The potential use of Resadiye/Tokat bentonite as a reinforcement in polypropylene (PP) and linear low density polyethylene (LLDPE) polymer matrix nanocomposites filler was investigated. At first, organoclays (OC) were prepared by cation exchange reaction (CER) between the raw bentonite (RB) and three quaternary ammonium salts with long alkyl tails (QA): hexadecyl trimethyl ammonium bromide [HMA] [Br], tetrabutyl ammonium tetrafluoroborate [TBA] [BF4], tetrakisdecyl ammonium bromide [TKA] [Br] and one quaternary phosphonium (QP) salt: tetrabutyl phosphonium tetrafluroborate [TBP] [BF4]. Characterization of resulting materials by XRD, TGA, FTIR and chemical analysis confirmed the formation of organoclays. Ternary composites of PP/organoclay/ maleic anhydride grafted polypropylene (MAPP) were prepared with two different grades of PPs in a co-rotating twin screw extruder. Composites prepared with these organoclays and PPs showed microcomposite formation. In the second part of the study, raw bentonite was purified by sedimentation, and characterization of purified bentonite (PB) by XRD, cation exchange capacity (CEC) measurement and chemical analysis (ICP) confirmed the success of purification method. PB was then modified with two QA`s: dimethyl dioctadecylammonium chloride [DMDA] [Cl], tetrakis decylammonium bromide [STKA] [Br] and one QP: tributyl hexadecyl phosphonium bromide [TBHP] [Br]. Organoclays from PB were used with the PP with lower viscosity, and ternary nanocomposites (PP/Organoclay2/MAPP5) were prepared in the extruder followed by batch mixing in an intensive batch mixer. Use of DMDA and TBHP OCs resulted in nanocomposite formation, while STKA resulted in microcomposite formation as observed by XRD and TEM. Young`s modulus and yield stress of the samples were enhanced through nanocomposite formation. In the last part of the study, ternary composites of LLDPE/Organoclay/ compatibilizer, a random terpolymer of ethylene, butyl acrylate and maleic anhydride (E-BA-MAH, Lotader&reg / 3210), were prepared by melt compounding in the batch mixer at two different clay concentrations (2 and 5 wt %) and fixed compatibilizer/organoclay ratio (&alpha / =2.5). A commercial organoclay, I34, was also used in LLDPE based nanocomposites to make a comparison. XRD and TEM analyses of the compounds prepared by DMDA and TBHP showed mixed nanocomposite morphologies consisting of partially intercalated and exfoliated layers. Young`s modulus and tensile strength of nanocomposites prepared with DMDA and TBHP showed generally higher values compared to those of neat LLDPE, while results were the highest in the composites prepared with commercial organoclay I34. Parallel disk rheometry was used as a supplementary technique to XRD, TEM and mechanical characterizations, and it was shown to be a sensitive tool in assessing the degree of dispersion of clay layers in the polymer matrix.

La crise de l’eau dans le monde et la pénurie des ressources en eau exigent une bonne gestion de cette précieuse ressource. La bonne gestion passe en premier lieu par un réseau d’adduction d’eau potable fiable avec un faible taux de fuite. Les fuites causées par la rupture des canalisations, phénomène assez fréquent en milieu urbain, s’amorcent sur un défaut dû à la corrosion ou autres. L’amorçage et la propagation de la fissure se fait par fatigue sous l’effet de contraintes engendrées par le passage des véhicules, ou brutalement à cause du phénomène de coup de bélier. La gravité de ces phénomènes dépend de plusieurs paramètres y compris la nature du matériau des conduites. Les matériaux polymères, comme le PEHD, occupent une bonne partie du marché de transport d’eau, grâce à leurs multiples qualités (coût réduit, facilité de pose, flexibilité), notamment dans les réseaux de distribution (réseau secondaire). L’utilisation de ce matériau dans les réseaux d’adduction (aqueducs) est en pleine expansion mais beaucoup moins étudier dans les travaux de recherche. L’objectif de la thèse consiste à étudier le risque de rupture des conduites en polyéthylène haute densité destinée à l’adduction d’eau potable ainsi que leurs résistances au phénomène de coup de bélier. Pour répondre à cette problématique, en premier lieu nous avons caractérisé expérimentalement le comportement mécanique à la rupture des conduites en PEHD. Ensuite, nous avons développé un outil numérique de calcul par élément fini permettant de modéliser la rupture des conduites. À l'issue de cette étude nous avons proposé un modèle semi-empirique reliant la pression d’amorçage d’une fissure à la taille du défaut préexistant ainsi qu’aux dimensions de la conduite. Finalement, nous avons appliqué les outils développés sur un réseau d’adduction d’eau potable existant. Le comportement d’une conduite en PEHD soumise à un phénomène de coup de bélier a été analysé / The water crisis in the world and the shortage of water resources require good management of this precious