Apresentamos um estudo de solidificaçaõ e lixiviacão de matrizes de vidros porosos de alto teor de sílica armazenando 20% em peso de solução aquosa simuladora de rejeitos nucleares de alto nível de radioatividade do tipo Savanah River Labratory. A matriz porosa foi preparada após o tratamento térmico de um vidro de 65% SiO2-27%B2O3-8%Na2O, que sofreu separação de fase à 560°C por 20 horas e lixiviado em HCl - 3N à 90°C. O tamanho dos poros (tipicamente de 100 à 250Å de diâmetro) , foi determinado utilizando o método BET. Após sinterização à 1300°C em ar, as amostras foram caracterizadas física e quimicamente através de testes de lixiviação padronizados MCC1, Soxhlet (MCC5) e Estagnante durante cerca de 28 dias. Determinamos a perda de peso total, o pH, as taxas de lixiviação diferencial e as concentrações acumuladas para os seguintes elementos: Si, Na, B, Ca, Mn, Al, Fe e Ni com técnicas de ICP e espectroscopia de chama para o caso do Na. Os resultados são comparados com os obtidos com vidros borosilicatos de referência, fabricados por fusão convencional (SRL 131, PNL 76-68, MCC 76-68, SRL TDS 131, AVM-Ml à M7), vidros fabricados pela técnica sol-gel (TDS 211), vidros de alto teor de sílica (CU PGM), synroc-D, cerâmicas manufaturadas, concreto FUETAP e matrizes metálicas. Os valores obtidos são similares àqueles obtidos com os melhores vidros borosilicato presentemente usados. / We present a study of the sinterization and of the leaching behavior of a high silica porous glass matrix containing 20 weight % of simulated solution of high level liquid nuclear waste of the type Savanah River Laboratory. The porous matrix has been prepared after heat treatment of a 65% SiO2-27%B2O3-8%Na2O glass, phase separate at 560°C for 20 hours and leached in 3N HCl at 90°C. The pore size (typically 100-250Å in diameter) has been determined by the BET method. After sinterization in air at 1300°C, the samples have been physically and chemically characterized during 28 days using the MCC1, Estagnant and Soxhlet (MCC5) standard tests. We have determined thetotal weight loss, the pH, the diferential leaching rate and the cumulative concentrations for the following elements: Si, Na, B, Ca, Mn, Al, Fe and Ni by ICP technique, for Na flames spectroscopy. The results are compared with these obtained with other reference borosilicate glasses made by conventional fusion techniques (SRL 131, PNL 76-68, MCC 76-68, SRL TDS 131, AVM-M1 to M7), glasses made by sol-gel technique (TDS-211), porous glasses matrix (CU PGM), synroc-D, tailored ceramics, FUETAP concrete and metallic matrix. The values obtained are similar to those found for the best borosilicate glass presently used.

A substituição da água por líquidos iônicos (LI) oferece uma alternativa promissora para o desenvolvimento de processos de separação de gases, principalmente devido à significativa demanda energética em processos convencionais que utilizam soluções aquosas de aminas. Esta proposta apresenta-se interessante por aliar as propriedades dos LI à reatividade de aminas perante o CO2. A físico-química que governa as interações entre os íons dos líquidos iônicos é bastante diversa das encontradas em solventes moleculares, sendo que ainda permanecem muitas questões fundamentais acerca destes materiais. A melhor compreensão das interações estabelecidas entre aminas e LI, e dos produtos formados após a reação com CO2, pode contribuir para o desenvolvimento de processos mais eficazes que permitam a substituição da água nos processos convencionais. O presente trabalho teve como objetivo investigar soluções das aminas primárias propilamina (PA), 2-metoxietilamina (MOEN) e monoetanolamina (MEA) em líquidos iônicos imidazólicos com diferentes ânions: 1-butil-3-metilimidazólio tetrafluoroborato (BMIBF4), hexafluorofosfato (BMIPF6), bis-(trifluorometilsulfonil)imida (BMITFSI) e dicianamida (BMIN(CN)2). Para tal, foram utilizadas as espectroscopias Raman e infravermelho (IR), cujos resultados foram suportados por cálculos baseados na teoria do funcional da densidade (DFT). Os resultados mostram que o modo de estiramento assimétrico do grupo NH2 das aminas, νas(NH2), é o mais adequado para se inferir sobre o grau de agregação das aminas em solventes orgânicos e em LI. No caso das reações das aminas com CO2 nos diferentes LI, o comportamento foi similar à reação com as aminas puras, ou seja, na PA houve cristalização, na MOEN, a formação de um líquido miscível com os LI, e na MEA, a formação de um gel com a subsequente separação de fases. Em particular, no caso da reação entre MEA e CO2 em LI, além da separação de fases, foi observada a diferente solubilidade dos produtos de reação dependendo do LI em questão. Em contraste ao processo convencional que utiliza soluções aquosas de aminas para a captura do CO2, acredita-se que a separação de fases observada em LI seja uma vantagem a ser explorada, já que permitiria um menor gasto energético na recuperação da amina absorvedora, além da recuperação do solvente não volátil / The replacement of water by ionic liquids (IL) offers a promising alternative for the development of gas separation processes, mainly due to the significant energy demand in conventional processes using aqueous solutions of amines. This proposal is exciting because it combines the properties of IL with the reactivity of amines towards CO2. The physical-chemistry that governs the interactions between the ionic liquids ions is quite different from those found in molecular solvents, and many fundamental questions still remain about these materials. A better understanding of the interactions between amines and IL, and the products formed after the reaction with CO2, may contribute to the development of more efficient processes to enable the replacement of water in conventional processes. This study aimed to investigate solutions of the primary amines propylamine (PA), 2-methoxyethylamine (MOEN) and monoethanolamine (MEA) in imidazolium ionic liquids with different anions: 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF4), hexafluorophosphate (BMIPF6), bis (trifluoromethylsulfonyl)imide (BMITFSI) and dicyanamide (BMIN(CN)2). For these purposes, the Raman and infrared (IR) spectroscopies were used, whose results were supported by calculations based on density functional theory (DFT). The results show that the asymmetric stretching mode of the amines group NH2, νas(NH2), are the most suitable for inferring the degree of aggregation of amines in organic solvents and IL. In the case of reactions of amines with CO2 in different IL, the behavior was similar to the reactions with neat amines, that is, it was observed crystallization with PA, the formation of a liquid miscible with IL in MOEN, and the formation of a gel-like product with subsequent phase separation in MEA. In particular, the case of the reaction between MEA and CO2 in IL, in addition to the phase separation, it was observed the different solubility of the reaction products depending on the IL concerned. In contrast to the conventional process using aqueous solutions of amines for the capture of CO2, it is believed that the phase separation observed in IL is an advantage to be exploited, since they allow lower energy consumption in the recovery of the amine absorber, besides the recovery of the non-volatile solvent.

