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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
91

Functional characterization and structural modeling of synthetic polyester degrading hydrolases from Thermomonospora curvata

Wei, Ren, Oeser, Thorsten, Then, Johannes, Kühn, Nancy, Barth, Markus, Schmidt, Juliane, Zimmermann, Wolfgang 11 June 2014 (has links) (PDF)
Thermomonospora curvata is a thermophilic actinomycete hylogenetically related to Thermobifida fusca that produces extracellular hydrolases capable of degrading synthetic polyesters. Analysis of the genome of T. curvata DSM43183 revealed two genes coding for putative polyester hydrolases Tcur1278 and Tcur0390 sharing 61% sequence identity with the T. fusca enzymes. Mature proteins of Tcur1278 and Tcur0390 were cloned and expressed in Escherichia coli TOP10. Tcur1278 and Tcur0390 exhibited an optimal reaction temperature against p-nitrophenyl butyrate at 60°C and 55°C, respectively. The optimal pH for both enzymes was determined at pH 8.5. Tcur1278 retained more than 80% and Tcur0390 less than 10% of their initial activity following incubation for 60 min at 55°C. Tcur0390 showed a higher hydrolytic activity against poly(ε-caprolactone) and polyethylene terephthalate (PET) nanoparticles compared to Tcur1278 at reaction temperatures up to 50°C. At 55°C and 60°C, hydrolytic activity against PET nanoparticles was only detected with Tcur1278. In silico modeling of the polyester hydrolases and docking with a model substrate composed of two repeating units of PET revealed the typical fold of α/β serine hydrolases with an exposed catalytic triad. Molecular dynamics simulations confirmed the superior thermal stability of Tcur1278 considered as the main reason for its higher hydrolytic activity on PET.
92

Preparation And Characterization Of Glass Fiber Reinforced Poly(ethylene Terephthalate)

Altan, Cansu 01 July 2004 (has links) (PDF)
Glass fiber reinforced poly(ethylene terephthalate), GF/PET has excellent potential for future structural applications of composite materials. PET as a semi-crystalline thermoplastic polyester has high wear resistance, low coefficient of friction, high flexural modulus and superior dimensional stability make it a versatile material for designing mechanical and electromechanical parts. Glass fibers are currently used as strength giving material in structural composites because of their high strength and high performance capabilities. In order to obtain high interfacial adhesion between glass fiber and polymer, glass fibers are treated with silane coupling agents. The objective of this study is to produce GF/PET composites with varying glass fiber concentration at constant process parameters in a twin screw extruder. Also, by keeping GF content constant, it is aimed to observe the effects of process parameters such as screw speed and feed rate on structural properties of the composites. Another objective of the study is to investigate the influence of different coupling agents on the morphological, thermal and mechanical properties and on fiber length distributions of the composites. Tensile strength and tensile moduli of the GF/PET composites increased with increasing GF loading. There was not a direct relation between strain at break values and GF content. The interfacial adhesion between glass fiber received from the manufacturer and PET was good as observed in the SEM photograps. Degree of crystallinity values increased with the addition of GF. Increasing the screw speed did not affect the tensile strength of the material significantly. While increasing the feed rate the tensile strength decreased. The coupling agent, 3-APME which has less effective functional groups than the others showed poor adhesion between glass fiber and PET. Therefore, lower tensile properties were obtained for the composite with 3-APME than those of other silane coupling agents treated composites. Number average fiber length values were reduced to approximately 300&amp / #61549 / m for almost all composites prepared in this study.
93

Noble and transition metal aromatic frameworks: synthesis, properties, and stability

