Made available in DSpace on 2016-06-02T19:10:02Z (GMT). No. of bitstreams: 1 TeseCL.pdf: 10208729 bytes, checksum: c527b49760e4f73c81deddd8b9282627 (MD5) Previous issue date: 2004-08-12 / Universidade Federal de Minas Gerais / The influence of the injection molding parameters on the morphology and mechanical properties of poly(phenylene sulfide), PPS, and of a 80/20(%wt) blend of PPS/block copolymer styrene-ethylene-butylene-styrene ,SEBS, were evaluated. The injection molding conditions were defined through an experimental design. The lower and upper limits of each variable were set considering the material characteristics and the machine capacity. The software MOLDFLOW® was used to simulate the injection molding process, to define the cooling and holding times, to guarantee the part quality and to obtain the shear rate and bulk temperature profiles at the end of the filling step. For PPS, it was observed that the variables with highest influence on the gradient of crystallinity along the part thickness and on the mechanical properties were melt (Tinj) and mold (Tm) temperatures. For the PPS/SEBS blend, the flow rate (Q), mold temperature and holding pressure (Ph) were the variables with highest influence on the morphology. The aspect ratio of the SEBS particles, dispersed on the PPS matrix, was almost unaffected by the changes of the injection conditions; on the other hand, the mean particle size (caliper length along the major axis) and the value of the dispersion function represented qualitatively well the morphological variations observed for the blend. The artificial neural networks, built with experimental data and trained with the group cross validation method (GCV), predicted with good precision the morphology and the mechanical properties, starting from the injection molding processing conditions, as well as the mechanical properties starting from the morphological aspects. / A influência das variáveis de processamento da moldagem por injeção na morfologia e nas propriedades mecânicas foi avaliada para o poli(sulfeto de p-fenileno), PPS, e para a blenda de PPS com o copolímero em bloco de estireno-etileno-butileno-estireno, SEBS, na concentração em massa 80/20 (PPS/SEBS). A definição das condições de injeção foi feita através de planejamento de experimentos. Os limites inferiores e superiores de cada variável foram definidos levando em consideração as características do material e a capacidade da máquina injetora. O programa computacional MOLDFLOW® foi utilizado para a simulação do processo de injeção para a definição dos tempos de resfriamento e de empacotamento, para garantia da qualidade do moldado e para a obtenção dos perfis de taxa de cisalhamento e de temperatura da massa ao final da etapa de preenchimento. Foi verificado que, no caso do PPS, as variáveis de maior influência no gradiente de cristalinidade ao longo da espessura da peça e nas propriedades mecânicas foram as temperaturas da massa polimérica fundida (Tinj) e do molde (Tm). No caso da blenda PPS/SEBS, a velocidade de injeção ou vazão (Q), a temperatura do molde e a pressão de empacotamento (Ph) foram as variáveis de maior influência na morfologia. A razão de aspecto das partículas de SEBS, dispersas na matriz de PPS, praticamente não foi alterada com a variação das condições de injeção, ao contrário do tamanho médio de partícula e do valor da função dispersão, que pôde representar qualitativamente bem as alterações morfológicas observadas na blenda. As redes neurais construídas a partir dos dados experimentais e treinadas com o método de validação cruzada em grupo (VCG) puderam predizer com boa precisão a morfologia e as propriedades mecânicas do moldado a partir das condições de processamento, bem como as propriedades mecânicas a partir da morfologia. Palavras-chave: morfologia, cristalinidade, blenda, propriedades mecânicas, moldagem por injeção, A influência das variáveis de processamento da moldagem por injeção na morfologia e nas propriedades mecânicas foi avaliada para o poli(sulfeto de p-fenileno), PPS, e para a blenda de PPS com o copolímero em bloco de estireno-etileno-butileno-estireno, SEBS, na concentração em massa 80/20 (PPS/SEBS). A definição das condições de injeção foi feita através de planejamento de experimentos. Os limites inferiores e superiores de cada variável foram definidos levando em consideração as características do material e a capacidade da máquina injetora. O programa computacional MOLDFLOW® foi utilizado para a simulação do processo de injeção para a definição dos tempos de resfriamento e de empacotamento, para garantia da qualidade do moldado e para a obtenção dos perfis de taxa de cisalhamento e de temperatura da massa ao final da etapa de preenchimento. Foi verificado que, no caso do PPS, as variáveis de maior influência no gradiente de cristalinidade ao longo da espessura da peça e nas propriedades mecânicas foram as temperaturas da massa polimérica fundida (Tinj) e do molde (Tm). No caso da blenda PPS/SEBS, a velocidade de injeção ou vazão (Q), a temperatura do molde e a pressão de empacotamento (Ph) foram as variáveis de maior influência na morfologia. A razão de aspecto das partículas de SEBS, dispersas na matriz de PPS, praticamente não foi alterada com a variação das condições de injeção, ao contrário do tamanho médio de partícula e do valor da função dispersão, que pôde representar qualitativamente bem as alterações morfológicas observadas na blenda. As redes neurais construídas a partir dos dados experimentais e treinadas com o método de validação cruzada em grupo (VCG) puderam predizer com boa precisão a morfologia e as propriedades mecânicas do moldado a partir das condições de processamento, bem como as propriedades mecânicas a partir da morfologia.

Les revêtements poudres UV suscitent un développement croissant en raison, entre autres, de leurs qualités et de leur respect de la législation sur la minimisation des émissions polluantes. Un nouveau revêtement poudre UV à base de (co)polyamide de faible masse molaire et porteur de fonctions réactives sous UV a été élaboré en vue d'une application sur des supports sensibles aux hautes températures. Nous avons donc synthétisé un copolyamide 6/11/12 alpha, oméga-insaturé présentant une température de fusion de 107°C et une masse molaire moyenne en nombre de 7250 g/mol. L'irradiation sous UV de ce copolyamide, en présence de 4 % en masse de benzophénone, a permis, par polymérisation des doubles liaisons allyliques et formation des liaisons covalentes au niveau des ponts amide, de compenser la perte de cristallinité en le réticulant. Le revêtement obtenu, bien que restant à optimiser, a montré globalement de meilleures propriétés que celles des matériaux références fournis par Arkema. / UV powder coatings are developed continuously because of their qualities and their respect for legislation on the minimization of polluting programs. A new UV powder coating (co)polyamide based of weak average molar mass and bearing UV-reactive functions has been worked out for high temperatures sensitive substrates application. We therfore synthesised an alpha,omega-insatured copolyamide 6/11/12 having a weak melting temperature of 107° C and a number-average molar mass of 7250 g/mol. Under UV radiation, and in presence of (-wt) 4% of benzophenone, polymerization of allylic double bonds of this copolyamide and formation of links at the level of amide functions allows to compensate the loss of crystallinity by crosslinking. The obtained coating, although remaining to optimise, showed properties on the whole better than those of reference materials provided by Arkema.

