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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Chemistry, mineralogy, and grain properties at Namib and High dunes, Bagnold dune field, Gale crater, Mars: A synthesis of Curiosity rover observations

Ehlmann, B. L., Edgett, K. S., Sutter, B., Achilles, C. N., Litvak, M. L., Lapotre, M. G. A., Sullivan, R., Fraeman, A. A., Arvidson, R. E., Blake, D. F., Bridges, N. T., Conrad, P. G., Cousin, A., Downs, R. T., Gabriel, T. S. J., Gellert, R., Hamilton, V. E., Hardgrove, C., Johnson, J. R., Kuhn, S., Mahaffy, P. R., Maurice, S., McHenry, M., Meslin, P.-Y., Ming, D. W., Minitti, M. E., Morookian, J. M., Morris, R. V., O'Connell-Cooper, C. D., Pinet, P. C., Rowland, S. K., Schröder, S., Siebach, K. L., Stein, N. T., Thompson, L. M., Vaniman, D. T., Vasavada, A. R., Wellington, D. F., Wiens, R. C., Yen, A. S. 12 1900 (has links)
The Mars Science Laboratory Curiosity rover performed coordinated measurements to examine the textures and compositions of aeolian sands in the active Bagnold dune field. The Bagnold sands are rounded to subrounded, very fine to medium sized (similar to 45-500m) with 6 distinct grain colors. In contrast to sands examined by Curiosity in a dust-covered, inactive bedform called Rocknest and soils at other landing sites, Bagnold sands are darker, less red, better sorted, have fewer silt-sized or smaller grains, and show no evidence for cohesion. Nevertheless, Bagnold mineralogy and Rocknest mineralogy are similar with plagioclase, olivine, and pyroxenes in similar proportions comprising >90% of crystalline phases, along with a substantial amorphous component (35%15%). Yet Bagnold and Rocknest bulk chemistry differ. Bagnold sands are Si enriched relative to other soils at Gale crater, and H2O, S, and Cl are lower relative to all previously measured Martian soils and most Gale crater rocks. Mg, Ni, Fe, and Mn are enriched in the coarse-sieved fraction of Bagnold sands, corroborated by visible/near-infrared spectra that suggest enrichment of olivine. Collectively, patterns in major element chemistry and volatile release data indicate two distinctive volatile reservoirs in Martian soils: (1) amorphous components in the sand-sized fraction (represented by Bagnold) that are Si-enriched, hydroxylated alteration products and/or H2O- or OH-bearing impact or volcanic glasses and (2) amorphous components in the fine fraction (<40m; represented by Rocknest and other bright soils) that are Fe, S, and Cl enriched with low Si and adsorbed and structural H2O. Plain Language Summary The Bagnold dune field is an active sand field with moving dunes and sits between the landing site of the Curiosity rover and rocks of interest higher up on Mount Sharp. When passing through the dune field, we used all of Curiosity's instruments to measure the chemistry, mineralogy, and grain size of sands in the Bagnold dune field in order to figure out where they came from, how the sands are transported, and what volatile materials (like water) lie within Martian soils. We found that the Bagnold sand dunes are very well sorted; no dusty materials are found within them, in stark contrast to soils seen previously with Curiosity and with rovers at other landing sites. We found that the coarser sand grains are enriched in the volcanic minerals olivine and pyroxene, confirming a prediction from orbit that wind-related activity seems to concentrate these phases. We also found that the dunes were much lower in water and other volatile elements like sulfur and chlorine versus all previous Mars soils. Using a combination of the rover's sieving system and chemical measurement tools, we figured out that two types of materials host water. In the first type of material, common in these sands, water is low in abundance (similar to 1%), very tightly bound to the grains, and is not released until temperatures >200 degrees C. In the second type of material, water is higher in abundance (2%) and more easily released by heating. Sieved water-bearing fine materials may be a useful resource for human explorers.
2

Transformation mechanisms to TiO and anatase from Ti thin film by anodizing and thermal annealing treatments

