As a preliminary starting point for the present study, physical and mechanical properties of polypropylene nanocomposites (PPNCs) for samples received from Queen's University Belfast have been evaluated. Subsequently, polymer/clay nanocomposite material has been produced at Bradford. Mixing and processing routes have been explored, and mechanical properties for the different compounded samples have been studied. Clay intercalation structure has received particular attention to support the ultimate objective of optimising tensile and fracture behaviour of isotropic and die-drawn PPNCs. Solid-state molecular orientation has been introduced to PPNCs by the die-drawing process. Tensile stress-strain measurements with video-extensometry and tensile fracture of double edge-notched tensile specimens have been used to evaluate the Young¿s modulus at three different strain rates and the total work of fracture toughness at three different notch lengths. The polymer composite was analyzed by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, wide angle x-ray diffraction, and transmission electron microscopy. 3% and 5% clay systems at various compatibilizer (PPMA) loadings were prepared by three different mixing routes for the isotropic sheets, produced by compression moulding, and tensile bars, produced by injection moulding process. Die-drawn oriented tensile bars were drawn to draw ratio of 2, 3 and 4. The results from the Queen's University Belfast samples showed a decrement in tensile strength at yield. This might be explained by poor bonding, which refers to poor dispersion. Voids that can be supported by intercalated PP/clay phases might be responsible for improvement of elongation at break. The use of PPMA and an intensive mixing regime with a two-step master batch process overcame the compatibility issue and achieved around 40% and 50% increase in modulus for 3% and 5% clay systems respectively. This improvement of the two systems was reduced after drawing to around 15% and 25% compared with drawn PP. The work of fracture is increased either by adding nanoclay or by drawing to low draw ratio, or both. At moderate and high draw ratios, PPNCs may undergo either an increase in the size of microvoids at low clay loading or coalescence of microvoids at high clay loading, eventually leading to an earlier failure than with neat PP. The adoption of PPMA loading using an appropriate mixing route and clay loading can create a balance between the PPMA stiffness effect and the degree of bonding between clay particles and isotropic or oriented polymer molecules. Spherulites size, d-spacing of silicate layers, and nanoparticles distribution of intercalated microtactoids with possible semi-exfoliated particles have been suggested to optimize the final PPNCs property. / SABIC

Thesis (DSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006. / Commercial polyolefins degrade under the influence of light, heat, chemical and mechanical factors. They are therefore stabilised to ensure that they maintain performance characteristics during their service life. Degradation results in changes in the molar mass, molar mass distribution, chemical composition and chemical composition distribution. Classical analytical techniques only provide averaged values of these properties. Much information is available in the open literature on the changes in molar mass, molar mass distribution and chemical composition of polypropylene upon degradation, but no information was available on the changes in chemical composition distribution (CCD) during degradation. This study describes the use of the following analytical techniques to study this: temperature rising elution fractionation (TREF), crystallisation analysis fractionation (CRYSTAF) and coupled size exclusion chromatography-Fourier transform infrared analysis (SEC-FTIR). The CRYSTAF results complimented those obtained by classical techniques: there was a broadening of the crystallisation peak (CCD), an increase in the soluble fraction and a decrease in crystallisation temperatures. SEC-FTIR analysis showed that most of the degraded products were concentrated in the low molar mass regions. TREF analysis was used to separate a degraded sample into fractions of different degrees of degradation. It was then possible to study the spatial heterogeneity in a thick, degraded polypropylene sample using SEC, FTIR and CRYSTAF. The degradation behaviour of selected Sasol propylene-1-pentene random copolymers was investigated. CRYSTAF, SEC-FTIR and TREF analyses provided information on the thermo-oxidative degradation behaviour differences between unstabilised polypropylene homopolymers and these propylene-1-pentene copolymers. It was found that the pentene copolymers degraded significantly faster compared to the homopolymers, even at low levels of pentene (< 3%). The reduction in stability was virtually linear with an increase in pentene content (up to 8 mol% pentene), indicating that higher levels of primary stabilisers are needed to ensure similar life spans for the Sasol propylene-1-pentene copolymers. The extrusion stability of the propylene-1-pentene copolymers was, however, similar to that of the polypropylene homopolymers, indicating that similar processing stabiliser packages may be used.