resource. Good management requires, first and foremost, a reliable drinking water supply system with low leakage rate. Leakage caused by the rupture of pipes, fairly frequent phenomenon in urban areas, initiate from a pre-existing defect in the pipe wall. The initiation and propagation of the crack occur under environmental stress caused by passing vehicles, or it can happen brutally due to water hammer phenomenon. The severity of these phenomena depends on several parameters including the nature of the piping material. Polymeric materials such as HDPE, take a great part of the water transport market, thanks to their many qualities (reduced cost, ease of installation, flexibility), especially in secondary network distribution system. Currently, the use of this material in the supply networks (aqueducts) is booming but less studied in research works. The aim of the present work is to study the failure of high density polyethylene pipes for the supply of drinking water and their resistance to water hammer phenomenon. In order to address this issue, first we have characterized experimentally the mechanical fracture behavior of HDPE pipe. Then, we have developed a finite element calculation tool allowing the modeling of pipes subjected to internal pressure loads. As a result of this numerical study, we proposed a semi-empirical model linking the failure pressure to the size of pre-existing defects as well as the pipe dimensions. Finally, we applied the developed tools on an existing drinking water system. The behavior of HDPE pipe subjected to a water hammer phenomenon was analyzed

[pt] Nanofolhas de ferrititanato com estrutura tipo lepidocrocita foram sintetizadas a partir de um precursor de baixo custo (areia ilmenítica), via rota hidrotérmica alcalina. Dois tipos de nanofolhas com alto e baixo teor de sódio foram obtidos: a) nanofolhas sódicas (NaLTs) e b) nanofolhas protonizadas (pLTs), obtidas mediante uma reação rápida de troca-ácida à temperatura ambiente. As capacidades de troca catiônica de ambos os tipos de nanofolhas foram determinadas seguindo-se a norma C 837 da ASTM. Após a síntese desses dois nanomateriais com diferentes teores de sódio foi estudado o processo de esfoliação em camadas de espessura sub-nanométrica, sob agitação intensa à temperatura de 60 C, utilizando-se como o agente de esfoliação pela primeira vez numa estrutura lepidocrocítica o sal cloreto de dimetildioctadecilamônio (2C18), visando a posterior aplicação das nanofolhas esfoliadas como reforço em nanocompósitos de matriz polimérica. O intuito de aplicar estes reforços em uma matriz polimérica foi buscar uma dispersão mais homogênea das folhas esfoliadas, além do aumento da compatibilidade das nanocargas com a matriz polimérica pela presença dos grupos orgânicos do sal quimicamente ligados às nanofolhas e, consequentemente, o incremento das propriedades térmicas e mecânicas do material polimérico. Dependendo do teor de sódio, foram obtidas nanofolhas esfoliadas e/ou intercaladas que foram posteriormente caracterizadas por fotometria de chama, espetroscopia de infravermelho, área superficial específica por adsorção de N2, termogravimetria, difração de raios-X de alto ângulo, espalhamento de raios-X a baixo ângulo, microscopia de força atômica e microscopia eletrônica de transmissão. Para a fabricação dos nanocompósitos foram utilizadas duas matrizes: a) uma de PEAD puro e b) a outra de PEAD com adição de uma porcentagem baixa, e constante, de polietileno funcionalizado com anidrido maleico (PE-g-MA), sendo reforçadas com as nanocargas protonizadas virgens (pLTs) e esfoliadas (pLTs-o-2C18) nas concentrações de 1,0; 2,0 e 4,0 por cento p. Finalmente, foram avaliadas as propriedades mecânicas e térmicas dos nanocompósitos por meio de ensaios de tração, termogravimetria, calorimetria diferencial de varredura e dilatometria. Os nanocompósitos preparados com pLTs virgem e os fabricados com a adição de agente de acoplamento de PE-g-MA apresentaram um aumento no módulo de Young de aproximadamente 12,8 por cento e 5,1 por cento para cargas de 4 por cento e 2 por cento em peso de pLTs virgem, respectivamente. Os nanocompósitos, que apresentam o maior aumento no limite de escoamento foram os reforçados com 4 por cento p de nanofolhas esfoliada (pLTs-o-2C18). No entanto, estes materiais apresentam uma diminuição no módulo de Young de aproximadamente 12 por cento. Os nanocompósitos com o maior aumento no módulo de Young foram os preparados com 4 por cento p pLTs ( aproximadamente 12,8 por cento), enquanto sua tensão no escoamento também foi melhorada (um aumento de aproximadamente 4 por cento). A incorporação de nanofolhas não afetou significativamente as propriedades de estabilidade térmica da matriz e uma diminuição no coeficiente de expansão térmica de 4 a 5,5 por cento foi apenas observada para nanocompósitos preparados com pLTs virgens. O grau de cristalinidade diminuiu para todos os nanocompósitos