Orientador: Maria Isabel Felisberti / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-12T12:37:28Z (GMT). No. of bitstreams: 1 Lima_JulianaAristeiade_D.pdf: 4425741 bytes, checksum: e0c47d6335f66cc31a0fe6e5ac1c0457 (MD5) Previous issue date: 2008 / Resumo: Neste trabalho foram estudadas blendas de poli(etileno-co-álcool vinílico) (EVOH), um copolímero semicristalino que combina segmentos hidrofílicos e hidrofóbicos e poli(metacrilato de metila) (PMMA), um polímero amorfo e hidrofílico. As blendas de EVOH, com teor de etileno variando de 27 a 44 mol %, e PMMA foram preparadas por casting a partir de soluções em DMF, e por mistura mecânica em um mini-misturador, objetivando: i) avaliar o comportamento de fases e a morfologia das blendas, EVOH/PMMA, em função da composição das misturas, do teor de etileno nos copolímeros de EVOH e do método de preparação; ii) obter os diagramas de fases das soluções binárias, EVOH/DMF, e ternárias, EVOH/PMMA/DMF, através do processo de separação de fases induzido termicamente (TIPS). O comportamento de fases das blendas, EVOH/PMMA, foi estudado através de Calorimetria Diferencial de Varredura (DSC) e Análise Dinâmico-Mecânica (DMA). A morfologia das blendas foi investigada por Microscopia Eletrônica de Varredura (SEM). As blendas independentemente do modo de preparação e da composição são imiscíveis. Como conseqüência desta imiscibilidade, as temperaturas de fusão (Tf) e cristalização (Tc) não são afetadas pela presença de PMMA. A morfologia das blendas varia com a composição e método de preparação. As blendas obtidas pelo método mecânico são compactas, apresentando morfologia de fase dispersa em uma matriz, com inversão de fases em aproximadamente 50 % em massa de cada componente. As soluções binárias, EVOH/DMF, e ternárias, EVOH/PMMA/DMF, foram submetidas a ensaios para a determinação das temperaturas de turvamento (Tturv) por microscopia ótica, e de cristalização dinâmica (Tcd), por DSC. As soluções binárias apresentaram comportamento UCST (upper critical solution temperature), sendo que a separação de fases L-L ocorre a temperaturas superiores à separação de fases S-L. O modelo de interações binárias prevê que a curva de separação L-L para as soluções EVOH- 38/DMF esteja situada a temperaturas superiores em relação às soluções EVOH-32/DMF e indica que a separação de fases resulta da baixa afinidade entre segmentos hidrofóbicos do EVOH com os segmentos do polímero contendo hidroxila e com o solvente, DMF, concordando com os dados obtidos experimentalmente. Filmes de EVOH obtidos pela evaporação do solvente mostraram-se densos, sem a presença de poros. As soluções ternárias também apresentaram comportamento UCST, resultando em duas fases macroscópicas, F1 e F2, à temperatura ambiente. A composição destas fases foi determinada por Análise Termogravimétrica (TGA), e os resultados mostraram que uma das fases macroscópicas é rica em EVOH e outra fase é rica em PMMA. As blendas resultantes da secagem dos sistemas ternários apresentaram duas camadas: uma densa e rica em PMMA e outra porosa e rica em EVOH. A presença de PMMA foi decisiva à formação de estruturas porosas / Abstract: In this work blends of poly (ethylene-co-vinyl alcohol) (EVOH), a semicrystalline copolymer which combines hydrophobic and hydrophilic segments and poly (methyl methacrylate) (PMMA), an amorphous and hydrophilic polymer were studied. EVOH blends, with ethylene content ranging from 27 to 44 mol% and PMMA were prepared by casting from solutions in DMF, and by mixing into a mini-mixer, with the objective of: i) evaluate the phase behavior and the morphology of the blends, EVOH/PMMA, depending on the composition of mixtures, the ethylene contents in the copolymers of EVOH and the conditions of mixing; ii) obtain the phase diagrams of the binary and ternary solutions, EVOH/DMF and EVOH/PMMA/DMF, respectively, by the process of thermally induced phase separation (TIPS). The phase behavior of the blends, EVOH / PMMA, was investigated by Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA). The morphology of the blends was investigated by Scanning Electron Microscopy (SEM). The blends independently of the method of preparation and of the composition are immiscible. As a result of immiscibility, the melting temperature (Tm) and the crystallization temperature (Tc) are not affected by the presence of PMMA. The morphology of the blends varies with the composition and with the method of preparation. The blends produced by the mechanical method is compact, showing morphology of dispersed phase in a matrix, with inversion of phases in about 50% by weight of each component. The binary solutions, EVOH-38/DMF and EVOH-32/DMF, were submitted to experiments to determine the cloud temperature (Tcloud) by optical microscopy, and the dynamic crystallization (Tcd), by DSC. The binary solutions show UCST behavior (upper critical solution temperature), and the L-L phase separation occurs at higher temperatures than the S-L phase separation. The binary interaction model provides the L-L line to the EVOH-38/DMF, solutions which was situated at higher temperatures than the EVOH-32/DMF solutions and indicates that the phase separation results from the low affinity between the hydrophobic segments of EVOH with the segments of the polymer containing hydroxyl and the solvent, DMF, which agrees with the data obtained experimentally. Films of EVOH obtained by the solvent evaporating seemed to be dense, without the presence of pores. The ternary solutions also had UCST behavior, resulting in two macroscopic phases, F1 and F2, at room temperature. The phase compositions were determined by Thermogravimetric Analysis (TGA), and the results showed that one of the macroscopic phases is rich in EVOH and the other phase is rich in PMMA. The blends resulting from drying of ternary systems had two layers: a dense and rich in PMMA and another porous and rich in EVOH. The presence of PMMA was crucial to the formation of porous structures / Doutorado / Físico-Química / Doutor em Ciências

