Os materiais bioativos são materiais sintéticos que possuem superfícies ativas em que os minerais presentes em tecidos duros podem se ligar quimicamente. Há alguns estudos em Odontologia, onde partículas desses materiais foram incorporadas aos Cimentos de Ionômero de Vidro (CIVs) e Cimentos de Ionômero de Vidro modificados por resina (CIVMRs) com o objetivo de se obter bioatividade, e conseqüente remineralização dentária. O presente estudo teve como objetivo avaliar os efeitos da incorporação de nanopartículas de vitrocerâmica bioativa nas propriedades de resistência à compressão e rugosidade de CIVMRs. Fuji II LC e Vitremer foram considerados os grupos controles. Materiais experimentais foram feitos através da incorporação de 2, 5 e 10% em peso de Biosilicato nestes CIVMRs. Seis corpos-de-prova de cada material foram confeccionados para o teste de resistência à compressão, que foi realizado em máquina de ensaios universal (Emic), a uma velocidade de 1,0 mm/min, depois de mantidos por 24 horas em água destilada a 37°C. Para análise da rugosidade, foram confeccionados dois corpos-de-prova de cada material, armazenados em água destilada por sete dias, para terem suas superfícies analisadas por meio de Microscopia de Força Atômica. Os dados da resistência à compressão e rugosidade foram submetidos à análise estatística por meio da Análise de Variância (ANOVA) a dois critérios e para comparações múltiplas foi aplicado o teste de Tukey, com nível de significância de 5%. Apenas os cimentos com 2% de nanopartículas de vitrocerâmica bioativa obtiveram resistência à compressão semelhante ao grupo controle, as demais concentrações contribuíram para a diminuição dessa resistência. A incorporação de 5% de nanopartículas de vitrocerâmica bioativa aumentou a rugosidade superficial dos CIVMRs estudados. / Bioactive materials are synthetic materials that have active surfaces that are capable to chemically bond to dental structures. There are some studies where particles of these materials were incorporated in Glass-ionomer cements (GIC) and Resin-modified glass-ionomer cements (RMGIC) trying to achieve bioactivity and dental remineralization. The aim of this study was to evaluate the effects of the incorporation of bioactive glass-ceramics nanoparticles on the compressive strength and roughness of RMGIC. Fuji II LC and Vitremer were considered the control groups. Experimental materials were made adding 2, 5 and 10% (weight) of Biosilicate into these RMGIC. Six specimens of each material were made to be tested on compressive strength performed with a universal testing machine (Emic) at a crosshead speed of 1.0 mm / min, after they were stored in distilled water for 24 hour at 37°C. To roughness analysis, two specimens of each material were made and stored in distilled water for 7 days and their surfaces were analyzed with a Atomic Force Microscope. Data of compressive strength and roughness were statistically analyzed by ANOVA and Tukey test for multiple comparisons. Only the RMGICs with 2% of bioactive glass-ceramic nanoparticles obtained compressive strength similar to the control RMGICs, the other concentrations decreased their compressive strength values. The incorporation of 5% of bioactive glass-ceramic nanoparticles increased the roughness of the RMGICs.