fabricados, no qual variou de 2,17 até 26 por cento. / [en] Ferrititanate nanosheets with lepidocrocite-like structure were synthesized from a low cost precursor (ilmenite sand) through alkaline hydrothermal route. Two types of nanosheets with high and low-sodium content were obtained: a) sodium rich nanosheets (NaLTs) and b) protonated nanosheets (pLTs), obtained by a rapid acid-exchange reaction at room temperature. The cation exchange capacities of both types of nanosheets were determinated according ASTM C 837. After the synthesis of these two nanomaterials with different sodium levels, it was studied the exfoliation process to obtain monolayers of nanometric lateral dimensions under intensive stirring at 60 C, using dimethyldioctadecylammonium cloride (2C18) as the exfoliating agent of the lepidocrocite-like ferrititanate nanosheets for the first time, aiming the further application of the exfoliated nanosheets as reinforcement in polymer matrix nanocomposites. The purpose of the addition of these nanofillers within a polymer matrix is to obtain a more homogeneous dispersion of exfoliated nanosheets, as well as the improvement of the compatibility between nanofillers and the polymer matrix, due to the presence of the organic groups from 2C18, chemically attached to nanosheets and hence, to promote the an increase on mechanical and thermal properties of the polymeric matrix. Depending on the sodium content, it was obtained exfoliated and/or intercalated nanosheets that were further characterized by flame photometry, infrared spectroscopy, specific surface area by N2 adsorption, thermogravimetry, X-ray powder diffraction (XRPD) and of small angle X-ray scattering (SAXS), atomic force microscopy (AFM) and transmission electron microscopy (TEM). For the manufacturing of nanocomposites two types of matrices were used: a) neat high density polyethylene (HDPE) and b) HDPE with the addition of a low percentage of polyethylene-graft-maleic anhydride (PE-g-MA). Pristine nanosheets (pLTs) and exfoliated nanosheets (pLTs-O-2C18) were used as nanofillers at loadings of 1.0; 2.0 and 4.0 wt percent. Finally, we assessed the mechanical and thermal properties of the as-prepared nanocomposites through tensile tests, thermogravimetry analysis (TGA), differential scanning calorimetry (DSC) and dilatometry. Nanocomposites prepared with pristine pLTs and those manufactured with the addition of PE-g-MA coupling agent showed an increase on the Young modulus of about 12,8 percent and 5,1 percent for loadings of 4wt percent and 2 wt percent of pristine pLTs, respectively. The nanocomposites that present the highest increase on yield stress were reinforced with 4 wt percent of exfoliated nanosheets (pLTs-o-2C18). However, these materials presents a decrease in the Young modulus of about 12 percent. The nanocomposites with the highest increase on Young Modulus were those prepared with 4 wt percent of pristine ( about 12,8 percent), and the yield stress was also improved (increase of about 4 percent). The incorporation of nanosheets did not affect significantly the thermal stability properties of the matrix and a decrease on the coefficient of thermal expansion was solely observed for nanocomposites prepared with pristine pLTs. The degree of crystallinity decreased for all the manufactured nanocomposites, in the range of about 2,17 t-26 percent for nanocomposites prepared with pristine pLTs and those fabricated with the addition of PE-g-MA, respectively. up to about pLTs with the addition of PE-g-MA.

[pt] O Polietileno de Alta Densidade (PEAD) é um dos materiais mais conhecidos e é utilizado em diversos campos de aplicação. Apesar de suas inúmeras qualidades, como baixa densidade, alta ductilidade e alta resistência específica, esse material possui algumas desvantagens que limitam a sua aplicabilidade, tais como baixa rigidez, baixa estabilidade térmica e alta expansividade térmica. Por outro lado, existe uma classe seleta de materiais que possuem coeficiente de expansão térmica (CET) negativo ou próximo de zero. Pertencem a esse grupo, por exemplo, as cerâmicas da família A2M3O12, como o In2W3O12 (tungstato de índio). Tendo isso em vista, a proposta deste trabalho foi estudar diferentes métodos de mistura física entre esses dois materiais para fabricar e caracterizar compósitos de PEAD reforçados por nanopartículas de In2W3O12 com CET reduzido e propriedades mecânicas aumentadas em relação ao polímero. Primeiramente, sintetizaram-se nanopartículas de In2W3O12 pelo método de coprecipitação. Suas temperaturas de cristalização (aproximadamente 530 graus Celsius) e de transformação de fase monoclínica/ortorrômbica (259 graus Celsius) foram determinadas por análise térmica simultânea, e seus parâmetros de rede à temperatura ambiente foram determinados por DRX. Além disso, calcularam-se os CET s intrínsecos do In2W3O12 para ambas as suas fases por DRX in situ com temperatura variável. Foi encontrado, pela primeira