Chung, Yu-Lin 25 February 2012 (has links)
The phase transformation of anodized Ti film has been studied. Although X-ray diffraction detected only the amorphous TiO2 phase, transmission electron microscopy analysis showed that TiO nanocrystallites less than 10 nm in size were also present, which was further supported by x-ray photoelectron spectroscopy analysis. Anatase was found to appear gradually by annealing the as-anodized specimen in air at 500¡V550 oC, which was accompanied by a simultaneous disappearance of TiO nanocrystallites. In contrast, only rutile is formed by annealing the Ti film at the same temperatures. The results indicate that TiO can induce the formation of anatase, which is explained by the close similarity between their structures. (Chapter 1) Anatase phase of TiO2 has been shown to have very good biocompability. It was frequently observed on Ti surfaces after anodizing and thermal annealing treatments. In this report the mechanisms of the Ti to TiO and the TiO to anatase phase transitions in anodizing and annealing treatments of Ti have been studied by transmission electron microscopy. Ti thin films of two strong textures were first grown on the (001)NaCl substrates. In addition to amorphous TiO2, the anodization treatment caused the formation of TiO with an orientation relationship of (11-20)Ti // (220)TiO with Ti. The subsequent thermal annealing treatment caused the TiO to anatase transition with an orientation relationship of {200}TiO //{200}A. Pure anatase film was prepared by this method. (Chapter 2)
3

The composition of photocatalytic nanofibres through electrospinning

Farao, Al Cerillio January 2014 (has links)
>Magister Scientiae - MSc / The aim of this study was to enrich electrospun fibres with the active mineral phase TiO2 nanoparticles and then to evaluate how well the composite fibres performed in the photocatalytic degradation of methylene blue (MB). Electrospun hydrophobic PAN polymer fibres were used as support structures for the TiO2 nanoparticles. The photocatalytic activity of the TiO2 enriched fibres for dye degradation was evaluated and the effect of external stressors on the fibres was assessed. A comparison was also made to determine whether the TiO2 - photocatalyst catalyst should be coated on top of, or loaded inside the electrospun PAN fibres
4

Influence of the solvent sorption, additivation, and chemical modification on the molecular mobility dynamics of Polyamide 6,6 amorphous phase and its consequences on the tensile and impact strength properties of this polymer

Rios de Anda, Agustin, Rios de Anda, Agustin 05 December 2012 (has links) (PDF)
This work forms part of a project aimed to develop Polyamide 6,6(PA6,6)-based automotive fuel tanks. PA6,6 is a good candidate for technical applications since it possesses good thermo-mechanical properties compared to its weight. These formulations must exhibit good impermeable properties to classic gasoline, to biofuels (gasoline containing ethanol), and to water which is found in the atmosphere, while keeping good impact behavior.The scientific issues are the better understanding of PA6,6-solvent interactions in the case of a series of solvents having different sizes and polarities and also for a set of ternary mixtures composed of ethanol, toluene, and isooctane at various concentrations that model biofuels. The effect of these solvents on the glass transition temperature Tg (molecular mobility signature) was assessed. The effect of additivating or chemically-modifying PA6,6 on the impact and barrier properties of the polymer was studied.In this work, it was described how the nature of a solvent conditions its sorption and its plasticizing effect on PA6,6. It was also observed that the PA6,6 inter-chain interactions also condition the solvent sorption. Moreover, a thermodynamic approach describing the sorption and plasticizing effects of ternary mixtures in PA6,6 was considered and developed. It was also observed that PA6,6 mechanical properties depend or are related to the amorphous phase molecular mobility state.
5

