På grund av den rådande klimatförändringen och de globala problem som plast orsakar i miljön blir det allt viktigare att dagens linjära materialanvändning ändras till en cirkulär användning. Inom fordonsindustrin har kravet på ökad tillgänglighet och kvalitet på återvunna material identifierats. Som följd startades forskningsprojektet Sustainable Vehicle Interior Solutions (SVIS) samordnat av RISE IVF där behovet av en mer hållbar produktion av fordonsinteriörer tas upp. Ett mål är att minska och återvinna produktionsavfall. Den här studien undersöker möjligheten att återvinna textil och plast från en interiör komponent av multimaterial, som i detta fall är en textilklädd plaststolpe. Stolpen är gjord av polykarbonat (PC)/poly(akrylnitril-butadien-styren) (ABS) plast och polyestertextil (PET). Mekanisk återvinning utfördes på den textilklädda stolpen. Möjligheten att separera textil från plast undersöktes och testades i en kvarn med en dammavskiljare. Prover innehållande olika mängder PET förberedes och återvanns för att studera påverkan av PET på materialegenskaperna. Två olika kompatibiliseringsmedel användes för att undersöka om blandningarnas kompatibilitet ökade. Hur väl textil separerats från plast analyserades genom jämförelse av bulkdensitet mellan proverna. För att undersöka effekten av kompatibiliseringsmedel och hur förekomsten av PET påverkar PC/ABS utfördes mekanisk testning, DSC och SEM. Resultaten visade att separationen av textil från plast inte var fullständig på grund av mycket hög vidhäftning mellan textilen och plasten. Bibehållna mekaniska egenskaper, förutom brottförlängning, erhölls för alla återvunna prover oavsett PET-mängd. Därför var det möjligt att dra slutsatsen om att förekomsten av PET inte påverkar materialets egenskaper negativt och att separation eller tillsats av kompatibiliseringsmedel inte är nödvändigt. Vidare visar resultaten att PET blir blandbar med PC men inte påverkar ABS-fasen. Kemisk återvinning genom glykolys utfördes på svart och beige polyestertextil av PET erhållet som avklipp från produktionen av stolparna. Glykolysen utfördes i laboratorieskala med etylenglykol (EG) som lösningsmedel. Reaktionen ägde rum vid 230℃ under 1 timme med överskott av lösningsmedel och en Mg-Al blandad oxidkatalysator. Slutprodukten separerades från rester genom flera filtreringssteg och analyserades med DSC. Från resultatet observerades det att den erhållna slutprodukten var den önskade bis(2-hydroxyetyl) tereftalat (BHET) monomeren. Färgämnen från textilen fanns fortfarande kvar i monomeren efter depolymerisation. Därför utfördes avfärgning. För den svarta textilen testades adsorption med aktivt kol och extraktion med etylenglykol som avfärgningsmetoder. För den beige textilen utfördes enbart adsorption med aktivt kol. De avfärgade produkterna analyserades genom färgmätning och/eller genom jämförelse med varandra. Resultatet visade att adsorption med aktivt kol är en effektiv avfärgningsmetod för den beige textilen, men inte för den svarta textilen. Framgångsrik avfärgning av den svarta textilen erhölls istället genom extraktion med etylenglykol. Sammanfattningsvis, mekanisk återvinning av den textilklädda stolpen resulterar i bibehållna värden för de mekaniska egenskaperna hos det återvunna materialet, förutom för brottförlängnigen. Detta bör göra det återvunna materialet lämpligt för användning i fordonsapplikationer, men inte för återvinning i ett slutet kretslopp (closed loop recycling) på grund av säkerhetsaspekter hos stolpen. Om hög kraft appliceras måste materialet kunna ändra form utan att gå sönder. Återvinning genom glykolys visar potential för att den avklippta polyestertextilen kan återvinnas i ett slutet kretslopp eftersom den avfärgade monomeren skulle kunna ompolymeriseras till ny PET. Det kan undersökas i framtida studier. / Due to the current climate change and the global