Im Rahmen der vorliegenden Arbeit wurde eine Auswertemethodik für anomale Röntgenkleinwinkelstreuung (ASAXS) zur nanochemischen Zusammensetzungsanalyse der beteiligten Phasen eines Probensystems entwickelt und auf eine Glaskeramik angewendet. Die nanochemische Analyse unterscheidet sich von den bekannten Verfahren der partiellen Strukturfaktoren bzw. -funktionen (PSF) durch die Anwendbarkeit auf nahezu jedes Probensystem, da keine einschränkenden Annahmen bezüglich der anomalen Korrekturfaktoren der atomaren Streufaktoren der einzelnen Elemente getroffen werden müssen. Im Gegensatz zu den üblicherweise verwendeten PSF''s werden die relevanten Probeneigenschaften, d.h. die Nanostruktur und die nanochemische Zusammensetzung, direkt aus den Verläufen der differenziellen Streuquerschnitte in Abhängigkeit von der Röntgenenergie und des Streuvektorbetrages bestimmt. Es wurden umfangreiche anomale Röntgenkleinwinkelstreuexperimente an einer ausgewählten Oxyfluorid-Glaskeramik durchgeführt und mit der entwickelten Methode analysiert. Die untersuchte Glaskeramik, welche mit den seltenen Lanthanoiden Erbium und Ytterbium dotiert ist, zeigt die nichtlineare optische Eigenschaft der Frequenzerhöhung. Es konnte gezeigt werden, dass es möglich ist, die gemittelte Zusammensetzung der Teilchenphase und die der amorphen Glasmatrix mittels ASAXS quantitativ zu bestimmen. Im Gegensatz zu EDX-Studien liefert ASAXS gemittelte Zusammensetzungen, die das Probensystem aus statistischer Sicht besser repräsentieren. Die nanochemische Zusammensetzungsanalyse der Glaskeramik lieferte das Ergebnis, dass das Cadmium kein Bestandteil der Nanopartikelphase ist, die eine gemittelte Zusammensetzung von 17%Pb 2%Er 17%Yb 64%F (at%) aufweist. TEM-Studien implizieren, dass die Nanopartikel im Glas näherungsweise als Rotationsellipsoide beschrieben werden können. Es wurde gezeigt, dass die Streukurven der ASAXS Studien mit einem solchen Strukturmodell modelliert werden können. / In the present work an evaluation method for anomalous small-angle X-ray scattering (ASAXS) to analyze nanochemical compositions of all involved phases of a sample has been developed and was applied to a glass ceramic. The nanochemical analysis differs from the known methods of partial structure factors or functions (PSF) by the applicability to virtually any system, because the new evaluation method does not require any limiting assumptions regarding the anomalous corrections of the atomic scattering factors of the individual elements. Unlike the PSF''s normally used, the relevant sample properties, i.e. nanostructure and nanochemical compostion, will be determined directly from the differential scattering cross sections as a function of the X-ray energy and the scattering vector. Extensive ASAXS experiments at a selected oxyfluoride glass ceramic were done and analyzed by the developed method. The investigated glass ceramic, which is co-doped with selected lanthanides like erbium and ytterbium, shows the nonlinear optical property of frequency upconversion. It was shown that it is possible to determine quantitatively the average compositions of all phases of a system using ASAXS. In contrast to EDX studies, ASAXS provides average compositions, which represent the sample better from a statistical point of view. The nanochemical composition analysis of the glass ceramic yielded the result that the cadmium is not part of the nanoparticle phase, which has an average composition of 17%Pb 2%Er 17%Yb 64%F (at%). TEM studies imply that the nanoparticles in the glass can be described by ellipsoids. It was shown that the scattering curves of the ASAXS studies can be simulated by such a structural model.