Fe-Cr based steels, i.e. stainless steels, possessing a combination of excellent corrosion resistance and good mechanical properties, have indispensable applications ranging from low-end cooking utensils, to sophisticated components for nuclear power plants. However, the bcc/bct phase containing stainless steels which have a miscibility gap (MG) suffer from the so-called “475 oC embrittlement” leading to hardness increase and toughness deterioration. It occurs due to demixing of Fe and Cr leading to the formation of Fe-rich (α) and Cr-rich (α′) regions in bcc/bct phases. The demixing is referred to as phase separation (PS). The goal of this work was to study PS in ferrite containing stainless steels mainly by small-angle neutron scattering (SANS). Firstly, the application of different experimental techniques for the study of phase separation in Fe-Cr based steels was reviewed and supplemented by new measurements. SANS was shown to be very sensitive to the nanostructure change caused by PS and capable of characterizing the early stages of PS in Fe-Cr alloys. However, atom probe tomography and transmission electron microscopy are complementary to SANS. Therefore, in order to have a more complete view of the microstructure, the combination of these techniques should be pursued. Secondly, the factors affecting the initial microstructure prior to aging treatment and the effect of the resulted initial microstructure on PS were systematically investigated using binary Fe-Cr model alloys. The critical temperature of the MG was determined to be located between 560 and 580 oC in binary Fe-Cr. The results indicate that the solution treatment temperature above the MG and the cooling rate after solution treatment have significant effects on the initial microstructure and thus on PS during subsequent aging. The mechanisms responsible for the changed aging behavior are Cr clustering, quenched-in vacancy and decomposition during cooling. Therefore, computational simulations should take into account these factors and the initial microstructure to make predictions that are more accurate. Thirdly, the study was extended to PS in commercial duplex stainless steels (DSSs) which are of practical importance in various industries, e.g., nuclear power. It is found that alloying elements have an important effect on PS in DSSs. The grade 2507 (25 %Cr, 7 %Ni) experiences stronger PS than grade 2205 (22 %Cr, 5 % Ni) for the same heat treatment. Moreover, the fracture mechanisms as well as the mechanical properties depend on the extent of PS.  Finally, the fundamental aspects regarding the neutron scattering behavior for Fe-Cr alloys were examined. The results show that the nuclear and magnetic scattering of neutrons depend on the evolution of the nanoscale compositional fluctuation in Fe-Cr alloys. The ratio of the magnitude of nuclear scattering versus magnetic scattering varies with the extent of PS. / Stål baserade på Fe-Cr systemet, det vill säga rostfria stål, som har en kombination av utmärkta korrosionsegenskaper och bra mekaniska egenskaper, har många tillämpningar; allt från köksredskap, till sofistikerade komponenter för kärnkraftverk. Rostfria stål som innehåller Bcc / bct-fasen och som således har en blandningslucka, är känsliga för den så kallade "475 °C försprödningen" som leder till en hårdhetsökning men kraftigt försämrad slagseghet. Detta uppstår på grund av en uppdelning av Fe och Cr som leder till bildandet av Fe-rika (a) och Cr-rika (a’) regioner i bcc / bct-fasen. Denna uppdelning brukar kallas fasseparation. Målet med detta arbete var att studera fasseparationen i ferrit-innehållande rostfria stål främst genom lågvinkel-spridning av neutroner (SANS). Till att börja med studerades och jämfördes olika experimentella tekniker för undersökning av fasseparation i Fe-Cr-baserade stål med nya SANS- mätningar. SANS visade sig vara mycket känslig för förändringar på nano-skala orsakad av fasseparation och tekniken visade sig även kapabel att karakterisera de tidiga stadierna av fasseparation i Fe-Cr-legeringar. För att få en mer fullständig bild av mikrostrukturen efter fasseparation, bör emellertid en kombination av SANS och komplementära tekniker, såsom atomsond och transmissions-elektronmikroskopi, användas. Vidare undersöktes de faktorer som påverkar den ursprungliga mikrostrukturen före åldringsbehandling, och effekten av den initiala mikrostrukturen på fasseparation studerades systematiskt med användning av binära modell-legeringar av Fe-Cr. Den kritiska temperaturen för blandningsluckan i Fe-Cr bestämdes vara belägen mellan 560 och 580 °C. Resultaten indikerar att temperaturen för upplösningsbehandling ovanför blandningsluckan och kylhastigheten har en signifikant inverkan på den initiala mikrostrukturen och därmed på fasseparationen under efterföljande åldring. Mekanismerna som är ansvariga för det förändrade åldringsbeteendet är: Cr-klustring, insläckta vakanser och fasseparation under kylning. Simuleringar av fasseparationen bör därför ta hänsyn till dessa faktorer och den ursprungliga mikrostrukturen för att göra mer exakta förutsägelser av hur mikrostrukturen utvecklar sig med åldringstiden. Fasseparationen i kommersiella duplexa rostfria stål (DSS), som är av stor praktisk betydelse i olika branscher, t ex kärnkraft, studerades också med SANS. Det visade sig att mängden av olika legeringselement har en viktig effekt på graden av fasseparation i DSS. Legeringen 2507 uppvisade en tydligare fasseparation jämfört med legering 2205 för samma värmebehandling. Brottmekanismerna såväl som de mekaniska egenskaperna visade sig bero på omfattningen av fasseparationen. Slutligen undersöktes de grundläggande aspekterna hos neutronspridnings-beteendet för binära Fe-Cr-legeringar. Resultaten visade att kärn- och magnetisk spridning av neutroner beror på utvecklingen av sammansättningsfluktuationerna på en nanoskala i Fe-Cr-legeringar. Förhållandet mellan magnetisk- och kärnspridning varierar med omfattningen av fasseparationen. / <p>QC 20171117</p>

