Phosphorus-containing high performance polymers have been extensively studied during the last 10 years. These materials are of interest for a variety of optical and fire resistant properties, as well as for their ability to complex with the inorganic salts. This dissertation has focused on the nature of the phosphonyl group interactions with hydroxyl containing polymers, such as the poly(hydroxy ether)s. These may be considered linear models of epoxy resins and are also closely related to dimethacrylate (vinyl ester) matrix resins that are important for composite systems. It has been shown that bisphenol A poly(arylene ether phosphine oxide/sulfone) homo- or statistical copolymers are miscible with a bisphenol A-epichlorohydrin based poly(hydroxy ethers) (PHE), as shown by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC), infrared spectroscopy and , solid state cross polarization-magic angle spinning nuclear magnetic resonance (CP-MAS). These measurements illustrate the strong hydrogen bonding between the phosphonyl groups of the copolymers and the pendent hydroxyl groups of the PHE as the miscibility inducing mechanism. Complete miscibility at all blend compositions was achieved with as little as 20 mole% of phosphine oxide units in the poly(arylene ether) copolymer. Replacement of the bisphenol A moiety by other diphenols, such as hydroquinone, hexafluorobisphenol A and biphenol did not significantly affect blend miscibilities. Miscible polymer blends with PHE were also made by blending poly(arylene thioether phosphine oxide), and fully cyclized phosphine oxide containing polyimides based on (prepared from 2,2'-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) and bis(m-aminophenyl) methyl phosphine oxide (DAMPO)) or bis(m-aminophenyl) phenyl phosphine oxide). Additional research has focused on the influence of these materials on the property characteristics of vinyl ester matrix resins and has shown that the concentration of phosphonyl groups controls the homogeneity of both oligomers and the resulting networks. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and fracture toughness measurements further confirmed the qualitative observations. Metal salts, such as CoCl2 and CuCl2 had earlier been demonstrated to form complexes/nanocomposites with phosphorus-containing poly(arylene ethers). It has been possible to prepare transparent films with 100 mol% of metal chlorides, based upon the phosphonyl groups. The films are transparent, unlike the opaque polysulfone control systems. FTIR results suggested the formation of inorganic salt and polymer complexes at low concentrations. TEM showed homogeneous morphology at low concentrations and excellent dispersion even at high mole % of salts. Cobalt materials reinforce the basic poly(arylene ether)s to provide higher modulus values and influence positively the char yield generated after TGA experiments in air. The cobalt salt/BPADA-DAMPO polyimide composites also yield transparent films, implying very small dimensions. Silica-polymer nanocomposites were also produced by mixing commercial silica colloid/N,N-dimethylacetamide (DMAc) fine dispersions (~ 12 nm) with bisphenol A poly(arylene ether phenyl phosphine oxide). The dry films produced by solution casting are transparent and silica colloids are evenly dispersed (~ 12 nm) into the polymer matrix as shown by TEM. These nanocomposites increased char yield compared with the polymer control, suggesting their fire retardant character. In comparison, the silica/polysulfone hybrid films prepared by the same methods were opaque and the char yield was not improved. This different phase behavior has been explained to be due to the hydrogen bonding between phosphonyl groups and silanol hydroxyl groups on the surface of the nanosilica. / Ph. D.

L‟objectif de cette thèse est de valoriser les polymères styréniques issus des déchets d‟équipements électroniques et électriques. Les polymères considérés sont le polystyrène (PS), le polystyrène choc (HIPS), le poly(acrylonitrile-butadiène-styrène) (ABS), l'ABS couplé avec du polycarbonate (ABS/PC) et le poly(styrène-acrylonitrile) (SAN). Une étude préliminaire a permis de définir deux mélanges à compatibiliser : le mélange PS/ABS et le mélange PS/PC. Pour le mélange PS/ABS, la voie de compatibilisation ionique est étudiée. L‟ajout d‟un copolymère présentant une structure ionique et la création d‟un réseau in-situ sont tentés. Ces deux voies n‟ont pas donné de résultats concluants en termes d‟amélioration des propriétés finales du mélange. Le mélange PS/PC est lui compatibilisé par ajout d‟un copolymère polystyrène bloc-poly(éthylène-butylène)-bloc-polystyrène greffé PC. Ce copolymère est tout d‟abord créé en mélangeur interne, afin d‟étudier différents catalyseurs susceptibles d‟initier le greffage, puis l‟extrusion réactive est utilisée pour synthétiser ce copolymère à grande échelle. Plusieurs taux de copolymère sont alors introduits dans le mélange PS/PC et l‟amélioration des propriétés et des microstructures prouve son effet compatibilisant / The aim of this work consists in the recycling of the styrenic polymers coming from waste of electric and electronic equipments. Polystyrene (PS), high impact polystyrene (HIPS), poly(acrylonitrile-butadiene-styrene) (ABS), its alloy with the polycarbonate (ABS/PC) and poly(styrene-acrylonitrile) (SAN) are considered. A preliminary study permits to choose two blends to study: PS/ABS and PS/PC. In the case of PS/ABS blend, the ionic way of compatibilization was studied. The addition of a copolymer containing an ionic structure and the creation of an ionic network in-situ are investigated. Both these attempts are not conclusive about the improvement of the final properties of the blend. The PS/PC blend is then compatibilized by adding a polystyrene-block-poly(ethylene-butylene)-block-polystyrene grafted polycarbonate. This copolymer is first created in an internal mixer, in order to study different catalysts able to initiate the grafting, and then the reactive extrusion is used to synthesize it on a large scale. Several amounts are introduced in the PS/PC blend and the improvement of the properties and microstructures proves its compatibilizing effect