Os materiais bioativos são materiais sintéticos que possuem superfícies ativas em que os minerais presentes em tecidos duros podem se ligar quimicamente. Há alguns estudos em Odontologia, onde partículas desses materiais foram incorporadas aos Cimentos de Ionômero de Vidro (CIVs) e Cimentos de Ionômero de Vidro modificados por resina (CIVMRs) com o objetivo de se obter bioatividade, e conseqüente remineralização dentária. O presente estudo teve como objetivo avaliar os efeitos da incorporação de nanopartículas de vitrocerâmica bioativa nas propriedades de resistência à compressão e rugosidade de CIVMRs. Fuji II LC e Vitremer foram considerados os grupos controles. Materiais experimentais foram feitos através da incorporação de 2, 5 e 10% em peso de Biosilicato nestes CIVMRs. Seis corpos-de-prova de cada material foram confeccionados para o teste de resistência à compressão, que foi realizado em máquina de ensaios universal (Emic), a uma velocidade de 1,0 mm/min, depois de mantidos por 24 horas em água destilada a 37°C. Para análise da rugosidade, foram confeccionados dois corpos-de-prova de cada material, armazenados em água destilada por sete dias, para terem suas superfícies analisadas por meio de Microscopia de Força Atômica. Os dados da resistência à compressão e rugosidade foram submetidos à análise estatística por meio da Análise de Variância (ANOVA) a dois critérios e para comparações múltiplas foi aplicado o teste de Tukey, com nível de significância de 5%. Apenas os cimentos com 2% de nanopartículas de vitrocerâmica bioativa obtiveram resistência à compressão semelhante ao grupo controle, as demais concentrações contribuíram para a diminuição dessa resistência. A incorporação de 5% de nanopartículas de vitrocerâmica bioativa aumentou a rugosidade superficial dos CIVMRs estudados. / Bioactive materials are synthetic materials that have active surfaces that are capable to chemically bond to dental structures. There are some studies where particles of these materials were incorporated in Glass-ionomer cements (GIC) and Resin-modified glass-ionomer cements (RMGIC) trying to achieve bioactivity and dental remineralization. The aim of this study was to evaluate the effects of the incorporation of bioactive glass-ceramics nanoparticles on the compressive strength and roughness of RMGIC. Fuji II LC and Vitremer were considered the control groups. Experimental materials were made adding 2, 5 and 10% (weight) of Biosilicate into these RMGIC. Six specimens of each material were made to be tested on compressive strength performed with a universal testing machine (Emic) at a crosshead speed of 1.0 mm / min, after they were stored in distilled water for 24 hour at 37°C. To roughness analysis, two specimens of each material were made and stored in distilled water for 7 days and their surfaces were analyzed with a Atomic Force Microscope. Data of compressive strength and roughness were statistically analyzed by ANOVA and Tukey test for multiple comparisons. Only the RMGICs with 2% of bioactive glass-ceramic nanoparticles obtained compressive strength similar to the control RMGICs, the other concentrations decreased their compressive strength values. The incorporation of 5% of bioactive glass-ceramic nanoparticles increased the roughness of the RMGICs.

The glass-ceramics containing apatite [Ca10(PO4)6(O,F2)] and wollastonite [CaO&amp / #8226 / SiO2] crystals as the predominant crystalline phases, (A-W glass-ceramics) were produced through controlled crystallization of the glasses in the MgO-CaO-SiO2-P2O5-F system. Phases formed in the crystallized counterpart of the glasses were identified by powder X-ray diffraction (XRD) analysis. The crystal morphology of the resultant glass-ceramics was examined using a scanning electron microscope (SEM). The crystallization kinetic parameters consisting of the activation energy for crystallization, (E), the Avrami parameter, (n), and frequency factor of the glass were determined with regard to small amount of TiO2 additions using non-isothermal differential thermal analysis (DTA). The values for E and n for apatite and wollastonite were 460 kJ/mol and 433 kJ/mol, and 3.1&plusmn / 0.1 and 1.5&plusmn / 0.1, respectively. When 4 wt% TiO2 was incorporated into the base glass, the values for E decreased to 408 and 320 kJ/mol for apatite and wollastonite, respectively / but the values for n increased from 3.1&plusmn / 0.1 to 3.3&plusmn / 0.1, and from 1.5&plusmn / 0.1 to 1.9&plusmn / 0.1 for apatite and wollastonite, respectively. TiO2 is an effective nucleating agent in this glass system for promoting the precipitation of both apatite and wollastonite crystals. Structure oriented changes in the indentation microhardness and tribological properties of the A-W glass-ceramics were evidenced. The microhardness at the free surface was 650&plusmn / 12 HV, but decreased with increasing depth distance from the free surface and attained 520&plusmn / 8 HV at a distance 0.5 mm below the free surface. The wear rate at the free surface was 0.7&plusmn / 0.05 &times / 10-4 mm3/Nm, but increased as the distance from the free surface increased and became 2.9&plusmn / 0.15 &times / 10-4 mm3/Nm at a distance 0.5 mm below the free surface. Tribological properties of the A-W glass-ceramics were compared with those of commercially available dental ceramics including IPS Empress 2&reg / , Cergo Pressable Ceramic&reg / , Cerco Ceram&reg / , Super porcelain EX-3&reg / , and bovine enamel. The wear rate, friction coefficient, and wear mechanisms of the A-W glass-ceramics were similar to currently used artificial dental materials.