Orientador: Maria Isabel Felisberti / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T22:37:44Z (GMT). No. of bitstreams: 1 Marques_RosalvadosSantos_D.pdf: 38406911 bytes, checksum: 574d251b2b2578b4a3d9fd0b4e82fcf7 (MD5) Previous issue date: 2014 / Resumo: Neste trabalho, estudou-se o comportamento de fases de soluções binárias e ternárias de poliolefinas funcionalizadas com hidroxilas (EVOH) e ácido carboxílico (PEAA) nos solventes dimetilformamida e álcool benzílico. Utilizou-se EVOH contendo 27 e 44 mol % e PEAA contendo 80 mol % de etileno. As soluções exibem o comportamento de fases do tipo UCST, apresentando separações de fases líquido-líquido (L-L) e sólido-líquido (S-L). As temperaturas de separação de fases L-L e S-L, TL-L e TS-L, respectivamente, foram determinadas para soluções com diferentes composições por inspeção visual e por DSC, respectivamente. Enquanto TS-L para as soluções binárias de EVOH varia fortemente da com a composição das soluções binárias, TS-L para as soluções binárias de PEAA é praticamente constante. Estes resultados foram interpretados sob a ótica de um modelo em que a cristalização do PEAA, que envolve os segmentos de etileno do copolímero, ocorre quase na ausência de solvente. Já a cristalização do EVOH, que envolve os segmentos hidroxilados, ocorre em meio ao solvente, em uma condição em que o potencial químico do polímero varia com a composição da solução. Este modelo pode ser comprovado por estudos de fluorescência empregando-se o pireno e o acetato de uranila como sondas hidrofóbica e hidrofílica, respectivamente. Estes estudos de fluorescência permitiram também acessar transições não detectáveis por DSC. As soluções ternárias homogêneas apresentam mais de uma separação de fases L-L quando submetidas a resfriamento. O diagrama de fases ternário foi construído determinando-se as composições das soluções em equilíbrio, decorrentes da primeira separação de fases L-L, por termogravimetria de alta resolução. Os diagramas de fases das soluções ternárias resultantes das combinações possíveis entre os diferentes polímeros e solventes apresentam regiões de miscibilidade limitadas localizadas em regiões próximas aos vértices, sendo as composições das fases em equilíbrio características de cada combinação nas soluções ternárias. Os materiais resultantes da evaporação do solvente de soluções submetidas ao processo TIPS (Temperature Induced Phase Separation) são compactos ou porosos, dependendo da afinidade polímero-solvente. Entretanto, as morfologias dos materiais resultantes de soluções ternárias submetidas ao processo TIPS são únicas e características do par polímero-polímero, demonstrando que a estratégia de combinação de polímeros para controlar a morfologia é viável / Abstract: The phase behavior of binary and ternary solutions of functionalized poliolefins with hydroxyls (EVOH) and carboxylic acid (PEAA) were studied using dimethylformamide and benzyl alcohol as solvents. PEAA containing 80 mol % and EVOH containing 27 and 44 mol % of ethylene were used. The binary and ternary solutions present a typical UCST behavior associated to liquid-liquid (L-L) and solid-liquid (S-L) phase separation. The temperatures related to L-L and S-L phase separation, TL-L e TS-L, respectively, were determined visually and using DSC, respectively. While TS-L depends on the EVOH solution composition, it is practically constant for PEAA solutions. These results were explained using a model in which the crystallization of PEAA from the solution occurs in absence of solvent, once it involves the polyethylene segments. On the contrary, the crystallization of EVOH from the solution, that involves the hydroxylated segments, occurs in presence of the solvent. This condition leads to the decrease of the chemical potential of EVOH in the solution. The models could be proved by fluorescence experiments using pyrene and uranyl acetate as hydrophobic and hydrophilic probes, respectively. Moreover, the fluorescence experiments allow accessing other transitions not detectable by DSC for ternary solutions. The homogeneous ternary solutions present more than one L-L phase separation by cooling. The ternary diagram was determined by the first L-L phase separation using the composition data accessed by high resolution thermogravimetry. The ternary solutions of all possible combination of polymers and solvents show a restricted miscibility window in the regions near the vertices. The composition of the phases in equilibrium is characteristic of each ternary solution, as well as, the morphology of the materials resulting from the evaporation of the solvent after the solution being subjected to TIPS (Temperature Induced Phase Separation) process. This process applied to binary and ternary solutions resulted in dense or porous materials depending on the polymer-solvent affinity. However, the morphology resulting from ternary solutions subjected to TIPS process and solvent evaporation is unique, showing that the strategy of combining different polymers is a viable route to control the morphology of polymers / Doutorado / Físico-Química / Doutora em Ciências

Ce travail de thèse a été consacré au développement de nanocomposites polymère (PVDF-co-HFP) – silice hautement chargés en nanoparticules par voie solvant. La combinaison d’un polymère fluoré ; ayant des propriétés mécaniques, diélectriques, piézoélectriques et pyroélectriques très intéressantes ; avec des nanoparticules de silice pourrait nous permettre le développement de nouvelles solutions dans le domaine de l’énergie. Ainsi nous avons étudié l’impact de la chimie de surface des nanoparticules de silice, des paramètres expérimentaux et du procédé par voie solvant sur la structure et les propriétés finales des matériaux obtenus. Pour la réalisation de ces matériaux par voie solvant, une solution P(VDF-co-HFP) – silice dans un solvant commun est préparée puis séchée. Dans le cadre de ce projet nous avons travaillé avec des cétones aliphatiques présentant différentes longueurs de chaînes: la Methyl Ethyl Ketone (MEK) et la 2-heptanone. Ainsi pour la préparation des solutions nous avons développé une approche générique pour transférer des nanoparticules en solution dans l’eau dans un solvant organique par l’intermédiaire d’un agent de transfert. Cependant, avant l’étape de dépôt et séchage, nous avons constaté que le PVDF et ses copolymères (dont le P(VDF-co-HFP)) forment un gel thermoréversible dans ces deux solvants ; avec ou sans