Carson, Cantwell G. 14 May 2009 (has links)
In the first section, the electrical conductivity of rhodium phenylene-diisocyanide polymer is reported to be 3.4E-11 S/cm. However, the conductivity also exhibits an inverse exponential decay in air with t = 8 days. This change is attributed to the oxidation of the isocyanide functional group to an isocyanate, leading to degradation in the long-range metal-metal bonding, the dominant conductivity mechanism. Using a more stable carboxylate ligand, the Cu terephthalate (TPA) system is studied and compared against the Mg, Co, Ni, and Zn terephthalates. A synthesis in N,N-dimethylformamide (DMF) is developed and large quantities of the Cu(TPA)DMF can be synthesized in air. The crystal structure of the Cu(TPA) DMF is shown to be in the C2/m spacegroup. Upon desolvation, the Cu(TPA) is shown to have a large surface area of 625 m2/g. The magnetic susceptibility of the Cu(TPA) indicates anti-ferromagnetic coupling between adjacent Cu centers in the same dimer. The thermal stability of the Zn, Ni, Co, and Mg terephthalates is shown to increase with decreasing symmetric carboxylate stretch in the IR. The magnetic susceptibilities of the Co and Ni terephthalates have paramagnetic behavior, with a Weiss temperature of T = -12.9 K and T = 8.8 for Co(TPA) DMF and Ni(TPA)DMF respectively. A heterometallic Zn-Cu terephthalate is synthesized with Cu concentrations ranging from 0 to 100%. Upon the addition of Cu, Zn-rich frameworks increase in surface area, change in thermal stability, and increase their solvent retention from 16% to 25%. Zn is shown to couple with Cu in the same dimer at a high rate, changing the behavior of the dimer from anti-ferromagnetic to paramagnetic. The Weiss temperature suggests weak ferromagnetic interaction.
94

Avaliação do desempenho de blocos de concreto estrutural dosados com politereftalato de etileno (PET) micronizado.

SILVA, José Bezerra da. 12 June 2018 (has links)
Submitted by Emanuel Varela Cardoso (emanuel.varela@ufcg.edu.br) on 2018-06-12T20:43:42Z No. of bitstreams: 1 JOSÉ BEZERRA DA SILVA – TESE (PPGEP) 2016.pdf: 3353599 bytes, checksum: f4b72aa0752341e7ae682a1f07daef15 (MD5) / Made available in DSpace on 2018-06-12T20:43:42Z (GMT). No. of bitstreams: 1 JOSÉ BEZERRA DA SILVA – TESE (PPGEP) 2016.pdf: 3353599 bytes, checksum: f4b72aa0752341e7ae682a1f07daef15 (MD5) Previous issue date: 2016-10-05 / Os blocos de concreto são os componentes mais importantes da alvenaria estrutural, uma vez que eles são os principais responsáveis pela resistência à compressão. Para que estes sejam de qualidade, a sua fabricação deve ser realizada utilizando materiais com propriedades adequadas e procedimentos de dosagem e cura controlada. A utilização de novos materiais na produção de blocos de concreto estrutural vem crescendo em todo o mundo, e , com isso, a possibilidade de utilizarem materiais alternativos, cuja principal preocupação é o equilíbrio entre os aspectos ambientais, tecnológicos e econômicos. Assim, este trabalho tem como objetivo principal avaliar o desempenho de blocos estruturais de concreto simples com adição de Politereftalato de etileno (PET) micronizado para uso na construção civil. Inicialmente as matérias-primas foram submetidas às caracterizações físicas, químicas e mineralógicas, e em seguida realizou-se o estudo da dosagem do concreto, objetivando-se determinar o proporcionamento dos materiais e os teores de PET a serem utilizados. Sequencialmente