vez, um CET intrínseco negativo para sua fase ortorrômbica, de alpha1 igual a menos 1,5 multiplicado por 10 elevado a menos 6 e K elevado a menos 1. Em seguida, fabricaram-se compósitos a partir de pellets de PEAD e das nanopartículas de In2W3O12 por microextrusão e microinjeção precedidas por uma etapa de pré-mistura. Dois parâmetros do processo de fabricação foram variados: a fração de carga no compósito (0,5; 2; 4 e 10 por cento) e o método de pré-mistura (sem pré-mistura; por vibração dentro de um moinho sem as bolas de moagem; e em uma autoclave giratória a 190 graus Celsius e pressão ambiente). Finalmente, os compósitos foram caracterizados por ensaios de tração, dilatometria e análise termogravimétrica. Todos os compósitos apresentaram incremento no módulo de elasticidade e no limite de escoamento, obtendo-se aumentos de até 45 por cento e 17 por cento, respectivamente, em relação ao PEAD puro. Os materiais preparados no moinho com 10 por cento p de reforço apresentaram os melhores resultados. De forma geral, os compósitos submetidos a algum tipo de pré-mistura tiveram melhores propriedades mecânicas do que os que não foram pré-misturados. Por outro lado, os compósitos não apresentaram uma grande redução no CET em relação ao PEAD. O melhor resultado encontrado foi uma redução de 6 por cento para os materiais sem pré-mistura com 4 por cento p de reforço. A temperatura de degradação dos compósitos sem pré-mistura também não apresentou melhora significativa. O maior incremento foi de 1,5 por cento em relação ao PEAD puro, encontrado para os materiais com 0,5 por cento p de carga. Finalmente, amostras de PEAD puro submetidas aos diferentes métodos de pré-mistura foram analisados por DSC. Constatou-se que a temperatura de fusão não é alterada, mas a entalpia de fusão e o grau de cristalinidade aumentam com a pré-mistura por vibração (8 por cento) e ainda mais com a pré-mistura na autoclave (15 por cento) em relação ao PEAD puro como recebido. / [en] High-density polyethylene (HDPE) is one of the most widely used materials. Despite its numerous qualities, such as low density, high ductility, and high specific strength, HDPE presents certain disadvantages that limit its applicability, like low stiffness, low thermal stability, and high thermal expansion. In contrast, there is a select group of materials that display negative or near-zero coefficient of thermal expansion (CTE). Ceramics belonging to the A2M3O12 family, which includes In2W3O12 (indium tungstate), are examples of such materials. Therefore, this dissertation proposes to examine different methods of physical mixture in order to produce and characterize HDPE composites reinforced with In2W3O12 nanoparticles with reduced CTE and better mechanical properties than the neat polymer. Firstly, In2W3O12 nanoparticles were synthesized by coprecipitation. Simultaneous thermal analysis proved their crystallization temperature and monoclinic/orthorhombic phase transition temperature to be approximately 530 Celsius degrees and 259 Celsius degrees, respectively. The lattice parameters at room temperature were determined by XRD, and the intrinsic CTE s for both phases were calculated by variable-temperature in situ XRD. For the first time, a negative intrinsic CTE was found for the orthorhombic phase (Alpha 1 equal than minus 1.5 multiplied 10 power minus 6 and K power minus 1). Secondly, composites were produced from HDPE pellets and the In2W3O12 nanoparticles by microextrusion and microinjection preceded by a pre-mixing step. Two fabrication parameters were analyzed: the filler content (0.5, 2, 4, and 10wt percent were used) and the pre-mixing method (no pre-mixture, by vibration within a mill without balls, and in a rotating autoclave at 190 Celsius degrees and ambient pressure). Finally, the composites were characterized by tensile tests, dilatometry, and thermogravimetric analysis. All of the composites presented higher Young s modulus and yield stress than neat HDPE, with increases of up to 45 percent and 17 percent, respectively. The best results were displayed by the materials that were pre-mixed in the mill with 10wt percent filler fraction. In general, both pre-mixing methods improved the composites mechanical properties. On the other hand, the polymer s CTE was not significantly reduced, being decreased by 6 percent in the best case. The degradation temperature showed almost no improvement, with a 1.5 percent increase for the composites with 0.5 percent filler content. Lastly, neat HDPE samples exposed to the different pre-mixing methods were analyzed by differential scanning calorimetry and compared with the as-received pellets. Results showed that the melting temperature was not affected by the mixing techniques, but both the enthalpy of fusion and the degree of crystallinity were increased by 8 percent and 15 percent for the samples pre-mixed by vibration in the mill and by rotation in the autoclave, respectively.