Glassy Bi-Sr-Ca-Cu-O (BSCCO) precursors were prepared by different melt-quenching methods to investigate the melt properties of the BSCCO system before the crystallization investigations were started. In order to fabricate superconductors having high critical temperature and current density using the glass-ceramic route, it is necessary to clarify the total chemical composition of the quenched precursor. For the first time the total chemical composition of such precursors has been directly measured by the direct element analysis and correlated with the taken process steps. The results from the element analysis demonstrated significant chemical deviations in composition with respect to the starting composition and strong chemical inhomogeneities of the sample. The crystallization dependence was investigated on numerous parameters for the BSCCO system such as initial composition, atmosphere, Sr:Ca ratio, average valence state of the glassy precursor and the dependence of Bi substitution by Pb. It could be demonstrated that the copper valence dependence on the phase formation and crystallization of the high-TC phase plays an important role in the BSCCO system. It could also be demonstrated that the smallest chemical deviation could strongly influence the phase formation in dependence of melt temperature, influencing not only the average copper valence but also the different cation concentrations. From literature there are barely any results or conclusions drawn of the chemical composition of the quenched glassy precursors that however is critical to control the crystallization behavior and understanding the influences on the superconductive properties as demonstrated in this work. / Amorphe Precursoren von dem Bi-Sr-Ca-Cu-O (BSCCO) System wurden durch verschiedene Methoden des Rascherstarrens hergestellt, um deren Schmelzeigenschaften vor dem Prozess der Kristallisation zu untersuchen. Um Supraleiter mit hoher kritischer Temperatur und Stromdichte mit der glas-keramischen Route anfertigen zu können, ist es notwendig, die chemische Zusammensetzung dieser amorphen Precursoren zu kennen. Erstmalig wurde die totale chemische Zusammensetzung der Precursoren durch die direkte Elementanalytik im Zusammenhang mit den jeweiligen Prozessschritten gemessen. Bei den Probeuntersuchungen zeigten sich wesentliche chemische Abweichungen von der nominalen Zusammensetzung und starke chemische Inhomogenitäten. In Abhängigkeit der Parameter nominale Zusammensetzung, Atmosphäre, Sr:Ca-Verhältnis, mittlerer Kupfervalenzzustand (für die Percursoren) und Bi Substitution mit Pb, ist die Kristallation ermittelt wurden. Es konnte gezeigt werden, dass der Kupfervalenzzustand eine wichtige Rolle in dem BSCCO System bei der Kristallisation von der Hoch-TC Phase spielt. Es hat sich auch herausgestellt, dass die kleinste chemische Abweichung stark die Phasenbildung beeinflussen kann. Diese Abweichung ist abhängig von der Schmelztemperatur, welche nicht nur den Kupfervalenzzustand sondern auch die Kationenkonzentrationen beeinflusst. In der Literatur finden sich wenig Veröffentlichungen oder Schlussfolgerungen zu dieser Thematik obwohl es die Kristallisationseigenschaften der Precursoren stark beeinflussen wird, wie es durch die vorliegende Arbeit bestätigt wurde.