foram moldados blocos de concreto nas dimensões de 14cmx19cmx29cm, com teores de 2,5%, 5,0%, 7,5% e 10% de Politereftalato de etileno micronizado em substituição ao agregado miúdo para a determinação das propriedades físicas e mecânicas. Observou-se que o PET provocou o aumento da absorção e a redução do peso específico do concreto, e que o teor de 2,5% resulta em valores de absorção que satisfazem os requisitos normativos para blocos de concreto estrutural em que se utiliza agregado normal ou leve. Para a resistência característica à compressão, observou-se que o PET promoveu a redução da resistência do concreto, e, quanto maior o teor de substituição, menor a resistência à compressão. No entanto, para os teores de 2,5%, 5,0% e 7,5% de PET os valores obtidos para a resistência característica permitiram classificá-los como blocos estruturais classe B, com função estrutural, para uso em elementos de alvenaria acima do nível do solo. Portanto, é viável, nos percentuais e nas condições estabelecidas nesta pesquisa, sob o ponto de vista técnico, a utilização do Politereftalato de etileno triturado em concreto para produção de blocos de alvenaria estrutural, por possibilitar a obtenção de propriedades físicas e mecânicas que satisfazem os parâmetros normativos. / The concrete blocks are the most important components of structural masonry, since they are mainly responsible for the compressive strength. For these to be quality, their manufacture must be carried out using materials with appropriate properties and strength and controlled curing procedures. The use of new materials in the production of structural concrete blocks has been growing throughout the world, and with it, the possibility of using alternative materials, whose main concern is the balance between the environmental, technological and economic. This work aims to evaluate the performance of simple concrete building blocks with the addition of polyethylene terephthalate (PET) micronized for use in construction. Initially, the raw materials were subjected to physical characterization, chemical and mineralogical, and then held the actual dosage of the study, aiming to determine the proportioning of the materials and PET content to be used. Sequentially were molded concrete blocks in the dimensions of 14cmx19cmx29cm, at levels of 2.5%, 5.0%, 7.5% and 10% of micronized polyethylene terephthalate replacing the fine aggregate for determining the physical and mechanical properties. It was observed that the PET caused the increased uptake and reduction of the specific weight of the concrete, and that the content of 2,5% results in absorption values which satisfy the regulatory requirements for structural concrete blocks which uses regular aggregate or light. For the characteristic compressive strength, it was observed that the PET caused a reduction of strength of concrete, and the higher the replacement content, the lower the compressive strength. However, for contents of 2.5%, 5.0% and 7.5% PET values obtained for the resistance trait enabled to classify them as class B structural units, structural function, for use in masonry units above ground level. Therefore, it is feasible, in percentages and conditions set out in this study, from a technical point of view, the use of polyethylene terephthalate triturated in particular for the production of masonry blocks, by enabling obtaining physical and mechanical properties which meet the normative parameters.
95