Role and properties of the confined amorphous phase of polymers

Walczak, Malgorzata 21 November 2012 (has links) (PDF)
The aim of the thesis was to elucidate the effect of confinement of amorphous phase of apolymer above its glass transition temperature being in contact with another polymer in a rigid state.Confinement is unavoidably connected with surfaces enforcing confinement. It is very difficult to separate theeffect of confinement from the effect of interfaces because both effects arise parallel and coincide. Multilayeredfilms were chosen as the base material for the studies because they contain multifold number of confined layerand response from confinement and interfaces is multifold increased. Hoping that some of experimentaltechniques are more sensitive to interfaces while others to confinement we selected the following:microcalorimetry, SSNMR, direlectrical spectroscopy and dynamic shear rheology. We have searched for theinfluence of PS on dynamics of phenyl rings of PC for PC/PS film with ratio 70/30 in the temperature rangefrom 296 K to 393 K employing PILGRIM pulse sequence. .We show that above the glass transition temperatureof PS, the PC component became more flexible. It is at the first glance the effect of the interface because there isno significant confinement of thicker PC layers. Dielectric relaxation spectroscopy measurements in our studyclearly provide evidence for deviations from a simple 2-phase structure in multilayered films PC/PS that is worthto be analyzed more in the future. The dielectric response of the multilayer samples was also modeled andcompared with experimental results. We obtained again discrepancies between the simulated spectra and themeasured spectra for multilayer films. Knowing the exact composition and viscoelastic behaviour of eachcomponent, the theoretical viscoelastic behavior of composites has been predicted numerically. Then,rheological tests have been made, and confronted with numerical predictions, to detect the confinement effect.The upper limit of thickness beyond which PS in confined layers at rubbery state becomes stiffer than in bulk isabout 150/200 nm. It appeared that the shear modulus of the thinnest PS layers (10 nm) is nearly 2.5 times largerthan that for bulk PS sample. We can note that Tg of PS layers also begins to increase beyond this upper limit ofthickness.. None of the experiment could clearly deliver the information about the effect of confinement orinterface on the behavior of PS layers alone. The results obtained here point out that separation of the effects ofconfinement and interfaces remains very difficult.
6

Role and properties of the confined amorphous phase of polymers / Rôle et propriétés de la phase amorphe confinée des polymères