Dans le cadre de cette thèse, nous avons étudié l'interaction contenant-contenu entre un emballage à base de polyéthylène haute densité (PEHD) et l'acétate d'amyle considéré comme diffusant. Nous nous sommes plus précisément intéressés à l'impact du phénomène de sorption et de diffusion sur les propriétés mécaniques en sollicitations statique et de fluage de flacons en PEHD à différents stades du vieillissement physique. Une campagne expérimentale a été menée et une base de données issue d'essais menés sur des éprouvettes prélevées sur des flacons ainsi que d'essais de structure réalisés sur des flacons a été constituée. L'analyse des différents résultats expérimentaux a notamment mis en évidence la nature fickienne du phénomène de diffusion et la chute de la résistance à la compression verticale des flacons. Nous avons ensuite proposé la modélisation du comportement mécanique du PEHD avec prise en compte du transfert de masse induit par le phénomène de diffusion. Des modèles élastoviscoplastique et de fluage ont été proposés et implémentés dans le code de calcul en éléments finis ABAQUS. Les paramètres de ces modèles ont été identifiés à partir de sollicitations simples par la résolution d'un problème d'optimisation, et les modèles ainsi identifiés ont été validés par la simulation numérique d'essais réalisés sur des flacons. Les résultats numériques obtenus sont en très bonne adéquation avec les mesures expérimentales. / As part of this thesis, we studied the container-content interaction between a high-density polyethylene-based packaging (HDPE) and amyl acetate considered as diffusing agent. We were specifically interested in the impact of sorption and diffusion phenomenon on mechanical properties of HDPE bottles under static and creep conditions at different stages of physical aging. Several uniaxialtests have been performed on samples cut from bottles and structural tests have been performed on bottles. The analysis of such various experimental results has highlighted in particular the Fickean nature of the diffusion phenomenon and the fall of the vertical compression strength. We have then focused onthe modeling of the mechanical behavior of HDPE taking into account the mass transfer induced by the diffusion phenomenon. Elasto-viscoplastic and creep models have been proposed and implemented in the finite elements code ABAQUS. The parameters of these models have been identified from simple tests by solving an optimization problem, and thus identified models have been validated by numerical simulation of vertical compression of HDPE bottles. Numerical results are in very good agreement with experimental measurements.

Le stress hydrique menacera plus que 40% de la population mondiale en 2050. Plus de 240 millions de personnes seront dépourvues d’accès à une source d’eau améliorée. En effet, pour assurer une gestion durable de cette ressource, la minimisation des ruptures dans les réseaux d'adduction d'eau potable est primordiale. La rupture des canalisations, phénomène assez fréquent en milieu urbain, s’amorce sur un défaut et sous l’effet des contraintes engendrées par un chargement inhabituel : coup de bélier, un phénomène de surpression. Depuis les années 80, le polyéthylène prend une part de plus en plus importante dans la fabrication des canalisations d'eau potable. Les jonctions sont les zones les plus dangereuses dans les réseaux. D'où l'importance d'étudier la résistance à la rupture des conduites coudées en PEHD. Pour résoudre ce problème, une étude est abordée par une approche expérimentale et une approche numérique par éléments finis pour caractériserle comportement à la fissuration des conduites coudées en PE100. Deux méthodologies sont proposées pour déterminer la ténacité du PEHD : la méthode de l'intégrale J et la méthode du déplacement d'ouverture en pointe de fissure ''CTOD''.La combinaison de ces outils permet de choisir la valeur critique de l'intégrale J comme valeur de la ténacité du PEHD.Ensuite, nous proposons une formule simplifiée basée sur la détermination de l'intégrale J en fonction de la pression dans les réseaux d'adduction d'eau potable en présence d'un défaut superficiel. Enfin, nous étudions le phénomène de coup de bélier pour déterminer la surpression avec un modèle mathématique développé dans cette thèse. Nous démontrons l'importance de l'interaction fluide-structure pour définir la pression au niveau des coudes / Water scarcity will be threatening more than 40% of the world population by 2050, more than 240 million people will not have a source of improved water. In fact, to ensure a sustainable management of this resource, the minimization of the leakages in drinking-water supply network is vital. Pipe rupture, a frequent phenomenon in urban zones, starts with a defect, under the effect of constraints caused by an unusual over pressure: Water Hammer. Since the 80s, polyethylene is being widely considered in manufacturing the pipelines water supply networks. Nevertheless, junctions are the most dangerous zones in the networks. As a result, it is vital to study the tear resistance of the angled conducts in PEHD. To solve this problem, a study is approached with an experimental investigation and a digital approach by fine elements in order to characterize the behavior in the fissuring of pipe bends PE100. Two methodologies are proposed to determine the tenacity of the PEHD: the method of the J-integral and the method of the sharp's movement opening of crack "CTOD ". The combination of these tools permits to choose the critical value of the integral J as a value of the tenacity of the HDPE. In addition, a simplified formula was proposed based on the calculation of the J-integral as a function of the pressure in water supply networks in the presence of a superficial defect. Finally, the water hammer phenomenon was investigated in order to determine the overpressure with a mathematical model which was developed in this thesis. The fluid-structure interaction was found to be important in defining the pressure at elbow pipe

