[pt] Sintetizar Bi-2223 por decomposição peritética com posterior recristalização para estudar a cristalinidade e o efeito da fase líquida na formação de amorfo é de suma importância em pesquisas de fitas supercondutoras 1G (1ª geração) de Bi-2223. Tal rota de tratamento de fitas 1G de fase Bi-2223 já foi demonstrada, mas ainda há desafios devido à sua estreita região de estabilidade, lenta formação e a volatilização de chumbo durante a decomposição. No presente trabalho, amostras de (Bi, Pb)-2223 com 6 porcento de fração de PbO (adicionados aos reagentes) foram aquecidas a temperaturas acima da decomposição peritética e resfriadas lentamente. Empregaram-se análises de DTA/TGA, MEV/EDS, DRX e Análise quantitativa (com uso do método de Rietveld, V(I) e R(T). Os resultados mostram que o balanço de fases e a microestrutura dependem da temperatura de decomposição para fita comercial e caseira e da fração de PbO somente para a fita caseira. Uma investigação sistemática por DRX foi realizada, a fim de elucidar tal processo. Foi observada uma recuperação parcial de Bi-2223 nas fitas estudadas e os resultados indicaram que a decomposição e a recristalização da fase Bi-2223, fase amorfa e fases secundárias geraram mudanças na microestrutura e nas propriedades elétricas da fita 1G seja monofilamentar ou multifilamentar. / [en] Synthesize Bi-2223 by peritectic decomposition with subsequent recrystallization to study the crystallinity and the effect of the liquid phase in the formation of amorphous is very important in research of superconducting tapes 1G Bi-2223. Such a route of treatment tapes 1G phase Bi-2223 has been demonstrated, but there are still challenges due to its narrow region of stability, and slow formation of lead volatilization during decomposition. In this work, samples of (Bi, Pb) -2223 with 6 percent PbO fraction (added to the reactants) were heated to temperatures above the peritectic decomposition and cooled slowly. Analyzes were employed DTA / TGA, SEM / EDS and DRX Quantitative analysis (using the Rietveld method, V (I) and R (T). Results show that the balance of phases and microstructure depend on the decomposition temperature for commercial and homemade ribbon and the fraction of PbO only homemade tape. a systematic investigation by DRX was performed in order to elucidate this process. was observed a partial recovery of Bi-2223 and studied the tapes results indicate that the decomposition and recrystallization of the phase Bi-2223 phase amorphous and secondary phases generate changes in microstructure and electrical properties of the tape 1G be monofilament or multifilament.

The diploma thesis is focused on the study of the mechanism of plasticization of polyhydroxyalkanoates (PHA) in vivo, focusing mainly on methods of isolation native PHA granules and physical and chemical methods of initiation their phase transitions. The literature search prepared in this work deals with this microbial polyester and further focuses on individual methods of isolating PHA from bacterial cells. The main task of the experimental work was to optimize the isolation process of native PHA granules, as well as to design and test processes that initiate the PHA crystallization in isolated granules, as well as analytical procedures to correctly detect this phase transition. Isolation of PHA granules from Cupriavidus necator was performed by enzymes, centrifugation several times and sonication of the cells. Fourier transform infrared spectroscopy (FTIR) and an enzymatic method in which amorphous PHA is selectively degraded by PHA-depolymerase with turbidimetric detection of its loss in dispersion was used to detect PHA crystallization. Techniques based on fluorescence staining of granules (fluorescence spectroscopy and flow cytometry) were used in a more detailed study of the mechanism of PHA plasticization in granules. The results of the analyzes confirmed, among other things, that the optimized procedure makes it possible to isolate granules in the amorphous state, which remain amorphous even after drying and are comparable to native granules in their basic physicochemical properties.

This master thesis deals with the direct synthesis of polymers from lactic acid. The theoretical part focuses on both natural and synthetic ways of production the lactic acid monomer, their advantages and properties. Furthermore, the theoretical part focuses on the synthesis of poly(lactic acid) (PLA) from lactide, and direct polycondensation from lactic acid discussing about influences of catalysts, co-catalysts as well as chain extenders. The experimental part focuses on the synthesis of PLA polymers and co-polymers wherein investigates suitable catalysts, reaction medium for azeotropic dehydration and co-catalyst influence on products. Thermal and analytical analysis of PLA polymers are mentioned at the end of the experimental part.