Walczak, Malgorzata 21 November 2012 (has links)
Le but de la thèse était de comprendre l’effet du confinement en épaisseur nanométrique sur lespropriétés d’un polymère amorphe au-dessus de sa transition vitreuse. Le confinement est inévitablement lié auxeffets de surface générant le confinement et on imagine immédiatement la difficulté qu’il y a à séparer les effetsde confinement et d’interfaces. Des films multi-nanocouches alternées de PS et PC obtenus par un procédéspécifique d’extrusion ont été choisis pour l’étude car l’effet du confinement comme celui des interfaces sontmultipliés et plus facilement détectable. En espérant que des techniques expérimentales soient plus sensibles àl’un des effets, nous avons plus particulièrement sélectionné la calorimétrie, la RMN, la spectroscopiediélectrique et la rhéologie dynamique en cisaillement. En RMN du solide, nous avons pu montrer que lamobilité des cycles phénoliques du PC augmente dans des films PC/PS en proportions respectives 70/30 pourdes températures supérieures à la température de transition vitreuse du PS. Cet effet peut être plutôt attribué àl’interface sachant que l’épaisseur des couches de PC est plus importante. Les essais de relaxation diélectriquemontre clairement un écart entre les réponses des films multi-couches et ceux pour les structures bi-composants.Ces résultats ont été confirmés par les écarts obtenus entre la réponse diélectrique simulée des films multi-couches obtenue à partir des réponses propres du PC et PS et celle mesurée. Ces résultats sont très prometteurs,mais demandent des études supplémentaires pour une analyse en profondeur. Connaissant le comportementrhéologique dynamique en cisaillement des matériaux PS et PC, celui des films multi-couches a été prédit. Ilapparait que le module élastique du PS augmente significativement lorsque l’épaisseur des couches de PSdescend en dessous d’un seuil plutôt élevée : 150 à 200 nm. En dessous de ce seuil, la transition vitreuse du PSmesurée par calorimétrie augmente également sensiblement. Aucune des modélisations proposées ne permetd’expliquer avec suffisamment de fidélité les résultats expérimentaux. / The aim of the thesis was to elucidate the effect of confinement of amorphous phase of apolymer above its glass transition temperature being in contact with another polymer in a rigid state.Confinement is unavoidably connected with surfaces enforcing confinement. It is very difficult to separate theeffect of confinement from the effect of interfaces because both effects arise parallel and coincide. Multilayeredfilms were chosen as the base material for the studies because they contain multifold number of confined layerand response from confinement and interfaces is multifold increased. Hoping that some of experimentaltechniques are more sensitive to interfaces while others to confinement we selected the following:microcalorimetry, SSNMR, direlectrical spectroscopy and dynamic shear rheology. We have searched for theinfluence of PS on dynamics of phenyl rings of PC for PC/PS film with ratio 70/30 in the temperature rangefrom 296 K to 393 K employing PILGRIM pulse sequence. .We show that above the glass transition temperatureof PS, the PC component became more flexible. It is at the first glance the effect of the interface because there isno significant confinement of thicker PC layers. Dielectric relaxation spectroscopy measurements in our studyclearly provide evidence for deviations from a simple 2-phase structure in multilayered films PC/PS that is worthto be analyzed more in the future. The dielectric response of the multilayer samples was also modeled andcompared with experimental results. We obtained again discrepancies between the simulated spectra and themeasured spectra for multilayer films. Knowing the exact composition and viscoelastic behaviour of eachcomponent, the theoretical viscoelastic behavior of composites has been predicted numerically. Then,rheological tests have been made, and confronted with numerical predictions, to detect the confinement effect.The upper limit of thickness beyond which PS in confined layers at rubbery state becomes stiffer than in bulk isabout 150/200 nm. It appeared that the shear modulus of the thinnest PS layers (10 nm) is nearly 2.5 times largerthan that for bulk PS sample. We can note that Tg of PS layers also begins to increase beyond this upper limit ofthickness.. None of the experiment could clearly deliver the information about the effect of confinement orinterface on the behavior of PS layers alone. The results obtained here point out that separation of the effects ofconfinement and interfaces remains very difficult.
7

Influence of the solvent sorption, additivation, and chemical modification on the molecular mobility dynamics of Polyamide 6,6 amorphous phase and its consequences on the tensile and impact strength properties of this polymer / Influence de la sorption des solvants, de l'additivation et de la modification chimique sur la mobilité moléculaire de la phase amorphe du Polyamide 6,6 et l'effet sur les propriétés en traction et en choc de ce polymère