Made available in DSpace on 2014-12-17T14:07:01Z (GMT). No. of bitstreams: 1 RosanneLFD_DISSERT.pdf: 2030152 bytes, checksum: fac9b7e6c23b892eb3fd86ea5b5f43bc (MD5) Previous issue date: 2011-11-17 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Among the options for plastics modification more convenient, both from a technical-scientific and economic, is the development of polymer blends by processing in the molten state. This work was divide into two stages, with the aim to study the phase morphology of binary blend PMMA / PET blend and this compatibilized by the addition of the poly(methyl methacrylate-co-glycidyl methacrylate-co-ethyl acrylate) copolymer (MMA-GMA-EA). In the first stage is analyzed the morphology of the blend at a preliminary stage where we used the bottle-grade PET in a Haake torque rheometer and the effect of compatibilizer in this blend was evaluated. In the second stage the blend was processed using the recycled PET in a single screw extruder and subsequently injection molding in the shape of specimens for mechanical tests. In both stages we used a transmission electron microscopy (TEM) to observe the morphologies of the samples and an image analyzer to characterize them. In the second stage, as well as analysis by TEM, tensile test, scanning electron microscopy (SEM) and atomic force microscopy (AFM) was performed to correlate the morphology with the mechanical properties. The samples used in morphological analyzes were sliced by cryo-ultramicrotomy technique for the analysis by TEM and the analysis by SEM and AFM, we used the flat face of the block after cut cryogenic. It was found that the size of the dispersed phase decreased with the addition of MMA-GMA-EA in blends prepared in a Haake. In the tensile test, the values of maximum tensile strength and modulus of elasticity is maintained in a range between the value of pure PMMA the pure PET, while the elongation at break was influenced by the composition by weight of the PMMA mixture. The coupling agent corroborated the results presented in the blend PMMA / PETrec / MMA-GMA-EA (80/15/5 %w/w), obtained by TEM, AFM and SEM. It was concluded that the techniques used had a good morphologic correlation, and can be confirmed for final analysis of the morphological characteristics of the blends PMMA / PET / Entre as op??es de modifica??o de pl?sticos mais convenientes, tanto do ponto de vista t?cnico-cient?fico como econ?mico, encontra-se o desenvolvimento de blendas polim?ricas por meio de processamento no estado fundido. Este trabalho foi dividido em dois est?gios, tendo como objetivo o estudo da morfologia de fases da blenda bin?ria PMMA/PET e desta compatibilizada pela adi??o do copol?mero poli(metacrilato de metila-co-metacrilato de glicidila-co-acrilato de etila) (MMA-GMA-EA). No primeiro est?gio analisou-se a morfologia da blenda e avaliou-se o efeito do compatibilizante, onde foi usado o PET grau garrafa em um re?metro de torque Haake. J? no segundo est?gio a blenda foi processada empregando desta vez o PET reciclado em uma extrusora monorosca, e posteriormente, moldada por inje??o em forma de corpos de prova para ensaios mec?nicos. Nos dois est?gios utilizou-se a microscopia eletr?nica de transmiss?o (MET) para observar as morfologias das amostras e um analisador de imagens para caracteriz?-las. No segundo estagio, al?m da an?lise por MET, foi realizado ensaio de tra??o, microscopia eletr?nica de varredura (MEV) e microscopia de for?a at?mica (MFA), buscando correlacionar a morfologia com as propriedades mec?nicas. As amostras utilizadas nas an?lises morfol?gicas foram fatiadas por meio da t?cnica crio-ultramicrotomia para na an?lise por MET e para as an?lises por MEV e por MFA, foi utilizada a face plana do tarugo p?s-corte criog?nico. Verificou-se que o tamanho da fase dispersa diminui em fun??o da adi??o do copol?mero MMA-GMA-EA nas blendas preparadas no re?metro Haake. No ensaio de tra??o, os valores de resist?ncia m?xima sob tra??o e m?dulo de elasticidade mantiveram-se em um patamar entre o valor de PMMA puro e do PET puro, enquanto que o alongamento na ruptura mostrou-se influenciada pela composi??o em massa de PMMA na mistura. O agente compatibilizante corroborou nos resultados apresentados da blenda PMMA/PETrec /MMA-MGA-EA (80/15/5), obtidos por MET, MFA e MEV. Concluiu-se que as t?cnicas morfol?gicas utilizadas apresentaram uma boa correla??o e corroboraram para an?lise final das caracter?sticas morfol?gicas das blendas PMMA/PET

