Ces travaux de thèse concernent l’étude du comportement thermo-physique de mélanges de polymères biosourcés chargés de poudre d’Inconel 718 mis en forme par Moulage par Injection de poudre Métallique. Des matériaux et procédés innovants pouvant permettre une amélioration du procédé ont été étudiés. L’utilisation de polyéthylène glycol (PEG), choisi pour ses propriétés de solubilité dans l’eau, et de polymères biosourcés, pour diminuer l’impact environnemental, ont été choisi. Les nuances de polymères biosourcés ont été choisies adaptées aux conditions du procédé de moulage par injection, il s’agit d’acide polylactique et de polyhydroalcanoates. De même, l’utilisation du CO2 à l’état supercritique comme solvant, a pour objectif de diminuer le temps de déliantage ainsi que d’augmenter la qualité des composants réalisés. Les résultats obtenus ont montré une dégradation du PEG et de l’acide stéarique lors des cycles de mélangeage de de moulage par injection dans les conditions d’utilisation des polymères biosourcés. L’utilisation des mélanges chargés composés de polymères biosourcés ont permis d’améliorer l’homogénéité des composants injectés, mais ont engendré des défauts lors de l’étape de déliantage. Ces défauts ont pu être éliminés par l’utilisation de CO2 à l’état supercritique comme solvant du PEG. Ce dernier procédé a permis une diminution importante du temps de déliantage ainsi qu’une amélioration de la qualité des composants finaux. Les composants densifiés possèdent les propriétés mécaniques correspondantes à l’Inconel 718. / The works done during this PhD focuses on the study of the thermo-physical behavior of bio sourced polymer blends loaded with Inconel 718 powder (feedstock) to be shaped by the Metal Injection Molding process (MIM). First, a review of the researches related to the MIM process was conducted to identify innovative materials and processes that can improve the MIM process. Thus, the use of polyethylene glycol (PEG), selected for its properties of solubility in water, and bio sourced polymers, in order to reduce the environmental impact, were selected. The bio sourced polymers have been selected in accordance with the conditions of the injection molding process, and the choice was made to use polylactic acid (PLA) and polyhydroalkanoates (PHA and PHBV). Similarly, the supercritical CO2 as solvent was chosen to reduce the time of binder removal as well as increasing the quality of components produced. Thermo-physical, mechanical and rheological characterizations were made to determine the behavior of the different feedstock formulations. The results showed a degradation of the PEG and of the stearic acid under the conditions of use of the biopolymers, during the mixing and the injection stages. The use of feedstock made of bio sourced polymers have improved the homogeneity of the injected components, but they have generated defects during the debinding step. These defects have been eliminated by the use of CO2 in the supercritical state as solvent of the PEG. This method has significantly decrease the time of binder removal and improved the quality of the final components. Finally, densified components have the mechanical properties corresponding to Inconel 718.