Made available in DSpace on 2016-12-08T17:19:22Z (GMT). No. of bitstreams: 1 Resumo - Elise Polli.pdf: 19187 bytes, checksum: e7f2882716d14778996d1b91cbfee632 (MD5) Previous issue date: 2014-02-07 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The foundry is the fastest way to obtain metals pieces through the casting of liquid metal in green sand moulds. The main components of foundry sands are natural sand, bentonite and carbonaceous additive. During the foundry process, the components lose their mixture characteristics, in addition to the decrease in volume, becoming necessary the discard part of the foundry sand, generating the wasted foundry sand (WFS). In Brazil are discarded approximately 2.76 millions of tons annually and this number has become an environmental concern due to the difficulty of dispose of the residue. In this context, several lines of research aimed at waste recycling has been studied, among than the use of WSF in glass and glassceramic. This work studies the incorporation of calcined WFS replacing the pure silica in percentages 25, 50, 75 e 100% in manufacturing of glass and glassceramic belonging to the quaternary system SiO2 CaO MgO Al2O3. The samples were melted in alumina crucibles at 1400 °C for one hour. After obtaining, the vitreous samples were underwent annealing at 750 °C for half hour and after, were submitted to spectroscopy ultraviolet visible and heat treatment to 900, 950 and 1000 °C to 90 minutes. After heat treatment, the samples were sent for X ray diffraction analysis, optical microscopy, and only the samples 50 and 100% were sent to scanning electron microscopy, in order to analyze the recrystallization of the samples. For the heat treatment to 900 ° C, the crystalline phases were found akermanita and diopside. As the temperature increased to 950 ° C, the first crystals gehlenita and melilite began to appear and crystallization increased with higher heat treatment temperature. The images obtained by both microscopies relate to the formation of a dendritic structure for the samples 25, 50 and 75% for the three heat treatments. For the heat treatment at 900 ° C crystallization is related to the diopside, and for treatment at 950 to 1000 ° C is related to melilita. For the sample was 100% on both the crystallization heat treatment. / A fundição é a maneira mais rápida para a obtenção de peças metálicas através do vazamento do metal líquido em moldes de areia verde. Os principais componentes das areias de fundição são as areias bases, bentonita e pó de carvão. Durante o processo de fundição, os componentes perdem as suas características de mistura, além da diminuição de volume, tornando- se necessário o descarte de parte dessa areia de fundição, gerando a areia descartada de fundição (ADF). No Brasil são descartadas aproximadamente 2,76 milhões ton de areia anualmente e esse número passou a ser uma preocupação ambiental devido à dificuldade do descarte do resíduo. Nesse âmbito, diversas linhas de pesquisa que visam à reciclagem do resíduo vêm sendo estudadas, entre elas a utilização de ADF em vidros e vitrocerâmicos. Este trabalho estuda a incorporação de ADF calcinada em substituição a sílica pura nas porcentagens de 25, 50, 75 e 100% na fabricação de vidros e vitrocerâmicos pertencentes ao sistema quaternário SiO2 Cão MgO Al2O3. As amostras foram fundidas em cadinhos de alumina a 1400 °C durante uma hora. Após da obtenção, as amostras vítreas foram recozidas a 750 °C por meia hora e após, foram submetidas a análise de espectroscopia de ultravioleta visível e também a tratamentos térmicos a 900, 950 e 1000 °C durante 90 min. Após os tratamentos térmicos todas as amostras foram encaminhadas para a análise de difração de raios X, microscopia óptica e apenas as amostras 50 e 100% de ADF foram encaminhadas para a microscopia eletrônica de varredura, a fim de analisar a recristalização das amostras. Para o tratamento térmico de 900 °C, as fases cristalinas encontradas foram a akermanita e o diopsídio. À medida que a temperatura aumentou aos 950 °C começaram a surgir os primeiros cristais de gehlenita e melilita e a cristalização aumentou com a maior temperatura de tratamento térmico. As imagens obtidas por ambas às microscopias relatam a formação de uma estrutura dendrítica para as amostras 25, 50 e 75% ADF para os três tratamentos térmicos. Para o tratamento térmico a 900 °C a cristalização está relacionada com o diopsídio, e para os tratamentos a 950 e 1000 °C está relacionada à melilita. Para a amostra 100% ADF houve a cristalização em ambos os tratamentos térmicos.

