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Nouveaux matériaux graphite/sel pour le stockage d'énergie à haute température. Étude des propriétés de changement de phase.Lopez, Jérôme 18 July 2007 (has links) (PDF)
Ce travail est une contribution à l'étude de nouveaux matériaux composites graphite/sel pour le stockage de l'énergie thermique à haute température (>200°C), l'objectif étant d'analyser et de comprendre l'influence du graphite et de la microstructure des matériaux graphite/sel sur les propriétés de transition de phase des sels. Cette thèse a été effectuée dans le cadre de deux projets : DISTOR (Européen) et HTPSTOCK (Français). Les apports majeurs de ce travail sont triples : <br />1) Il apporte une base de données importante (propriétés de changement de phase solide-liquide) sur six sels et les composites correspondants grâce à l'analyse calorimétrique effectuée. <br />2) Des modélisations rigoureuses de la fusion de sels en milieu confiné dans plusieurs géométries ont été proposées pour comprendre pourquoi lors de la première fusion des composites mis en forme par compression, des problèmes de fuite de sel ont été observés. Ces modèles montrent que la morphologie de ces matériaux sont à l'origine de ces phénomènes : la matrice de graphite contraint l'expansion volumique du sel lors de la fusion : le sel fond sous pression ce qui aboutit à une fusion sur une large gamme de température et à une perte de densité énergétique. L'analyse de sensibilité aux divers paramètres (géométriques et physiques) montre que le module de rigidité de la matrice est le paramètre sur lequel il faut agir lors de l'élaboration des matériaux pour estomper ce phénomène. <br />3) Enfin ce travail propose une formulation thermodynamique des phénomènes de surface/interface et de présence d'impuretés dissoutes pouvant aboutir à un abaissement de la température de fusion. Il semble que les avancements de fusion observés (~5°C) soient essentiellement dus à la présence d'impuretés dissoutes (apportées par le graphite) dans le liquide, un effet Gibbs-Thomson pouvant aussi s'ajouter (~1°C, lié à la taille des amas de cristaux).
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Etude et modélisation des propriétés de systèmes réactifs thermodurcissables en cours de réticulation pour la simulation du procédé RTMLEROY, Eric 27 November 2000 (has links) (PDF)
L'objectif de la thèse est de développer des méthodologies d'étude et de caractérisation permettant de modéliser l'évolution du comportement de polymères thermodurcissables lors de leur mise en œuvre par le procédé de Moulage par Transfert de Résine (RTM).<br />La première partie donne une description globale de ce procédé et du savoir-faire actuel en matière de modélisation. Elle met en évidence la nécessité d'une modélisation précise des comportements cinétique et chimiorhéologique du polymère thermodurcissable utilisé.<br />Les travaux réalisés dans ces deux domaines sont ensuite présentés et illustrés par la caractérisation d'un système composite modèle dicyanate-ester / fibres de verre.<br />La deuxième partie concerne la modélisation des cinétiques de réticulation et a pour finalité de développer les méthodes de caractérisation par calorimétrie, ces dernières apparaissant comme une étape charnière entre les connaissances en chimie des thermodurcissables et la modélisation du procédé RTM.<br />Enfin, la dernière partie regroupe les travaux réalisés dans les domaines de la rhéologie et des écoulements. Ceux-ci concernent à la fois la caractérisation de la perméabilité des renforts, l'étude de la chimiorhéologie et le suivi in situ des propriétés rhéologiques au cours du procédé par spectrométrie diélectrique.
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Stabilité et Structure d'Agrégats Catanioniquesvautrin, claire 02 July 2004 (has links) (PDF)
Le système catanionique CTAOH - C13COOH - H2O étudié forme des colloïdes de charge contrôlée<br />lorsque les tensioactifs sont mis en solution. Le diagramme de phase établi ici présente des agrégats particuliers<br />(micelle, vésicule, disque, phase lamellaire). L'étude de la CMC a fait apparaître des interactions<br />fortes entre monomères : le coefficient d'interaction est de -10kT. Du point de vue microscopique, nous<br />avons montré par diffusion couplée WAXS et WANS que les chaînes alkyl s'organisent suivant un réseau<br />hexagonal et que les têtes ioniques conservent un ordre liquide. Par ailleurs, les liaisons hydrogène<br />participent à la cohésion du système, et les propriétés mécaniques de la membrane sont assez proches<br />de celles d'un phospholipide. Les mesures des compressibilités par propagation acoustique et cuve de<br />Langmuir nous ont permis d'estimer le module d'Young à 100MPa. L'analyse calorimétrique par DSC a<br />montré que la transition de fusion de chaînes dépend de la composition de l'échantillon.
