No / The advances of the polymer melt flow-induced crystallization behaviour and its influence on mechanical properties of high density polyethylene (HDPE) in micron injection (MI) were studied in the present paper. Analysis of mechanical performance, including yield stress and elongation at break, for samples adopted from different regions in a molded plaque showed that a higher injection speed, a higher mold temperature and a longer cooling time could effectively enhance the yield stress but negatively promoted the ductility. Then, the mechanisms of such variation of mechanical performance and the factors affecting it were investigated by means of differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and polarized light microscopy (PLM). The super high shear rate during cavity feeding in MI molding not only induced a typical three-layered structure but also developed a highly oriented fibrously morphological structure in the skin layer. However, such fully oriented morphology was much negative in the interlayer and even could not be observed in the core layer. The results from SEM and PLM observations indicated that the orientation morphology varied significantly through the plaque's cross-section and thickness of the each layer changed with the process parameters and geometric position, and finally led to variation of the mechanical performance.

<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)

Ph. D. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / Investment casting process is the most suitable technique for producing high quality castings which are dimensionally accurate with excellent surface finish and complex in nature. Recently with the ever-changing manufacturing landscape, the process has been increasingly used to produce components for the medical, aerospace and sports industry. The present study looked at three investigative scenarios in the development of a pattern material for investment casting process: (i) the development of wax/ethyl vinyl acetate (EVA) and wax/linear low-density polyethylene (LLDPE) blends as the carrier vehicle materials for the development of pattern material for investment casting; (ii) the development of wax/EVA/polymethyl methacrylate (PMMA) based investment casting pattern and lastly (iii) the development of wax/LLDPE/PMMA based investment casting pattern material. The first part of the studies elucidates the effects in terms of the thermal, mechanical, surface and rheological properties when paraffin wax in blended with poly EVA and LLDPE. The developments involved the extrusion of seven formulations for EVA and also LLDPE using a twin-screw extrusion compounder. The paraffin wax weight percent investigated ranged from 33% to 87% thus encompassing both low and high wax loading ratios. The thermal properties of the developed binary blends were characterized via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The mechanical properties were characterized using three-point bending test. The thermo-mechanical and rheological properties were determined using thermomechanical analysis (TMA) and a rheometer respectively. A scanning electron microscope (SEM) was used to study the surface texture of the extruded blends. The thermal properties indicated that the thermal stability of paraffin wax is improved when it is blended with both EVA and LLDPE. DSC curves showed two endothermic melting peaks and two exothermic crystallisation peaks. In the case of wax/EVA blends, there was no distinct peak showing the independent melting of neat wax and EVA. The peak at a temperature of 50 – 72 °C corresponds to the melting of the wax/EVA blend. In the case of wax/LLDPE blends, the peak at 50 -66 °C corresponds to the melting of wax whereas the large peak at 112 - 125°C corresponds to the melting of the LLDPE. Wax/EVA and wax/LLDPE had improved mechanical properties as compared to that of neat wax. The rheological properties of both the EVA based and LLDPE based blends indicated that the viscosity of the blends increased as compared to that of neat wax. SEM confirmed that EVA alters the wax crystal habit at higher concentrations. In the case of wax/LLDPE blends, at 20-30 % wax content, a heterogeneous surface was observed, indicating the immiscibility of the paraffin wax within the LLDPE matrix. At a high wax content, there was agglomeration of wax. LLDPE allows amorphous structure of wax to disperse easily between the chains. The second part of the studies focussed on the wax/EVA filled with poly (methyl methacrylate) (PMMA) microbeads. TGA behaviour on the pyrolysis of wax/EVA/PMMA showed that the compounds volatilise readily with virtually no residue remaining above 500 °C. The DSC curves indicated that, the incorporation of PMMA reduced the crystallinity of wax/EVA blend. A distinct endothermic peak and another small peak was observed in all the formulations. The mechanical properties of wax/EVA/PMMA improved significantly. The methylene group present in both wax and EVA combined to form a blend with enhanced mechanical properties whereas the PMMA microbeads improved the needle penetration hardness. The melt viscosity of wax/EVA/PMMA increased as the EVA and/or the PMMA content is increased. The rheological experimental data fitted with the data predicted using the modified Krieger and Dougherty expression. The maximum attainable volume fraction of suspended PMMA particles was at max = 0.81. The SEM micrograph of wax/EVA/PMMA revealed a near perfect spherical nature for the filler particles in the wax/EVA polymer matrix. It further shows that the PMMA microbeads were weakly bonded and well distributed in the wax/EVA matrix. The third part of the studies focussed on the wax/LLDPE filled with Poly (methyl methacrylate) (PMMA) microbeads. The incorporation of LLDPE and PMMA into paraffin wax had a strong influence on the thermal properties, tensile properties, flow properties and its morphology. The TGA analysis showed that there was a slight observable decrease in the melting onset temperatures when the wax content was increased. From the DSC curves, the corresponding values of onset temperatures observed are between melting and crystallization temperature of neat paraffin wax and neat LLDPE. The short chains of the paraffin wax and the fragments formed by scission of wax chain have sufficient energy to escape from the matrix at lower temperatures. The slight decrease in peak temperatures associated with melting and crystallization could be attributed to the decrease in the average lamellar thickness of the blends. The tensile properties by three-point bending tests indicated an increase in the stress with an increase in the LLDPE content. This can be attributed to the formation of paraffin wax crystals in the amorphous phase of the blend which may influence the chain mobility. Since the paraffin wax used for this study had a low viscosity as compared to LLDPE, both LLDPE or PMMA had an influence on the viscosities of the blends. The data obtained from the experiments fitted with the data predicted obtained from the modified Krieger and Dougherty expression. The maximum attainable volume fraction of suspended PMMA particles was at max = 0.74. Similar observation with that of wax/EVA/PMMA was made in terms of the morphology of the wax/LLDPE/PMMA blends. The excellent thermal stabilities, the superior mechanical strength of wax/EVA/PMMA and wax/LLDPE/PMMA and the flow properties with relatively high EVA and also with high PMMA loadings, open new opportunities for EVA and LLDPE based pattern material for in investment casting process. It is worth pursuing further comprehensive studies since it offers a strong potential for realizing further technological improvement in the field of investment casting and rapid prototyping technologies.

No / The in-line development of crystalline morphology and orientation during melt extrusion of low density polyethylene (LDPE) tape at nil and low haul-off speeds has been investigated using Small-Angle X-Ray Scattering (SAXS). The processing parameters, namely haul-off speed and distance down the tape-line have been varied and the resulting crystalline morphology is described from detailed analysis of the SAXS data. Increasing haul-off speed increased orientation in the polymer tape and the resulting morphology could be described in terms of regular lamellar stacking perpendicular to the elongation direction. In contrast, under nil haul-off conditions the tape still showed some orientation down the tape-line, but a shish-kebab structure prevails. The final lamellae thickness (similar to 50 angstrom) and bulk crystallinity (similar to 20%), were low at, for all processing conditions investigated, which is attributed to the significant short-chain branching in the polymer acting as point defects limiting lamellae crystal growth. (C) 2013 Elsevier Ltd. All rights reserved.

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.