problems plastics cause in the environment, it becomes increasingly important that today’s linear use of materials is changed to a circular use. In the automotive industry, the demand for increased availability and quality of recycled materials has been recognized. Following this, the research project Sustainable Vehicle Interior Solutions (SVIS) coordinated by RISE IVF was started in which the need for a more sustainable production of vehicle interiors is addressed. An objective is to reduce and recycle production waste. This study investigates the possibility to recycle textile and plastic from an interior multi-material component which in this case is a textile dressed plastic pillar. The pillar is made of polycarbonate (PC)/poly(acrylonitrile butadiene styrene) (ABS) plastic and polyester (PET) textile.  Mechanical recycling was performed on the textile dressed pillar. The possibility to separate textile from plastic was investigated and tested in a mill with a dust separator. Samples containing different amounts of PET were prepared and recycled to study the influence of PET. Two different compatibilizers were used to investigate potential improvement in compatibility of the blends. The level of separation of textile from plastic was analyzed by comparison of bulk density between the samples. To investigate the effect of compatibilizers and how the presence of PET influences the PC/ABS, mechanical testing, DSC and SEM were performed. The results showed that the separation of textile from plastic was not complete due to very high adhesion between the textile and plastic. Retained mechanical properties, except for the strain at break, were obtained for all recycled samples. Therefore, it could be concluded that the presence of PET does not affect the properties of the material negatively and separation or addition of compatibilizer is unnecessary. The results further show that PET becomes miscible with PC but does not affect the ABS phase. Chemical recycling through depolymerization with glycolysis was performed on black and beige polyester (PET) textile waste obtained as cut-off from the production of the pillars. The glycolysis was performed in lab-scale with ethylene glycol (EG) as solvent. The reaction took place at 230℃ for 1h with excess of solvent and a Mg-Al mixed oxide catalyst. The final product was separated from residues through several filtration steps and analyzed with DSC. From the result it could be observed that the obtained final product was the desired bis(2-hydroxyethyl) terephthalate (BHET) monomer. Dyes from the textile were still present in the monomer after depolymerization. Therefore, decolorization was performed. For the black textile, adsorption with active carbon and extraction with ethylene glycol were tested as decolorization methods. For the beige textile, solely adsorption with active carbon was performed. The decolorized products were analyzed by color measurement and/or through comparison to each other. The result showed that adsorption with active carbon is an effective decolorization method for the beige textile, but not for the black textile. Successful decolorization of the black textile was instead obtained by extraction with ethylene glycol.  To conclude, mechanical recycling of the textile dressed pillar results in retained values of the mechanical properties of the recycled material, except for the strain at break. This should make the recycled material suitable for use in automotive application, though not closed loop recycling because of safety aspects of the pillar. If high force is applied, the material needs to be able to change shape without breaking. Recycling through depolymerization shows potential for closed loop recycling of the polyester textile cut-off since the decolorized monomer could be repolymerized into new PET. This could be investigated in future studies.