A co-pirólise é uma rota promissora, uma vez que minimiza o impacto ambiental causado pela disposição do plástico de maneira inadequada, evita seu acúmulo em lixões e permite um melhor aproveitamento de um recurso natural não-renovável, o petróleo, matéria prima importante para a geração de energia e obtenção de produtos químicos. O presente trabalho teve como objetivo a definição das condições experimentais mais propícias à obtenção de líquidos pirolíticos com alta fração de óleo diesel, resultantes da co-pirólise de polietileno de alta densidade (PEAD) pós-consumo com gasóleo pesado tilizando-se catalisador de FCC (Fluid Catalytic Cracking). Como instrumento de otimização das condições experimentais, optou-se pela Metodologia Planejamento Fatorial. Foi também estudado o efeito das condições experimentais, como: a temperatura de reação, a relação gasóleo/polietileno e a quantidade de catalisador no meio reacional. As amostras de polietileno, gasóleo e catalisador foram submetidas à co-pirólise em sistema de leito fixo, sob fluxo constante de nitrogênio, variando-se a temperatura entre 450 C a 550 C, a quantidade de PEAD no meio reacional foi de 0,2 a 0,6 g, e a quantidade de catalisador foi de zero a 0,06 g, mantendo-se fixa a quantidade de gasóleo em 2 g. Foram efetuadas as caracterizações física e química do gasóleo, polietileno pós-uso e do catalisador. Como resultado, obteve-se a produção de 87% de fração de óleo diesel em duas condições diferentes: (a) 550 0C de temperatura sem catalisador; (b) 500 0C de temperatura e 25% de catalisador FCC. Em ambos os casos, a quantidade de gasóleo pesado e PEAD foram constantes (2 g Gasóleo; 0,2 g PEAD), assim com o tempo de reação de 15 minutos. A fração de óleo diesel obtida neste estudo alcançou o poder calorífico de 44,0 MJ/Kg que é similar ao óleo diesel comercial. É importante ressaltar que em ambos os casos nenhum resíduo foi produzido, sendo uma rota ambientalmente importante para reciclagem de embalagens plásticas contaminadas com óleo lubrificante originárias de postos de serviço, visando à recuperação de ambos conteúdo energético e orgânico dos resíduos de embalagens plásticas pós-uso / In this work it was studied the co-pyrolysis process applied to HDPE plastic package with motor oil residues with Heavy Gas Oil and FCC Catalyst. The main objective of this work was to find the experimental conditions that enhanced the diesel fuel fraction in the pyrolitic oil. Factorial Design Methodology (FDM) was developed to enhance diesel fuel fraction (C9-C23) from waste high-density polyethylene (HDPE) and heavy gas oil (HGO) through copyrolysis. FDM was used for optimization of the following reaction parameters: temperature, catalyst and HDPE amounts. The HGO amount was constant (2.0 g) in all experiments. The model optimum conditions were determined to be temperature of 550 C, HDPE = 0.20 g and no FCC catalyst. Under such conditions, 94% of pyrolytic oil was recovered, of which diesel fuel fraction was 93% (87% diesel fuel fraction yield), no residue was produced and 6% of noncondensable gaseous/volatile fraction was obtained. Seeking to reduce the cost due to high process temperatures, the impact of using higher catalyst content (25 %) with a lower temperature (500 C) was investigated. Under these conditions, 88% of pyrolytic oil was recovered (diesel fuel fraction yield was also 87%) as well as 12% of the noncondensable gaseous/volatile fraction. No waste was produced in these conditions, being an environmentally friendly approach for recycling the waste plastic. The diesel fuel fraction obtained in this study achieved heating value (44.0 MJ/Kg) similar to commercial diesel oil. This paper demonstrated the usefulness of using FDM to predict and to optimize diesel fuel fraction yield with a great reduction in the number of experiments. Based on experimental results, co-pyrolysis can represent a significant role in future in the recovery of both energetic and organic content of HDPE plastic package with motor oil residues

Submitted by GIOVANNI BARRERA TORRES null (gbarrerat01@gmail.com) on 2017-08-04T04:24:40Z No. of bitstreams: 1 TESE VERSÃO FINAL Giovanni Barrera Torres.pdf: 6197644 bytes, checksum: d321626a0e947c39627bbfe43b7aaf87 (MD5) / Approved for entry into archive by LUIZA DE MENEZES ROMANETTO (luizamenezes@reitoria.unesp.br) on 2017-08-04T19:37:47Z (GMT) No. of bitstreams: 1 torres_gb_dr_prud.pdf: 6197644 bytes, checksum: d321626a0e947c39627bbfe43b7aaf87 (MD5) / Made available in DSpace on 2017-08-04T19:37:47Z (GMT). No. of bitstreams: 1 torres_gb_dr_prud.pdf: 6197644 bytes, checksum: d321626a0e947c39627bbfe43b7aaf87 (MD5) Previous issue date: 2017-06-21 / Asociación Universitaria Iberoamericana de Postgrado (AIUP) / A presente pesquisa foi projetada para promover o desenvolvimento de compósitos poliméricos a partir da mistura de polietileno de baixa densidade (PEBD) com borracha natural (BN) reforçada com a cinza, resíduo da queima do bagaço, a cinza da cana de açúcar (CBC). Uma das propostas desta pesquisa foi direcionar uma aplicação