Made available in DSpace on 2014-12-17T14:07:18Z (GMT). No. of bitstreams: 1 LaureniceMP_DISSERT.pdf: 7523564 bytes, checksum: 3bb1b06da6a21522b0974a84935760a3 (MD5) Previous issue date: 2014-12-28 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The development of new materials to fill the demand of technological advances is a challenge for many researchers around the world. Strategies such as making blends and composites are promising alternatives to produce materials with different properties from those found in conventional polymers. The objective of this study is to evaluate the effect of adding the copolymer poly(ethylene methyl acrylate) (EMA) and cotton linter fibers (LB) on the properties of recycled poly(ethylene terephthalate) (PETrec) by the development of PETrec/EMA blend and PETrec/EMA/LB blend composite. In order to improve the properties of these materials were added as compatibilizers: Ethylene - methyl acrylate - glycidyl methacrylate terpolymer (EMA-GMA) and maleic anhydride grafted polyethylene (PE-g-MA). The samples were produced using a single screw extruder and then injection molded. The obtained materials were characterized by thermogravimetry (TG), melt flow index (MFI) mensurements, torque rheometry, pycnometry to determinate the density, tensile testing and scanning electron microscopy (SEM). The rheological results showed that the addition of the EMA copolymer increased the viscosity of the blend and LB reduces the viscosity of the blend composite. SEM analysis of the binary blend showed poor interfacial adhesion between the PETrec matrix and the EMA dispersed phase, as well as the blend composite of PETrec/EMA/LB also observed low adhesion with the LB fiber. The tensile tests showed that the increase of EMA percentage decreased the tensile strength and the Young s modulus, also lower EMA percentage samples had increased the elongation at break. The blend composite showed an increase in the tensile strength and in the Young`s modulus, and a decrease in the elongation at break. The blend formulations with lower EMA percentages showed better mechanical properties that agree with the particle size analysis which showed that these formulations presented a smaller diameter of the dispersed phase. The blend composite mechanical tests showed that this material is stronger and stiffer than the blend PETrec/EMA, whose properties have been reduced due to the presence of EMA rubbery phase. The use of EMA-GMA was effective in reducing the particle size of the EMA dispersed phase in the PETrec/EMA blend and PE-g-MA showed evidences of reaction with LB and physical mixture with the EMA / O desenvolvimento de novos materiais para atender as necessidades dos avan?os tecnol?gicos ? um desafio enfrentado por pesquisadores de todo o mundo. No que diz respeito aos materiais polim?ricos, estrat?gias como a confec??o de blendas e comp?sitos s?o alternativas promissoras para atender a demanda por materiais com propriedades diferentes das encontradas nos pol?meros convencionais. O objetivo deste trabalho ? avaliar o efeito da adi??o do copol?mero poli(etileno-acrilato de metila) (EMA) e da fibra de linter de algod?o (LB) nas propriedades do poli(tereftalato de etileno) reciclado (PETrec). Para isto, foram desenvolvidos a blenda PETrec/EMA e o comp?sito da blenda PETrec/EMA/LB. Com o intuito de melhorar as propriedades destes materiais foram adicionados agentes compatibilizantes: terpol?mero etileno-acrilato de metila-metacrilato de glicidila (EMA-GMA) e o polietileno enxertado com anidrido mal?ico (PE-g-MA). As misturas foram produzidas por meio de uma extrusora monorosca e, em seguida, moldados por inje??o. As caracteriza??es realizadas foram termogravimetria (TG), medida de ?ndice de fluidez (MFI), reometria de torque, determina??o da densidade por picnometria, ensaio de tra??o uniaxial e microscopia eletr?nica de varredura (MEV). Os resultados reol?gicos mostraram que a adi??o do copol?mero EMA aumentou a viscosidade da mistura e o LB reduziu a viscosidade da blenda PETrec/EMA. A an?lise por MEV da blenda bin?ria mostrou baixa ades?o interfacial entre a matriz de PETrec e a fase dispersa de EMA, assim como no comp?sito da blenda PETrec/EMA/LB, tamb?m observou-se uma baixa ades?o com a fibra de LB. Os ensaios de tra??o mostraram que o aumento da porcentagem de EMA diminuiu a resist?ncia m?xima e o m?dulo de elasticidade, e, para as formula??es com menor porcentagem de EMA verificou-se um aumento do alongamento na ruptura. O comp?sito da blenda apresentou um aumento na resist?ncia m?xima e no m?dulo de elasticidade, e uma redu??o no alongamento de ruptura. As formula??es da blenda com menores porcentagens de EMA apresentaram propriedades mec?nicas melhores, que corrobora com as an?lises de tamanho de part?cula que mostraram que estas formula??es apresentaram menor di?metro m?dio de fase dispersa. Os resultados de ensaios mec?nicos do comp?sito da blenda mostraram que essa mistura resultou em um material com maior resist?ncia mec?nica e rigidez do que a blenda PETrec/EMA, cujas propriedades foram reduzidas em fun??o da fase borrachosa EMA. O uso do EMA-GMA foi eficiente na redu??o do tamanho de part?culas da fase dispersa do EMA na blenda PETrec/EMA e o PE-g-MA apresentou ind?cio de rea??o com o LB e mistura f?sica com o EMA