Philosophiae Doctor - PhD / This work investigated the synthesis of Al2O3-coated TiO2 nanotubes via the anodisation technique for application in DSCs. TiO2 nanotube arrays with an average length of 15 μm, diameter of 50 nm and wall thickness of 15 nm were synthesised via anodisation using an organic neutral electrolyte consisting of 2 M H2O + 0.15 M NH4F + ethylene glycol (EG) at an applied voltage of 60 V for 6 hours. In addition, scanning electron microscope (SEM) micrographs showed that anodisation at these conditions yields nanotubes with smooth walls and hexagonally shaped, closed bottoms. X-ray diffraction (XRD) patterns revealed that the as-anodised nanotubes were amorphous and as such were annealed at 450 °C for 2 hours in air at atmospheric pressure, which yielded crystalline anatase TiO2 nanotubes. Highresolution transmission electron microscope (TEM) images revealed that the nanotube walls comprised of individual nano-sized TiO2 crystallites. Photoluminescence (PL) spectroscopy showed that the optical properties, especially the bandgap of the TiO2 nanotubes are dependent on the crystallinity, which in turn was dependent on the structural characteristics, such as the wall thickness, diameter and length. The PL measurements were supplemented by Raman spectra, which revealed an increased in the quantum confinement of the optical phonon modes of the nanotubes synthesised at low anodisation voltages, consequently yielding a larger bandgap The annealed nanotubes were then coated with a thin layer of alumina (Al2O3) using a simple sol-gel dip coating method, effectively used to coat films of nanoparticles. Atomic force microscopy (AFM) showed that the average nanotube diameter increased post sol-gel deposition, which suggests that the nanotubes are coated with a layer of Al2O3. This was confirmed with HR-TEM, in conjunction with selected area electron diffraction (SAED) and XRD analyses, which showed the coating of the nanotube walls with a thin layer of amorphous Al2O3 with a thickness between 4 and 7 nm. Ultraviolet-visible (UVvis) absorbance spectra showed that the dye-adsorption ability of the nanotubes are enhanced by the Al2O3 coating and hence is a viable material for solar cell application. Upon application in the DSC, it was found by means of photo-current density – voltage (I – V) measurements that a DSC fabricated with a 15 μm thick layer of bare TiO2 nanotubes has a photon-to-light conversion efficiency of 4.56%, which increased to 4.88% after coating the nanotubes with a layer of alumina. However, these devices had poorer conversion efficiencies than bare and Al2O3-coated TiO2 nanoparticle based DSCs, which boasted with efficiencies of 6.54 and 7.26%, respectively. The low efficiencies of the TiO2 nanotube based DSCs are ascribed to the low surface area of the layer of nanotubes, which yielded low photocurrent densities. Electrochemical impedance spectroscopy (EIS) showed that the electron lifetime in the alumina coated nanotubes are almost 20 times greater than in a bare layer of nanoparticles. In addition, it was also found that the charge transfer resistance at the interface of the TiO2/dye/electrolyte is the lowest for an Al2O3-coated TiO2 layer.

Les isolateurs diélectriques utilisés dans les disjoncteurs haute tension développés par Areva, sont fabriqués à partir du PET (polyéthylène téréphtalate). Ce polymère semi-cristallin a remplacé, depuis quelques années, les résines époxy. Il a été choisi pour ses propriétés mécaniques et diélectriques, mais surtout pour sa recyclabilité. Le souci dans cette application, concerne l’évolution dans le temps de ses caractéristiques sachant les contraintes d’application. En effet, dans les conditions de travail, les isolateurs maintiennent des conducteurs électriques. Les pertes thermiques affectent certaines zones pouvant atteindre, voire dépasser, la température de transition vitreuse du matériau [70-80°C]. Par conséquence, les pièces isolatrices subissent un phénomène de vieillissement qui nécessite un suivi dans le temps afin d’étudier l’évolution de leur caractéristiques Dans ce contexte, nous avons étudié le vieillissement thermique du PET. Ainsi des échantillons ont été mis dans des étuves sous vide, chacune réglée à une température : 60, 80, 115 et 125°C pendant différentes durées (jusqu’à 12 mois de vieillissement), puis retirés et testés au fur et à mesure du vieillissement. Différentes techniques ont été employées pour analyser les propriétés du semi-cristallin en question, i.e. l’étude calorimétrique différentielle (DSC), les diffractions aux rayons X aux grands et petits angles (WAXS/SAXS). L’analyse thermomécanique (DMA) et finalement les essais de traction.Les résultats de DSC révèlent une augmentation du taux de cristallinité. Les analyses thermomécaniques ont montré une faible augmentation du module de Young