Polyethylene (PE) resins being non-polar in nature and having a high degree of crystallinity have limited miscibility and compatibility when blended with polar polymers. The miscibility and compatibility of these blends are generally worsened when they are prepared by direct injection moulding without a precompounding process. Such situations are commonly encountered in particular by polymer converters when blending colour and/or additive concentrates, commonly known as masterbatches. Typically, masterbatches are mixtures containing high loading of pigments and/or additives predispersed in a suitable solid vehicle (commonly known as carrier) such as a polyethylene resin. These masterbatches are usually used for the colouration of a wide range of polymers and the carrier used must therefore be compatible with these matrix (host) polymers. The preliminary stage of this study involved the investigation of the properties of blends based on high density polyethylene (HDPE) and a range of engineering thermoplastics (ABS, PC, PBT, PA6), prepared by injection moulding. Five different types of compatibilisers namely, ethylene-vinyl acetate (EVA) copolymer, ethylene-methyl acrylate (EMA) copolymer, ethylene-glycidyl methacrylate (E-GMA) copolymer, ethylene-methyl acrylateglycidyl methacrylate (E-MA-GMA) terpolymer and maleic anhydride grafted HDPE (HDPE-g-MAH) copolymer were evaluated with respect to their efficiencies in compatibilising HDPE with the four engineering polymers. The pre-compounded HDPE/compatibiliser binary blends at 2 different blend ratios (1:1 and 3:1) were added at 15 wt% concentration to each engineering thermoplastics and test samples were produced directly by injection moulding. Results of mechanical testing and characterisation of the blends showed that glycidyl methacrylate compatibilisers, E-MA-GMA, in particular have the most universal compatibilising effectiveness for a range of engineering thermoplastics including ABS, PC, PBT, and PA6. Blends compatibilised with E-MA-GMA compatibiliser had the best notched impact performance irrespective of matrix polymer type. The presence of an acrylic ester (methyl acrylate) comonomer in E-MA-GMA resulted in increased polarity of the ii compatibiliser leading to improved miscibility with the polar matrix polymers demonstrated by fine blend morphologies, melting point depression and reduction in crystallinity of the HDPE dispersed phase. The second stage of this study involved the reactive modification of HDPE using a low molecular weight di-functional solid diglycidyl ether of bisphenol A (DGEBA) type epoxy resin compatibilised with HDPE-g-MAH in an attempt to improve its compatibility with ABS, PBT and PA6. The maleic anhydride moieties in HDPE-g-MAH served as reactive sites for anchoring the epoxy moieties while the HDPE backbone was miscible with the HDPE resin. An excessive amount of reactive groups resulted in the formation of crosslinked gels while the addition of EVA co-compatibiliser helped in the reduction of gel content and further improved the dispersion of the epoxy. The effectiveness of epoxy grafted HDPE (with and without EVA co-compatibiliser) in compatibilising ABS/HDPE, PBT/HDPE, and PA6/HDPE was investigated by injection moulding of 5 wt% functionalised HDPE with these matrix polymers into test bars for mechanical testing, and characterisation by differential scanning calorimtery (DSC) and optical microscopy. The reactively functionalised HDPE blends, improved the mechanical properties of ABS and PA6 blends especially with EVA as co-compatibiliser. However, the mechanical properties of PBT blends were unmodified by the functionalised HDPE which was believed to be due to end-capping of the PBT chain-ends by ungrafted epoxy resins.

The presented diploma thesis deals with the evaluation of the influence of the addition of 30, 60 and 90 % of recycled material on the structure and mechanical properties of high-density polyethylene (HDPE), where recycled material represents both HDPE from a several years old part and material multiple reprocessed by extrusion. The changes of supramolecular structure were examined by calorimetric measurement, which did not indicate degradation of the material due to multiple extrusion. Mechanical properties were investigated by tensile tests and dynamic-mechanical analysis. Both measurements showed the same trend, where the first and second pass of the material through the extruder led to improved mechanical properties, e.g. to increase stiffness, while the influence of the third and fourth passes through the extruder had not a significant effect on the mechanical properties. In terms of the structure and mechanical properties, a positive effect of the combination of material after the second extrusion passing (30%) with virgin material was recorded.

