The use of kaolinite for preparing functionalized materials for specialized applications is still a relatively niche research subject. This is in spite of its low cost, high availability, and the potential for covalently grafting organic functional groups to its inner and outer surfaces. These grafted compounds have been shown to be highly resistant to heat and solvents, making them very useful for certain applications, for example in polymer nanocomposite materials that require high thermal resistance during polymer processing. Solid state NMR has been shown to play an essential role in solving the structure of functionalized kaolinite materials, however the current knowledge base for these functionalized kaolinites is notably lacking for some nuclei such as 1H, 27Al and 17O. Research was undertaken to address these concerns by developing new synthetic strategies for preparing kaolinite based materials for use as nanocomposites and to examine commonly prepared modified kaolinite precursors materials by 1H and 27Al MAS NMR in an attempt to demonstrate their utility for characterizing kaolinite intercalated and grafted complexes. Solid state 1H NMR of a natural kaolinite, kGa-1b, identified two main proton signals attributed to inner and inner surface hydroxyl protons. The different affinity of these two types of hydroxyl groups towards exchange with deuterium was used to differentiate between the two. The 1H NMR spectra of a DMSO intercalated kaolinite, kDMSO, and a methanol grafted kaolinite, kmethoxy, were fitted with high accuracy using models consistent with the known structures of these materials. The 27Al MAS NMR spectra of a natural kaolinite, kGa-1b, a DMSO intercalated kaolinite, kDMSO, and a methanol grafted kaolinite, kmethoxy measured at 21.1T showed little difference between one another, while noticeable differences could be seen at 4.7T. 27Al MQMAS experiments found almost no difference between these materials in the multiple quantum dimension, suggesting the differences that were observed are a result of differences in quadrupolar parameters rather than chemical shifts. The 27Al NMR spectra of kGa-1b, kDMSO and kmethoxy were fitted with good accuracy using models consistent with known structures of these materials. Different Al(III) sites with CQ values varying by up to 0.6MHz were found. The 27Al NMR spectra of two different methanol grafted kaolinites were also compared and it was found that the intensities of the sites with lower values of CQ were dependent on the quantity of grafted aluminum sites. The interlayer space of kaolinite was functionalized with a block copolymer: poly(ethylene)-block-poly(ethylene glycol) using a kaolinite pre-intercalated with DMSO, kDMSO, and with a biodegradable polymer: poly(lactide) using a kaolinite pre-intercalated with urea, kurea, both by using melts of the polymer. The polymers were found to completely displace their precursors from the interlayer space giving a monolayer type arrangement of the polymer. Attempts were made to graft compounds containing polymerizable functional groups: 3-allyloxy-1,2-propanediol and ethylene glycol vinyl ether to kaolinite’s inner surfaces using a kaolinite pre-intercalated and grafted with methanol, kmethoxy, and a kaolinite pre-intercalated with DMSO, kDMSO, respectively. Both compounds were found to displace their precursors from the interlayer space, adopting a monolayer type arrangement. 13C and 29Si NMR results suggest 3-allyloxy-1,2-propanediol’s allyl group remains intact and partially keys into the clay mineral’s siloxane rings. Ethylene glycol vinyl ether was found to undergo intramolecular cyclization to form an acetal product, consuming its vinyl group in the process. This reaction was observed using an unmodified kaolinite, kGa-1b, suggesting that the clay mineral’s surfaces, both inner and outer, act as an acid catalyst.