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Evaluation et amélioration du comportement à long terme d'élastomères pour une application isolateur électriqueTomer, Namrata Singh 20 October 2006 (has links) (PDF)
Ce travail de thèse traite de l'étude du comportement à long terme de revêtements élastomères utilisés pour la protection de jonc central en époxy et fibres de verre pour l'isolateur électrique. Quatre formulations industrielles à base de polydimethylsiloxane (PDMS) ou d'Ethylène Propylène Diène Monomère (EPDM) sont étudiées. Nous comparons l'évolution des propriétés des différentes compositions afin de mettre en évidence l'influence des constituants et celle de la matrice polymère sur le vieillissement. La charge de trihydrate d'aluminium a été identifiée comme étant le point critique de la formulation en présence des vapeurs d'acide nitrique. Les formulations à base PDMS sont peu sensibles aux vieillissements usuels (thermique et photochimique). Aucune oxydation n'est détectée après 10 000 heures d'exposition. La formulation à base d'EPDM présente à la fois une oxydation classique d'élastomère diénique, et des réactions de réticulation au cours des vieillissements photochimique et thermique. La technique de DSC-thermoporosimétrie est largement utilisée pour mettre en évidence les réactions de réticulation. Elle permet de déterminer la taille et la distribution des mailles du réseau polymère. Elle constitue une nouvelle approche de la réticulation des élastomères. Suite à cette étude nous pourrons retenir le meilleur outil pour caractériser rapidement la période d'induction avant dégradation et modification d'une propriété. Une importante sur-réticulation, au cours des vieillissements photochimique et thermique est observée pour les formulations siloxanes et EPDM. Une étude plus fondamentale sur les polysiloxanes non réticulés, non chargés est également proposée. Elle permet de mieux appréhender le comportement en vieillissement des silicones par rapport aux réactions de réticulation en particulier et d'étudier les relations structure-propriétés. Les PDMS ne s'oxydent pas mais se dégradent en donnant lieu à des réactions de réticulation et de scissions de chaînes au cours des vieillissements photochimique, ou thermique. Ils ne réagissent pas sous vapeur acide nitrique. En revanche les polysiloxanes avec une chaîne carbonée pendante s'oxydent et donnent lieu a des réactions de réticulation et de scissions de chaînes au cours de vieillissements photochimique, et thermique et se dégradent sous vapeur acide nitrique. Enfin, nous avons testé des nouvelles formulations stabilisées en présence de vapeurs acide nitrique et en vieillissement photochimique.
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Phase Transformations in Solid Pharmaceutical Materials Studied by AFM, ESCA, DSC and SAXSMahlin, Denny January 2004 (has links)
<p>Mixing excipients is a common way to produce pharmaceutical materials with suitable properties for drug formulation. An understanding of the basic mechanisms involved in the formation and transformation of the structures of solid state mixtures is crucial if one is to be able to produce materials with the desired properties in a reliable way. </p><p>In the first part of the thesis, the atomic force microscopy (AFM) technique was used to visualise the re-crystallisation of spray-dried amorphous particles comprised of lactose and PVP. The transformation was quantified on a single particle level and analysed with a common kinetic model, the JMAK-equation. The way in which the PVP was incorporated into the particles and the impact this had on their physical stability on exposure to increasing levels of humidity was investigated. The amount and, to a certain extent, the molecular weight of the PVP affected the moisture induced crystallisation of the particles. The inhibition was further discussed in terms of nucleation and growth. </p><p>In the second part of the thesis, the formation of phases in solid dispersions of monoolein (MO) in PEGs was studied by the use of SAXS and DSC. Upon solidification of a melt, the components phase separated, resulting in a PEG-rich phase and an MO phase. MO was intercalated into the amorphous domains of the lamellar structure of PEG. A second MO phase appeared in the mixtures where the average molecular weight of PEG was 1500 and 4000 g/mol. It was hypothesised that this second phase was formed in conjunction with the expulsion of MO as the PEG unfolded. </p><p>This thesis describes the application of two relatively unexplored solid state techniques on two different solid mixtures of pharmaceutical interest and, in so doing, contributes to the knowledge of phase formation and transformations in the solid state.</p>
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Macromolecules at Interfaces / Makromolekyler på ytorLarsericsdotter, Helén January 2004 (has links)
<p>In this thesis, the structure and stability of globular proteins adsorbed onto nanometer-sized hydrophilic silica particles were investigated using differential scanning calorimetry (DSC), hydrogen/deuterium exchange (HDX), and mass spectrometry (MS). The adsorption process itself was characterized with fluorescence and absorption spectroscopy and surface plasmon resonance (SPR). The combination of these methods offered a unique insight into adsorption-induced changes within proteins related to their adsorption characteristics. DSC contributed with thermodynamic information on the overall structural stability within the protein population. HDX in combination with MS contributed information on the structure and stability of adsorbed proteins with focus on changes within the secondary structure elements. In order to increase the structural resolution in this part of the investigation, proteolysis was performed prior to the MS analyzing step. Knowledge on the protein adsorption process was utilized in a practical approach called ligand fishing. In this approach, SPR was used to monitor the chip-based affinity purification of a protein with MS used for protein identification.</p><p>Adsorption isotherms revealed that electrostatic interactions play an important role in the adsorption of proteins to hydrophilic surfaces. DSC investigation revealed that the thermal stability of proteins reduces with increasing electrostatic attraction between the protein and the surface and that this effect diminishes at higher surface coverage. The mass-increase due to exchange between protein hydrogen atoms and deuterium atoms in solution was investigated as a function of time. This gave insight into adsorption-induced changes in the structural stability of proteins. By combining DSC and HDX-MS, it was possible to differentiate between adsorption-induced changes in the secondary and tertiary structure. Additionally, if limited proteolysis was performed, the investigations gave insight into the orientation and protein segment specific changes in the stability of proteins adsorbed to silica surfaces. The adsorption of proteins to silica particles also provided the basis for a new experimental design that allows handling of minute amounts of proteins in a ligand fishing application, as used in the field of functional proteomics.</p>
