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Ces travaux de thèse portent sur la caractérisation thermique à l’échelle micrométrique d’un alliage à base de tellure lorsque ce matériau se trouve à l’état fondu, à haute température. À cette fin, une cellule innovante d’emprisonnement du matériau fondu a été conçue, et mise en place. Des structures de tellure au volume du microlitre ont été déposées sur un substrat de silicium et recouverts par la suite d’une couche de protection capable de les emprisonner dans une matrice : silice amorphe et alumine amorphe. La technique de la Radiométrie Photothermique Modulée a été utilisée pour étudier les propriétés thermiques de ce type de cellules et de ces constituants. La résistance thermique de dépôt a été ainsi estimée en utilisant un modèle d’étude des transferts de la chaleur utilisant le formalisme des impédances thermiques. Ceci nous a permit dans le cas de l’alumine amorphe de déterminer sa conductivité thermique et la résistance thermique de contact avec le substrat jusqu’à 600°C. Un long processus de conception, de mesure et d’analyse a été nécessaire afin d’obtenir une cellule capable de résister aux contraintes des hautes températures. À l’heure actuelle seule la caractérisation thermique jusqu’à 300°C a été possible à cause de l’instabilité mécanique de ce dépôt hétérogène. Ceci a été confirmé par des caractérisations physico-chimiques par techniques XRR, XRD et SEM. / This thesis is devoted to the thermal characterization of molten materials, namely chalcogenide glass-type tellurium alloys, at the micrometer scale. An experimental setup of Photothermal Radiometry (PTR), formerly developed for solid state measurements, has been adapted for this purpose. Using MOCVD technique, a random lattice of sub-micrometric tellurium alloy structures is grown on a thermally oxidized silicon substrate. These structures are then embedded in a protective layer (silica or alumina) to prevent evaporation during melting. Measurements are then performed from room temperature up to 650°C. SEM and XRD measurements performed after annealing show that these samples withstand thermal stress only up to 300°C. The coating’s thermal boundary resistance is estimated by a heat transfer model based on the thermal impedance formalism. Moreover, the thermal conductivity and thermal boundary resistance of thin amorphous alumina by low temperature ALD are measured from the room temperature to 600°C.

No / Rheological characterisation of hydroxyapatite -high density polyethylene (HA-HDPE) composites has been performed in terms of isothermal compressibility and wall slip. Addition of HA to the polymer melt decreases the compressibility of the melt. The unfilled HDPE was found to exhibit wall slip at shear stresses as low as 0.10 MPa. The flow curves of the composites showed three distinct regions: a gradient at low shear rates; a plateau region; and a gradient at higher shear rate. An increase in rheometer pressure seems to suppress the slip in composites. The 40 vol.-% HA-HDPE composite exhibited two critical shear stresses, one corresponding to wall slip, which occurs in the lower shear rate region of the flow curve, and the other corresponding to a plateau, which is identified with the stick-slip behaviour of unfilled HDPE reported in the literature. The plateau shear stress increased with filler volume fraction and this effect is attributed to the decreased compressibility of the melt. A good correlation with a negative correlation coefficient was found to exist between compressibility and shear stress in the plateau region. The slip observed in unfilled HDPE and at low shear rates in the 40 vol.-% HA- HDPE systems has been explained in terms of a low molecular weight polymer layer formed at the melt/wall interface. The large interfacial slip observed in the plateau region is attributed to complete disentanglement of adsorbed chains from free chains at the melt/wall interface at and beyond the plateau region.

No / Experimental observations of melt temperature profiles and melting performance of extruder screws are reported. A novel temperature sensor consisting of a grid of thermocouple junctions was used to take multiple temperature readings in real time across melt flow in a single screw extruder. Melt pressure in the die and power consumption were also monitored. Three extruder screws at a range of screw speeds were examined for a commercial grade of low density polyethylene. Results showed melt temperature fields at low throughputs to be relatively independent of screw geometry with a flat-shaped temperature profile dominated by conduction. At high throughputs, melting performance and measured temperature fields were highly dependent upon screw geometry. A barrier-flighted screw with Maddock mixer achieved significantly better melting than single flighted screws. Low temperature "shoulder" regions were observed in the temperature profiles of single-flighted screws at high throughput, due to late melting of the solid bed. Stability of the melt flow was also dependent upon screw geometry and the barrier-flighted screw achieving flow with lower variation in melt pressure and temperature. Dimensionless numbers were used to analyze the relative importance of conduction, convection, and viscous shear to the state of the melt at a range of extrusion conditions.

Pfropfcopolymere definierter Architektur wurden auf Basis von drei neu synthetisierten multifunktionellen Kopplungsreagenzien mit N-Acyllactam- und Benzoxazinongruppen über zweistufige selektive Schmelzereaktionen erfolgreich synthetisiert. Dabei wurde die Selektivität der Schmelzereaktionen durch die Reihenfolge der Zugabe der funktionellen Ausgangsoligomere und die Temperatur kontrolliert. Die erhaltenen Pfropfcopolymere stellen thermoplastische Elastomere mit hoher Zugfestigkeit und zugleich hoher Dehnung dar.

Pfropfcopolymere definierter Architektur wurden auf Basis von drei neu synthetisierten multifunktionellen Kopplungsreagenzien mit N-Acyllactam- und Benzoxazinongruppen über zweistufige selektive Schmelzereaktionen erfolgreich synthetisiert. Dabei wurde die Selektivität der Schmelzereaktionen durch die Reihenfolge der Zugabe der funktionellen Ausgangsoligomere und die Temperatur kontrolliert. Die erhaltenen Pfropfcopolymere stellen thermoplastische Elastomere mit hoher Zugfestigkeit und zugleich hoher Dehnung dar.