Sur l'analyse multiéchelle du changement de morphologie du PET sous l'effet de la température ou des sollicitations mécaniques / Multi-scale analysis of the morphological changes of the PET under the effect of temperature or mechanical stress

Gong, Yang Hao 06 June 2018 (has links)
Dans ce travail de thèse, nous nous sommes intéressés à la simulation de l’évolution de la microstructure d’un polymère. Plus précisément, nous avons étudié le changement de la morphologie du polyéthylène téréphthalate (PET) sous l’effet de différents mécanismes. Ces simulations sont réalisées par la méthode des champs de phase. Il s’agit d’une méthode basée sur l’équation de Cahn-Hilliard ou l’équation de Ginzburg-Landau. Elle utilise un paramètre d’ordre pour décrire l’état du matériau, des variables thermodynamiques et cinématiques. Ainsi on peut décrire l’évolution d’une microstructure sans suivre l’interface et ainsi reproduire l’évolution de la structure cristalline sphérolitique qui apparait lors d’une cristallisation induite par la température. Dans le cadre d’un changement de morphologie induit par la température, le calcul par champ de phase a été simulé par la méthode de différences finies et la méthode d’éléments finis. Le coefficient cinétique a été identifié à partir de données expérimentales de la littérature. En introduisant un modèle du champ de phases multiples (the MPF model) on a aussi simulé l’évolution de plusieurs sphérolites et gérer la jonction lorsque deux sphérolites se rencontrent. La croissance et la jonction des sphérolite a été modélisée par la méthode d’éléments finis : elle reproduit parfaitement l’évolution expérimentale de cristallisation isotherme d’un polymère. En comparant ces résultats avec le modèle macroscopique d’Avrami, une évaluation de la constante d'Avrami, K(T), a été discutée en fonction des fluctuations des conditions initiales (positions et taille des germes).Dans le cadre de la cristallisation induite par la déformation mécanique, nous avons couplé le champ de phase aux équations de la mécanique pour un comportement viscoélastique différent pour chaque phase. L’influence, sur la cristallisation et l’orientation, de la déformation, de la vitesse de sollicitation, du contraste entre les phases sont étudiées et comparées qualitativement aux observations expérimentales. Il s’agit d’une étude préliminaire qui devra être poursuivie et affinée afin de prédire une morphologie plus réaliste / In this thesis work, we are interested in simulating the evolution of the microstructure of a polymer. In particular, we have studied in the morphology change of polyethylene terephthalate (PET) under different mechanisms. These simulations carried out by the phase field simulation. This method based on the Cahn-Hilliard equation or the Ginzburg-Landau equation. It uses an order parameter to describe the state of material, thermodynamic and kinetic variables. Thus we can describe the microstructure evolution without tracking the interface (which would require complex remeshing) and reproduce the evolution of the crystalline structure within the polymers, for example the growth of spherulites which appear during crystallization induced by temperature. Within the scope the morphology changing by the temperature, the evolution of phase field simulation is performed by the finite difference method and the finite element method. The kinetic coefficient is adjusted in order to fit the experiment data in of the literature. We introduce the multiphase field model (the MPF model) in order to simulate the evolution of several spherulites and to describe the junction of spherulites. The growth and junction of spherulites have been modeled by the finite element method and nicely reproduced in comparing the experimental evolution of isothermal crystallization of a polymer. Comparing these results with the Avrami macroscopic model, an evaluation of the Avrami constant, K (T), was discussed according to the fluctuations of the initial conditions (positions and size of the germs).In the following part, we study the crystallization induced by mechanical deformation. We are interested in the viscoelastic model to simulate the induced crystallization of PET in plane stress. The phase field model coupled to mechanics will be presented. Different viscoelastic behaviors have been considered for each phase. The influence on crystallization and orientation of the deformation, the stress velocity and the contrast between the phases are studied and compared qualitatively with the experimental observations. This is a preliminary study that will have to be continued in order to predict a more realistic morphology
96

[en] RECYCLING OF PET BOTTLES, AIMING AT SUBSTITUTION OF SMALL AGGREGATE IN MORTAR / [pt] RECICLAGEM DE PET, VISANDO A SUBSTITUIÇÃO DE AGREGADO MIÚDO EM ARGAMASSAS