Due to the wide range of properties of plastics (e.g. low density, low electrical and thermal conductivity), conventional materials will be increasingly substituted by polymers. Multifarious requirements on technical parts intensify the demand for joining processes, which ensure the reliable joining of incompatible thermoplastics. In this case, material bonded joints are approaching their limits. The present study focusses on the welding of two incompatible thermoplastic polymers (polyamide and polyethylene) by using adapted blend materials, which are compatible to both joining components. The results prove the feasibility of this method and indicate the high potential regarding the reachable joint strength. Furthermore, the study demonstrates the challenges regarding the suitable application of blend materials and deals with open scientific questions concerning their industrial usage.

L’EVOH est un copolymère thermoplastique semi-cristallin composé de segments de polyéthylène et d’alcool polyvinylique de proportion variable. Grâce notamment à une importante densité d’énergie cohésive lui conférant d’excellentes propriétés barrière à l’oxygène et aux arômes en condition anhydre, ce matériau est aujourd’hui largement utilisé dans l’élaboration d’emballages alimentaires multicouches. Sa grande sensibilité à l’eau, provoquant une détérioration importante des propriétés du matériau en conditions hydratées, reste cependant la principale problématique liée à son utilisation actuelle. Dans ce contexte, les travaux ont dans un premier temps porté sur la compréhension approfondie du comportement d’hydratation de l’EVOH afin de mettre en évidence des relations propriétés-structure, ce qui n’avait pas été réalisé jusqu’à présent. Deux axes de recherches ont ensuite été développés dans le but d’améliorer les propriétés barrière du matériau aussi bien à l’état anhydre qu’à l’état hydraté, tout en conservant une bonne transparence et une tenue mécanique correcte: le mélange de polymère d’une part, et l’approche nanocomposite d’autre part. Le choix de la voie fondu, procédé de mise en œuvre peu décrit dans la littérature pour ces systèmes, et celui des charges ont été guidés par la possibilité de transposer facilement les études à l’échelle industrielle / EVOH is a semi-crystalline thermoplastic copolymer composed of polyethylene and polyvinyl alcohol segments in various contents. Thanks to an important cohesive energy density leading to excellent oxygen and food aromas barrier properties in anhydrous state, this material is currently widely used in the elaboration of multilayer food packaging. Its high moisture sensitivity, causing an important deterioration of the properties of the material in hydrated conditions, still constitutes the main inconvenient for its current use. In this context, the studies were firstly focused on the detailed comprehension of the hydration behavior of EVOH in order to underline properties-structure relations, which was still unrealized. Two research axes were then developed in order to improve the barrier properties of the material in both dry and hydrated states, while remaining mechanical behavior and transparency stable: the polymers blend, on the one hand, and the nanocomposite approach on the other hand. The choice of the melting way, rarely described in the literature for these systems, and the one of the fillers nature were dictated by the possibility to easily transpose the experiments to an industrial scale

No description available.

