristic of the product and rancid), flavor (characteristic of the product, acid and rancid) and texture (viscosity and granularity). The “manteiga da terra” produced to this study met the standards established by the brazilian legislation with results of 98.96% for fat, 0.07% for moisture, 0.97% for non-fat solids and 0.78% for acidity. The major fatty acids found in the product were oleic (22.66%), palmitic (21.18%) and stearic (13.86%). Saturated fatty acids accounted for 53.72% and unsaturated for 32.24% of the total. There were significant differences for acidity between samples stored at 30, 45 and 60°C, with final values of 0.89, 1.0 and 1.11%, respectively. The peroxide values showed significant increases from 0.50 to 1.30 and 3.99 mEq.kg-1 in samples stored at 45 and 60°C, in this order. The TBARS value was 0.08 mgMDA.kg-1 in the initial time and there were significant increases in the samples stored at 45 and 60°C, with values of 0.12 and 0.19 mgMDA.kg-1, respectively, at the end of 56 days. The parameters L*, a* and b* for objective color characterized the yellow color of the product, with decrease in yellow tone during storage, especially at higher temperatures. The activation energy found for the system was 50.2 kJ.mol-1 and the induction period (in days) was 616 to 5°C, 103 to 30°C, 52 to 45°C and 26 to 60°C. Microbiological analysis indicated the absence of contamination for all samples. In the sensory analysis, the samples kept at 60°C for 56 days had the lowest scores for yellow tone color, opacity, characteristic odor and taste, visual viscosity and viscosity felt at the mouth. On the other hand, they showed a significant increase for the characteristic odor and taste of rancid. The results indicated that the “manteiga da terra” is a stable product for a long period under normal storage conditions. / A manteiga da terra é um produto característico da região nordeste brasileira e consiste de uma forma de gordura anidra proveniente do leite de vaca. Este produto é susceptível às rancificações hidrolítica e oxidativa, responsáveis por alterações sensoriais indesejáveis, diminuição na qualidade nutricional e impacto econômico para a indústria. Neste estudo, foram avaliadas a estabilidade térmica e alterações nos perfis físico-químicos e sensoriais durante o armazenamento em temperaturas de 5, 30, 45 e 60ºC nos tempos 0, 14, 28, 42 e 56 dias. Nas análises físico-químicas, foram realizadas a composição centesimal e o perfil de ácidos graxos no tempo inicial e a avaliação dos efeitos do armazenamento nos parâmetros de acidez, índice de peróxidos, valor de TBARS e cor objetiva. Com estes dados, foram estimados a energia de ativação e o período de indução da amostra. Foram realizadas análises microbiológicas para coliformes a 35 e a 45ºC. A Análise Descritiva Quantitativa (ADQ) foi utilizada na avaliação sensorial dos atributos: aparência (cor amarela, opacidade, homogeneidade e viscosidade visual), odor (característico de manteiga da terra e de ranço), sabor (característico de manteiga da terra, ácido e de ranço) e textura (viscosidade e granulosidade). A manteiga da terra elaborada atendeu aos parâmetros estabelecidos pela legislação com resultados de 98,96% de matéria gorda, 0,07% de umidade, 0,97% de sólidos não gordurosos e 0,78% de acidez. Os ácidos graxos majoritários do produto foram o oleico (22,66%), o palmítico (21,18%) e o esteárico (13,86%). Os ácidos graxos saturados corresponderam a 53,72% e os insaturados a 32,24% do total. No índice de acidez, houve diferença significativa nas amostras armazenadas a 30, 45 e 60ºC, com teores finais de 0,89, 1,01 e 1,11%, respectivamente. Quanto ao índice de peróxidos, inicialmente com 0,50 mEq.kg-1, houve aumentos significativos para as amostras armazenadas a 45 e 60ºC, com índices finais de 1,30 e 3,99 mEq.kg-1, nesta ordem. O valor de TBARS inicial foi de 0,08 mgMDA.kg-1, com aumento significativo nas amostras armazenadas a 45 e 60ºC, com valores de 0,12 e 0,19 mgMDA.kg-1, respectivamente, ao final dos 56 dias. Quanto à cor objetiva, os parâmetros L*, a* e b* caracterizam a cor amarela da amostra que, durante o armazenamento, apresentou um clareamento na tonalidade do amarelo, em especial nas temperaturas mais elevadas. A energia de ativação encontrada para o sistema foi de 50,2 kJ.mol-1 e o período de indução (em dias) foi de 616 para 5ºC, 103 para 30ºC, 52 para 45ºC e de 26 para 60ºC. As análises microbiológicas indicaram ausência de contaminação para todas as amostras. Na análise sensorial, as amostras armazenadas a 60ºC por 56 dias foram as que obtiveram os menores escores para a tonalidade da cor amarela, opacidade, odor e sabor característicos de manteiga da terra, viscosidade visual e viscosidade sentida na boca. Em contrapartida, apresentaram também aumento significativo para o odor e o sabor característicos do ranço. Os resultados do estudo indicaram que a manteiga da terra é um produto que se mantém estável por um longo período, sem alterações importantes antes dos 103 dias de estocagem à temperatura ambiente.