As vitrocerâmicas bioativas são materiais sintéticos capazes de aderirem quimicamente aos minerais presentes na estrutura dentária. A união dos cimentos de ionômero de vidro modificados por resina (CIVMRs) à dentina pode ser influenciada por diferentes tipos de tratamentos prévios à restauração. Os objetivos deste estudo foram: avaliar a resistência à compressão, a rugosidade e a adesão à dentina de CIVMRs (Fuji II LC e Vitremer) após a incorporação de partículas de vitrocerâmicas bioativas (Biosilicato®); foi ainda, avaliar a resistência à degradação da adesão à dentina dos CIVMRs, utilizando-se EDTA como pré-tratamento dentinário. Para o teste de resistência à compressão foram confeccionados cilindros sendo que 2, 5 e 10 % em peso de partículas de vitrocerâmica bioativa foram incorporadas aos pós dos CIVMRs, armazenados em água destilada por 24h a 37°C até a realização dos testes. A rugosidade dos cimentos experimentais (2% de vitrocerâmica bioativa) e controles foi avaliada por microscopia de força atômica (MFA) após armazenamento a seco e em 100 % de umidade por 1 mês. Para os testes de microtração, as superfícies das cavidades foram tratadas seguindo-se as instruções dos fabricantes ou utilizando-se EDTA. Os espécimes foram restaurados com os CIVMRs experimentais (2% de vitrocerâmica) e controles. Após as restaurações, os espécimes foram armazenados em água por 24h e 7d. Para o teste de degradação, os CIVMRs foram armazenados por 24h, 3m e imersos em 10% de hipoclorito de sódio por 5h. Os dentes foram seccionados em palitos e submetidos ao teste de microtração. ANOVA e teste de múltiplas comparações foram realizados (p<0,05). O modo de fratura foi classificado em adesivo, misto e coesivo e alguns espécimes foram analisados em microscopia eletrônica de varredura (MEV). Apenas os cimentos com 2% de vitrocerâmica bioativa obtiveram resistência a compressão semelhante ao grupo controle. Para os grupos controles, Fuji II LC apresentou-se mais rugoso que o Vitremer e o seu armazenamento à seco aumentou sua rugosidade. A condição de armazenamento, seco ou úmido, não afetou a rugosidade dos CIVMRs experimentais. A vitrocerâmica bioativa aumentou significantemente a adesão à dentina dos CIVMRs após armazenamento por 24h, exceto para o Fuji II LC quando EDTA foi utilizado. A aplicação de EDTA aumentou significantemente os valores de resistência adesiva. No estudo de degradação da união, valores de resistência adesiva significantemente maiores foram obtidos nos grupos onde a dentina foi pré-tratada com EDTA. A resistência adesiva do Fuji II LC à dentina não foi afetada pelos métodos de degradação utilizados. Valores de resistência adesiva significantemente menores foram observados para os espécimes restaurados com Vitremer após os dois métodos de degradação, exceto quando a dentina foi prétratada com EDTA. As falhas do tipo mistas foram prevalentes. Em conclusão, 2% de partículas de vitrocerâmica bioativa podem ser incluídas nos CIVMRs sem afetar suas propriedades mecânicas. A rugosidade dos CIVMRs experimentais não foi afetada pelo meio de armazenamento. A inclusão de vitrocerâmicas bioativas aumentou a resistência adesiva somente após armazenamento de 24h. A utilização de EDTA como pré-tratamento dentinário aumentou a resistência adesiva para todas as condições e preveniu a degradação da interface adesiva do Vitremer. / Bioactive glass-ceramics are synthetic materials capable of chemically bonding to dental structures. Adhesion of resin-modified glass-ionomer cements (RMGICs) to dentin may be influenced by different types of dentin pre-treatments. The objective of this study was to analyze the compressive strength, roughness and adhesion to dentin of RMGICs (Fuji II LC and Vitremer) after the incorporation of bioactive glassceramic particles (Biosilicate). Additionally, the durability of the RMGICs adhesion was analyzed after the application of EDTA as a pre-treatment of dentin. Cylinders of RMGICs with incorporation of 2, 5 and 10 % in weight of bioactive glass-ceramic particles were made for compressive strength, and stored in water for 24h at 37°C. Roughness of control and experimental (2% bioactive glass-ceramic) RMGICs was analyzed by atomic force microscopic (MFA) after storage in dry and humidity conditions for 1 month. For the microtensile test, the surfaces of the cavities were treated following the manufacturers instructions or by applying EDTA. The cavities were restored with control and experimental (2% bioactive glass-ceramic) RMGICs. After restorations, the specimens were stored in water for 24h and 7 days. For the degradation test, the RMGICs were stored for 24h, 3 months or immersed in 10% NaOCl for 5h. Teeth were sectioned in beams and submitted to microtensile test. ANOVA and multiple-comparisons