SUSAN SALES CANELLAS 28 October 2005 (has links)
[pt] O desenvolvimento de tecnologias que utilizem energias limpas e a gestão integrada dos resíduos domiciliares e industriais visando uma reengenharia nos conceitos sócio-empresariais é uma necessidade urgente. A sociedade, principalmente nos países desenvolvidos, prioriza produtos de empresas que possuam atividades socialmente corretas. A indústria da construção civil, como uma das maiores geradoras de resíduos, podendo chegar a 3000 kg/hab.ano, não pode se eximir desta atitude. Uma vez que consome grandes quantidades de recursos naturais, um grande número de estudos para substituição de bens naturais não renováveis está sendo realizado nesse setor, aliando materiais convencionais com resíduos industriais e urbanos. Um dos materiais que vem sendo utilizado nestas pesquisas são as embalagens pós- consumo de PET ( polietileno tereftalato ), resíduos que estão atingindo percentuais cada vez maiores na composição do lixo urbano, com presença crescente no meio ambiente. Esse trabalho visa apontar uma nova perspectiva de utilização desse material, propondo a substituição parcial da areia natural, por material granulado oriundo de garrafas de PET, objetivando a produção de argamassas para uso na construção civil. No presente estudo, foram realizadas substituições nas proporções de 10, 30 e 50% , tendo sido observado a melhor possibilidade de utilização do percentual de 30%, devido a não ter apresentado perdas significativas na plasticidade e nas resistências a compressão e a tração. Foi possível concluir que o compósito obtido tem potencial para ser utilizado na confecção de artefatos de concreto, sem grande responsabilidade estrutural e em mobiliários urbanos, além de seu uso permitir uma economia significativa de volumes de areia lavada, um recurso natural cuja extração tem causado grandes danos ao ecossistema dos rios e suas margens. / [en] The development of technology that uses clean energy and the integrated management of domestic and industrial residues aiming at a new engineering in the social and company relationship, is a urgent necessity. The society, mainly in developed countries, are already giving priority to the products of companies that possess identity with socially correct activities. The industry of construction, as one of the larger generator of residues, that produces around 3000kg/hab.year, and can not exempt of this purpose. Since the civil construction consumes great amount of natural sector resources, a large number of studies aiming at the substitution of natural sand, considered a non renewable material, is being carried out, particularly by, mixing conventional material with industrial and urban residues. The material used in these this study, was granulated PET (polyethylene tereftalate), obtained from beverage bottles, residues that are reaching a high percentage in the composition of the urban wastes. The objective of this research aimed at create a new perspective for construction materials, by crushing bottles of PET and using the produced material as a substitute of the natural sands for production of mortar. In this study was used the PET/sand ratios of 10, 30 and 50%, being 30%, the best ratio observed, due to a still good workability, an acceptable compressive and tensile strengths. The innovation, proposed in this study for instance, in the production of pieces of concrete, without great structural value, and in urban furnitureleading to a significant economy of volumes of sands, a resource whose extraction has been caused great damages to the present ecosystem of the rivers and in its edges.
97

Functionalisation of electrospun nanofibre for lanthanide ion adsorption from aqueous solution

Pereao, Omoniyi Kolawole January 2018 (has links)
Philosophiae Doctor - PhD (Chemistry) / Rare earth elements (REEs) have widespread use and importance for industrial applications due to their metallurgical, optical and electronic properties. Several typical hydrometallurgical techniques such as adsorption, chemical precipitation, filtration, ion exchange and solvent extraction techniques have been used for separation and recovery of the rare earth metals from aqueous solutions. Adsorption was recognised as one of the most promising methods due to its simplicity, high efficiency and availability. Many adsorbents are being investigated but there are few adsorbents containing specific functional groups in practical use for REEs recovery. This aim of this study was to develop a nanofibre based adsorbent containing glycolic acid functional groups for the recovery of rare earth metals. Polystyrene (PS) and polyethylene terephthalate (PET) nanofibres were prepared by the electrospinning technique, glycolic acid functional groups were grafted onto the PS or PET nanofibres and the potential of the two modified nanofibre adsorbents for adsorption of Ce3+ or Nd3+ from aqueous solution were investigated and compared. The adsorption experiments were carried out to investigate the effect of different adsorption parameters such as pH, contact time and initial concentration in a batch system in order to achieve the objectives of this research.
98

Nanocompositos de poli (tereftalato de etileno) grau garrafa reciclado e montmorilonita organofilica / Recycled bottle-grade poly(ethylene terephthalate) based nanocomposites with organo-modified montmorillonite