L’objectif de cette thèse est de contribuer à la compréhension et à la modélisation de la cristallisation induite. Le phénomène est caractérisé pour deux matériaux : le PET et le caoutchouc naturel réticulé. Les conditions favorables au phénomène, de type caoutchoutique sont déterminées par analyses calorimétriques et spectroscopiques. La microstructure qui se développe au cours de la déformation est observée par diffraction des rayons X.Le PET est déformé en traction uni- et biaxiale. Une partie des étirages est suivie d’une relaxation des contraintes, une autre est suivie d’une trempe rapide. Il ressort de l’étude que l’étirage du PET dans ces conditions n’aboutit pas à l’obtention d’un cristal PET avec toutes les périodicités qui lui sont propres.Le caoutchouc naturel est déformé en traction uniaxiale et en cisaillement précédé d’un étirage uniaxial. En cisaillement, la phase cristalline obtenue au cours du pré-étirage ou du cisaillement tourne et tend à s’orienter comme les directions des déformations principales mais avec un retard angulaire. L’extension principale est utilisée pour étudier la phase cristalline obtenue pour les différents modes de sollicitation.Un modèle de comportement visco-hyperélastique, décrit dans le cadre de la thermodynamique des processus irréversibles, est étendu afin de reproduire le durcissement mécanique lié au développement d’une phase organisée/cristalline. Le modèle permet de reproduire les différents comportements mécaniques observés expérimentalement. / The present PhD thesis aims at a better understanding and modeling of strain-induced-crystallization. The phenomenon is characterized for two polymers: PET and crosslinked natural rubber. Strain conditions leading to strain-induced-crystallization are determined by thermal and dynamic mechanical analysis. The developing microstructure is observed by X-ray scattering.The PET is stretched in uni- and biaxial tension. A part of samples is rapidly quenched after stretching and another is submitted to a stress relaxation after stretching. The studies demonstrate that the stretching of PET does not enable the formation of a complete PET crystal with all its own families of planes.The crosslinked natural rubber is stretched in uniaxial tension and in shear preceded by uniaxial stretching. In shear, the crystalline phase, appeared during the pre-stretching or during the shear rotates and has a tendency to orient as the directions of the principal strains. The principal elongation is used to compare the crystallization under the different stresses.A constitutive modeling for visco-hyperelastic behaviors, in a complete thermodynamics framework of irreversible processes, is extended in order to reproduce le mechanical hardening related to the development of an organized/crystalline phase. The modeling successes in reproducing the experimental behaviors in uploading/unloading for various strain conditions.

Made available in DSpace on 2015-04-22T22:02:02Z (GMT). No. of bitstreams: 1 Dissertacao Vera Lucia Imbiriba Bentes.pdf: 2492256 bytes, checksum: 6177030a4e14eea635a818dbbb2b0e91 (MD5) Previous issue date: 2008-11-18 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The growing use and application of plastic materials have raised the index of residues of these materials in the great cities, mainly poli(ethylene tereftalate) (PET). Amongst the recycling techniques proposals to minimize the accumulation of these polymeric residues, the chemical recycling, has intensified the interest, on the part of the scientific community, a time that products of a high aggregate value can be achieved, that they can be used in new industrial processes. Of this form, the present work had as objective, to investigate the solubility of the PET postconsumer in different chemical agents, to promote the depolymerization chemical of the PET by hydrolysis basic and to carry preliminary study of the degradation of monomers post-hydrolysis through heterogeneous Fenton reaction using pure and Co- and Mn-doped magnetites catalysts, as source of Fe2+ in H2O2 having as molecule of reference for the study, the methylene blue (MB). The hydrolysis reaction was carried in reflux system under temperature of 110 oC for three hours using NaOH 7.5 mol L-1 as catalytic and the gotten products had been characterized by spectroscopic method in the region of the IV. The reactions of heterogeneous Fenton had been monitored by UV-visible measurements. Between the gotten results, it could be verified (i) PET solubility in phenol concentrated solution of about 40 