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High-Capacity Cool Thermal Energy Storage for Peak Shaving - a Solution for Energy Challenges in the 21st centuryHe, Bo January 2004 (has links)
Due to climatic change, increasing thermal loads inbuildings and rising living standards, comfort cooling inbuildings is becoming increasingly important and the demand forcomfort cooling is expanding very quickly around the world. Theincreased cooling demand results in a peak in electrical powerdemand during the hottest summer hours. This peak presents newchallenges and uncertainties to electricity utilities and theircustomers. Cool thermal storage systems have not only the potential tobecome one of the primary solutions to the electrical powerimbalance between production and demand, but also shift coolingenergy use to off-peak periods and avoid peak demand charges.It increases the possibilities of utilizing renewable energysources and waste heat for cooling generation. In addition, acool storage can actually increase the efficiency of combinedheat and power (CHP) generation provided that heat drivencooling is coupled to CHP. Then, the cool storage may avoidpeaks in the heat demand for cooling generation, and this meansthat the CHP can operate at design conditions in most oftime. Phase Change Materials (PCMs) used for cool storage hasobtained considerable attention, since they can be designed tomelt and freeze at a selected temperature and have shown apromising ability to reduce the size of storage systemscompared with a sensible heat storage system because they usethe latent heat of the storage medium for thermal energystorage. The goal of this thesis is to define suitable PCM candidatesfor comfort cooling storage. The thesis work combines differentmethods to determine the thermophysical properties oftetradecane, hexadecane and their binary mixtures, anddemonstrates the potential of using these materials as PCM forcomfort cooling storage. The phase equilibrium of the binarysystem has been studied theoretically as well asexperimentally, resulting in the derivation of the phasediagram. With knowledge of the liquid-solid phase equilibriumcharacteristics and the phase diagram, an improvedunderstanding is provided for the interrelationships involvedin the phase change of the studied materials. It has beenindicated that except for the minimum-melting point mixture,all mixtures melt and freeze within a temperature range and notat a constant temperature, which is so far often assumed in PCMstorage design. In addition, the enthalpy change during thephase transition (heat of fusion) corresponds to the phasechange temperature range; thus, the storage density obtaineddepends on how large a part of the phase change temperaturerange is valid for a given application. Differential Scanning Calorimetery (DSC) is one frequentlyused method in the development of PCMs. In this thesis, it hasbeen found that varying results are obtained depending on theDSC settings throughout the measurements. When the DSC runs ata high heating/cooling rate it will lead to erroneousinformation. Also, the correct phase transition temperaturerange cannot be obtained simply from DSC measurement. Combiningphase equilibrium considerations with DSC measurements gives areliable design method that incorporates both the heat offusion and the phase change temperature range. The potential of PCM storage for peak shaving in differentcooling systems has been demonstrated. A Computer model hasbeen developed for rapid phase equilibrium calculation. The useof phase equilibrium data in the design of a cool storagesystem is presented as a general methodology. Keywords:Comfort cooling, peak shaving, PCM, coolthermal storage system, DSC, phase change temperature range,the heat of fusion, phase equilibrium, phase diagram. Language:English
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Phase Transformations in Solid Pharmaceutical Materials Studied by AFM, ESCA, DSC and SAXSMahlin, Denny January 2004 (has links)
Mixing excipients is a common way to produce pharmaceutical materials with suitable properties for drug formulation. An understanding of the basic mechanisms involved in the formation and transformation of the structures of solid state mixtures is crucial if one is to be able to produce materials with the desired properties in a reliable way. In the first part of the thesis, the atomic force microscopy (AFM) technique was used to visualise the re-crystallisation of spray-dried amorphous particles comprised of lactose and PVP. The transformation was quantified on a single particle level and analysed with a common kinetic model, the JMAK-equation. The way in which the PVP was incorporated into the particles and the impact this had on their physical stability on exposure to increasing levels of humidity was investigated. The amount and, to a certain extent, the molecular weight of the PVP affected the moisture induced crystallisation of the particles. The inhibition was further discussed in terms of nucleation and growth. In the second part of the thesis, the formation of phases in solid dispersions of monoolein (MO) in PEGs was studied by the use of SAXS and DSC. Upon solidification of a melt, the components phase separated, resulting in a PEG-rich phase and an MO phase. MO was intercalated into the amorphous domains of the lamellar structure of PEG. A second MO phase appeared in the mixtures where the average molecular weight of PEG was 1500 and 4000 g/mol. It was hypothesised that this second phase was formed in conjunction with the expulsion of MO as the PEG unfolded. This thesis describes the application of two relatively unexplored solid state techniques on two different solid mixtures of pharmaceutical interest and, in so doing, contributes to the knowledge of phase formation and transformations in the solid state.