silice. Cette gélification impacte certainement l’étape de solvent casting or aucun consensus concernant les mécanismes responsables de la gélification de ce polymère n’a été trouvé dans la littérature. Il apparait primordial de comprendre les mécanismes de gélification du P(VDF-co-HFP) avant d’étudier les propriétés des nanocomposites. Pour cela nous avons étudié l’influence de différents paramètres : nature du solvant, concentration en copolymère, température, présence de charges (concentration et chimie de surface) sur les mécanismes de gélification (Chapitre 3). La cinétique de gélification a été étudiée par tube-tilting et rhéologie linéaire. Une combinaison de RMN 19F, DSC, SAXS, WAXS et rhéologie non-linéaire a été utilisée pour déterminer les mécanismes réponsables de la gélification du P(VDF-co-HFP) dans ces solvants. La 19F RMN a montré l'existence d'un réseau de polymère où des zones rigides agiraient comme des noeuds de réticulation. Ce comportement n'a été observé qu'à l'état gel: aucun réseau de polymère ou aucune zone rigide n'existent quand la solution de polymère est à l'état liquide. La nature et la fraction volumique de ces zones rigides présentes à l'état gel ont été étudiés par DSC et diffraction des rayons X. Une faible fraction de cristallites, qui correspondrait aux zones rigides, a été observée dans ces gels. Dans une troisième étape (Chapitre 4), l'impact de l'addition de silice sur la gélification du P(VDF-co-HFP) a été étudié. Pour cela, des gels polymère-silice ont été formulés dans la MEK et la 2-heptanone en utilisant deux sources de silice nanométrique: celle préparée par transfert de phase et une solution commerciale Nissan. Nous avons observé que la présence de silice impacte peu la gélification du polymère contrairement au procédé, et plus particulièrement à la présence d'eau résiduelle dans le matériau. La rhéologie non linéaire des gels dans la 2-heptanone, chargés ou non en silice, a ensuite été étudiée sous LAOS. Le comportement de ces matériaux varie avec la contrainte et passe d'un régime élastique à un régime visqueux. Cependant avant de passer dans le domaine visqueux, les gels non chargés montre un fort strain-hardening. Au contraire, l'incorporation de nanoparticules inhibe le strain-hardening. Dans une dernière étape, des films P(VDF-co-HFP)-silice ont été préparés par voie solvant. Des matériaux homogènes contenant jusqu'à 40wt% de nanoparticules ont été obtenus, avec des états de dispersions différents et finement controlés. L'impact de la concentration et de l'état de dispersion sur les propriétés mécaniques a été finalement étudiés / The general context of this PhD thesis is the development of highly filled polymer– silica model nanocomposites by solvent route, based on copolymers of vinylidene fluoride and hexafluoropropylene, denoted as P(VDF-co-HFP). Due to their unique combination of mechanical, dielectric, piezoelectric and pyroelectric properties, PVDF and VDF-copolymers combined with silica are good candidates for new advanced applications like actuation or energy harvesting. In this context, the primary objective was to understand how the filler surface chemistry and formulation parameters, as well as the solvent casting process, affect the final structure and properties of the materials. To elaborate P(VDF-co-HFP) nanocomposites with silica by solvent casting, a first step was to prepare solutions of silica and the polymer in a common solvent which will be subsequently dried. Aliphatic ketone solvents of various chain length, namely methyl ethyl ketone (MEK) and 2-heptanone, were used. For this purpose a generic approach to transfer silica nanoparticles from water to organic solvent through a transfer agent was developed. VDF-based copolymer solutions (filled or not with nanoparticles) exhibit thermoreversible gelation in ketone solvents, which may subsequently impact the processing of materials by solvent casting. Studying the phenomenology of PVDF gelation in thus of major concern for controlling the processing of those nanocomposites. No general consensus on the gelation mechanisms is found in the literature. In this context, the gelation of a semi-crystalline P(VDF-co-HFP) in MEK or 2-heptanone was studied. The gelation kinetics was investigated by tube-tilting and linear rheology. A combination of 19F Nuclear Magnetic Resonance (NMR), DSC, SAXS, WAXS and nonlinear rheology was used to probe the structure of these systems and the gelation mechanisms. 19F NMR shows the occurrence of a polymer network-like structure with rigid zones which may act as cross-links. Such a behavior is only observed in the gel state: no polymer network or rigid zones are present when the polymer solution is in the liquid state. The nature and volume fraction of the rigid zones present in the gel state were investigated with DSC and X-ray diffraction. A small crystalline fraction, which may correspond to the rigid zones, is observed in gels. In a third step, the impact of adding silica nanoparticles on the gelation kinetics of P(VDF-co-HFP) was studied. To do so, copolymer – silica gels were formulated in MEK and 2-heptanone using two sources of organic silica solutions, the one prepared previously by phase transfer and a commercial one from Nissan. We found that the presence of silica nanoparticles hardly disturbs the gelation of P(VDF-co-HFP). Conversely, the process, and more particularly the presence of residual water within the material, has a strong impact on the structure of the gels and gelation kinetics.The nonlinear rheological properties of the P(VDF-co-HFP) physical gels filled or not with silica nanoparticles were investigated in 2-heptanone only (as MEK is too volatile), using Large Amplitude Oscillatory Shear (LAOS) experiments (Chapter 5). The behavior of all materials changes from elastic at small strain to viscous at high strain amplitudes. Before abruptly changing from elastic to viscous behavior, unfilled gels exhibit strong strain-hardening. Incorporating silica nanoparticles is found to inhibit strain-hardening. In a last step, P(VDF-co-HFP) – silica solid films were obtained by solvent casting the previously prepared systems. Homogeneous materials filled up to 40 wt% of silica nanoparticles were obtained, with different and finely controlled dispersion states of nanoparticles, related to the structure of the initial gels or solutions. The impact of the concentration and dispersion state of the fillers on the mechanical performances (particularly the mechanical toughness) was investigated