oC; (ii) the chemical recycling of the PET presented yield of 99.72 % with recovery of monomers terephthalic acid (AT) and ethylene glycol (EG) monomers which were characterized by IV; (iii) the study of degradation of the methylene blue (MB) 20 mg L-1 was monitored by UV-visible measurements in λmax = 663 nm thus the kinetic model that better described the process was of the pseudo first-order, disclosing bigger capacity of degradation for the doped magnetite catalysers with Co and Mn, respectively; (iv) degradation of AT, was observed in λmax = 283 nm and had a similar behavior to the reference molecule; (v) the loss of the organic load of the solution afterhydrolysis of the PET was bottle was analyzed qualitatively by comparison of the spectrums obtained by FT-IV/ATR before and after of the heterogeneous Fenton reaction. Thus the results gotten in this work are considered satisfactory and promising for news studies future. / O crescente uso e aplicação de materiais plásticos tem elevado os índices de resíduos desses materiais nos lixões das grandes cidades, principalmente, o poli(tereftalato de etileno) (PET). Dentre as técnicas de reciclagem propostas para minimizar o acúmulo desses resíduos poliméricos, a reciclagem química, tem despertado maior interesse por parte da comunidade científica, uma vez que se podem obter produtos de elevado valor agregado, que podem ser utilizados em novos processos industriais. Dessa forma, o presente trabalho teve como objetivos, investigar a solubilidade do PET pós-consumo em diferentes agentes químicos, promover a despolimerização química do PET via hidrólise básica e realizar estudo preliminar da degradação dos monômeros pós-hidrólise através de reação de Fenton heterogênea utilizando catalisadores de magnetitas pura e dopadas com Co e Mn, como fonte de Fe2+em presença de H2O2, tendo como molécula de referência para o estudo, o corante azul de metileno (MB). A reação de hidrólise foi conduzida em sistema de refluxo sob temperatura de 110oC por três horas, utilizando NaOH 7,5 molL-1 como catalisador da reação e os produtos finais foram caracterizados por método espectroscópico na região de absorção do IV. As reações de Fenton heterogênea foram monitoradas através de medidas espectrofotométricas na região do UV-visível. Entre os resultados obtidos, pôde-se verificar (i) a solubilidade do PET em solução concentrada de fenol ∼ 40 oC; (ii) a reciclagem química do PET apresentou rendimento de 99,72 % com recuperação dos monômeros do ácido tereftálico (AT) e de etileno glicol (EG) que foram caracterizados por IV; (iii) o estudo da degradação da molécula de referência, MB 20 mg L -1, foi monitorado em λ = 663 nm, de maneira que o modelo cinético que melhor descreveu o processo foi o de pseudo primeira-ordem, revelando maior capacidade de degradação para os catalisadores de magnetitas dopadas com Co e Mn, respectivamente; (iv) a degradação do AT, foi observado em λ = 283 nm e teve comportamento semelhante ao da molécula de referência; (v) a perda de carga orgânica da solução pós-hidrólise do PET foi feita qualitativamente por comparação dos espectros IV/ATR das amostras de solução pós-hidrólise antes e depois de submetida á reação de Fenton. De maneira geral os resultados obtidos neste trabalho são considerados satisfatórios e promissores para outros futuros estudos.

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 2014-12-17T14:07:12Z (GMT). No. of bitstreams: 1 JucikleciaSR_DISSERT.pdf: 18878091 bytes, checksum: 13af0d90d6b4b0980975e46b7393cd8c (MD5) Previous issue date: 2013-08-23 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / This work studied the immiscible blend of elastomeric poly(methyl methacrylate) (PMMA) with poly(ethylene terephthalate) (PET) bottle grade with and without the use of compatibilizer agent, poly(methyl methacrylate-co-glycidyl methacrylate - co-ethyl acrylate) (MGE). The characterizations of torque rheometry, melt flow index measurement (MFI), measuring the density and the degree of cristallinity by pycnometry, tensile testing, method of work essential fracture (EWF), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were performed in pure polymer and blends PMMA/PET. The rheological results showed evidence of signs of chemical reaction between the epoxy group MGE with the end groups of the PET chains and also to the elastomeric phase of PMMA. The increase in the concentration of PET reduced torque and adding MGE increased the torque of the blend of PMMA/PET. The results of the MFI also show that elastomeric PMMA showed lower flow and thus