Rios de Anda, Agustin 05 December 2012 (has links)
Ce travail s’inscrit dans le projet de développement des réservoirs essence pour voitures à partir des formulations Polyamide 6,6 (PA6,6). Le PA6,6 est un bon candidat pour des applications techniques car il possède des bonnes propriétés thermomécaniques rapportés à son poids. Ces formulations doivent montrer des bonnes propriétés barrière aux essences classiques, aux biofuels (essence contenant de l’éthanol) et aussi à l’eau qui est présente dans l’atmosphère, tout en ayant une bonne tenue aux chocs.Les enjeux scientifiques sont la meilleure compréhension des interactions entre le PA6,6 et des solvants purs de polarités et tailles différentes mais aussi des mélanges ternaires composés d’éthanol, toluène et isooctane à différentes concentrations et qui modélisent les biofuels. On veut aussi étudier l’effet de ces solvants sur la température de transition vitreuse Tg qui est la signature de la mobilité moléculaire de la phase amorphe. Ensuite, l’effet de l’additivation ou de l’ajout des co-monomères sur les propriétés barrière et mécaniques, notamment les propriétés choc, a été étudié. Dans ce travail nous avons pu décrire comment la nature d’un solvant conditionne sa sorption et son effet plastifiant dans le PA6,6. On a aussi observé que la nature et les interactions interchaînes de la matrice polymère conditionnent aussi la prise en solvants. De plus, une approche thermodynamique a été proposée pour étudier et comprendre la sorption de mélanges ternaires éthanol-toluène-isooctane et leur effet plastifiant dans le PA6,6. On a aussi montré que les propriétés mécaniques du PA6,6 dépendent ou sont liées à l’état de mobilité moléculaire de la phase amorphe de ce polymère. / This work forms part of a project aimed to develop Polyamide 6,6(PA6,6)-based automotive fuel tanks. PA6,6 is a good candidate for technical applications since it possesses good thermo-mechanical properties compared to its weight. These formulations must exhibit good impermeable properties to classic gasoline, to biofuels (gasoline containing ethanol), and to water which is found in the atmosphere, while keeping good impact behavior.The scientific issues are the better understanding of PA6,6-solvent interactions in the case of a series of solvents having different sizes and polarities and also for a set of ternary mixtures composed of ethanol, toluene, and isooctane at various concentrations that model biofuels. The effect of these solvents on the glass transition temperature Tg (molecular mobility signature) was assessed. The effect of additivating or chemically-modifying PA6,6 on the impact and barrier properties of the polymer was studied.In this work, it was described how the nature of a solvent conditions its sorption and its plasticizing effect on PA6,6. It was also observed that the PA6,6 inter-chain interactions also condition the solvent sorption. Moreover, a thermodynamic approach describing the sorption and plasticizing effects of ternary mixtures in PA6,6 was considered and developed. It was also observed that PA6,6 mechanical properties depend or are related to the amorphous phase molecular mobility state.
8

[en] EVOLUTION OF CRYSTALLINITY IN FIRST GENERATION (BI-PB)-2223 TAPES DURING PROCESSING WITH PERITECTIC DECOMPOSITION / [pt] EVOLUÇÃO DA CRISTALINIDADE EM FITAS 1G (BI - PB)-2223 SUBMETIDAS A PROCESSAMENTO COM DECOMPOSIÇÃO PERITÉTICA

28 October 2021 (has links)
[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.
9

Scenarios of Structure Stabilization and the Emergence of Transport Properties in AlMnCu - alloys