ao resíduo, que é um material abundante e descartado, gerado no processo usual das usinas. A borracha natural empregada foi obtida a partir do látex de seringueira de Hevea Brasiliensis, Clone RRIM 600 muito cultivado no Brasil. A fim de se estudar separadamente a interação entre a CBC junto a BN e os agentes de vulcanização. Foi estudada numa primeira etapa: a mistura de borracha natural com a cinza de bagaço da cana até desenvolver uma mistura chamada de master, com boas propriedades de tensão e deformação. Foram produzidos compósitos elastoméricos aplicando agente silano como sistema de acoplamento. Numa segunda etapa o master compatibilizado foi misturado ao PEBD sem o uso de agentes de vulcanização; a finalidade destes compósitos foi de estudar a interação dos constituintes visando obter um compósito com o mínimo de agentes químicos e funcional para a indústria. Numa última etapa foram desenvolvidas blendas e compósitos termoplásticos vulcanizáveis (TPV); nesta etapa foram aplicados os agentes de vulcanização empregados na primeira etapa da pesquisa. As amostras foram estudadas por meio das técnicas de análises estruturais (FT-IR); físico-mecânicas (tensão e deformação; dinâmicas e mecânicas, DMA); térmicas (DSC e TG); dureza (Shore A). Foram obtidos resultados sobressalientes em comparação com as amostras sem agentes de vulcanização nas amostras com 50 % de master e 50 % de PEBD na resposta de elongação e tensão; a dureza acima do Shore A 85 obtida, foi produto da porcentagem da fase de PEBD presente nas amostras; nas análises térmicas foi possível observar degradação acima dos 160 oC resultando uma boa característica para aplicações industriais. Com os resultados obtidos tornou-se possível direcionar tanto a CBC como os compósitos para aplicações tecnológicas a fim de serem utilizados na fabricação de cabos de ferramentas, amortecedores, produtos para o lar, entre outros. / The present research was aimed to promote the development of polymeric composites from the mixture of low density polyethylene (LDPE) with natural rubber reinforced with ash, residue of the burning of sugarcane bagasse (SCB). One of the proposals of this research was to direct an application to the residue, which is an abundant and discarded material, generated in the usual process of the plants. The natural rubber used was obtained from rubber latex clone of Hevea Brasiliensis, Clone RRIM 600 widely cultivated in Brazil. In order to study separately the interaction between SCB with NR and vulcanization agents. It was developed in the first stage: the mixing of natural rubber with the sugarcane bagasse ash to develop a mixture called master, with good tensile and deformation properties. Elastomeric composites were produced by applying silane as a coupling agent. In a second stage the compatibilized master was mixed to the LDPE without the use of vulcanization agents; the purpose of these composites was to study the interaction of the constituents in order to obtain a composite with the minimum of chemical and functional agents for the industry. In the latter stage vulcanizable thermoplastic blends and thermoplastic composites were developed; In this stage the vulcanization agents used in the first stage of the research were applied. The samples were studied using structural analysis techniques (FT-IR); Physical-mechanical (tension and deformation, dynamic and mechanical, DMA); (DSC and TG); Hardness (Shore A). Sparing results were obtained in comparison with the samples without vulcanization agents in samples with 50 % of master and 50 % of LDPE in the strain and stress response; the hardness above Shore A 85, obtained was the product of the percentage of the LDPE phase present in the samples; In the thermal analyzes it was possible to observe degradation above 160 oC resulting in a good characteristic for industrial applications. With the results obtained, it became possible to target both SCB and composites for technological applications in order to be used in the manufacture of tool cables, shock absorbers, household products, among others. / AIUP: A0 185864

A co-pirólise é uma rota promissora, uma vez que minimiza o impacto ambiental causado pela disposição do plástico de maneira inadequada, evita seu acúmulo em lixões e permite um melhor aproveitamento de um recurso natural não-renovável, o petróleo, matéria prima importante para a geração de energia e obtenção de produtos químicos. O presente trabalho teve como objetivo a definição das condições experimentais mais propícias à obtenção de líquidos pirolíticos com alta fração de óleo diesel, resultantes da co-pirólise de polietileno de alta densidade (PEAD) pós-consumo com gasóleo pesado tilizando-se catalisador de FCC (Fluid Catalytic Cracking). Como instrumento de otimização das condições experimentais, optou-se pela Metodologia Planejamento Fatorial. Foi também estudado o efeito das condições experimentais, como: a temperatura de reação, a relação gasóleo/polietileno e a quantidade de catalisador no meio reacional. As amostras de polietileno, gasóleo e catalisador foram submetidas à co-pirólise em sistema de leito fixo, sob fluxo constante de nitrogênio, variando-se a temperatura entre 450 C a 550 C, a quantidade de PEAD no meio reacional foi de 0,2 a 0,6 g, e a quantidade de catalisador foi de zero a 0,06 g, mantendo-se fixa a quantidade de gasóleo em 2 g. Foram efetuadas as caracterizações física e química do gasóleo, polietileno pós-uso e do catalisador. Como resultado, obteve-se a produção de 87% de fração de óleo diesel em duas