Les réactions de macrocyclisation sont souvent difficiles à réaliser du point de vue expérimental, puisque la dilution élevée nécessaire requiert un montage encombrant et la purification du mélange est souvent complexe en raison d’une mauvaise sélectivité de cyclisation. Ces raisons peuvent compliquer la planification des voies de synthèse, ce qui dissuade souvent les chimistes d’utiliser les macrocycles pour différentes applications. Dans les dernières années, notre groupe de recherche a développé une méthode nommée stratégie de séparation de phase. Il s’agit d’un nouveau protocole permettant de faire des réactions de macrocyclisation de façon monotope et dans un milieu beaucoup plus concentré, tout en évitant les réactions parasites d’oligomérisation, facilitant ainsi la purification des macrocycles obtenus. Cette thèse décrit le développement et l’application de stratégies permettant de surmonter les défis liés aux réactions de macrocyclisation. Dans la première partie de la thèse, le protocole de la stratégie de séparation de phase a pu être utilisé pour la synthèse de squelettes macrocycliques complexes, comme celui du produit naturel ivorenolide A (Chapitre 4) et celui de l’anti-viral vaniprevir (Chapitre 6). Ce protocole a permis de réaliser l’étape de macrocyclisation dans un milieu réactionnel 120 fois plus concentré, tout en maintenant un niveau de sélectivité de macrocyclisation élevé. Dans la deuxième partie de la thèse, le développement d’une nouvelle synthèse d’acétylures de soufre catalysée par un complexe de cuivre a permis la synthèse d’une librairie de macrocycles peptidiques (Chapitre 8). L’incorporation du motif acétylure de soufre a aussi permis la diversification de ce dernier afin de greffer plusieurs étiquettes bioactives. Pour terminer, l’étendue de la réaction intermoléculaire de la nouvelle réaction de formation de thioalcynes a été explorée (Chapitre 9). Ceci a permis la synthèse d’alcynes disubstitués par des hétéroatomes ainsi que la fonctionnalisation de peptides contenant une cystéine non protégée. Des études mécanistiques expérimentales et computationnelles de la nouvelle méthode de synthèse de thioalcynes ont aussi été réalisées. / Macrocyclization reactions can be problematic due to poor selectivity of cyclization versus oligomerization. As such, difficult purification of complex mixtures and/or the use of complex and cumbersome experimental setups are often necessary. The drawbacks can complicate synthetic pathways and deter chemists from exploring the unique chemical space of macrocycles. Our group has developed a new macrocyclization strategy called phase separation strategy, a protocol enabling one-pot macrocyclization reactions at much higher concentration. In the present thesis, the challenges associated with macrocyclization reactions are tackled by the development and the application of new strategies. First, the phase separation strategy protocol was used to synthesize the backbone of complex macrocycles like the natural product ivorenolide A (Chapter 4) and the antiviral vaniprevir (Chapter 6). With the use of the phase separation strategy protocol, macrocyclization reactions were performed at concentrations 120 times higher than traditional protocols while maintaining a high level of macrocyclization selectivity. Second, the development of a new copper-catalyzed synthesis of alkynyl sulfides for the synthesis of a macrocyclic peptide library is described (Chapter 8). The macrocyclic peptides were also tagged with several biomarkers by diversification of the resulting alkynyl sulfide motif. Finally, the scope of the intermolecular copper-catalyzed reaction was explored (Chapter 9). Using the method, bis-heteroatom substituted alkynes were synthesized and modification of unprotected cysteine sidechains was possible. Furthermore, the mechanistic reaction pathway of the new alkynyl sulfide synthesis was studied experimentally and computationally.

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In unserem täglichen Leben begegnen wir Tropfen oft in physikalischen Systems, beispielsweise als Öltropfen in Salatsoße. Diese Tropfen sind meist chemisch inaktiv. In biologischen Zellen bilden Proteine und RNA zusammen Tropfen. Zellen sind chemisch aktiv, so dass die Tropfenkomponenten neu gebildet, abgebaut und modifiziert werden können. In dieser Doktorarbeit wird das dynamische Verhalten von chemisch aktiven Tropfen mit analytischen und numerischen Methoden untersucht. Um das dynamische Verhalten von solchen aktiven Tropfen zu untersuchen, benutzen wir ein Minimalmodell mit zwei Komponenten, die zwei Phasen bilden und durch chemische Reaktionen ineinander umgewandelt werden. Die chemischen Reaktionen werden durch das Brechen von Detailed Balance aus dem Gleichgewicht gehalten, so dass die Tropfen chemisch aktiv sind. Wir konzentrieren uns auf den Fall, in dem Tropfenmaterial im Tropfen in die äußere Komponente umgewandelt wird, und in der äußeren Phase erzeugt wird. Wir finden ein vielfältiges dynamisches Phasendiagramm mit Regionen, in denen Tropfen schrumpfen und verschwinden, Regionen, in denen Tropfen eine stabile stationäre Größe besitzen, und Regionen, in denen eine Forminstabilität zu komplexer Tropfen-Dynamik führt. In der letzten Region deformieren sich Tropfen typischenweise prolat, verformen sich zu einer Hantel, und teilen sich in zwei Tochtertropfen, die wieder anwachsen. Dies kann zu Zyklen von Wachstum und Teilung von Tropfen führen, bis die Tropfen das gesamte Volumen füllen. Während spherische Tropfen durch die chemischen Reaktionen entgegen ihrer Oberflächenspannung deformiert werden, können Tropfen- Zylinder und Platten durch chemische Reaktionen stabilisiert werden. Generell ist die Dynamik von Tropfen ein hydrodynamisches Problem, da die Oberflächenspannung von deformierten Tropfen