qui pourrait être le résultat d’une évolution de la cristallisation. Les températures de fusion sont restées quasiment stables, par contre une augmentation des températures de transition vitreuse a été remarquée. Les analyses des spectres de diffraction aux rayons X aux grands angles, ont confirmé la croissance du taux de cristallinité. En outre les longues périodes calculées, diminuent. Nous avons ainsi vérifié l’apparition de cristallites dans phase amorphe. Par ailleurs un comportement de fragilité continue en fonction du temps et de la température du vieillissement, a été constaté. Les observations au MEB ont révélé la présence d’une importante quantité de particules supposées être des agents nucléants (talc, SiO2, MgO…) / For insulating application, AREVA has chosen PET (polyethylene terephthalate) to substitute the epoxy resin as material for insulators in High Voltage Gas Insulated Substation. The main problem of this application is the fact that in operating conditions, the temperature of the PET plates would reach even exceed its glass transition [70°C-80°C]. The material undergoes aging phenomena which affect the temperature-dependent properties. The current investigation aims at observing and analyzing the gradual evolution of the mechanical, morphological and dielectric properties during thermal aging. To reach this goal, semi crystalline PET samples have been aged under vacuum at different temperatures i.e. 60°C, 80°C, 115°C and 125°C for various periods of time (until 12 months). The characterizations have been performed using several techniques: Differential scanning calorimetric (DSC), wide and small angle X-ray scattering (WAXS/SAXS), thermo-mechanical analysis (DMA), tensile test and morphological observation.The DSC measurements show that the crystallinity ratio increases with temperature and time of aging. The glass transition has increased. However no significant changes have been seen on the melting temperature. The DMA results agree with the DSC measurement in so far as it has revealed an expected increase of the Young modulus for all the samples studied. Significant differences have been observed using X-ray scattering: while the crystallinity ratio did increase, the long period has decreased specially for the case of aging at 115 and 125°C. The DMA measurements showed an almost stable glass transition around 80°C but an increase for samples aged at 125°C. When the samples have been subjected to the tensile test, a significant brittleness rise has been noticed. In addition, the SEM has revealed the presence of important amount of nucleant agent (talc, SiO2, MgO …)

Afin d'étudier la granulo- et la morpho-dépendance des propriétés d'énergies de surface de solides divisés, plusieurs lots de TiO2 anatase ont été synthétisés. Une série de matériaux parfaitement définis avec des morphologies allant de sphéroïdale à facettée, dans des gammes de tailles allant de 4 à 20 nm a été obtenue grâce aux modifications de conditions de pH et la présence d'acides organiques. La combinaison de différentes molécules sonde a permis de déterminer l'hétérogénéité énergétique superficielle de ces matériaux, aux interfaces solide/gaz et solide/liquide. La volumétrie de quasi-équilibre à basse pression (N2/Ar) couplée à la méthode de modélisation DIS et la microcalorimétrie à écoulement de gaz (NH3) ont mis en évidence les contributions des différentes faces cristallographiques et les effets de la cristallinité. Ces mêmes propriétés ont été analysées grâce à la titration potentiométrique en milieu aqueux (H+/OH-), couplée à la procédure TDIS (détermination du PCN et des distributions d'affinité de protons). Cette stratégie a permis une étude complète des propriétés superficielles énergétiques et géométriques des nanomatériaux. / In order to study the relationships between the particle size, the morphology and the surface energy properties of divided solids, several batches of TiO2 anatase were synthesized. A series of materials with morphologies ranging from spheroidal to well faceted, with particle sizes ranging from 4 to 20 nm were obtained by adjusting the pH conditions and the presence of organic acids. The surface heterogeneity of these materials, at solid/gas and solid/liquid interfaces, was studied by combining various molecular probes. The low pressure quasi-equilibrium adsorption volumetry (N2/Ar) coupled with the DIS modeling approach and the flow adsorption microcalorimetry (NH3) have evidenced the various contributions of crystallographic faces and the effect of the crystallinity. These properties have also been analyzed using potentiometric titration in aqueous medium (H+/OH-), coupled with the TDIS procedure, to determine PZC and proton affinity distributions. Such a strategy has led to a complete study of the energetic and geometric surface properties of these nanomaterials.