Este trabalho apresenta o estudo de um sistema polimérico bi-componente formado por Poli(Ácido carboxílico)-Poli(Eter-poliol), constituído primariamente de um polímero acrílico polimerizado pelo processo de polimerização em solução aquosa por mecanismo de radicais livres ao qual foi adicionado seqüencialmente, um Poli(Eter-poliol), ambos de baixo peso molecular médio. Tal sistema tem por finalidade atuar como dispersante-ligante em sistema cerâmico à base de caulim CADAM, uma vez que este sistema apresenta propriedades termoplásticas e termorrígidas a diferentes temperaturas. Foram sintetizados 03 protótipos de um sistema polimérico e o critério para escolha teve como base o pH do sistema em sentido generalizado, isto é, compreendendo as diversas fases de preparação dos polímeros e sua aplicação final. É do conhecimento comum que a reação de esterificação entre grupos COOHOH requer catálise ácida para ocorrer, o qual usualmente é realizada em pH abaixo de 4 e, neste ensaio, este pH ácido é devido à presença de ácido para-toluenosulfônico, que atua como catalisador de esterificação. Em tal intervalo de pH, em virtude do ponto isoelétrico do caulim ser comumentemente abaixo de 4, a estabilização da dispersão de caulim por repulsão eletrostática utilizando polímeros sintéticos é improvável de ocorrer, razão pela qual buscou-se mecanismos alternativos para obtenção de uma tal estabilização, entre os quais o mecanismo estérico surge como opção. O sistema polimérico do presente estudo apresenta-se na forma de uma solução aquosa sendo, de fato, uma mistura homogênea de um copolímero de ácido acrílico, N- metiloacrilamida e metacrilato de metoxipolietileno glicol e um poli(eter-poliol). O poli(eter-poliol) e N-metilolacrilamida presentes no sistema polimérico são principais fontes de grupo hidroxila para reação de poliesterificação e formação de ligações cruzadas à temperatura de 150 a 200 °C. No estado termoplástico o sistema polimérico produzido pela mistura poli(ácido carboxílico)-poli(eter-poliol) pode ser utilizado como dispersante de argilas com especial fóco sobre caulim como tratado neste trabalho. A propriedade dispersante pode ser atribuida à presença de grupos carboxílicos e metoxipolietilenoglicol aleatoriamente distribuídos ao longo da cadeia polimérica e, também, ao baixo peso molecular médio. A temperaturas entre 150 a 200 °C, o polímero é reticulado (crosslinked) por reação de poliesterificação, catalisada por ácido, entre grupos carboxila e grupos hidroxila, sendo as hidroxilas provenientes tanto de poliol como de N-metilolacrilamida (NMAM). Assim, do ponto de vista térmico comporta-se como termorrígido, sendo nesta condição insolúvel em água e adequado atuar como ligante na manufatura de materiais cerâmicos. Medidas de mobilidade eletroforética e viscosidade são aplicadas à caracterização de caulim e do sistema polimérico a fim de avaliar a potencialidade de aplicação como dispersante desta argila. Também, as transições dos estados termoplásticos para termorrigidos foram determinadas por análise termogravimétrica (TG) e análise dinâmico mecânica (DMA) nos polímeros isoladamente e depois com medidas de resistência mecânica do sistema caulim/polímero. O sistema apresentou comportamento dispersante em água e ligante após cura. Um sistema polimérico assim sintetizado foi propriamente curado por calor tornando- se, na forma termorrígida, um ligante para peças cerâmicas com propriedades mecânicas de alto desempenho, como resistência a flexão no estado cru (green strenght). / This work presents the study of a polymeric bi-component system made from Poly(carboxylic acid)-Poly(ether-polyol) primarily constituted of an acrylic acid polymerized through the process of aqueous solution polymerization by free radical mechanism, to which a poly(ether-polyol) has been sequentially added, both of them of low average molecular weight. Such a system has the aim to act as dispersing-binding balance on CADAM kaolin targeting to evaluate the applicability potential or the preparation of ceramic bodies as this polymeric system presents thermoplastic and thermosetting properties at different temperatures. Were made the synthesis of 03 polymeric system prototypes which criteria for choice was based on pH of the system at whole sense, that is, regarding the several steps for polymers preparation and its final application. It is knowledge that esterification reaction between COOH-OH groups requires acid catalyst to occur, which usually is done at pH below 4 and, in this work this pH is due to p-toluene sulfonic acid that act as esterification catalyst. In this range of pH, due to the isoeletric point of kaolin to be below 4 the electrostatic stabilization of dispersion is unlikely to occur, from which reason was looked for an alternative mechanism to achieve the dispersion stabilization, among them the steric mechanism arises an option. The polymeric system of this study is the form of an aqueous solution, which actually is a homogeneous blend of a copolymer of acrylic acid, N-Methylolacrylamide Methoxypolyethyleneglycol Methacrylate (MPEGMA) and Poly(ether-polyol). The Poly(etherpolyol) and the N-Methylolacrylamide presents at the polymeric system are the main sources of hydroxyl groups to enhance the polyesterification reaction for further crosslinking at temperatures from 160 to 200 °C. At the thermoplastic state the polymeric system made by Poly(carboxilic acid)poly(ether-polyol) macromolecules may be used as clay dispersant focusing on kaolin for this work. The dispersant property may be attributed to the carboxylic and methoxypolyethyleneglycol group randomly distributed along the polymeric chain backbone and, also to the low average molecular weight. At temperatures between 150 to 200 °C, the polymer is crosslinked by polyesterification reaction catalized by acid between carboxyl groups and hydroxyl groups, in such way that hydroxyls groups comes both from the polyol base polymer and NMethylolacrylamide (NMAM) present at first polymer backbone. Thus, through a thermal standpoint it behaves as thermoset being that, under this condition, water insoluble and adequate to act as binder for manufacturing of ceramic materials. Electrophoretic mobility and viscosity measurements were applied for the characterization of kaolin and the polymeric system targeting to the evaluation its potential application as a dispersant for this clay. Also, the transitions from the thermoplastic to the thermoset state have been determined by thermo-gravimetric analysis (TG) and dynamicmechanical analysis (DMA) for the Poly(carboxylc acid)poly(ether-polyol) polymers alone and further by mechanical resistance measurements for a clay-polymer system. The system has presented both dispersant behavior on aqueous media and binder just afterward cure. A polymeric system thus synthesized was properly cured by heat turning and then, at the thermoset state, become suitable for act as a binder for ceramic bodies with high performance mechanical properties measured as flexural resistance at green strength.