Made available in DSpace on 2016-08-19T12:56:45Z (GMT). No. of bitstreams: 1 Dissertacao Darlan.pdf: 2834733 bytes, checksum: f7d35c098bddf8713fbdbe733565fdef (MD5) Previous issue date: 2013-07-12 / During several years, adulterated gasoline has been commercialized across all Brazil. Often such product has higher alcohol content, water traces or organic solvents insertion (e.g. paint thinner and/or turpentine). The use of nonconforming gasoline, in the short and long terms, has several problems for consumers, for the vehicle and the environment. Thus, this work aims to propose a low cost technique for analyzing gasoline blends, in relation to its oxygenated addition. Both capacitance and dielectric constant (relative permittivity) were determined by means of a high precision LCR-meter, using a metal concentric sensor. Therefore, gasoline blends were prepared by adding 16, 18, 20, 22, 24, 26, 28 and 30% of AEAF to the initial petroleum-based fuel and their dielectric constants were measured at frequencies of 0.3, 0.4, 0.5 and 0.6 kHz. The same samples were analyzed by the reference method, the Test Tube Test. According to statistical modeling, the frequency of 0.6 kHz showed the most significant results for all samples. The results show that at 95% confidence level, there is no significant difference between the two methods, indicating a good correlation between the proposed method and then standard one. However, when the density was used as evaluating parameter, instead of dielectric constant, for the same samples, a substantial discrepancy of the obtained values were observe, suggest a low sensibility of such methodology. / Vários são os casos de não conformidade da gasolina comercial, principalmente pelo excesso de etanol, ou ainda pela adição de água ou solventes leves como thinner e aguarrás. O uso de gasolina não conforme, a curto e longo prazo, traz diversos problemas para o consumidor, para o veículo e ao meio ambiente. No presente trabalho estudou-se a qualidade da gasolina tipo C, comercializada nos postos revendedores de combustível, no que diz respeito à concentração de álcool etílico anidro combustível (AEAC). Análises estas, realizadas através de medidas de constante dielétrica (permissividade relativa) utilizando sensor capacitivo. Misturas de gasolina A e AEAC foram preparadas nas concentrações de 16, 18, 20, 22, 24, 26, 28 e 30% de AEAC, sendo suas constantes dielétricas medidas nas frequências de 0,3; 0,4; 0,5 e 0,6 kHz. Utilizando tratamento estatístico verificou-se que a frequência de 0,6 kHz apresentou resultados mais significativos para leitura de AEAC das misturas preparadas. Nessa mesma frequência, amostras comerciais de gasolina e amostras de gasolinas não conformes contaminadas com gasolina A e AEAC foram submetidas à análise. As mesmas amostras foram submetidas à análise pelo método de referência, o Teste da Proveta. Os resultados obtidos mostram que, no nível de confiança de 95%, não há diferença significativa entre os dois métodos. Medidas de massas específicas também foram realizadas com as misturas gasolina A e AEAC (16 a 30%) para modelamento de curva de calibração com finalidade de determinar o teor de AEAC e posterior comparação com os resultados oriundos da constante dielétrica e do teste da proveta, entretanto, o método não se mostrou eficiente para análise das amostras de gasolina comercial e amostras de gasolinas não conformes analisadas.

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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Wide applications of anhydrous rare-earth (RE) trichlorides RECl₃ in organometallic chemistry, for the synthesis of optical and magnetic materials, and as catalysts require a facile approach for their synthesis. The known methods use or produce toxic substances, are complicated and have limited reliability and upscaling. It has been shown that task-specific ionic liquids (ILs) can dissolve many metal oxides without special reaction conditions at moderate temperature, making the metals accessible to downstream chemistry. Using imidazolium chloridoaluminate ILs, pure crystalline anhydrous RECl₃ (RE=La−Nd, Sm−Dy) can be synthesized in one step from RE oxides in high yield. The Lewis acidic IL acts as solvent and reaction partner. The by-product [Al₄O₂Cl₁₀]²⁻, which was detected spectroscopically, remains in solution. The reacted IL can be removed quantitatively by washing. ILs with various imidazolium cations and AlCl₃ content and the effect of temperature and reaction time were tested.