Integrally moulded hinges and tension bands are important features in packaging components for plastic closures and their function is critically dependent on the flow induced micromorphology in the hinge section. Polymer characteristics and processing of the hinge also have an influence on the hinge properties obtained. This study is aimed at obtaining interrelationships between polymer characteristics, in-cavity flow, microstructure development and hinge properties, to produce hinges with enhanced functional properties. Three different virgin polypropylene (PP) grades were investigated (homopolymer PP-H, random copolymer PP-RC and impact copolymer PP-IC) and injection moulding simulation was carried out using Moldflow software. In-cavity data acquisition has been carried out for different sets of injection moulding conditions, using high performance transducers and a data acquisition system. A comparison between Moldflow simulation and practical injection moulding data suggests that, for thin wall injection moulded components the real time pressure data are in close agreement during the injection stage. During the packing stage there is some disagreement between these data, since the thickness of hinge and tension band sections are 0.4 mm and 0.5 mm respectively, suggesting that these dimensions are extending the capability of the software. An extensive study using a design of experiments (DoE) approach was carried out on both practical and predictive data. Injection velocity and melt temperature were the most influential factors on the component mechanical properties. From the optical micrographs it is observed that PP-RC has a finer micro-structure compared to PP-H and PP-IC and some micrographs confirm Moldflow simulation results in which hesitation effects are evident, as the flow converges into the thin hinge and tension band sections. PP-clay nanocomposites (PP-CN) were prepared using a twin screw compounder. Transmission electron microscopy (TEM) has shown some evidence of dispersion and exfoliation of the clay particles in the PP matrix. However, X-ray diffraction (XRD) results show a reduction in inter-layer spacing of PPCN s possibly due to clay compaction. The addition of nano-clay however has not resulted in any significant improvements in the mechanical properties of hinges and tension bands. The high degree of molecular orientation induced in the hinge and tension-band sections appears to mask any improvements attributed to the addition of nano-clay. From the reprocessed and post consumer recyclate (PCR) study conducted on hinges and tension bands, it is seen that with an increase in both the re-processing and PCR content there is a decrease in the component strength of around 14%, giving scope to potentially use PCR in future packaging applications. Investigations conducted on colour pigments (violet and green) reveal that the onset of crystallisation for green pigmented mouldings is considerably higher (16°C) than for natural and violet mouldings. Optical micrographs also reveal a finer microstructural texture for green components, indicating a high nucleating capability of the green pigment. Irrespective of the colour, both for hinges and tension bands, the yield stress values were around twice as high as the values quoted in the manufacturer s data sheet for isotropic PP, due to the high levels of molecular orientation in the hinge and tension band sections. In order to industrially validate the findings from the DoE study, commercial closures were produced in industry on a production tool then characterised. In the case of tension bands, there was a good agreement between the results obtained from lab scale and industrial study due to the relatively simple geometry. For hinges this agreement is not so clear. Finally a comparison of mechanical properties of the 3 PP grades shows that PP-H has a higher yield stress compared to PP-IC and PP-RC and yield stress is significantly higher (yield strain values are lower) than values quoted by the manufacturer. The PhD study has confirmed the process conditions that are able to optimise all the interactive effects to improve functional properties in high volume parts in the packaging industry.

Objets très communs dans l’aire de culture tibétaine, les tsha tsha, fabriqués à l’aide de moules, sont des images en argile figurant des stūpa, des divinités bouddhiques, des personnages historiques, ainsi que des inscriptions. Leur fabrication est avant tout considérée comme une pratique religieuse visant à générer des mérites mais aussi à purifier les actions négatives. Réalisés en masse, ils constituent des témoignages fidèles et mésestimés des développements iconographiques et stylistiques qui ont marqués l’art bouddhique tibétain au fil des siècles. En l’absence d’études antérieures, un travail de recensement systématique des matériaux relatifs aux tsha tsha a fait apparaître une richesse documentaire insoupçonnée susceptible d’éclairer non seulement l’histoire de l’art tibétain, mais également certains aspects relevant de l’anthropologie religieuse, de la philologie, ou encore de la paléographie. Dans le cadre de notre thèse, nous avons privilégié une démarche globalisante prenant en considération l’ensemble des données disponibles en procédant conjointement à l’étude d’un très large corpus de pièces sélectionnées, à celle de la littérature afférente, et aux observations de terrain. Dans cette perspective, nous avons envisagé l’étude des tsha tsha sous divers angles: l’origine et l’histoire de la diffusion de cette pratique au Tibet, la terminologie relative à ces objets, les techniques de fabrication, les usages, l’iconographie, les styles et enfin les inscriptions présentes à leur surface ou introduites. Cette approche nous a permis de révéler finement l’ampleur et les développements que cette pratique bouddhique d’origine indienne a connu dans le monde tibétain. / Very commonplace in the Tibetan world, tsha tshas are clay impressions produced from a mould depicting, either in relief or moulded in the round, stūpas, Buddhist deities, historical figures and inscriptions. Making them is essentially considered to be a religious practice intended to generate and accumulate merit but also to purify negative deeds and obscurations. Produced in mass and generally preserved inside sealed edifices, tsha tshas are true yet underrated evidence of the iconographic and stylistic developments that have marked Tibetan Buddhist art over the centuries. In the absence of any previous studies, the task of establishing a systematic inventory of sources related to tsha tshas revealed an unsuspected wealth of material for elucidating not only the history of Tibetan art, but also some aspects of religious anthropology, philology, or paleography. In this doctoral research, we favored a globalizing approach that takes into account all the available data by studying a very large corpus of selected pieces, of the literature related to the tsha tshas, as well as field observations. In this context, we considered the study of tsha tshas from different angles: the origin and history of how this practice spread through Tibet, the terminology for these objects, the techniques for making them, their uses, iconography, styles and finally the inscriptions that are found on their surface or inside them. This approach has allowed us to explain more accurately the true extent of this Buddhist practice of Indian origin and the developments it has undergone in the Tibetan world since its introduction in about the 8th-9th centuries to the present day.