hydrodynamische Flüsse erzeugt. Wir finden, dass chemische Reaktionen entgegen die Oberflächenspannung Arbeit verrichten können, so dass die Tropfenteilung auch unter Berücksichtigung hydrodynamischer Flüsse möglich ist. Diese Doktorarbeit zeigt, dass die Kombination von chemische Reaktionen und Phasenseparation unter Nichtgleichgewichtsbedingungen zu neuem dynamischen Verhalten führen kann. Die Ergebnisse zeigen die Relevanz von chemischen Reaktionen zum Verständnis von Phasenseparation in biologischen Systemen auf, und können bei der Umsetzung der diskutierten Phänomene in experimentellen Systemen helfen. Die Tropfenteilung, die in dieser Doktorarbeit diskutiert wird, erinnert an die Teilung von biologischen Zellen. Davon motiviert schlagen wir vor, dass die Teilung von chemisch aktiven Tropfen ein Mechanismus für die Replikation von Tropfen-artigen Protozellen am Ursprung des Lebens gewesen sein könnte.:1. Introduction 2. Theory of multi-component phase-separating systems with chemical reactions 3. Minimal model for chemically active droplets in two formulations 4. Shape instability of spherical droplets with chemical reactions 5. Dynamical behavior of chemically active droplets 6. Shape instability of droplets with various geometries 7. Role of hydrodynamic flows in chemically driven droplet division 8. Chemically active droplets as a model for protocells at the origin of life 9. Conclusion Appendices / In our everyday environment, we regularly encounter liquid-liquid phase separation in physical systems such as oil droplets in vinegar. These droplets tend to be chemically inert. In biological cells, protein and RNA may together form liquid droplets. Cells are chemically active, so that droplet components can be created, degraded and modified. In this thesis we study the influence of nonequilibrium chemical reactions on the shape dynamics of a droplet theoretically, using analytical and numerical methods. To discuss the dynamical behavior that results from combining phase separation and chemical reactions in sustained nonequilibrium conditions, we introduce a minimal model with only two components that separate into distinct phases. These two components are converted into each other by chemical reactions. The reactions are kept out of equilibrium by breaking of detailed balance, so that the droplet becomes active. We concentrate on the case where the reaction inside the droplet degrades droplet material into the outer component, and where the reaction outside creates new droplet material. We find that chemically active droplets have a rich dynamic phase space, with regions where droplets shrink and vanish, regions where droplets have a stable stationary size, and regions where the flux-driven instability leads to complex dynamic behavior of droplets. In the latter, droplets typically elongate into a dumbbell shape and then split into two symmetrical daughter droplets. These droplets then grow until they have the same size as the initial droplet. This can lead to cycles of growth and division, so that an initial droplet divides until droplets fill the simulation volume. We analyze the stationary spherical state of the droplet, which is created by a balance of the fluxes driven by the chemical reactions. We find that stationary droplets may have a shape instability, which is driven by the continuous fluxes across the droplet interface and which may trigger the division. We also find that while reactions may destabilize spherical droplet shapes despite the surface tension of the droplet, they can have stabilizing effects on cylindrical droplets and droplet plates. Generally, the shape dynamics of droplets is a hydrodynamic problem because surface tension in non-spherical droplets drives hydrodynamic flows that redistribute material and deform the droplet shape. We therefore study the influence of hydrodynamic flows on the shape changes of chemically active droplets. We find that chemical reactions in active droplets can perform work against surface tension and flows, so that the droplet division is possible even in the presence of hydrodynamic flows. The present thesis highlights how the combination of basic physical behaviors – phase separation and chemical reactions – may create novel dynamic behavior under sustained nonequilibrium conditions. The results demonstrate the importance of considering chemical reactions for understanding the dynamics of droplets in biological systems, as well as proposes a minimalist model for experimentalists that are interested in creating a system of dividing droplets. Finally, the division of chemically active droplets is reminiscent of the division of biological cells, and it motivates us to propose that chemically active droplets could have provided a simple mechanism for the self-replication of droplet-like protocells at the origin of life.:1. Introduction 2. Theory of multi-component phase-separating systems with chemical reactions 3. Minimal model for chemically active droplets in two formulations 4. Shape instability of spherical droplets with chemical reactions 5. Dynamical behavior of chemically active droplets 6. Shape instability of droplets with various geometries 7. Role of hydrodynamic flows in chemically driven droplet division 8. Chemically active droplets as a model for protocells at the origin of life 9. Conclusion Appendices