Diplomová práca sa zaoberá prípravou teromplastických kompzoitov s PMMA a PC matricou s potenciálnym využitím v automobilovom priemysle. Ako výstuž boli použité krátke sklenené, uhlíkové a PBO (poly(p-fenylén benzobisoxazol)) vlákna známe pod obchodným názvom Zylon®. Práve do PBO vlákien boli vkladané veľké nádeje vzhľadom na ich ohromujúce mechanické vlastnosti. Vplyv objemového zlomku vlákien na modulu pružnosti, pevnosť a ťažnosť kompozitov bol skúmaný. Experimentálne zistený modul pružností bol porovnaný so semi-empirickým Halpin-Tsai modelom. Prídavok sklenených a uhlíkových vlákien viedol k značnému zvýšeniu modulu pružnosti. Ukázalo sa, že po istej hodnote objemového zlomku dochádza k poklesu pevností kompozitov v dôsledku zvyšujúceho sa počtu defektov. Prídavok PBO vlákien preukázal len nepatrný vystužujúci efekt. Viskoelastické vlastností kompozitov boli skúmané pomocou dynamicko mechanickej analýzy (DMA). Termogravimetrická analýza (TGA), konfokálna laserová rastrovacia mikroskopia (CLSM) a rastrovacia elektrónová mikroskopia (SEM) boli využité k štúdiu štruktúry kompozitov.

El sector de puericultura y ortopédico son sectores de gran relevancia, donde aspectos como el confort, adaptabilidad, calidez, etc. adquieren sentido. Los cauchos basados en silicona líquida (LSR) son clave en estos sectores, ofreciendo interesantes propiedades tanto a nivel técnico como de percepción positiva por parte del usuario. No obstante, la transformación de estos materiales es algo más compleja que el conjunto de plásticos de uso común y además, debido a su naturaleza reticular, resulta un material difícil de reciclar. El proceso de inyección es un proceso de conformado de los materiales poliméricos termoplásticos que representa una notable importancia económica y tecnológica. Bajo estas premisas, el objetivo principal de este trabajo de investigación es el desarrollo de materiales para el sector ortopédico - puericultura a partir del empleo de materiales de naturaleza reticular reversible (elastómeros termoplásticos) que puedan procesarse mediante técnicas de inyección convencionales y que sean capaces de aportar una buena inercia térmica para confort, mediante el empleo de materiales microencapsulados con cambio de fase (PCMs). Para ello, se plantea un conjunto de mezclas de un sistema basado en dos grados comerciales de elastómero termoplástico de SEBS (copolímero en bloque de estireno-etileno/butileno-estireno) con durezas extremas. Ello conlleva el planteamiento de objetivos parciales como la caracterización reológica del sistema (desarrollando un modelo de predicción de comportamiento mediante software de simulación), la modelización del comportamiento mecánico de las mezclas, la optimización del procesado de las mezclas aditivadas con PCMs (analizando la respuesta mecánica y térmica) y el estudio de la inercia térmica de las mismas para la mejora del confort de estos materiales y su potencial empleo en los sectores industriales mencionados, como sustitutos en las aplicaciones de la silicona líquida inyectada. / Juárez Varón, D. (2011). Procesado, modelización y caracterización de mezclas industriales de SEBS con materiales con cambio de fase (PCM) para la mejora del confort térmico en aplicaciones de ortopedia y puericultura [Tesis doctoral]. Editorial Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/11551 / Palancia

The large amount of non-degradable plastic waste has become a significant environmental concern, leading to an increased need for degradable plastics. Here in, to create degradable polymers, polyesters were produced through radical ring opening polymerization using cyclic ketene acetals. The cyclic ketene acetal monomer 5,6-benzo-2-methylene-1,3-dioxepane has been prepared for the synthesis of homo- and copolymers with methyl methacrylate, α-methylene-γ-valerolactone, α-methylene-γ-butyrolactone, cholesterol methacrylate and limonene acrylate. The polymerization was conducted using radical ring opening polymerization both in bulk and solution polymerization. The structural characteristics of the polymer were determined by different characterization methodologies, including TGA, DSC, SEC, FTIR