Bizarria, Maria Trindade Marques 27 February 2007 (has links)
Orientadores: Lucia Helena Innocentini Mei, Marcos Akira d'Avila / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-10T08:22:57Z (GMT). No. of bitstreams: 1 Bizarria_MariaTrindadeMarques_M.pdf: 2194752 bytes, checksum: 4e957a01de264fbcff7d460f5c539bac (MD5) Previous issue date: 2007 / Resumo: O estudo de nanocompósitos de poli(tereftalato de etileno) reciclado (PETr), principal objeto deste trabalho, foi dividido em duas partes. Preliminarmente, foram preparados nanocompósitos de PETr, com diversos teores (1, 3 e 5% em massa) de montmorilonita organicamente modificada (MMTm), pelo método de intercalação no estado fundido, em uma extrusora de dupla rosca corotacional à velocidade de 250 rpm. Buscando um melhor entendimento sobre as implicações que envolvem a preparação de nanocompósitos com respeito ao sistema PETr/MMTm disponível comercialmente, na segunda parte deste estudo, além de diferentes teores (neste caso 2,5 e 5,0%), distintas velocidades da rosca foram também utilizadas (250 e 150 rpm). Adicionalmente, para efeitos comparativos, foram ainda processados nanocompósitos com equivalentes formulações, porém com matriz de PET virgem. Como na primeira parte, a morfologia dos corpos de prova moldados por injeção foi avaliada por difração de raios-X (DRX) e microscopia eletrônica de transmissão (MET). As propriedades térmicas e mecânicas dos nanocompósitos obtidos foram então analisados por calorimetria diferencial exploratória (DSC) e testes de impacto e tração. As imagens de MET mostraram uma morfologia mista exibindo lamelas intercaladas e também algumas esfoliadas. Uma pequena quantidade de agregados pôde também ser observada. Teores mais elevados de MMTm conduziram a valores mais altos de cristalização desenvolvida dentro do molde de injeção, o que indica que a MMTm atuou como agente nucleante como ficou evidenciado pela diminuição e pelo aumento das temperaturas de cristalização, a frio e a partir do fundido, respectivamente, nos nanocompósitos resultantes. Os valores máximos para o módulo de Young foram observados nos nanocompósitos contendo 5% de MMTm processados a 150 rpm. A análise morfológica efetivamente revelou um maior grau de esfoliação para os nanocompósito baseados em matriz de PET virgem. Contudo a termo-estabilidade dos nanocompósitos de PETr, durante o processo de injeção, foi relativamente superior àquela mostrada pelos de PET virgem. A obtenção de nanocompósitos de PET reciclado (com vistas a futuras aplicações de engenharia) mostrou-se viável, mesmo quando comparada à de nanocompósitos com matriz do material virgem / Abstract: The study of the recycled poly(ethylene terephthalate) (rPET) nanocomposites, which was the main object of this work, has been divided into two parts. At first, nanocomposites of rPET with several amounts (1, 3 and 5wt.%) of an organic modified montmorillonite (mMMT) were prepared by direct melt intercalation process in a co-rotating twin-screw extruder at 250 rpm. In order to obtain a better understanding about the implications that involve the preparation of nanocomposites regarding the system rPET and a commercial mMMT, in the second part of this study, besides different amounts of mMMT (2.5 and 5.0% in this case), different screw rotation speed (250 and 150 rpm) were also used. In addition, as a reference, nanocomposites with the same formulations but with virgin PET matrix were also processed. As in the first part, the morphology of the injection-molded formulations was evaluated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thermal and mechanical properties of the resulting nanocomposites were then analyzed by differential scanning calorimetry (DSC), tensile and impact tests. The TEM images showed a mixed morphology with intercalated and some exfoliated platelets, a little amount of aggregated platelets could also be observed. Higher concentrations of mMMT led to higher values of crystallization into the mold. This indicates that mMMT actuated as nucleating agent, as evidenced by a decrease and an increase in both cold and melt crystallization temperatures in the obtained nanocomposites, respectively. Maximum enhancement in Young¿s modulus was observed in the nanocomposites containing 5 wt% of mMMT processed at 150 rpm. The morphological analysis has effectively revealed a better degree of exfoliation for the nanocomposites based in virgin PET matrix. However, the thermal stability of the rPET nanocomposites, during de injection-molding process, was relatively better than those of the virgin PET. The obtaining of rPET nanocomposites, having in mind future engineering applications showed availability even when compared with virgin material nanocomposites / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química
99

Estudo da estabilização termo-oxidativa e hidrolítica do poli (tereftalato de etileno) (PET) reciclado pós-consumo