The thesis deals with the study of the influence of concentration and different types of surfactants (Igepal CO-520, Arkopal N110, Igepal CO-890, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, dodecyltrimethylammonium bromide and Dehyton PL) on the environmental stress cracking resistance of high-density polyethylene by means of Full Notch Creep Test. Furthermore, the influence of ligamental stress (3,5; 4,0 a 4,5 MPa), pH of the prepared active environment and type of the water used as a solvent for the surfactants on the time to failure was monitored. An accelerating effect was observed at increased concentration, stress and molecular weight. Faster failure was achieved after exposure to ionic types compared to nonionic. The rate of the notch opening was determined. The brittle and ductile behavior during the process of failure was evaluated by microscopic analysis of the morphology of the fracture surfaces. Based on the pH change after the test, the stability of the active environment was evaluated. Deteriorating quality of surfactant solutions was observed. Raman spectroscopy and Fourier transform infrared spectroscopy were used to detect the surfactant on the surface of the test specimen after the test.

<p> The effect of capillary dimensions on the die swell of molten polymers is investigated. Low and high density polyethylene, polypropylene, polystyrene are used to make investigation It is found the die swell decreases vii th L/D. The plot of die swell index (d/D) vs. L/D has the shape of anexponential decay curve. </p> <p> Bagley's decaying equation is used to fit the data. The effect of Deborah number on die swell phenomenon is also studied. 'I'he relationship between the recoverable shear strains of infinitely long capillary and the one with dimensions ratio L/D is obtained. This relationship could be used to estima te the die swell of short capillary from its value at equilibrium and polymer characteristics. </p> / Thesis / Master of Engineering (MEngr)

Made available in DSpace on 2014-12-17T15:41:46Z (GMT). No. of bitstreams: 1 StevieHLpdf.pdf: 1475886 bytes, checksum: e83c49569bddebb612701e2de7e607bc (MD5) Previous issue date: 2009-08-31 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In last years it has talked a lot about the environment and the plastic waste produced and discarded. In last decades, the increasing development of research to obtain fuel from plastic material, by catalytic degradation, it has become a very attractive looking, as these tailings are discarded to millions worldwide. These materials take a long time to degrade themselves by ways said natural and burning it has not demonstrated a viable alternative due to the toxic products produced during combustion. Such products could bring serious consequences to public health and environment. Therefore, the technique of chemical recycling is presented as a suitable alternative, especially since could be obtain fractions of liquid fuels that can be intended to the petrochemical industry. This work aims to propose alternatives to the use of plastic waste in the production of light petrochemical. Zeolites has been widely used in the study of this process due to its peculiar structural properties and its high acidity. In this work was studied the reaction of catalytic degradation of high-density polyethylene (HDPE) in the presence HZSM-12 zeolites with different acid sites concentrations by thermogravimetry and pyrolysis coupled with GC-MS. The samples of the catalysts were mixed with HDPE in the proportion of 50% in mass and submitted to thermogravimetric analyses in several heating rates. The addition of solids with different acid sites concentrations to HDPE, produced a decrease in the temperature of degradation of the polymer proportional the acidity of the catalyst. These qualitative results were complemented by the data of activation energy obtained through the non-isothermal kinetics model proposed by Vyazovkin. The values of Ea when correlated to the data of surface acidity of the catalysts indicated that there is a exponential decrease of the energy of activation in the reaction of catalytic degradation of HDPE, in function of the concentration of acid sites of the materials. These results indicate that the acidity of the catalyst added to the system is one of the most important properties in the reaction of catalytic degradation of polyethylene / Nos ?ltimos anos tem-se falado muito sobre o meio ambiente e sobre o lixo pl?stico produzido e descartado. Nas ?ltimas d?cadas, o crescente desenvolvimento de pesquisas com o intuito de obter combust?veis a partir de material pl?stico, via degrada??o catal?tica, tem-se tornado uma busca muito atrativa, j? que esses rejeitos s?o descartados aos milh?es em todo mundo. Esses materiais levam muito tempo para se degradar por meios ditos naturais e sua incinera??o n?o tem se demonstrado uma alternativa vi?vel devido aos produtos t?xicos produzidos durante sua combust?o. Tais produtos conseq?entes poderiam trazer s?rios problemas de sa?de p?blica e