and 1D 1H-NMR. The results obtained from 1H-NMR analysis showed the composition of the copolymers. TGA analysis revealed the thermal stability of the polymers and their degradation patterns. DSC analysis provided information about the glass transition temperatures (Tg’s) of the polymers. Moreover, the Tg indicated the presence and amounts of comonomers in the copolymers. Overall, the results showed the influence of different comonomers on the properties of the polymers by successfully incorporating the comonomers in the polymer. The thermal properties for polymers containing methyl methacrylate became more thermally stable. The Tg, analyzed with DSC, shifted from the Tg of homopolymers indicating the incorporation of both monomers. The polymers were successfully degraded via hydrolysis in alkaline conditions breaking them down into smaller pieces making them easier to recycle. To conclude, the results all indicate that the incorporation of BMDO and thereby possibly other CKA-monomers into the polymer chains of commonly used plastics could provide valuable tools in the recycling of said plastics.

No description available.

Ce mémoire par article est une étude des différences hémodynamiques entre la dextro-transposition des gros vaisseaux (TGV) avec communication interventriculaire (CIV) et la TGV avec septum intact (SI) pendant la période fœtale et périopératoire. Il est à noter que SI fait référence au septum inter ventriculaire et non au septum inter auriculaire. La présence d’une communication inter auriculaire étant, comme nous le verrons dans ce travail, un élément important de la physiologie des fœtus/nouveau-nés porteur de TGV. Le document est divisé en deux parties importantes. La première partie est composée du chapitre 1 qui présente une revue de littérature détaillant les notions importantes à la compréhension de la problématique et du chapitre 2 qui décrit la méthodologie utilisée pour répondre à la question de recherche. On détaille d’abord les méthodes d’acquisition des échocardiographies fœtales ainsi que les principales mesures effectuées à partir de celles-ci. Ensuite, on y décrit les technologies de la spectroscopie proche infrarouge avancée et de la spectroscopie à corrélation diffuse (NIRS-DCS) permettant de recueillir les données hémodynamiques sur la microvascularisation cérébrale des nouveau-nés. La seconde partie est constituée du chapitre 3 qui est le manuscrit accepté au journal Ultrasound in Obstetric & Gynecology pour publication. Celui-ci décrit les différences hémodynamiques entre les patients ayant une TGV&CIV et les TGV&SI et présente les différences retrouvées en échocardiographie fœtale et en hémodynamie cérébrale périopératoire étudiée à l’aide de la NIRS avancée. Ensuite, nous présentons dans le chapitre 4 une discussion sur les principaux impacts cliniques et sur d’éventuelles améliorations. / This master’sthesis is composed of an article and a study. They present hemodynamic differences between patients with transposition of the great arteries (TGA) and ventricular septum defect (VSD), and TGA with intact ventricular septum (IVS) during fetal and perioperative periods. This document is divided into two principal sections. The first section includes Chapter 1 that presents a review of literature detailing important notions to understand the problematic, and Chapter 2, that describes the methodology used to answer our research question. First, we detailed acquisition data and measured parameters of the fetal echocardiography exams. Then, we describe advanced near infrared spectroscopy (NIRS-DCS) technology that allowed hemodynamic data acquisition on the cerebral microvascularization of neonates. The second section is composed of Chapter 3, the manuscript accepted in Ultrasound in Obstetric & Gynecology journal for publication. The aim of this article is to describe hemodynamic differences between patients with TGA&VSD and TGA&IVS. It describes fetal echocardiography and cerebral perioperative hemodynamic differences studied with advanced NIRS. Next, we present in Chapter 4 a more detailed discussion with principal impacts on the clinical field and future improvements.