Durant ces dernières décennies les matériaux composites organiques ont subi un très grand essor dans le domaine des structures aéronautiques. Leur principal avantage est d’alléger les structures tout en gardant de bonnes propriétés mécaniques. De plus, leur microstructure leur permet d’avoir un caractère multi-fonctionnel, ce qui facilite leur intégration pour remplacer les technologies existantes. Dans l’industrie aéronautique, il existe un besoin croissant de grande quantité de petite et moyenne pièces (clips, éléments de jonctions). Cependant, il est aujourd’hui difficile de fabriquer en série des pièces ayant des formes tridimensionnelles complexes par des procédés conventionnels (autoclave). Ainsi, l’orientation envisagée est d’utiliser les procédés de la « famille » automobile pour des applications aéronautiques « semi-structurales », comme le moulage par injection de composites thermoplastiques renforcés de fibres courtes. Cette application nécessite une maîtrise et une fiabilisation du procédé ainsi que des propriétés induites. Ceci a été réalisé par l’identification et la quantification des effets des paramètres qui influent significativement sur la microstructure et les propriétés macroscopiques, par un plan d’expériences. De plus, le dimensionnement de telles pièces requiert une modélisation robuste du comportement mécanique pour prédire au mieux leur capacité d’utilisation. Les données sur la microstructure ont permis d’alimenter un modèle micromécanique comportant un critère d’endommagement de l’interface fibre/matrice. Développé sur un code éléments finis industriel, il a permis de prédire les résultats expérimentaux d’une pièce industrielle. / During the last decades, organic composite materials have undergone great development in the field of aeronautical structures. Their main avantage is to reduce the structures weight while maintaining good mechanical properties. In addition, their microstructure allows them to have a multi-fuctional nature, which facilitates their integration to replace existing technologies. In the aviation industry, there is a growing need for large amount of small and medium parts (clips, connecting elements). However, nowadays it is difficult to produce parts with complex by conventional methods dimensional shapes (autoclave). Thus, the considered path is tu use methods of the automotive “family” for “semi-structual” aerospace applications such as injection-moulding of thermoplastic composites reinforced by short fibres. This application requires a mastery and reliability of the process and the induced properties. This was achieved by the identification and quantification of the parameters effects that significantly influence the microstructure and macroscopic properties, by a design of experiments. Moreover, the dimensioning of such parts requires a robust mechanical behabior modelling to predict the best use of their capacity. The data on the microstructure enable to feed a micromechanical model featuring damage criteria of the fiber/matrics interface. Developed on a industrial finite element code, it was used to predict the experimental results of an industrial part.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Aesthetic and functional excellence in dental prosthetic rehabilitation has been achieved with the increase of advanced ceramics in dentistry. Processing techniques such as heat press injection moulding and CAD/CAM (computer-aided design/computer aided manufacturing) impart decreased porosity to the microstructure, as well as simplicity and automation of the process. In order to examine the machining surface finish of a leucite glass-ceramic produced using Brazilian raw materials, heat-pressed performs were obtained. These preforms had dimensions close to those of the final crown infrastructure in order to allow fast and easy final matching and finish-milling by using a Brazilian milling