Les déchets plastiques s'accumulent depuis plusieurs décennies dans les océans où ils se fragmentent en particules appelés microplastiques lorsque leur taille est inférieure à 5 mm. Ces microplastiques sont retrouvés dans toutes les eaux du globe, dans les sédiments ainsi que dans de nombreux organismes marins. Le devenir physicochimique à long terme de ces particules et leur possible fragmentation en nanoplastiques sont complexes, encore peu documentés et nécessitent des études en laboratoire.Afin de comprendre les processus liés à la photodégradation et à la fragmentation des polymères dans l’environnement, mais également dans le but d’'appréhender l’évolution des fragments générés au cours de l’irradiation, un protocole de vieillissement accéléré en milieu abiotique a été mis en place sur des polymères modèles. Le suivi de l’oxydation et de la fragmentation des deux polymères étudiés,polyéthylène basse densité et polypropylène, a été mené à l’aide de techniques spectroscopiques (infrarouge, Raman), DSC, angles de contact, et microscopiques (lumière polarisée, MEB, AFM…).Ce travail a permis de mettre en évidence l’influence significative de l’environnement et de la morphologie initiale des polymères sur leurs cinétiques de vieillissement et leurs mécanismes de fissuration. Ainsi des distributions en nombres, tailles et formes de fragments très différentes ont été obtenues pour les deux polymères selon la présence d’eau. Enfin, après un long temps d’irradiation, des produits de dégradation ont pu être détectés mais la production significative de nanoplastiques n’a pas été démontrée. L'hypothèse d'une taille limite de fragmentation devrait être envisagée. / Plastic wastes have been accumulating for several decades in the oceans where they break up into particles called microplastics when their size is less than 5 mm. These microplastics are found in all earth’s waters, in sediments and in many marine organisms. Their long-term physico-chemical fate and their possible fragmentation into nanoplastics are complex, still poorly documented and require laboratory studies.In order to understand the processes related to photodegradation and fragmentation of polymers, but also in order to understand the evolution of these fragments during irradiation, an accelerated aging protocol in abiotic conditions has been set up. The oxidation and fragmentation of two model polymers, low density polyethylene and polypropylene, were monitored using spectroscopic techniques (InfraRed, Raman), DSC, contact angles and microscopic technics (light microscopy, polarized light, SEM, AFM ...).This work has demonstrated a significant influence of the environment and the initial morphology of the polymers on their kinetics of aging and cracking mechanisms. This lead to significantly different distributions in numbers, sizes and shapes of the generated fragments. Moreover, after a long time of irradiaiton, other degradation products could be detected but the significant production of nanoplastics has not been demonstrated. The possibility of a size limit below which the fragmentation rate of plastics would strongly decrease should be considered.

Process-induced Long-term Deformation Behavior of Injection Molded Semicrystalline Thermoplastics Injection molding is a very complex process because the polymer experiences a complex thermorheological history during molding that influences the molecular orientation, residual stresses, frozen-in free volume and crystallinity inside the part. These generally govern the final part properties. Therefore it is highly desirable to anticipate the effect of process parameters on the resulting microstructure and mechanical properties of the finished part in the long run. In the case of a semicrystalline thermoplastic part, the problem in understanding the deformation behavior arises from its two-phase structure and a tendency exists to concentrate primarily on the effect of the crystalline phase on the deformation behavior, while the contribution of the amorphous phase is less investigated. In this work, the influence of the processing parameters on the deformation behavior of injection molded semicrystalline thermoplastic parts, viz., syndiotactic Polystyrene (sPS) and Polybutylene terepthalate (PBT), has been monitored through creep. The resulting internal structures due to processing have been determined and the deformation behavior has been analyzed. It has been observed that only the rate of cooling shows a remarkable effect on the long-term viscoelastic behavior of an injection molded semicrystalline thermoplastic part as it influences not only the crystalline, but also the free volume fraction, whereas the different states of frozen-in orientations and pressure-induced densification have only a negligible effect. Besides, physical aging also plays an important role in the deformation behavior of the injection moldings which was manifested with the decrease in the tendency to creep. Therefore, it was suggested that the cooling rate during injection molding and the aging time can significantly affect the long-term deformation behavior of the injection molded semicrystalline thermoplastics. The results also showed that when no significant effect is observed in terms of short-term mechanical properties by changing the processing conditions, but while considering the long-term behavior they show a significant effect.