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Macromolecules at Interfaces / Makromolekyler på ytorLarsericsdotter, Helén January 2004 (has links)
In this thesis, the structure and stability of globular proteins adsorbed onto nanometer-sized hydrophilic silica particles were investigated using differential scanning calorimetry (DSC), hydrogen/deuterium exchange (HDX), and mass spectrometry (MS). The adsorption process itself was characterized with fluorescence and absorption spectroscopy and surface plasmon resonance (SPR). The combination of these methods offered a unique insight into adsorption-induced changes within proteins related to their adsorption characteristics. DSC contributed with thermodynamic information on the overall structural stability within the protein population. HDX in combination with MS contributed information on the structure and stability of adsorbed proteins with focus on changes within the secondary structure elements. In order to increase the structural resolution in this part of the investigation, proteolysis was performed prior to the MS analyzing step. Knowledge on the protein adsorption process was utilized in a practical approach called ligand fishing. In this approach, SPR was used to monitor the chip-based affinity purification of a protein with MS used for protein identification. Adsorption isotherms revealed that electrostatic interactions play an important role in the adsorption of proteins to hydrophilic surfaces. DSC investigation revealed that the thermal stability of proteins reduces with increasing electrostatic attraction between the protein and the surface and that this effect diminishes at higher surface coverage. The mass-increase due to exchange between protein hydrogen atoms and deuterium atoms in solution was investigated as a function of time. This gave insight into adsorption-induced changes in the structural stability of proteins. By combining DSC and HDX-MS, it was possible to differentiate between adsorption-induced changes in the secondary and tertiary structure. Additionally, if limited proteolysis was performed, the investigations gave insight into the orientation and protein segment specific changes in the stability of proteins adsorbed to silica surfaces. The adsorption of proteins to silica particles also provided the basis for a new experimental design that allows handling of minute amounts of proteins in a ligand fishing application, as used in the field of functional proteomics.
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Biological membrane interfaces involved in diseases : a biophysical studyLindström, Fredrick January 2006 (has links)
Interactions between peptides and biological lipid membranes play a crucial role in many cellular processes such as in the mechanism behind Alzheimer’s disease where amyloid-beta peptide (Abeta)is thought to be a key component. The initial step of binding between a surface active peptide and its target membrane or membrane receptor can involve a non specific electrostatic association where positively charged amino acid residues and a negatively charged membrane surface interact. Here, the use of high resolution MAS NMR provides a highly sensitive and non perturbing way of studying the electrostatic potential present at lipid membrane surfaces and the changes resulting from the association of peptides. The interaction between pharmacologically relevant peptides and lipid membranes can also involve incorporation of the peptide into the membrane core and by complementing the NMR approach with differential scanning calorimetry (DSC) the hydrophobic incorporation can be studied in a non invasive way. By using 14N MAS NMR on biological lipid systems for the first time, in addition to 31P, 2H NMR and differential scanning calorimetry (DSC), gives a full picture of the changes all along the phospholipid following interactions at the membrane interface region. Being able to monitor the full length of the phospholipid enables us to differentiate between interactions related to either membrane surface association or hydrophobic core incorporation. This approach was used to establish that the interaction between nociceptin and negatively charged lipid membranes is electrostatic and hence that nociceptin can initially associate with a membrane surface before binding to its receptor. Also, it was found that Abeta can interact with phospholipid membranes via two types of interactions with fundamentally adverse effects. The results reveal that Abeta can associate with the surface of a neuronal membrane promoting accelerated aggregation of the peptide leading to neuronal apoptotic cell death. Furthermore it is also shown that Abeta can anchor itself into the membrane and suppress the neurotoxic aggregation of Abeta.
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