Gillani, Syed Sajid Ali 13 June 2016 (has links) (PDF)
Thin films of a ternary alloys between aluminum, manganese and copper (AlMnCu), prepared at low temperature, are reported in the present work. It is a study along two binary edges (Al100−xMnx and Al100−xCux (from literature)), the first almost along the entire range of concentrations, and two different cuts through the ternary system. The first cut begins at amorphous Al50Mn50 and adds Cu step by step (from literature). The second cut begins at amorphous Al60Cu40 and varies Al and Mn such that the Cu-content stays constant. There is a wide amorphous range, purely amorphous or with additional quasi-crystalline local features, and there are ranges where mixtures between amorphous and nano- or partially crystalline phases with a high content of lattice defects exist. The work exclusively deals with the development of the static structure and its thermal stability, as well as the development of its electronic transport properties. The ternary AlMnCu is a model for a deeper understanding of different scenarios of structure stabilization and their interaction, with consequences on the emergence of physical properties. The analysis focuses on self-organizing spherical-periodic, global resonance effects between two global subsystems of the alloy under consideration, the Fermi gas as one and the forming static structure of ions as the other. The global resonances are self organizing by i.e. an exchange of characteristic momenta and energy between the subsystems and trigger, besides a particular structure, particle-density anomalies and/or hybridization effects. The work shows strong evidence of a combined action of the particle-density anomalies with the effective valence of the atoms involved, in order to maintain the resonance condition under all circumstances. Whereas at high Al-content, additionally, local features of quasi-crystallinity arise, closer to pure Mn phase separations arise, causing mixtures of amorphous with nano-crystalline phases or crystals with a high content of lattice distortions. Reports on density anomalies, hybridization effects, and angular correlations, have been published quite often. In the present work, besides similar effects in a ternary system, first indications for phase separations and lattice defects as additional scenarios of stabilizing condensed matter are reported. The resonance, seen as spherical-periodic-order at short- and medium-range distances in real space, causes in reciprocal space a resonance maximum (analogous to a Bragg peak in crystals). Its location on the axis of the scattering vector is defined by the electron system and a pseudo-gap in the electronic density of states arise at the Fermi energy. The origin of the structural order and its thermal stability, the pseudo-gap at the Fermi energy, as well as the transport properties with its anomalies, all are attributed to the resonance. The spherically-periodic atomic order in an amorphous phase is analogous to the planar order in a crystal. The interatomic distances between the nearest neighboring shells at short- and medium range distances coincide with half the Fermi wavelength, also called Friedel-wavelength. / In der vorliegenden Arbeit wird über bei niedriger Temperatur hergestellte dünne Schichten aus einem ternären Legierungssystem zwischen Aluminium, Mangan und Kupfer (AlMnCu) berichtet, über zwei binäre Randlegierungen (Al100−xMnx und Al100−xCux (aus der Literatur)) und über zwei verschiedene Schnitte durch den ternären Bereich. Ein Schnitt durch den ternären Bereich beginnt bei amorphem Al50Mn50 und fügt schrittweise Cu zur Legierung (aus der Literatur). Der zweite Schnitt beginnt bei amorphem Al60Cu40 und fügt schrittweise Al und Mn so zu, dass der Cu-Gehalt konstant bleibt. Es gibt amorphe Bereiche, teilweise mit weiteren lokal quasi-kristallinen zusätzlichen Merkmalen, sowie Bereiche, in denen Mischungen aus amorphen mit nano oder teilkristallinen Phasen auftreten. Die Arbeit behandelt die Entwicklung der statischen Struktur und deren thermische Stabilität, sowie die Entwicklung elektronischer Transporteigenschaften. Das ternäre AlMnCu ist ein Modellsystem für ein tieferes Verständnis der verschiedenen Szenarien struktureller Stabilisierung und deren Interaktion, mit Auswirkungen auf ein tieferes Verständnis der mit der Struktur sich entwicklenden physikalischen Eigenschaften. Die Analyse konzentriert sich auf sich selbstorganisierende sphärisch-periodische, globale Resonanzeffekte zwischen zwei globalen Untersystemen des gewählten Materialsystems, der Fermi-Kugel als einem und der sich bildenden statischen Struktur der Ionen als dem anderen. Die globalen Resonanzen bilden sich u.a. durch einen Austausch von charakteristischen Impulsen und Energie zwischen den Untersystemen, die neben einer bestimmten Struktur zunächst auch Teilchendichteanomalien und/oder Hybridisierungseffekte erzeugen. Die vorliegende Arbeit zeigt dabei starke Anzeichen für eine kombinierte Wirkung dieser Effekte um die Resonanzbedingung unter allen Umständen beizubehalten. Bei hohen Al-Anteilen treten zusätzlich lokale Merkmale von quasi-Kristallinität, mit 5-facher Winkelkorrelation auf, um auch diesen Bereich strukturell zu stabilisieren. Bei hohen Mn-Anteilen sind es lokale Phasentrennung in amorphe und nano-kristalline Phasen oder hohe Anteile von Gitterdeffekten, die zusätzlich auftreten. Über Dichteanomalien, Hybridisierungseffekte und Winkelkorrelationen wurde in der Vergangenheit bereits mehrfach berichtet. In der vorliegenden Arbeit sind es, neben der modellhaften Behandlung dieser im ternären System, die Hinweise zu Phasentrennung und Gitterdeffekten als zusätzliche Szenarien zur Stabilisierung kondensierter Materie, über die erstmalig berichtet wird. Die auf dem Austausch von Impuls beruhende Resonanz, als sphärisch-periodische-Ordnung im nahen und mittleren Abstandsbereich des Ortsraumes zu sehen, verursacht im reziproken Raum ein Resonanzmaximum (analog zu einem Bragg-peak in kristallinen Systemen), dessen Lage auf der Achse der Streuvektoren vom Elektronensystem definiert wird, und eine Pseudolücke in der elektronischen Zustandsdichte der Elektronen an der Fermi-Energie. Letztendlich werden die Entstehung der strukturellen Ordnung selbst, ihre thermische Stabilität, als auch die Transporteigenschaften mit ihren Anomalien auf diese Pseudolücke und demzufolge auf die Resonanz zurückgeführt. Die sphärisch-periodische Ordnung der Atome in einer amorphen Phase ist analog zur planaren Ordnung in einem Kristall. Die Atomabstände zwischen den Nächstnachbarschalen im mittleren, aber auch nahen Abstandsbereich, stimmen über große Distanzen mit der halben Fermi-Wellenlänge überein, die man auch als Friedel-Wellenlänge bezeichnet.
10