In this PhD research the liquid-liquid phase separation phenomena in Gd-based alloys was investigated in terms of phase equilibria, microstructure formation upon quenching the melt and corresponding magnetic properties of phase-separated metallic glasses. The phase diagrams of the binary subsystems Gd-Zr and Gd-Ti were experimentally reassessed. Especially the phase equilibria with the liquid phase could be determined directly by combining in situ high energy synchrotron X-ray diffraction with electrostatic levitation of the melt. The Gd-Zr system is of eutectic type with a metastable miscibility gap. The eutectic composition at 18 ± 2 at.% Zr, the liquidus line and the coexistence of bcc-Zr and bcc-Gd at elevated temperature could be determined. The Gd-Ti system is a monotectic system. The experimental observations in this work led to improved new Gd-Zr and Gd-Ti phase diagrams. The phase equilibria of the ternary Gd-Ti-Co system were analyzed for two alloy compositions. The XRD patterns for molten Gd35Ti35Co30 gave direct evidence for the coexistence of two liquid phases formed by liquid-liquid phase separation. The first experimental and thermodynamic assessment of the ternary Gd–Ti–Co system revealed that the stable miscibility gap of binary Gd–Ti extends into the ternary Gd–Ti–Co system (up to about 30 at.% Co). New phase-separated metallic glasses were synthesized in Gd-TM-Co-Al (TM = Hf, Ti or Zr) alloys. The microstructure was characterized in terms of composition and cooling rate dependence of phase separation. Due to large positive enthalpy of mixing between Gd on the one side and Hf, Ti or Zr on the other side, the alloys undergo liquid-liquid phase separation during rapid quenching the melt. The parameters determining the microstructure development during phase separation are the thermodynamic properties of the liquid phase, kinetic parameters and quenching conditions. By controlling these parameters and conditions the microstructure can be tailored both at microscopic and macroscopic length scales. This includes either droplet-like or interconnected microstructures at the microscopic level and glass-glass or glass-crystalline composites at the macroscopic level. Essential parameter for the quenched in microstructure is the temperature dependence of liquid-liquid phase separation, which is determined by the chemical composition of the alloy: on the one hand, earlier and/or later stages of spinodal decomposition or almost homogeneous glassy states are obtained if the critical temperature of miscibility gap Tc is close to the glass transition temperature Tg; and on the one hand, coarsening and secondary precipitations of the liquids are obtained if Tc is much higher than Tg. Finally, the influence of the microstructure developed by phase separation on their magnetic properties had been investigated. The saturation magnetization σS depends on the overall amount of Gd atoms in the alloys and is not remarkably affected by phase separation processes. The Curie temperature TCurie of the magnetic transition is influenced by the changed chemical composition of the Gd-rich glassy phases compared to that of monolithic Gd-Co-Al glasses. / In dieser Doktorarbeit wurde die flüssig-flüssig Phasenentmischung von Gd-basierten Legierungen hinsichtlich der Phasengleichgewichte, der Gefügeentwicklung während der Schmelzabschreckung und dazugehöriger magnetischer Eigenschaften, untersucht. Die Zustandsdiagramme der binären Untersysteme Gd-Zr undGd-Ti wurden experimentell ermittelt.. Insbesondere konnten die Phasengleichgewichte mit der flüssigen Phase mittels in-situ Röntgenbeugungsmessunngen an elektrostatisch levitierten Schmelzen direkt, bestimmt werden. Das Gd-Zr System stellt ein ein eutektisches Phasendiagram dar und besitzt eine metastabile Mischungslücke. Die eutektische Zusammensetzung wurde mit 18 ± 2 at.%Zr bestimmt und der Verlauf der Liquiduslinie bei erhöhten Temperaturen wurde experimentell ermittelt. Experimentell wurde die Koexistenz von kubisch-raumzentrierten Zr und Gd in einem Bereich bei hohen Temperaturen nachgewiesen. Das Gd-Ti-System ist von monotektischer Art. Die experimentellen Beobachtungen dieser Arbeit trugen wesentlich zur Verbesserung der Beschreibung der Phasendiagaramme Gd-Zr- und Gd-Ti-Phasenbei. Die Phasengleichgewichte des ternären Gd-Ti-Co-Systems wurde anhand zweier Legierungszusammensetzungen untersucht. Die Röntgenbeugungsdiffraktogramme der geschmolzenen Legiereung Gd35Ti35Co30 sind ein direkter Beleg für die Koexistenz zweier flüssiger Phasen, aufgrund der flüssig-flüssig Phasenentmischung. Die erste experimentelle und thermodynamische Auswertung des ternären Gd-Ti-Co-Systems zeigt, dass sich die stabile Mischungslücke des binären Gd-Ti-Systems ins ternäre Gd-Ti-Co-System bis zu ungefähr 30 at.% Co erstreckt. Es wurden neue Gd-TM-Co-Al (TM = Hf, Ti oder Zr)-basierte metallische Gläser, die separierte Phasen besitzen, hergestellt. Ihr Gefüge wurden hinsichtlich Zusammensetzung- und Abkühlratenabhängigkeit der Phasenentmischung charakterisiert. Aufgrund der großen positiven Mischungsenthalpie zwischen Gd auf der einen und Hf, Ti oder Zr auf der anderen Seite, weisen diese Legierungen eine flüssig-flüssig Phasenentmischung während der Abschreckung aus der Schmelze auf. Die Einflussgrößen, die die Gefügeentwicklung während der Phasenentmischung bestimmen, sind die thermodynamischen Eigenschaften der flüssigen Phase, die kinetische Parameter und die Abschreckbedingungen. Indem diese Parameter und Bedingungen kontrolliert werden, kann das Gefüge auf makro- sowie mikroskopischer Längenskala maßgeschneidert werden. Dies beinhaltet entweder tropfenförmige oder miteinander verbundene Gefüge auf einer mikroskopischen Skala und Glas-Glas oder Glas-Kristall Komposite auf einer makroskopischen Längenskala. Ein wesentlicher Parameter für das abgeschreckte Gefüge ist die Temperatur-Abhängigkeit der flüssig-flüssig Phasenentmischung, die durch die chemische Zusammensetzung der Legierung bestimmt wird. Frühere und/oder spätere Stadien der spinodalen Entmischung oder nahezu homogene amorphe Zustände können abhängig von dem Temperaturunterschied zwischen kritischer Temperatur der flüssig-flüssig Phasenentmischung und der Glasübergangstemperatur erhalten werden. Wenn die kritische Temperatur der Mischungslücke, Tc, viel höher ist als die des Glasübergangs, Tg, können makroskopische Vergröberungen der tropfenförmigen Verteilung der flüssigen Phase und sekundäre flüssige oder kristalline Ausscheidungen in den gebildeten amorphen Phasen erhalten werden. Durch die Phasenentmischung und die erhaltenen heterogenen Gefüge werden die magnetischen Eigenschaften beeinflusst.. Die Sättigungsmagnetisierung,σS, hängt von der gesamten Anzahl der Gd-Atome der Legierung ab und wird nicht bemerkenswert vom Phasenentmischungsprozess beeinflusst. Die Curie Temperatur TCurie wird im Vergleich zu monolithischen Gd-Co-Al Gläsern, und abhängig von der chemischen Zusammensetzung der Gd-reichen Phase, verändert.