machine (MTC Robotica), supported by DentMILL (SEACAM) CAM software. As a control and reference manufacturing process, four crown infrastructures were milled by using CEREC®-3 machine. Aimed at achieving a machinable microstruture, two different heating schedule were tested for ceramizing the feldsphatic glass ingots. X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), nanoindentation test and fracture toughness measurement by indentation method were used as characterization methods. Comparison of the properties of the experimental material with those published by other investigator on similar commercial materials conducted to the conclusion that it is a machinable glass-ceramic with acceptable features for application in dental prosthetic rehabilitation. Preforms milling simulation using MTC Robotica machine conducted to the prediction of very long milling time (18h), even considering preforms possessing dimensions similar to those of the desired milling end product, a manufacturing time much greater than those found in commercial CAD/CAM dental milling machines. / A reabilitação protética do elemento dentário com excelência estética e funcional tem sido alcançada através do amplo uso de cerâmicas avançadas na odontologia. Técnicas de processamento como moldagem por injeção a quente e usinagem por CAD/CAM (computer-aided design/computer aided manufacturing) conferem ao material uma microestrutura com menor porosidade, além de simplificar e permitir automação de sua execução. Com o objetivo de avaliar a superfície usinada de uma vitrocerâmica feldspática leucítica produzida a partir de matéria prima nacional, foram confeccionadas pré-formas deste material pela técnica de moldagem por injeção sob pressão a quente. Estas pré-formas têm dimensões aproximadas a da peça final com a finalidade de serem usinadas na fresadora CNC nacional de baixa rotação (MTC Robótica), auxiliada pelo software CAM DentMILL (SEACAM). Além disso, foram usinadas peças do mesmo material no sistema CEREC®, como forma de controle. Para a obtenção de uma microestrutura com melhor usinabilidade, foram testadas duas metodologias de ceramização das pastilhas de vidro feldspático. A caracterização do material foi realizada por meio da difração de raios X (DRX), microscopia eletrônica de varredura (MEV), microscopia de força atômica (AFM), ensaios de nanoindentação e de tenacidade à fratura pelo método da indentação. A partir da comparação das propriedades deste material aos dados obtidos na literatura sobre materiais similares existentes no mercado foi possível classificar o material como usinável e indicar sua aplicação na clínica odontológica reabilitadora. A simulação da usinagem das pré-formas na fresadora MTC Robótica, mesmo com dimensões aproximadas a da peça final, apresentou um tempo de usinagem muito longo (18h), o que a tornou inviável comparada aos sistemas CAD/CAM consolidados no mercado.

L'extraction aqueuse des lipides de la graine de tournesol est étudiée en contacteur agité. La diffusion à l'intérieur des particules est le facteur limitant de l'échange de matière. Les protéines sont impliquées dans l'entraînement et la stabilisation des lipides par l'eau. Le fractionnement de la plante entière est également étudié avec l'eau en extrusion bi-vis. Un extrait et un raffinat sont obtenus séparément et en une seule étape continue. Des rendements d'extraction en huile de 55 % peuvent être obtenus sous forme d'émulsions huile/eau. Leur stabilité est assurée par la présence à l'interface de tensioactifs : les phospholipides et les protéines voire les pectines. Les extraits se composent aussi d'une phase hydrophile. Prépondérante, elle contient des composés hydrosolubles (protéines, pectines…). Riches en fibres, les raffinats présentent une teneur significative en protéines au comportement thermoplastique. Ils peuvent être transformés en agromatériaux par thermomoulage.