The aim of the present thesis is to explore sustainable low cost environmentally friendly composite materials. It is a step by step experimental research. Firstly, taking under consideration the so far commercial available non-organic materials used as reinforcement and the petroleum based resins used as matrices, composite materials were fabricated and mechanically characterized. Different components in micro- and nano- scale were combined. Afterwards, the non-organic materials used as reinforcements were substituted by different types of non conventional natural-based fillers. The fillers (corn starch and olive pit granules) were in powder form, derived from agricultural local resources and additionally flax fabric used to produce laminated composites. All the semi-green epoxy composites were characterized by means of three-point bending testing. Moreover, the manufactured composites were induced in several sources of damage and their residual properties were extensively investigated. More precisely, the effect of the strain-rate and low velocity impact as well as of thermal fatigue, on the mechanical properties of the olive pit and the flax fabric reinforced resin was studied. Since, conventional and semi-green composite materials were fabricated and experimentally investigated, the final objective of the present thesis was to produce novel green composites materials by substituting the petroleum-based epoxy resin with a biodegradable derived from natural resources biopolyester. In order to accomplish this target, polylactic acid (PLA) was combined with olive pits in powder form at different concentrations. Olive pits, is almost unknown non-traditional filler to composites, obtained during the oil extraction process. It is a raw material characterized by its low cost and its abundance, since it consists a waste product of the olive oil industry. In order to successfully accomplish this part of research, experiments were taken place in France at the CMGD (Centre des Matériaux de Grande Diffusion) Institute of the École Nationale Supérieure des Mines d’ Alés, under the guidance of Prof. A. Bergeret within the framework of research cooperation with the main supervisor of this thesis, Prof. G. Papanicolaou. The most important feature of the present green composites is their satisfactory mechanical and thermal performance in combination with their complete biodegradability. The PLA/olive pit composites could be applied to various components with moderate strength such as automotive interiors, interior building applications, durable goods, serviceware and food packaging material The aim of this part of the study was to investigate the effect of three types of olive pit powder at different weights fractions on the physical and mechanical properties of polylactide (PLA) matrix composites. For the preparation of the powder, two different grinding procedures were applied, producing three types of olive pit powder. Various measurements were accomplished to determine characteristics such as the density and the size distribution and the shape of the powder. Different PLA/ olive pits powder composites were manufactured by extrusion and injection molding. A comparative study between the different composites was made in order to investigate the matrix-filler interactions, occurring between the PLA and olive pit granules and their overall physical, mechanical and thermomechanical properties were investigated by means of TGA, FT-IR, DSC, SEM, flexural and uni-axial tensile testing. Finally, theoretical predictive models were applied in most of the composite materials