Cette thèse porte sur la relation entre le procédé de préparation et la structure des nanocomposites polypropylène/argile. Les échantillons ont été préparés au mélangeur interne dans un premier temps. Des observations au microscope électronique à balayage, complétées par des analyses en diffraction des rayons X ainsi que des mesures rhéologiques ont permis de caractériser l’état de dispersion de l’argile à différentes échelles au sein du matériau. Nous avons comparé trois argiles organophiles et montré que la compatibilité chimique entre l’argile et la matrice est un facteur primordial afin d’obtenir une bonne dispersion : la Cloisite 20 et la Dellite 67G montrent de bons états de dispersion à toutes les échelles au contraire de la Cloisite 30B. Nous avons ensuite mis en évidence l’influence de la vitesse de rotation ainsi que du temps de mélange sur l’état de dispersion de l’argile. Le seuil de percolation de l’argile dans le polypropylène a été déterminé. Le lien entre état de dispersion et cristallinité du polypropylène a également été étudié.Les échantillons ont ensuite été préparés par extrusion bivis. L’influence de la vitesse de rotation sur l’état de dispersion de l’argile a été mise en évidence, tout autant que la dégradation de la matrice aux plus fortes vitesses. L’évolution de l’état de dispersion le long de la vis a montré que si l’intercalation était rapidement atteinte sur la vis, l’exfoliation progressait linéairement avant de saturer sur les dernières zones. L’utilisation d’une température de régulation plus faible ou d’une matrice plus visqueuse n’ont pas permis d’améliorer l’état de dispersion de l’argile ni d’éviter la dégradation de la matrice. Enfin, l’utilisation du logiciel Ludovic© a permis de mieux appréhender les phénomènes thermomécaniques mis en jeu lors de l’extrusion, mais également d’optimiser le procédé. / This PhD focuses on the relationship between the preparation process and the structure of polypropylene/clay nanocomposites. First, the samples were prepared via an internal mixer. Scanning electron microscopy observations, completed by X-ray diffraction analysis and rheology measurements enabled us to characterize the clay dispersion state in the nanocomposite at different scales. Three organoclays were compared. It was shown that the chemical compatibility between the clay and the matrix was essential to ensure a good dispersion: Cloisite 20 and Dellite 67G showed good dispersion states at all scales, whereas Cloisite 30B did not. The influence of rotor speed and mixing time on the clay dispersion state was shown. The percolation threshold of the clay was determined. The link between dispersion state and crystallinity was also studied.The samples were then prepared via a twin-screw extruder. The influence of screw speed on the clay dispersion state was demonstrated, as well as the matrix degradation at high screw speed. The evolution of the dispersion state along the screw profile showed that intercalation was reached early in the screw profile, whereas exfoliation evolved linearly until the last mixing elements. A lower barrel temperature, as well as a more viscous matrix did not improve the clay dispersion state, and did not prevent the matrix degradation. Finally, the Ludovic© software allowed us to apprehend the thermomechanical phenomena involved during extrusion, but also to optimize the process.

Diploma thesis is summarizing sources and technology of PHB and its physical and chemical properties compared to other polymers. Thesis mentions usage and function of certain additives in PHB matrix and their impact on the final product. Practical part of the thesis is concerned with technological parameters and degradation of the PHB during extrusion. The thesis also observes behaviour of nucleating agents on crystallinity and crystallization properties of prepared compounds. Degradation was analyzed by MFI and colour difference against standard material, FTIR was not successfully used for the purpose of degradation. Crystallinity and crystallization behaviour was analysed by DSC and optical microscopy with heated operating table. Graphs were created from results of analysis and suitable usage of each nucleating agent was considered. Boron nitride was selected as the most suitable nucleating agent due to creating higher amount of smaller spherulites.