High molecular weight PBTTT-C₁₂ is blended with the pure trimer, BTTT-3, to enhance intergrain connectivity and charge transport. Analysis of the morphology and crystallinity of the blends shows that the polymer and oligomer are well-integrated, leading to high hole mobilities, greater than 0.1 cm² V⁻¹ s⁻¹, in films that contain as much as 83% oligomer.

No description available.

Ce travail s'est concentré sur la compréhension de l'influence de la formulation et plus spécifiquement de la silice précipitée sur la résistivité électrique de séparateurs en polyéthylène destinés à des batteries au plomb. Les séparateurs de batteries en polyéthylène sont composés de silice précipitée, de polyéthylène ultra haute masse molaire (UHMWPE) et d'huile organique. La première partie de ce travail a été d'élaborer à l'échelle du laboratoire, des membranes modèles en polyéthylène. La seconde a été de comprendre l'influence de certains facteurs sur les propriétés structurales et physicochimiques des membranes. Ces facteurs sont principalement la quantité d'huile, la quantité et le grade de silice précipitée, les conditions de température lors de la cristallisation de la membrane et le mode de mise en œuvre utilisé. Les influences des quantités d'huile et de silice sur la cristallisation du polyéthylène sont méticuleusement étudiées, montrant que l'huile aide à augmenter la cristallinité finale de l'UHMWPE et que la silice joue un rôle de réservoir d'huile. Il a également été mis en évidence que la quantité ainsi que le grade de silice influencent la quantité de porosité de la membrane mouillable par l'électrolyte. La présence de silice en surface des pores est responsable de la mouillabilité de la membrane. Un paramètre empirique a donc été proposé dans le but de pouvoir quantifier l'efficacité de l'état de dispersion/distribution de la silice précipitée dans la membrane. Pour terminer, pour une formulation et un même mode de mise en œuvre, il est possible de discriminer l'efficacité des grades de silice précipitée pour l'application séparateur de batterie / This work is devoted to understand the effect of the formulation and more specifically of the precipitated silica on the resistivity of the PE-separators. The PE-separators are designed for the lead-acid batteries. PE-separators are composed of precipitated silica, ultrahigh molecular weight polyethylene (UHMW-PE) and organic oil. The first part of this work was to elaborate PE-separator models at a laboratory scale. Then, the factors impacting the structural and physico-chemicals properties of PE-separators were investigated. These factors are mainly the amounts of oil, precipitated silica, the grade of the precipitated silica, the temperature conditions of crystallization and the device used to elaborate the membrane. The influence of the amounts of oil and precipitated silica on the crystallization of the polyethylene wasthoroughly described showing that the oil helps to increase the final crystallinity of UHMWPE and that the silica plays a role of oil reservoir. Moreover, it was shown that the amount and the grade of precipitated silica have an influence on the wettable part of the porosity of the PE-separators. The coating of the pores by the precipitated silica is responsible of the wettability of the membranes by the electrolyte. Thus, an empirical parameter has been proposed in order to quantify the efficiency of the dispersion and distribution of the precipitated silica in the membrane. The more the membranes are wettable by the electrolyte the more the resistivity of the membranes is decreased. To finish, for a same amount of components and a same method of processing, it is possible to discriminate the efficiency of each grade of precipitated silica for the battery separator application

Indiana University-Purdue University Indianapolis (IUPUI) / Osteogenesis imperfecta is a rare congenital disease commonly characterized by brittle bones caused by mutations in the genes encoding Type I collagen, the single most abundant protein produced by the body. The murine model (oim) exists as a natural mutation of this protein, converting its heterotrimeric structure of two Col1a1 molecules and a single Col1a2 molecule into homotrimers composed of only the former. This defect impacts bone mechanical integrity, greatly weakening their structure. Femurs from male wild type (WT), heterozygous (oim/+), and homozygous (oim/oim) mice, all at 12 weeks of age, were assessed using assays at multiple length scales with minimal sample processing to ensure a near-physiological state. Atomic force microscopy (AFM) demonstrated detectable differences in the organization of collagen at the nanometer scale that may partially attribute to alterations in material and structural behavior obtained through mechanical testing and reference point indentation (RPI). Changes in geometric and chemical structure through the use of µ-Computed Tomography and Raman spectroscopy respectively indicate a smaller, brittle phenotype caused by oim. Changes within the periodic D-spacing of collagen point towards a reduced mineral nucleation site, supported by reduced mineral crystallinity, resulting in altered material and structural behavior in oim/oim mice. Multi-scale analyses of this nature offer much in assessing how molecular changes can compound to create a degraded, brittle phenotype.

博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University