manufactured in the present work. These models making use of minimal number of experimental results can satisfactorily predict the residual properties of damaged materials, irrespectively of the type of the material investigated and the damage source. Namely, the Modulus Predictive Model (ΜPM), the Residual Properties Model (RPM) and the Residual Strength after Impact Model (RSIM), have been successfully applied. A big number of interesting conclusions have been derived from the present work. However, a general conclusion is that a totally green composite with useful properties and applications is a promising target for the humanity and the planet survivability. / Σκοπός της παρούσας διδακτορικής διατριβής είναι η κατασκευή και μελέτη συνθέτων υλικών χαμηλού κόστους ενισχυμένων με φυσικά υλικά, φιλικά προς το περιβάλλον. Η επίτευξη αυτού του στόχου πραγματοποιήθηκε σταδιακά. Αρχικά, πραγματοποιήθηκε μια εκτεταμένη μελέτη διαφορετικών συνθέτων υλικών τα οποία ήταν εξ’ ολοκλήρου κατασκευασμένα από ανόργανα και συνθετικά υλικά. Γι’ αυτό το σκοπό κατασκευάστηκαν και μελετήθηκαν οι μηχανικές ιδιότητες συνθέτων υλικών που έχουν ως μήτρα μια εμπορικά διαθέσιμη πετροχημική εποξειδική ρητίνη. Η εποξειδική ρητίνη ενισχύθηκε με ανόργανα υλικά σε μικρο- (συμπαγή και κενά σφαιρίδια γυαλίου) και νανο- (νανοσωλήνες άνθρακα πολλαπλού τοιχώματος) διαστάσεις. Στη συνέχεια, βασιζόμενη στο ήδη υπάρχον επιστημονικό υπόβαθρο, καθώς η μεταπτυχιακή μου εργασία ειδίκευσης ήταν στο ίδιο ερευνητικό πεδίο με το αντικείμενο της διδακτορικής μου διατριβής, γίνεται προσπάθεια περαιτέρω εξέλιξης της έρευνας που σχετίζεται με την μελέτη και κατασκευή συνθέτων φιλικών προς το περιβάλλον. Ως εκ τούτου, το επόμενο στάδιο της πειραματικής μελέτης στα πλαίσια εκπόνησης της διατριβής αυτής, ήταν η κατασκευή και χαρακτηρισμός, ως προς την μηχανική τους συμπεριφορά, συνθέτων υλικών πολυμερικής εποξειδικής μήτρας ενισχυμένης με διαφορετικού τύπου φυσικές ενισχύσεις και περιεκτικότητες. Οι φυσικές ενισχύσεις που επιλέχθηκαν να μελετηθούν ήταν τόσο σε μορφή κόκκων και μικρο-ινών, όσο και σε μορφή υφάσματος. Τα εγκλείσματα που χρησιμοποιήθηκαν ήταν σκόνη από κόκκους ελαιοπυρήνα και σκόνη αμύλου καλαμποκιού. Στα σύνθετα υλικά ενισχυμένα με κόκκους ελαιοπυρήνα, έγινε μελέτη της επίδρασης των διαφορετικών ρυθμών παραμόρφωσης στις μηχανικές τους ιδιότητες, ενώ στα σύνθετα υλικά ενισχυμένα με την σκόνη αμύλου μελετήθηκαν εκτενώς οι στατικές μηχανικές τους ιδιότητες. Επιπλέον, κατασκευάστηκαν πολύστρωτα σύνθετα υλικά χρησιμοποιώντας για τις διάφορες στρώσεις ύφασμα από ίνες λιναριού. Τα πολύστρωτα σύνθετα υλικά χαρακτηρίστηκαν ως προς τις μηχανικές τους ιδιότητες, υποβλήθηκαν σε θερμική κόπωση και υπέστησαν κρούση χαμηλής ενέργεια. Οι εναπομένουσες μηχανικές ιδιότητες των υλικών αυτών μελετήθηκαν τόσο πειραματικά όσο και θεωρητικά. Ο απώτερος στόχος αυτής της διδακτορικής διατριβής ήταν να γίνει η δυνατή η κατασκευή συνθέτων υλικών τα οποία να είναι πλήρως βιοδιασπώμενα και φιλικά προς το περιβάλλον. Για το σκοπό αυτό, το τρίτο και τελευταίο στάδιο της έρευνας που διεξήχθη στα πλαίσια της παρούσας διατριβής, ήταν η κατασκευή εξολοκλήρου φυσικών συνθέτων υλικών έχοντας ως μήτρα ένα βιοδιασπώμενο πολυεστέρα φυτικής προέλευσης, το πολύ (γαλακτικό οξύ), ενισχυμένο με σκόνη από κόκκους ελαιοπυρήνα. Ο ξηρός ελαιοπυρήνας που χρησιμοποιήθηκε, αποτελεί μέρος των αποβλήτων που προκύπτουν από την διαδικασία παραγωγής ελαιολάδου. Ο ελαιοπυρήνας σε αυτή την μορφή έχοντας μηδαμινό κόστος απαντάται σε εξαιρετικά μεγάλες ποσότητες και σε σημαντικό ποσοστό εναποτίθεται στους περιβάλλοντα χώρους των μονάδων παραγωγής