tests were used (p<0.05). Mode of failure was classified in adhesive, mixed and cohesive, some specimens were analyzed by scanning electronic microscopic. Only the RMGICs with 2% of bioactive glassceramic obtained compressive strength similar to the control RMGICs. The storage conditions, dry or humidity, did not affect the roughness of experimental RMGICs. Bioactive glass-ceramic significantly increased the adhesion to dentin of RMGICs after storage for 24h, except for Fuji II LC when EDTA was applied. The application of EDTA significantly increased the values of bond strength. For the degradation study, high values of bond strength were also observed in groups where the dentin was pre-treated with EDTA. The bond strength of Fuji II LC to dentin was not affected by the degradation methods. Vitremer specimens presented significantly lower bond strength values after degradation methods, except when EDTA was applied. Mixed failures were the most prevalent in all groups. In conclusion, 2% of bioactive glassceramic particles may be included in RMGICs without affecting their mechanical properties. Roughness of experimental RMGICs was not affected by storage conditions. The incorporation of bioactive glass-ceramic increased the bond strength after storage for 24h. The application of EDTA as a pre-treatment of dentin increased the bond strength for all conditions studied and prevented the degradation of adhesive interface of Vitremer.

Ce travail porte sur le fractionnement des produits de fission et les actinides mineurs (simulées par des terres rares) dans une vitrocéramique borosilicate riche en molybdène contenant des cristallites de powellite (CaMoO4) étudié par techniques d'analyse élémentaire (LIBS, LA-ICP-MS, et l'EMPA). Il a été montré que des terres rares et Sr (émetteur bêta) sont incorporés préférentiellement dans la phase powellite, tandis que Al, Fe, Zr, Zn et Cs (sources bêta-decay) restent dans le verre. Le comportement de monocristaux orientés de powellite dopé en terres rares (simulants des actinides mineurs) sous irradiations est décrit et commenté afin de comprendre son comportement à long terme dans des conditions de stockage, en utilisant l'interférométrie optique, la spectroscopie Raman, TEM, et la spectroscopie de photoluminescence. On observe que l'irradiation induit un gonflement dans powellite augmentant avec la dose d'irradiation (de 0,012 à 1,2 dpa). La saturation est atteinte à 1,2 dpa. Une contrainte anisotrope associée à un changement du volume de la maille dans le monocristal de powellite a été mis en évidence et analysée par suivi de la position des raies v1 (Ag) et v3 (Eg) des modes Raman. Le désordre induit dans la structure de powellite irradiée est signé par l'augmentation de la largeur des raies Raman. La caractérisation fine par TEM indique que les dommages structuraux induits dans la powellite irradiée suivent l'évolution suivante de la structure cristalline : défauts ponctuels, dislocations, mosaïcité. Il a été confirmé à la fois par Raman et par TEM que la structure powellite résiste fortement à l'irradiation et n'atteint jamais l'état d'amorphisation dans la gamme dpa étudiée (0,012 à 5,0) / The fractionation of fission products and minor actinides (simulated by rare-earth elements) is studied in a Morich borosilicate glass-ceramic containing powellite (CaMoO4) crystallites, using elemental analysis techniques (LIBS, LA-ICPMS, and EMPA). For Mo-rich borosilicate glass-ceramic containing powellite crystallites, it was suggested that rare earth elements and Sr (beta-decay source) are prone to incorporate into the powellite phase, while Al, Fe, Zr et Cs (beta-decay source) and Zn remain in the glass matrix. The behavior of rare-earth (surrogates of radioactive minor actinides) doped powellite single crystal under irradiations figure out its longterm behavior in storage conditions, using optical interferometry, Raman spectroscopy, TEM, and luminescent spectroscopy. It is observed that the irradiation-induced swelling in powellite first increased with irradiation dose (0.012 to 1.2 dpa), then reached saturation after 1.2 dpa Anisotropic stress and lattice volume change induced by irradiation in powellite single crystal were found and analyzed by determining the peak position of V1 (Ag) et V3 (Eg) Raman modes. Structure disorder of irradiated powellite in medium-range order was represented by the Raman linewidth broadening. According to the TEM characterization, the structural damages of irradiated powellite followed an evolution of crystalline structure, point defects, dislocations, mosaicity. It was confirmed by both Raman and TEM that powellite resisted strongly and never reached amorphization within the studied dpa range (0.012 to 5.0)

No description available.