ambiental. Logo, a t?cnica da reciclagem qu?mica apresenta-se como uma alternativa adequada, inclusive porque podemos obter fra??es leves do petr?leo que podem ser destinadas ao setor petroqu?mico. Este trabalho tem como objetivo propor alternativas para o aproveitamento de lixo pl?stico na produ??o de combust?veis l?quidos. Ze?litas tem sido amplamente utilizada no estudo desse processo devido ?s suas propriedades estruturais peculiares e sua alta acidez. Neste trabalho, investigou-se a rea??o de degrada??o de Polietileno de Alta Densidade (PEAD) na presen?a de HZSM-12, com diferentes concentra??es de s?tios ?cidos, atrav?s da termogravimetria e pir?lise acoplada ? cromatografia ? g?s e ao espectr?metro de massa (Py-GC-MS). As amostras de catalisadores foram misturadas com PEAD na propor??o de 50% em massa e submetidas a an?lises em diferentes taxas de aquecimento. A adi??o de catalisadores com diferentes concentra??es de s?tios ?cidos produziu uma diminui??o na temperatura de degrada??o do pol?mero proporcional ? acidez do catalisador. Estes resultados qualitativos foram complementados por dados da energia de ativa??o (Ea) obtidos atrav?s do modelo cin?tico n?o-isot?rmico proposto por Vyazovkin. Os valores das Ea quando correlacionados com os dados da acidez superficial dos catalisadores, indicaram que h? uma redu??o exponencial da Ea da rea??o catal?tica de degrada??o em fun??o da concentra??o dos s?tios ?cidos dos materiais, indicando que esta propriedade ? significativa neste tipo de rea??o

O presente trabalho foi desenvolvido para avaliar o potencial de utilização de um reator anaeróbico fabricado em PEAD Polietileno de Alta Densidade, produzido pelo processo de rotomoldagem em substituição aos reatores convencionais construídos em concreto e alvenaria, trabalhando em regime de batelada e enterrados no solo. Os estados de tensões e deformações foram avaliados utilizando o programa de Elementos Finitos ABAQUS versão 6.5 e a malha dos nós utilizando o programa MSC PATRAN 2005 formando 7329 nós e 2004 elementos, em uma malha otimizada para as regiões de maior curvatura (pontos concentradores de tensão). O carregamento é formado com uma pressão interna do biogás de 5 kPa acrescido da carga hidrostática de biomassa de 6000 kgf em uma fundação elástica calculada pela razão tensão/recalque a partir do Módulo de Elasticidade equivalente do solo (Esolo). Comparando o estado de tensões avaliado durante o carregamento foi possível constatar que a maior tensão obtida no elemento mais crítico para a utilização mais provável do reator atingiu o valor de 7,46 MPa (não supera 40% do menor valor de resistência à tração e ao cisalhamento do PEAD de 20 MPa) e a maior razão de deformação dR/R foi de 1.0%. O caso mais crítico avaliado foi quando o reator está enterrado, totalmente vazio, em solo com Esolo = 1,55 MPa e o material com EPEAD = 1550 MPa e com uma sobrecarga superficial no terreno de 20kN/m2 gerando uma tensão de 17,80 MPa no elemento 1955 (atingindo 89% do menor valor de resistência à tração e ao cisalhamento do PEAD igual a 20 MPa). Os resultados obtidos comprovam que o reator produzido em PEAD substitui com vantagens os modelos fabricados em concreto ou alvenaria, suportando a pressão interna do biogás e a carga de biomassa. / The present work was developed to evaluate the potential of uses of an anaerobic reactor manufactured in HDPE High Density Polyethylene produced by the rotomolding process in substitution to the conventional reactors built in stonemasonry, working in a batch regime and buried in the soil. The state of tensions and the deformations were assessed using the program of Finite Elements ABAQUS version 6.5 and the mesh of the knots using the program MSC PATRAN 2005 forming 7329 knots and 2004 elements, in an optimized mesh for the areas of larger curvature (tension concentrator points). The loading is formed with an internal pressure of the biogas of 5kPa added of biomass hydrostatic load of 6000 kg in an elastic foundation calculated by the ratio pressure/settling starting from the Module of equivalent Elasticity of the soil (Esolo). Comparing the state of tensions assessed during the loading was possible to verify that the largest tension obtained in the most critical element goes the most probable utilization of the reactor, reached the value of 7, 46 MPa (it doesn't surpass 40% of the smallest resistance value to the traction and to the shearing strain of HDPE of 20 MPa) and the largest ratio of dR/R deformation was of 1.0%. The most critical assessed case was when the reactor is buried in soil with Esolo = 1,55 MPa and material with EPEAD = 1550 MPa, totally empty and with a superficial overload in the land of 20kN/m2 generating a tension of 17,80 MPa in the element 1955 (reaching 89% of the smallest resistance value to the traction and the shearing strain of a 20 MPa HDPE). The obtained results confirmed that the reactor produced in HDPE substitutes with advantages the models manufactured in stonemasonry, supporting the internal biogas pressure and the biomass load.