higher viscosity than PET. In the results of picnometry observed that increasing the percentage of PET resulted in an increase in density and degree crystallinity of the blends PMMA/PET. The tensile test showed that increasing the percentage of PET resulted in an increase in ultimate strength and elastic modulus and decrease in elongation at break. However, in the phase inversion, where the blend showed evidence of a co-continuous morphology and also, with 30% PET dispersed phase and compatibilized with 5% MGE, there were significant results elongation at break compared to elastomeric PMMA. The applicability of the method of essential work of fracture was shown to be possible for most formulations. And it was observed that with increasing elastomeric PMMA in the formulations of the blends there was an improvement in specific amounts of essential work of fracture (We) and a decrease in the values of specific non-essential work of fracture (βWp) / Neste trabalho ? estudada a blenda imisc?vel poli(metacrilato de metila) (PMMA) elastom?rico com poli(tereftalato de etileno) (PET) grau garrafa com e sem o uso do agente compatibilizante, poli(metacrilato de metila-co-metacrilato de glicidilaco- acrilato de etila) (MGE). As caracteriza??es de reometria de torque, medida de ?ndice de fluidez (MFI), determina??o da densidade e do grau de cristalinidade por picnometria, ensaio de tra??o uniaxial, m?todo do trabalho essencial fratura (EWF), microscopia eletr?nica de varredura (MEV) e microscopia eletr?nica de transmiss?o (MET), foram realizadas nos pol?meros puros e nas blendas PMMA/PET. Os resultados reol?gicos apresentaram ind?cios de rea??o qu?mica entre o grupo ep?xi do MGE com os grupos finais de cadeias do PET e, tamb?m, com a fase elastom?rica do PMMA. O aumento na concentra??o de PET reduziu o torque e a adi??o do MGE aumentou o torque da blenda PMMA/PET. Os resultados de MFI mostraram tamb?m que, o PMMA elastom?rico apresentou menor fluidez e, consequentemente, maior viscosidade que o PET. Nos resultados de picnometria observou-se que, o aumento da porcentagem de PET proporcionou um aumento na densidade e no grau de cristalinidade das blendas PMMA/PET. Os ensaios de tra??o mostraram que, o aumento da porcentagem de PET proporcionou um aumento na resist?ncia m?xima e no m?dulo de elasticidade e uma diminui??o no alongamento na ruptura. Entretanto, na invers?o de fase, onde a blenda apresentou ind?cios de uma morfologia cocont?nua e tamb?m, com 30% de fase dispersa PET e compatibilizada com 5% de MGE, verificaram-se resultados expressivos de alongamento na ruptura em rela??o ao PMMA elastom?rico. A aplicabilidade do m?todo do trabalho essencial de fratura mostrou-se poss?vel para a maioria das formula??es. Observou-se ainda que, com o aumento do PMMA elastom?rico nas formula??es das blendas, ocorreu uma melhoria nos valores do trabalho essencial espec?fico de fratura (We) e uma redu??o nos valores do trabalho n?o essencial espec?fico de fratura (βWp)

Made available in DSpace on 2016-06-02T20:36:56Z (GMT). No. of bitstreams: 1 6787.pdf: 6528368 bytes, checksum: 59d1763870e2de400270ed05b0ac6675 (MD5) Previous issue date: 2015-03-25 / Universidade Federal de Sao Carlos / Polyelectrolytes complexes (PECs) are defined as materials formed by combining oppositely charged polyelectrolytes together via ionic interaction. PECs have some unique physical properties such as non-solubility in common organic solvents, high surface hydrophilicity, tunable surface charge, and stable structures. A new type of PEC based on chitosan (CS) and sulfonate poly(ethylene terephthalate) (SPET) were synthesized in two different media, buffer solution and salt solution acidified with acetic acid. Fourier transform infrared spectroscopy (FTIR), zeta potencial, X-ray diffraction, thermal gravity analysis and differential scanning calorimetry were used to characterize the chemical structure, particle charge, crystallinity and thermal stability. To assess how the internal structure of the PEC and the subsequent membrane formation can affect water and salts transport capacity of microporous polycarbonate membrane, PECs solutions were spread via casting in commercial membranes with pore size of 5 μm. These membranes were characterized by Scanning Electron Microscopy (SEM), Water Vapor Flux, Resistance to Ion Migration and Membrane Potential. FTIR results indicated the electrostatic interaction of polyelectrolyte to form the polyelectrolyte complex. From the results of zeta potential it was found that the surfaces of CS/SPET nanoparticles have