condições diferentes: (a) 550 0C de temperatura sem catalisador; (b) 500 0C de temperatura e 25% de catalisador FCC. Em ambos os casos, a quantidade de gasóleo pesado e PEAD foram constantes (2 g Gasóleo; 0,2 g PEAD), assim com o tempo de reação de 15 minutos. A fração de óleo diesel obtida neste estudo alcançou o poder calorífico de 44,0 MJ/Kg que é similar ao óleo diesel comercial. É importante ressaltar que em ambos os casos nenhum resíduo foi produzido, sendo uma rota ambientalmente importante para reciclagem de embalagens plásticas contaminadas com óleo lubrificante originárias de postos de serviço, visando à recuperação de ambos conteúdo energético e orgânico dos resíduos de embalagens plásticas pós-uso / In this work it was studied the co-pyrolysis process applied to HDPE plastic package with motor oil residues with Heavy Gas Oil and FCC Catalyst. The main objective of this work was to find the experimental conditions that enhanced the diesel fuel fraction in the pyrolitic oil. Factorial Design Methodology (FDM) was developed to enhance diesel fuel fraction (C9-C23) from waste high-density polyethylene (HDPE) and heavy gas oil (HGO) through copyrolysis. FDM was used for optimization of the following reaction parameters: temperature, catalyst and HDPE amounts. The HGO amount was constant (2.0 g) in all experiments. The model optimum conditions were determined to be temperature of 550 C, HDPE = 0.20 g and no FCC catalyst. Under such conditions, 94% of pyrolytic oil was recovered, of which diesel fuel fraction was 93% (87% diesel fuel fraction yield), no residue was produced and 6% of noncondensable gaseous/volatile fraction was obtained. Seeking to reduce the cost due to high process temperatures, the impact of using higher catalyst content (25 %) with a lower temperature (500 C) was investigated. Under these conditions, 88% of pyrolytic oil was recovered (diesel fuel fraction yield was also 87%) as well as 12% of the noncondensable gaseous/volatile fraction. No waste was produced in these conditions, being an environmentally friendly approach for recycling the waste plastic. The diesel fuel fraction obtained in this study achieved heating value (44.0 MJ/Kg) similar to commercial diesel oil. This paper demonstrated the usefulness of using FDM to predict and to optimize diesel fuel fraction yield with a great reduction in the number of experiments. Based on experimental results, co-pyrolysis can represent a significant role in future in the recovery of both energetic and organic content of HDPE plastic package with motor oil residues

The use of agricultural waste, such as rice husk (RH), for the production of cheap and eco-friendly polymer composites has emerged as a promising field of interest. The aim of this work was the preparation of high-density polyethylene (HDPE)-based composites reinforced with rice husk and an organic pro-oxidant (EG) for the production of seedlings tubes. Photodegradation and degradation tests in simulated soil were performed for 90 and 180 days in order to study the decomposition of these composites. The SEM and OM images suggest that degradation of the composites samples was more extensive than the pure HDPE samples, probably because the composites present intense light absorption in the UV range, facilitating the degradation process even before biodegradation begins. In addition, after introducing RH particles in the polymeric matrix, the mechanical tensile and flexural properties, experienced significant changes, suggesting that the RH particles were homogeneously dispersed throughout the polymer matrix. In addition, it was possible to identify microorganisms with polyethylene biodegradation activity, such as Aspergillus niger, Penicillium spp., Trichoderma spp., Rhizopus spp. The results have demonstrated that HDPE, RH, and EG are attractive materials for the design of polymeric composites for the production of seedlings tubes with excellent mechanical properties, being, also, easily decomposed in the environment once discarded. / O uso de resíduos agrícolas, como a casca de arroz (CA), para a produção de compósitos poliméricos baratos e eco-amigáveis surge como um campo de interesse promissor. O objetivo deste trabalho foi a preparação e caracterização de compósitos à base de polietileno de alta densidade (PEAD) com casca de arroz e um oxibiodegradante orgânico (EG) para a produção de tubetes florestais. Os testes de fotodegradação e degradação em solo simulado foram realizados por 90 e 180 dias, a fim de estudar a decomposição desses compósitos. As imagens de microscopia eletrônica de varredura e microscopia óptica sugerem que a degradação das amostras dos compósitos foi mais extensa do que a amostra de PEAD puro, provavelmente porque os compósitos apresentam intensa absorção de luz na faixa UV, facilitando o processo de degradação mesmo antes da biodegradação. Além disso, após a introdução de partículas de casca de arroz na matriz polimérica, as propriedades mecânicas de tração e flexão, experimentaram mudanças significativas, sugerindo que as partículas de CA foram dispersas homogeneamente em toda a matriz de polímero. Além disso, foi possível a identificação de microrganismos com atividade de biodegradação do polietileno, como Aspergillus níger, Penicillium spp., Trichoderma spp., Rhizopus spp. Os resultados demonstraram que o compósito de PEAD, CA e EG são materiais atraentes para a produção de tubetes com excelentes propriedades mecânicas, sendo, também, facilmente decompostos no ambiente, após serem descartados. / São Cristóvão, SE