του ελαιολάδου. Η ερευνητική εργασία που σχετίζεται με αυτό το αντικείμενο του διδακτορικού έλαβε χώρα στην Γαλλία στο École Nationale Supérieure des Mines d’ Alés, στο ερευνητικό ινστιτούτο CMGD (Centre des Matériaux de Grande Diffusion) υπό την επίβλεψη της καθηγήτριας A. Bergeret, στα πλαίσια ερευνητικής συνεργασίας του επιβλέποντα καθηγητή Γ. Παπανικολάου και της ερευνητικής του ομάδας. Τα πειράματα που διεξήχθησαν στο ερευνητικό ινστιτούτο CMGD, περιελάμβαναν αρχικά την προετοιμασία των κόκκων του ελαιοπυρήνα στην κατάλληλη μορφή για να είναι δυνατή η χρησιμοποίησή τους ως ενισχυτικό υλικό. Έγινε κονιορτοποίηση των κόκκων από την οποία προέκυψαν δύο τύπου σκονών που διέφεραν ως προς την διασπορά του μεγέθους των κόκκων, ενώ μια τρίτη σκόνη ελαιοπυρήνα είχε ήδη προετοιμαστεί με διαφορετική μέθοδο κονιορτοποίησης στο τμήμα Επιστήμης των Υλικών του Πανεπιστήμιου Πατρών. Έγινε εκτενής χαρακτηρισμός των φυσικών και μορφολογικών ιδιοτήτων όλων των σκονών ελαιοπυρήνα που χρησιμοποιήθηκαν για την κατασκευή των συνθέτων υλικών με μήτρα το PLA. Προσδιορίστηκαν διαφορετικού τύπου πυκνότητες και η διασπορά του μεγέθους των κόκκων. Έγινε θερμική ανάλυση με δοκιμή θερμοζυγού (TGA), μορφολογικός χαρακτηρισμός με χρήση ηλετρονικού μικροσκοπίου σάρωσης (SEM) καθώς και χαρακτηρισμός με φασματοσκοπία υπερύθρου με μετασχηματισμό Fourier (FT IR) και ακτίνων-Χ. Αφού ολοκληρώθηκε ο χαρακτηρισμός των ιδιοτήτων της ενισχυτικής φάσης, στη συνέχεια κατασκευάστηκαν σύνθετα υλικά μήτρας PLA ενισχυμένα με τους κόκκους ελαιοπυρήνα σε διαφορετικές περιεκτικότητες. Η προετοιμασία των σύνθετων αυτών υλικών πραγματοποιήθηκε σε δύο στάδια. Αρχικά έγινε μια πρώτη μορφοποίηση με εξώθηση (extrusion). Τα σύνθετα υλικά που προέκυψαν από την εξώθηση που ήταν στη μορφή δισκίων (pellets) χαρακτηρίστηκαν και αυτά με διάφορες τεχνικές (WAXD, DSC, TGA). Τα σύνθετα υλικά υπό μορφή δισκίων για να αποκτήσουν την τελική τους μορφή ως δοκίμια κατάλληλα για μηχανικές δοκιμές κατά τα πρότυπα ISO 527, μορφοποιήθηκαν με έγχυση (Injection molding). Τα σύνθετα υλικά στην τελική τους μορφή χαρακτηρίστηκαν με διάφορες τεχνικές (WAXD, DSC, TGA), έγινε χαρακτηρισμός των μηχανικών τους ιδιοτήτων και μορφολογική παρατήρηση των επιφανειών τους ύστερα από την μηχανική τους αστοχία (SEM). Τέλος, σε πολλά από τα σύνθετα υλικά που κατασκευάστηκαν και μελετήθηκαν πειραματικά, εφαρμόστηκαν διαφορετικά ημιεμπειρικά μοντέλα ανάλυσης και πρόβλεψης της μηχανικής τους συμπεριφοράς. Στο κυρίως κείμενο της διδακτορικής διατριβής, περιγράφεται σε ξεχωριστό κεφάλαιο το σύνολο των θεωρητικών μοντέλων που εφαρμόστηκαν στα πειραματικά αποτελέσματα. Στα επιμέρους κεφάλαια που παρουσιάζονται και αναλύονται τα πειραματικά αποτελέσματα, παρατίθενται η σύγκρισή τους με τις αντίστοιχες προβλέψεις που πρόεκυψαν από την εφαρμογή των θεωρητικών μοντέλων. Από τη σύγκριση αυτή παρατηρούμε ότι τα θεωρητικά μοντέλα που εφαρμόστηκαν που είναι το μοντέλο πρόβλεψης του μέτρου ελαστικότητας κοκκωδών υλικών, ΜPM (Modulus Predictive Model), το μοντέλο πρόβλεψης της υποβάθμισης ιδιοτήτων ύστερα από διαφορετικές είδους καταπονήσεις (θερμική κόπωση, κρούση χαμηλής ενέργειας και του ρυθμού παραμόρφωσης σε κάμψη τριών σημείων), RPM (Residual Properties Model) και το μοντέλο πρόβλεψης της υποβάθμισης της αντοχής των υλικών ύστερα από κρούση, Residual Strength after Impact Model (RSIM), έδωσαν ικανοποιητικές προβλέψεις για την μεταβολή των ιδιοτήτων κάνοντας χρήση ελάχιστων μόνο πειραματικών σημείων. Στην παρούσα διατριβή συνδυάστηκαν δύο διαφορετικού τύπου πολυμερικές ρητίνες με πληθώρα ενισχυτικών υλικών για την κατασκευή και μελέτη της μηχανικής τους συμπεριφοράς, τόσο πειραματικά όσο και θεωρητικά με την εφαρμογή ημιεμπειρικών μοντέλων πρόβλεψης και ανάλυσης. Για την κατασκευή των δοκιμίων, ανάλογα με τον τύπο του υλικού της μήτρας και της ενίσχυσης, εφαρμόστηκαν διαφορετικές τεχνικές και σύνθετες πειραματικές διαδικασίες. Ενώ, για την μελέτη των μηχανικών, θερμομηχανικών και μορφολογικών τους ιδιοτήτων εφαρμόστηκε σημαντικός αριθμός διαφορετικών τεχνικών χαρακτηρισμού.