positive charges of about 25 to 44 mV. TGA curves showed that the PECs were more stable than their polyelectrolytes. The deposition of the PEC on the membranes was confirmed by SEM images and the increase of water vapor flux of membranes indicated that the presence of the complex significantly alter the hydrophilic profile of the polycarbonate matrix. The microfiltration of Saccharomyces cerevisiae cells demonstrated that membranes modified with PECs retained more of these organisms than the commercial membrane without modification. / Complexos de polieletrólitos (PECs) são definidos como materiais formados pela combinação de polieletrólitos de cargas opostas via interação eletrostática. PECs possuem algumas propriedades únicas como não solubilidade em solventes comuns, alta hidrofilicidade, superfícies modificáveis e estruturas estáveis. Um novo tipo de PEC baseado em quitosana (QT) e poli(tereftalato de etileno) sulfonado (PET-S) foi sintetizado em dois meios diferentes, uma solução tampão ácida e uma solução salina acidificada. Espectroscopia de infravermelho com transformada de Fourier (FTIR), potencial zeta, difração de raios X, análise termogravimétrica e calorimetria diferencial exploratória foram usados para caracterizar a estrutura química, carga da partícula, cristalinidade e estabilidade térmica. Para avaliar como a estrutura interna do PEC e a subsequente formação de membrana pode afetar o transporte de água e sais em membranas de policarbonato microporosas, soluções de PEC foram espalhadas via casting em membranas comerciais com tamanho de poro de 5 μm. As membranas foram caracterizadas utilizando microscopia eletrônica de varredura, transporte de vapor de água, resistência a migração iônica e potencial de membrana. Resultados de FTIR comprovaram a interação eletrostática entre os polieletrólitos e consequentemente a formação dos PECs. O potencial zeta dos PECs apontou que eles apresentam superfícies positivas que variam de 25 a 44 mV. O TGA demonstrou que os PECs são termicamente mais estáveis do que seus polieletrólitos precursores. A deposição dos PECs sobre as membranas foi confirmada pelo MEV e o aumento do fluxo de vapor de água indicou que a presença dos PECs altera significativamente o caráter hidrofílico do policarbonato. A microfiltração de células Saccharomyces cerevisiae mostrou que as membranas modificadas com PECs reteram mais desses organismos do que a membrana comercial sem modificação.

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El propósito de esta tesis doctoral fue evaluar la influencia de los diferentes procesos de gestión de residuos, tales como la valorización material, energética y biológica de dos poliésteres clave de la industria del embalaje: el actual no-renovable poli (tereftalato de etileno) (PET) y el potencial candidato para sustituirlo en un futuro próximo, la polilactida (PLA) de base renovable. Se utilizaron diversas plantas piloto para simular las condiciones de la degradación sufrida por PET y PLA en el reciclado mecánico, la pirólisis, la combustión y el enterramiento en suelo. Los cambios fueron monitorizados por calorimetría diferencial de barrido (DSC), análisis dinámico-mecánico-térmico (DMTA), análisis termogravimétrico (TGA), espectrometría infrarroja con transformada de Fourier (FTIR), espectroscopia de correlación 2D-IR para el análisis de gases (EGA), espectrometría de masas MALDI-TOF, microscopía electrónica de barrido (SEM), índice de fluidez de masa fundida (MFR), ensayos de tracción e impacto Charpy y viscosimetría. Se han propuesto, desarrollado y aplicado diversas estrategias y procedimientos analíticos para establecer parámetros fiables para ser utilizados como indicadores de la degradación y por tanto controlar la influencia de cada proceso de valorización en la calidad del material. El comportamiento de PET y PLA reciclados mecánicamente se evaluó en base a sus propiedades químicas, microestructurales, mecánicas y térmicas. Se observó una pérdida general de prestaciones de PET y PLA reprocesado una vez y dos veces, respectivamente. Además, las propiedades de los materiales reciclados de PLA fueron mejores en términos relativos a los productos reciclados de PET. Las descomposiciones térmica y termo-oxidativa causadas por los procesos de pirolisis y combustión se evaluaron sobre la estabilidad térmica, gases emitidos y cinéticas de descomposición. Se destaca el uso de la combustión controlada para ambos polímeros, ya que se necesita menos energía para iniciar la descomposición, y la mezcla de gases que se desprenden es más homogénea. / Badía Valiente, JD. (2011). Strategies and analytical procedures for a sustainable plastic waste management. An application to poly (ethylene terephthalate) and polylactide in the packaging sector [Tesis doctoral]. Editorial Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/12890