Freitas, Flavia Leticia Silva January 2018 (has links)
Orientadora: Profa. Dra. Sandra A. Cruz / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2018. / O poli (tereftalato de etileno) é um material amplamente utilizado principalmente em garrafas e embalagens de rápido descarte, gerando, consequentemente, um elevado volume de resíduos pós-consumo. A reciclagem deste polímero destaca-se como uma alternativa para a sua (re)utilização e, um dos meios para minimizar a sua degradação é pelo emprego de aditivos. Assim, nesta tese de doutorado foram estudados os efeitos de três diferentes classes de aditivos: antioxidantes, desativadores de metais e anti-hidrólise, considerando suas capacidades de minimizar os efeitos degradativos na reciclagem de PET pós-consumo. Em uma primeira etapa, os efeitos sinérgicos e antagônicos do emprego de tais aditivos foram estudados por meio de planejamento de experimentos. Nesta etapa foram avaliadas de maneira individual e combinada cinco variáveis que influenciam na estabilidade do PET (umidade, antioxidante primário, desativador de metais, policarbodiimida e blenda de antioxidantes primários e secundários). Os resultados das medidas de viscosidade intrínseca mostraram que os antioxidantes tiveram pouca contribuição na estabilização do PET reciclado e o desativador de metais não apresentou coeficiente significativo no intervalo de confiança de 95%. Já o aditivo anti-hidrólise, representado pelo composto policarbodiimida, foi a variável que apresentou maior efeito na estabilização do PET reciclado, enquanto a umidade mostrou um efeito negativo. Assim, pôde-se concluir que as reações de hidrólise se sobrepõem às reações de degradação termo-oxidativa. Posteriormente, em uma segunda etapa, a influência da policarbodiimida na estabilização do PET foi analisada por meio da avaliação de suas propriedades térmicas e reológicas. Foi observado então que com a adição de 10% deste aditivo a viscosidade intrínseca aumentou aproximadamente 94% quando comparado ao PET flakes sem processamento, indicando a sua funcionalidade como um extensor de cadeias. Desta forma, foi possível a obter materiais com diferentes faixas de massa molar de acordo com a concentração empregada de aditivo. Os ensaios térmicos provaram que a policarbodiimida pode atuar como um estabilizante termo-oxidativo permitindo assim ampliar a faixa de trabalho do PET para temperaturas mais elevadas (350°C), além de proporcionar uma redução na temperatura de cristalização de até 37 °C com o aumento da concentração do aditivo. / Polyethylene terephthalate is a widely used material for bottles and rapid discard packaging, thus generating a high volume of post-consumer waste. The recycling of this polymer stands out as an alternative to its reuse and one of the means to minimize its degradation is by the use of additives. Thus, in this doctoral thesis the effects of three different classes of additives were studied: antioxidants, metal deactivators and anti-hydrolysis, considering their abilities to minimize the degradation effects on post-consumer PET recycling. In a first step, the synergistic and antagonistic effects of the use of such additives were studied through design of experiments. In this step, five variables that influence in the PET stability (humidity, primary antioxidant, metal deactivator, polycarbodiimide and blends of primary and secondary antioxidants) were evaluated individually and in combination. The results of the intrinsic viscosity measurements showed that the antioxidants had little contribution in the stabilization of the recycled PET and the metal deactivator showed no significant coefficient in the 95% confidence interval. The anti-hydrolysis additive, represented by the polycarbodiimide compound, was the variable that presented the greatest effect on the stabilization of recycled PET, while humidity showed a negative effect. Thus, it could be concluded that the hydrolysis reactions overlap the thermo-oxidative degradation reactions. Later, in a second stage, the influence of polycarbodiimide on the stabilization of PET was analyzed by means of the evaluation of its thermal and rheological properties. It was then observed that with the addition of 10% of this additive the intrinsic viscosity increased approximately 94% when compared to unprocessed PET flakes, indicating their functionality as a chain extender. In this way, it was possible to obtain materials with different ranges of molar mass according to the concentration of additive used. Thermal tests have proven that polycarbodiimide can act as a thermo-oxidative stabilizer thus allowing the working range of PET to be extended to higher temperatures (350 °C), as well as to provide a reduction in crystallization temperature of up to 37 °C with concentration of the additive.
100