Enhancement of the mechanical performance of semi-crystalline polyamides by tailoring the intermolecular interaction in the amorphous phase / Amélioration des performances mécaniques des polyamides semi-cristallins via la modification des interactions intermoléculaires de la phase amorphe

Hussein, Naji 09 December 2013 (has links)
L’utilisation du Polyamide 66 dans l’industrie automobile est en forte croissance car il offre à un bon compromis légèreté/propriétés mécaniques pour les applications de structure. A noter que pendant le service d’un véhicule, les pièces en polyamides sont souvent soumises à des sollicitations mécaniques très sévères aboutissant à une dégradation progressive du matériau. Récemment. E. Mourglia-Seignobos (thèse 2009), a montré que l’endommagement du polyamide 66 implique des mécanismes de cavitation et de microcraquelure dans la phase amorphe. Afin d'améliorer la durabilité de ce matériau, nous avons modifié la cohésion de sa phase amorphe via l'introduction de fonction phénolique à forte interactions intermoléculaires. Nous proposons une méthode de préparation de copolyamides bloc, à base du polyamide 66 et des noyaux phénoliques, par extrusion réactive. Nous montrons que, contrairement à la co-polycondensation classique, la structure cristalline de ces copolymères n’a pas été significativement modifiée, surtout à faible taux de PA6HIA. Les propriétés mécaniques et particulièrement la tenue en fatigue de ces copolymères dépassent largement celles du PA66. Les résultats obtenus mettent en évidence l’impact de la cohésion de la phase amorphe sur les propriétés ultimes de polymères semi-cristallins d’une part, et ouvrent la voie vers une meilleure augmentation de la durabilité de ces matériaux via le perfectionnement de leur phase cristalline d’autre part. / The use of polyamides in the automotive industry has grown significantly over the last years with the demand to reduce vehicle weight and also to increase fuel efficiency. Polyamide 66 having excellent chemical resistance, mechanical strength and toughness becomes the largest engineering thermoplastic used in automotive components. These latter are often submitted to repeated stress during service and their mechanical properties decline progressively until the failure. E. Mourglia-Seignobos (thesis 2009), pointed out that damage of polyamide 66 involves voids nucleation and growth in the amorphous phase. In order to improve the durability of this material, we tailored the cohesive energy of its amorphous phase by introducing phenolic moieties offering strong intermolecular H-bonds interactions. We proposed a preparation method of block copolyamides containing aliphatic polyamide 66 and phenolic groups (PA6HIA) by reactive extrusion. Microstructural characterizations pointed out that crystalline properties of resulting copolymers are not significantly altered at low PA6HIA content and that reactive extrusion is more appropriate than the in-situ copolymerization for the preparation of these materials. We showed that PA66/6HIA copolyamides having undisturbed crystalline features exhibit superior mechanical performance than the standard PA66, particularly longer lifetime under cyclic loading. The results of this work put in evidence the impact of the amorphous phase on the ultimate properties of semi-crystalline polymers in one hand, and open the way to a better increase of the durability of these materials by improving their crystalline features in another hand.

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