Glassy Bi-Sr-Ca-Cu-O (BSCCO) precursors were prepared by different melt-quenching methods to investigate the melt properties of the BSCCO system before the crystallization investigations were started. In order to fabricate superconductors having high critical temperature and current density using the glass-ceramic route, it is necessary to clarify the total chemical composition of the quenched precursor. For the first time the total chemical composition of such precursors has been directly measured by the direct element analysis and correlated with the taken process steps. The results from the element analysis demonstrated significant chemical deviations in composition with respect to the starting composition and strong chemical inhomogeneities of the sample. The crystallization dependence was investigated on numerous parameters for the BSCCO system such as initial composition, atmosphere, Sr:Ca ratio, average valence state of the glassy precursor and the dependence of Bi substitution by Pb. It could be demonstrated that the copper valence dependence on the phase formation and crystallization of the high-TC phase plays an important role in the BSCCO system. It could also be demonstrated that the smallest chemical deviation could strongly influence the phase formation in dependence of melt temperature, influencing not only the average copper valence but also the different cation concentrations. From literature there are barely any results or conclusions drawn of the chemical composition of the quenched glassy precursors that however is critical to control the crystallization behavior and understanding the influences on the superconductive properties as demonstrated in this work. / Amorphe Precursoren von dem Bi-Sr-Ca-Cu-O (BSCCO) System wurden durch verschiedene Methoden des Rascherstarrens hergestellt, um deren Schmelzeigenschaften vor dem Prozess der Kristallisation zu untersuchen. Um Supraleiter mit hoher kritischer Temperatur und Stromdichte mit der glas-keramischen Route anfertigen zu können, ist es notwendig, die chemische Zusammensetzung dieser amorphen Precursoren zu kennen. Erstmalig wurde die totale chemische Zusammensetzung der Precursoren durch die direkte Elementanalytik im Zusammenhang mit den jeweiligen Prozessschritten gemessen. Bei den Probeuntersuchungen zeigten sich wesentliche chemische Abweichungen von der nominalen Zusammensetzung und starke chemische Inhomogenitäten. In Abhängigkeit der Parameter nominale Zusammensetzung, Atmosphäre, Sr:Ca-Verhältnis, mittlerer Kupfervalenzzustand (für die Percursoren) und Bi Substitution mit Pb, ist die Kristallation ermittelt wurden. Es konnte gezeigt werden, dass der Kupfervalenzzustand eine wichtige Rolle in dem BSCCO System bei der Kristallisation von der Hoch-TC Phase spielt. Es hat sich auch herausgestellt, dass die kleinste chemische Abweichung stark die Phasenbildung beeinflussen kann. Diese Abweichung ist abhängig von der Schmelztemperatur, welche nicht nur den Kupfervalenzzustand sondern auch die Kationenkonzentrationen beeinflusst. In der Literatur finden sich wenig Veröffentlichungen oder Schlussfolgerungen zu dieser Thematik obwohl es die Kristallisationseigenschaften der Precursoren stark beeinflussen wird, wie es durch die vorliegende Arbeit bestätigt wurde.