Remoção de corante de poli(tereftalato de etileno) (PET) através de recristalização e sua posterior despolimerização em meio ácido / Removing dye from poly(ethylene terephthalate) (PET) by recrystallization and its subsequent depolymerization in acid medium

Stefanelli, Talita Katiuska Takizawa Dias, 1983- 23 August 2018 (has links)
Orientadores: Maria Regina Wolf Maciel, Glaucia Maria Ferreira Pinto / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-23T20:46:02Z (GMT). No. of bitstreams: 1 Stefanelli_TalitaKatiuskaTakizawaDias_M.pdf: 1571611 bytes, checksum: 5c787cef4fc94a299d2b85a0e62656e1 (MD5) Previous issue date: 2013 / Resumo: O consumo de polímeros sintéticos no Brasil e no mundo vem aumentando há décadas, numa clara demonstração do enorme sucesso conseguido por esses materiais nas mais variadas aplicações. As características típicas dos polímeros sintéticos, como seu custo praticamente irrisório, baixo peso, boa resistência mecânica, impermeabilidade, transparência e capacidade de coloração mais impressão lhe conferiram trunfos irresistíveis para seu uso massivo na forma de embalagens, uma aplicação extremamente importante numa sociedade voltada para o consumo. O grande problema dos polímeros sintéticos reside na sua curta vida útil, o que conduz a um rápido aumento da corrente de resíduos, como é o caso das embalagens. Dentro desse âmbito, a reciclagem passa ser uma alternativa promissora. Por definição, a reciclagem é um processo de transformação dos materiais previamente separados para posterior utilização; é a recuperação de resíduos mediante uma série de operações que permitem que materiais processados sejam aproveitados como matéria-prima no processo gerador ou em outros. A primeira etapa deste trabalho foi a tentativa de fazer a despolimerização de PET utilizando o processo de destilação molecular. Os resultados mostraram que não é possível utilizar o destilador molecular na despolimerização do PET. Na segunda etapa deste trabalho o pet pósconsumo foi submetido à recristalização para remoção do corante, utilizando ácido trifluoracético como solvente, na tentativa de uma nova alternativa de reciclagem para este material. O material modificado e o PET pós-consumo foram caracterizados por termogravimetria (TG) e calorimetria exploratória diferencial (DSC) / Abstract: The use of synthetic polymers in the world and particularly in Brazil has been increasing for decades representing the huge success achieved by these materials in various applications. The main characteristics of synthetic polymers are their low cost and weight, good mechanical strength, impermeability, transparency and the possibility of coloring, which results in their massive use in the form of packaging an application extremely important in a society focused on consumption. Despite all its advantages, the polymers are generally used in the manufacture of objects whose useful life it is extremely short, like bottled water and soft drinks , produced with polyethylene terephthalate (PET), or as previously mentioned, in packs of all species, resulting in a rapid increase in the waste stream. In this scenario, recycling becomes a promising alternative. By definition, recycling is a process of transformation materials previously separated for later use or is the recovery of waste by means of a series of operations that allow processed materials to be utilized as raw material in generating process or in other process. The first stage of this work was to attempt to make the depolymerization of PET using molecular distillation process, but results showed that it is not possible to use the molecular distiller for the depolymerization of this type of polymer. In the second stage of the work, post-consumer PET was subjected to recrystallization to remove the dye, using trifluoroacetic acid as solvent in in a new attempt to recycle this material. The modified material and post-consumer PET were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) / Mestrado / Desenvolvimento de Processos Químicos / Mestra em Engenharia Química

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