O presente trabalho foi desenvolvido para avaliar o potencial de utilização de um reator anaeróbico fabricado em PEAD Polietileno de Alta Densidade, produzido pelo processo de rotomoldagem em substituição aos reatores convencionais construídos em concreto e alvenaria, trabalhando em regime de batelada e enterrados no solo. Os estados de tensões e deformações foram avaliados utilizando o programa de Elementos Finitos ABAQUS versão 6.5 e a malha dos nós utilizando o programa MSC PATRAN 2005 formando 7329 nós e 2004 elementos, em uma malha otimizada para as regiões de maior curvatura (pontos concentradores de tensão). O carregamento é formado com uma pressão interna do biogás de 5 kPa acrescido da carga hidrostática de biomassa de 6000 kgf em uma fundação elástica calculada pela razão tensão/recalque a partir do Módulo de Elasticidade equivalente do solo (Esolo). Comparando o estado de tensões avaliado durante o carregamento foi possível constatar que a maior tensão obtida no elemento mais crítico para a utilização mais provável do reator atingiu o valor de 7,46 MPa (não supera 40% do menor valor de resistência à tração e ao cisalhamento do PEAD de 20 MPa) e a maior razão de deformação dR/R foi de 1.0%. O caso mais crítico avaliado foi quando o reator está enterrado, totalmente vazio, em solo com Esolo = 1,55 MPa e o material com EPEAD = 1550 MPa e com uma sobrecarga superficial no terreno de 20kN/m2 gerando uma tensão de 17,80 MPa no elemento 1955 (atingindo 89% do menor valor de resistência à tração e ao cisalhamento do PEAD igual a 20 MPa). Os resultados obtidos comprovam que o reator produzido em PEAD substitui com vantagens os modelos fabricados em concreto ou alvenaria, suportando a pressão interna do biogás e a carga de biomassa. / The present work was developed to evaluate the potential of uses of an anaerobic reactor manufactured in HDPE High Density Polyethylene produced by the rotomolding process in substitution to the conventional reactors built in stonemasonry, working in a batch regime and buried in the soil. The state of tensions and the deformations were assessed using the program of Finite Elements ABAQUS version 6.5 and the mesh of the knots using the program MSC PATRAN 2005 forming 7329 knots and 2004 elements, in an optimized mesh for the areas of larger curvature (tension concentrator points). The loading is formed with an internal pressure of the biogas of 5kPa added of biomass hydrostatic load of 6000 kg in an elastic foundation calculated by the ratio pressure/settling starting from the Module of equivalent Elasticity of the soil (Esolo). Comparing the state of tensions assessed during the loading was possible to verify that the largest tension obtained in the most critical element goes the most probable utilization of the reactor, reached the value of 7, 46 MPa (it doesn't surpass 40% of the smallest resistance value to the traction and to the shearing strain of HDPE of 20 MPa) and the largest ratio of dR/R deformation was of 1.0%. The most critical assessed case was when the reactor is buried in soil with Esolo = 1,55 MPa and material with EPEAD = 1550 MPa, totally empty and with a superficial overload in the land of 20kN/m2 generating a tension of 17,80 MPa in the element 1955 (reaching 89% of the smallest resistance value to the traction and the shearing strain of a 20 MPa HDPE). The obtained results confirmed that the reactor produced in HDPE substitutes with advantages the models manufactured in stonemasonry, supporting the internal biogas pressure and the biomass load.