Plasma-based surface modifications offer many interesting possibilities for the production of high value-added polymeric materials. In this work, different plasma-based synthetic concepts were employed to endow poly(ethylene terephthalate) (PET) fabrics with accessible amine functionalities. These concepts were compared to find out the appropriate engineering methods, which can be further accepted by textile industries to overcome the limited reactivity of PET fabric surfaces, while the bulk characteristics are kept unaffected. Amine functionalities were introduced onto the surface of PET fabrics using either low-pressure ammonia plasma treatment or coating oxygen plasma-treated PET fabric with cationic polyelectrolytes. Two different cationic polyelectrolytes were used in this study namely poly(diallyldimethylammonium chloride) as an example of strong polyelectrolytes and poly(vinyl amine-co-vinyl amide) as an example of weak polyelectrolytes. The modified surfaces were characterized by a combination of various surface-sensitive techniques such as X-ray photoelectron spectroscopy (XPS), electrokinetic measurements and time-dependent contact angle measurements. Furthermore, the amine functionalities introduced by different surface modifications were used for the subsequent immobilization of various classes of anionic dyes to evaluate the efficiency of different surface modifications. Color strength (K/S) and fastness measurements of colored fabrics were also explored. Their results can be taken as a measure of the extent of the interaction between different modified surfaces and anionic dyes. Finally, it was demonstrated that anchoring poly(vinyl amine-co-vinyl amide) layer onto PET fabric surfaces modified with low-pressure oxygen plasma is an efficient approach to improve coloration behavior and to overcome different problems related to PET fabrics coloration, such as coloration of PET/wool blend fabric with a single class of dyes. This is a crucial step towards the substrate independent surface coloration, which becomes dependent on the properties of the top layer rather than chemical structure of the fibers.

Plasma-based surface modifications offer many interesting possibilities for the production of high value-added polymeric materials. In this work, different plasma-based synthetic concepts were employed to endow poly(ethylene terephthalate) (PET) fabrics with accessible amine functionalities. These concepts were compared to find out the appropriate engineering methods, which can be further accepted by textile industries to overcome the limited reactivity of PET fabric surfaces, while the bulk characteristics are kept unaffected. Amine functionalities were introduced onto the surface of PET fabrics using either low-pressure ammonia plasma treatment or coating oxygen plasma-treated PET fabric with cationic polyelectrolytes. Two different cationic polyelectrolytes were used in this study namely poly(diallyldimethylammonium chloride) as an example of strong polyelectrolytes and poly(vinyl amine-co-vinyl amide) as an example of weak polyelectrolytes. The modified surfaces were characterized by a combination of various surface-sensitive techniques such as X-ray photoelectron spectroscopy (XPS), electrokinetic measurements and time-dependent contact angle measurements. Furthermore, the amine functionalities introduced by different surface modifications were used for the subsequent immobilization of various classes of anionic dyes to evaluate the efficiency of different surface modifications. Color strength (K/S) and fastness measurements of colored fabrics were also explored. Their results can be taken as a measure of the extent of the interaction between different modified surfaces and anionic dyes. Finally, it was demonstrated that anchoring poly(vinyl amine-co-vinyl amide) layer onto PET fabric surfaces modified with low-pressure oxygen plasma is an efficient approach to improve coloration behavior and to overcome different problems related to PET fabrics coloration, such as coloration of PET/wool blend fabric with a single class of dyes. This is a crucial step towards the substrate independent surface coloration, which becomes dependent on the properties of the top layer rather than chemical structure of the fibers.