First artificial PHB granules were prepared under the terms of this thesis. The effect of used PHB solvent, ultrasonic bath temperature and time, solvent evaporation temperature and stabilizing agent nature was investigated using dynamic and electrophoretic light scattering. The most proper parameters were demonstrated at samples which were prepared by dissolving of PHB in chloroform, stabilizing with CTAB or lecithin, ultrasonifying at 35 °C followed by chloroform evaporating at 60 °C. Based on ATR-FTIR and Raman spectroscopy results, it was found out that PHB within the artificial granules were in crystalline form. The native PHB granules were isolated from Cupriavidus necator using either lysosyme, deoxyribonuclease and cell disruption by ultrasonification or digestion with alcalase, SDS and EDTA. Granules obtained by both isolation procedures were characterized by ATR-FTIR, Raman spectroscopy, light scattering techniques and DSC. According to the analyses results, the second mentioned procedure turned out to be more effective for obtaining the polymer in amorphous state. Furthermore, the polymer within granules recovered by using this procedure was thermally more stable. Last but not least, the native PHB granules samples were exposed to effect of acetone, lipase and sodium hypochlorite, assuming that polymer crystallinity should be increased by these chemicals in varying degrees. The highest degree of crystallinity was achieved after their treatment with lipase.

<div>Drug solubility is a persistent challenge in pharmaceutical product development. The objective of this research is to develop a formulation/processing strategy by means of a biodendrimeric solid dispersion (BDSD) platform, for increasing the solubility and dissolution rate of poorly water-soluble drugs. The BSDS platform combines a novel type of excipient, referred to as DLB, with a new application of the hot melt extrusion (HME) process.</div><div><br></div><div>Four model compounds – phenytoin (PHT), griseofulvin (GSF), ibuprofen (IBU), and loratadine (LOR) – were used to evaluate the solubilization effect of an octenylsuccinate-modified dendrimer-like biopolymer (OS-DLB). Shake-flask solubility measurements show that OS-DLB exerts significant solubilizing effect when present at less than 0.2% in water. The presence of hydrophobic C₈ chains on OS-DLB creates the type of favorable nonpolar microenvironment necessary for producing a parallel liquid phase equilibrium responsible for the increase in the total amount of drug dissolved in aqueous media. The higher the hydrophobicity of the drug, the higher the observed solubilization effect. Isothermal titration calorimetry studies show that drug solubilization by OS-DLB occurs by means of entropy-driven interactions. These studies also show that the intermolecular interaction between IBU and OS-DLB in solution exhibits very small energy change upon mixing but a stronger effect on entropy. In comparison, the intermolecular interaction between the less hydrophobic GSF and OS-DLB have significant effects on both enthalpy and entropy. Consequently, in terms of solubilization enhancement, it was found that the interaction between IBU and OS-DLB is entropy-driven (more favorable), while in the case of GSF, the interacting molecules are arranged to maximize enthalpic interaction.</div><div><br></div><div>Based on the solubility studies, a formulation/processing approach for enhancing the dissolution rate of the model drugs was developed. The biopolymer serving as both carrier and solubilizing agent, was coprocessed with poloxamer, functioning as a processing aid, using hot melt extrusion (HME) as an enabling technology. The result is a non-amorphous solid dispersion, exhibiting high and long-lasting supersaturation upon dissolution. A 3-factor, 3-level Box-Behnken design was implemented to define the optimal design space for the formulation/extrusion process. The results obtained from multivariate data analysis (partial least squares and principal components analysis) and response surface modeling suggest that drug release performance of IBU BDSDs is strongly influenced by the processing variables, while maximum release of GSF from the BDSDs can be attained through selective combination of functional excipients.<br></div>

Landlebende Pflanzen weisen differenzierte Gewebetypen auf, die neben der Aufrechterhaltung physiologischer Stoffwechselvorgänge äußeren mechanischen Belastungen standhalten müssen. Durch zweckmäßige Verteilung von Festigkeitsgeweben über den Sprossquerschnitt erlangen Pflanzen die notwendigen Versteifungen und Stabilitäten. Zur ortsaufgelösten Darstellung der unterschiedlichen Pflanzengewebe wird auf die Methode der Ramanspektroskopie zurückgegriffen. Dazu werden valide ramanspektroskopische Methoden entwickelt, die die Bestimmung der Cellulosekristallinität sowie die Quantifizierung des Lignins und der Hemicellulosen zum Ziel haben. Am Beispiel eines Pflanzenquerschnittes des Gemeinen Flachs Linum usitassimum werden die spektroskopischen Methoden angewandt und die Verteilung der unterschiedlichen Gewebetypen aufgezeigt und diskutiert.