Composites are the materials which can be used for a wide variety of applications andproducts such as sports equipment, aerospace and marine because of light and stiffnessproperties. Composites are often made from thermoset resin with glass fibers.In this study, two ways of recycling composites were evaluated, which are microwavepyrolysed composites (MGC) and mechanical composites (GC). These glass fibers weregoing to be compounded with Polypropylene (PP) or Maleic Anhydride ModifiedPolypropylene (MAPP) and then injection moulded the sample by Micro-compounder.In order to get better adhesion to the polymer, a coating was added. The Neoxil 5682-polypropylene water emulsion was evaluated.The samples were characterized by Tensile Testing, Thermogravimetric Analysis (TGA),Different Scanning Calorimetry (DSC), and Dynamic Mechanical Analysis (DMA) to find aoptimum combination of recycled glass fiber reinforced polymer.Microwave pyrolysis is a new research area. The glass fiber, polymer oil and gas can beobtained by heating the composite with microwaves to in an inert atmosphere. The polymeroil can be distillated and then evaluated with GC-MS; in order to obtain the chemicalcompositions.Keywords: Composites, grinded and microwave pyrolyse composites (MGC), grindedcomposites (GC), Polypropylene (PP), Maleic Anhydride Modified Polypropylene (MAPP),Micro-compounder, Tensile Testing, Thermogravimetric Analysis (TGA), Different ScanningCalorimetry (DSC), and Dynamic Mechanical Analysis (DMA), Microwave pyrolysis,polymer oil, distillation, GCMS Analysis. / Program: MSc in Resource Recovery - Sustainable Engineering

Despite the recent development in PLA and PLGA based medical devices, there are still needs to further improve the mechanical performance of bioresorbable medical implants and their bioactivity. This is normally done by optimizing the filler compositions in selected groups ofbiodegradable polymer matrices. In this study, the effects of various filler levels on mechanical strength and thermal properties of PLA and PLGA composites were investigated. Composites containing different dosage of osteoconductive HAp with various particles size (0-5μm, 0-50 μm, nano size), β-TCP, bioactive glass and biodegradable Poly-L-lactide and Polylactide-glycolic acid was manufactured with melt blending, using a twin-screw extruder.The samples were investigated by Differential Scanning Calorimetry (DSC), thermo gravimetric analysis (TGA), Scanning Electron Microscopy (SEM), viscometer, three points bending machine, and Optical Microscopy (OM). The Extruder produced a porous profile. The result from TGA and SEM indicated that there was homogenous filler dispersion in the matrix after compounding.The result from DSC and Viscometer shows that there was some degradation duringcompounding. Mechanical properties of composites were modified by adding filler to matrix. The addition of Bioactive glass, as a filler, increases the degradation of the polymer matrix. The best filler that was applied is 0-5μm and nano HAp. Also in in-vitro degradation part of this thesis work, the effects of calcium phosphate materialsare investigated on degradation process.