Abstract The main object of this thesis was to research injection mouldable 0–3 type ceramic polymer composites and their dielectric and magnetic properties in the GHz frequency region. The work has been divided into three sections. In the first section, two–phase ceramic polymer composites containing dielectric and magnetic fillers have been investigated and their characteristics analysed by reference to pre–existing mixing rules. The exploitation of these composites in miniaturizing devices, such as antennae, is presented and discussed. The second part describes three phase composites containing different nanosize additives (silver, silicon and alumina fibres) towards improving their dielectric properties. In the third part, some periodical and multilayer structures for ceramic polymer composite layers are proposed. In the case of two–phase ceramic polymer composites, with 37 vol.% of dielectric filler (Barium Strontium Titanate, BST) embedded into a thermoplastic polymer (ER140) matrix, the highest measured relative permittivity was 15 with a dielectric loss value of 0.008 at 1 GHz. With 43 vol.% of magnetic filler (hexaferrite, CO2Z) in ER182 matrix, the highest achieved relative permeability was 1.8 with a magnetic loss value of 0.077 at 1 GHz. Composites with Co2Z filler provide a 77% size reduction, and could thus be used advantageously in antennae. It was found that a 2–6 vol.% nanoaddition in BST–ER140 composites enhanced the relative permittivity drastically with only a minor effect on the dielectric losses. In particular, with only 2 vol.% addition of nanosize silver particles into the BST–ER140 composite, a 52% increase in the relative permittivity was obtained, with no significant change in the dielectric losses (tan δε = 0.004). Vertically and horizontally periodical dielectric composite structures comprising layers of different dielectric properties have been fabricated as well as multilayered structures containing dielectric and magnetic layers. The measurement results indicate that such multimaterial multilayer structures are good candidates for components with reduced dielectric and magnetic losses. / Tiivistelmä Väitöstyön tavoitteena oli tutkia ruiskuvalettavien 0–3 –liitännäisten keraami-polymeerikomposiittien ominaisuuksia erityisesti niiden GHz-taajuusalueen dielektristen ja magneettisten ominaisuuksien kannalta. Työ on jaettu kolmeen osaan. Ensimmäisessä osassa on tutkittu kaksikomponenttisia keraami-polymeerikomposiitteja, joissa täytemateriaali on joko dielektristä tai magneettista materiaalia. Komposiittien ominaisuuksia on analysoitu jo olemassa olevien seosmallinnuskaavojen avulla. Komposiittien hyödyntämistä erilaisten sovellusten, kuten antennien, minityrisoinnissa on myös käsitelty. Toinen osa käsittelee kolmikomponenttisia komposiitteja, joissa lisäaineena on käytetty pieniä määriä nanomateriaaleja (hopea- ja piipartikkelit sekä alumiinioksidikuitu) tarkoituksena parantaa komposiitin dielektrisiä. Kolmannessa osassa on tutkittu periodisia ja monikerroksisia keraami- polymeerikomposiittirakenteita rakenteita. Kaksikomponenttisten keraami-polymeerikomposiittien tapauksessa suurin permittiivisyyden arvo 15 dielektristen häviöiden ollessa 0.008 (mittaustaajuus 1 GHz) saatiin komposiitille, jossa dielektristä täytemateriaalia (Barium Strontium Titanaatti, BST) oli 37 tilavuus-% termoplastisessa polymeerimatriisissa (ER140). Korkein saavutettu permeabiliteetin arvo 1.8 magneettisten häviöiden ollessa 0.077 (mittaustaajuus 1 GHz) saatiin komposiitille, jossa magneettista täyteainetta (hexaferriitti, Co2Z) oli 43 tilavuus-% ER182 -matriisissa. Tämä täyteaine mahdollistaa nykyistä jopa 77 % pienempien antennielementtien kehittämisen. Tukimuksessa todettiin 2–6 tilavuus-% nanomateriaalin lisäyksen BST-ER140 -komposiitteihin kasvattavan permittiivisyyttä merkittävästi juurikaan vaikuttamatta dielektrisiin häviöihin. Erityisesti 2 tilavuus-% hopeananopartikkeleiden lisäys BST-ER140 -komposiitteihin kasvatti permittiivisyyttä 52 % dielektristen häviöiden (tan δε =  0.004) kasvamatta. Työssä on myös tutkittu periodisesti (vertikaali ja horisontaali) koostettuja dielektrisiä komposiittirakenteita, jossa eri kerroksissa on erilaiset dielektriset ominaisuudet sekä monikerrosrakenteita, joissa vuorottelevat dielektriset ja magneettiset kerrokset. Mittaukset osoittivat, että monimateriaaliset monikerrosrakenteet ovat hyviä kandidaatteja komponentteihin, jotka vaativat pieniä dielektrisiä ja magneettisiä häviöitä.