The goal of the work is to study possibilities for the modification of interface in immiscible polymer blends, which determine to a large degree of the blend properties. For this purpose novel coupling agents (named SCA) containing 2-oxazoline, 2-oxazinone, and hydrosilane reactive sites have been prepared. In blends of amino- functional and carboxylic acid terminated polymers the oxazoline and oxazinone units of the SCA react selectively with one of the polymers and, therefore, the SCA should locate at the interface. The remaining hydrosilane sites can now be used for further modification, e.g. for crosslinking. In the thesis we discussed the effect of the SCA on the morphology and thermal and rheological properties of blends based on carboxylic acid terminated polystyrene (PS) and amino-terminated polyamide 12 (PA) or poly(methyl methacrylate) (PMMA). The morphology of the blends and the location of the SCA strongly depends on the processing conditions. The crosslinkability of the interface could be proven by changes in the solubility behavior of the blends.

Acceptor copolymers with low lowest unoccupied molecular orbital (LUMO) energy levels are key materials for organic electronics. In the present work, quaternization of pyridine-flanked diketopyrrolopyrrole (PyDPPPy) is used to lower the LUMO energy level of the resulting monomer (MePyDPPPy) by as much as 0.7 eV. The drastically changed electronic properties of MePyDPPPy hinder a second methylation step even in an excess of trimethyloxonium tetrafluoroborate and thereby give access to the asymmetric functionalization of N-heterocycle-flanked DPP building blocks. The corresponding n-type polymeric ionene PMePyDPPPyT2 with bithiophene as comonomer forms thixotropic organogels with the p-type polythiophene P(g42T-TT), indicative of specific cross-interactions between this couple of copolymers. Gelation of polymer blend solutions, which is absent for other couples of p-type/ n-type polymers, is of general interest for (co)processing and orientation of different electronic polymers simultaneously into films or filaments. Detailed optical and electronic characterization reveals that films processed from organogels exhibit ground-state electron transfer (GSET) enabled by suitably positioned highest occupied molecular orbital (HOMO) and LUMO energy levels of P(g42T-TT) (−4.07 eV) and PMePyDPPPyT2 (−4.20 eV), respectively. Furthermore, molecular interactions related to gelation and GSET do not appear to significantly influence the morphology of the polymer blend films.

The rise in the world population can be correlated with an increase in energy need. Fossil fuels are not going to able to cover this need in energy because not only are they limited, they also have a negative effect on the environment. A reason the more to switch renewable energy. One of the most popular renewable energy source is solar energy. The organic solar cell could be a low-cost, light-weight and flexible option for photovoltaics. This thesis will discuss the morphology of the active layer of an organic solar cell. The polymer poly(9,9-dioctylfluorenyl-2,7-diyl) and the fullerene derivate [6,6]-phenyl C61-butyric acid methyl ester were used as model components for the active layer. These two components were processed in different solvents, different ratios, different total concentrations and were either dip- or spin-coated on glass substrates. These samples were analyzed with atomic force microscopy, steady state and time resolved fluorescence and UV/Vis spectroscopy. The analysis show that the morphology of the films processed in chloroform and tetrahydrofuran would react very similar in α-phase and β-phase by dip- and spin-coated samples. Xylene would react the opposite as tetrahydrofuran and chloroform while ethylbenzene would react little with different samples. / De stijging in wereldpopulatie kan gelinkt worden met een stijging in energieverbruik. Het is niet aan te raden om fossiele brandstoffen te gebruiken voor deze energiestijging want niet alleen zijn ze beperkt aanwezig op aarde ook zijn ze niet goed voor het milieu. Een reden te meer om naar duurzame energie over te schakelen. Één van de meeste populaire energiebronnen is zonne-energie. Hierbij zou de organische zonnecel een goedkope, lichte en flexibele optie zijn. Deze thesis zal de morfologie van de actieve laag van een zonnecel bespreken. Het polymeer poly(9,9-dioctylfluorenyl-2,7-diyl) en het fullereen derivaat [6,6]-fenyl C61-butylzuur waren de twee model componenten voor de actieve laag. Deze twee componenten werden in verschillende oplosmiddelen, verschillende verhoudingen en verschillende totaal concentraties bereidt en werden vervolgens gedipcoated of gespincoated op glazen substraten. De stalen werden vervolgens geanalyseerd door atomic force microscopy, steady state en time resolved fluorescence en UV/Vis spectroscopy. De analyse toont dat de morfologie van de films bereidt in chloroform en tetrahydrofuraan gelijkaardig reageren in α- fase en β-fase bij gedipt- en gespincoaten stalen. Terwijl xyleen net omgekeerd reageert als chloroform en tetrahydrofuraan. Bij ethylbenzeen zou de fases maar heel weinig veranderen bij de verschillende stalen.