Die Produktion verschiedener Arten von Gütern ist im globalen Kontext gesellschaftlicher Entwicklung fortwährend an die Verfügbarkeit von Ressourcen gebunden und durch diese zunehmend begrenzt. In den bis heute entstandenen Wertschöpfungsketten basiert die verlustarme und effiziente Verteilung von Produkten, Zwischenprodukten, Halbzeugen sowie auch Rohstoffen auf den spezifisch auf die jeweiligen Erfordernisse eingestellten Funktionen ihrer Verpackungen. Als Bindeglied in nahezu allen Teilen der Produktion werden die Verpackung und ihre Herstellung innerhalb des mit Abstand größten Teils ihrer Anwendung, den Konsumgüterverpackungen als Beispiel für die Diskussion von Einsatzpotentialen naturfaserbasierter Materialien verwendet. Die Habilitationsschrift stellt die Ausgangssituation in der weltweiten Konsumgüterproduktion und Ressourcenverfügbarkeit dar und ordnet die Position naturfaserbasierter Packmittel in diese ein. Es werden Technologien zur Formgebung naturfaserbasierter Materialien zu Packmitteln zusammenfassend dargestellt. Die Ziehtechnik wird im Speziellen in Form eines Leitfadens in ihren Wirkmechanismen und Prozessvarianten sowie in Bezug auf ihre technische Umsetzung dargestellt. Es werden Beispiele konkreter Anwendungsmöglichkeiten diskutiert.

Die Produktion verschiedener Arten von Gütern ist im globalen Kontext gesellschaftlicher Entwicklung fortwährend an die Verfügbarkeit von Ressourcen gebunden und durch diese zunehmend begrenzt. In den bis heute entstandenen Wertschöpfungsketten basiert die verlustarme und effiziente Verteilung von Produkten, Zwischenprodukten, Halbzeugen sowie auch Rohstoffen auf den spezifisch auf die jeweiligen Erfordernisse eingestellten Funktionen ihrer Verpackungen. Als Bindeglied in nahezu allen Teilen der Produktion werden die Verpackung und ihre Herstellung innerhalb des mit Abstand größten Teils ihrer Anwendung, den Konsumgüterverpackungen als Beispiel für die Diskussion von Einsatzpotentialen naturfaserbasierter Materialien verwendet. Die Habilitationsschrift stellt die Ausgangssituation in der weltweiten Konsumgüterproduktion und Ressourcenverfügbarkeit dar und ordnet die Position naturfaserbasierter Packmittel in diese ein. Es werden Technologien zur Formgebung naturfaserbasierter Materialien zu Packmitteln zusammenfassend dargestellt. Die Ziehtechnik wird im Speziellen in Form eines Leitfadens in ihren Wirkmechanismen und Prozessvarianten sowie in Bezug auf ihre technische Umsetzung dargestellt. Es werden Beispiele konkreter Anwendungsmöglichkeiten diskutiert.

This master’s thesis deals with influence of gas content in structure of polymer materials to mechanical properties. Test specimens were prepared by MuCell technology from polyphthalamide reinforced by 50 % of glass fiber content. The theorethical part of this thesis is focused on polymer materials with attention to polyamides and injection moulding technology. In the experimental part, the dependence between the characteristics obtained from the tensile test and the Charpy impact test on the amount of gas in the polymer is examined.