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2009 / Polypropylene is an extremely versatile material and has a broad spectrum of applications due to the variations in properties which are possible with this material. The variations in the properties of the material are governed by the microstructure of the chains constituting the polymer. The microstructure varies according to the production methods, i.e. the polymerisation conditions. Varying the manner in which the polymer is produced therefore changes the properties of the material allowing the polymers’ use for different applications. The most important factor affecting the way in which the polymers are produced is the nature of the active sites on the catalyst. Changing the chemical environment of the active sites changes the way in which the polymerisation is controlled and greatly affects the types of chains produced and thus polymer properties. The study examines the structure-property relationships of polyolefins with specific focus on the polypropylene homopolymer. The temperature rising elution fractionation (TREF) technique is used extensively in order to isolate specific fractions of the polymer. The importance of specific TREF fractions is investigated via a two pronged investigative methodology. On the one hand specific TREF fractions are removed from a sample, allowing the analysis of the properties of the material without that specific fraction, thereby revealing the influence which the fraction in question has on the properties. The other branch of the study investigates the chemical modification of the active sites of a Ziegler-Natta catalyst so as to be able to modify the properties of the polymer in the reactor, in a similar manner to physically removing fractions. The techniques are related and it was discovered that the amount of the fractions of the polymer, found to be important using the one technique, also turned out to be important using the other method. Initial method development work utilised a polypropylene-1-pentene copolymer since the molecular heterogeneity of this material is such that large differences are observed upon removal of fractions. The technique was then applied to a Ziegler-Natta catalysed polypropylene homopolymer. Each TREF fraction is successively removed and the residual material analysed. Specific TREF fractions were found to play a significant role in determining the polymer properties since there was a drastic reduction in properties upon removal of these fractions. The polymerisation of propylene was also performed at a variety of conditions in order to investigate different ways in which the catalyst system could be modified. Specific reaction conditions were chosen for in-depth analysis and structure-property correlation. The chemical modification of the active sites was accomplished via the introduction of an external Lewis base (electron donor) to the polymerisation system, and also by varying the external donor/catalyst ratio used. Two different external donors were used during the study namely Diphenyl-dimethoxysilane (DPDMS) and methyl-phenyl-dimethoxysilane (MPDMS). It is observed that there are definite links between the amounts of specific fractions present in the polymer and the polymer properties, as observed via both the physical removal of fractions and the chemical modification of active sites.

Thesis (MEng)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: FRC (Fibre-reinforced concrete) has become a common form of secondary and even primary reinforcing in some applications throughout the world. In South Africa, the structural applications are limited primarily to steel fibres while cheaper, lighter and more durable synthetic fibres have been side-lined due to low stiffnesses. The purpose of this research project is to investigate the behaviour of synthetic fibre-reinforced concrete (SynFRC) using fibres which are locally available in South Africa, and to propose a performance-based specification and test method for the use of these fibres. In order to achieve this, single fibre pull-out tests were performed on four locally available polypropylene fibres. It was found that the average bond stresses of the fibres are influenced primarily by the fibre cross sectional shape, longitudinal geometry and surface treatment, and secondarily by the aspect ratio. The W/C ratio had little effect on the single fibre performance of non-treated fibres, but appeared to have a slight effect on the single fibre performance of the surface treated fibre. From the experimental results, the highest fibre bond stress will be generated by using a fibre with an X-shaped cross section, longitudinal crimping and applying a surface treatment to this fibre. It also appears that the bond stress distribution for flat fibres is close to uniform, while the bond stress distribution for non-flat crimped fibres has a high mechanical interlock component at the surface end. Macro-mechanical performance tests were performed by means of the BS EN 14651 (2007) three point beam bending test and the ASTM C1550 (2012) Round Determinate Panel Test (RDPT). These tests were selected following a thorough literature review. The RDPT was found to be more consistent and able to identify trends which the three point beam bending test could not. In addition, the three point beam bending test’s most popular output, the Re,3 value tended to be misleading with varying W/C ratios, and it is recommended that the equivalent flexural tensile strength be used instead if the three point beam bending test is used. The macro-mechanical testing showed that increasing the fibre dosage did increase post-cracking performance. The flat fibres’ performance was significantly better than that of the non-flat fibres, and also increased at a faster rate with increasing fibre dosage. The post-cracking performance decreased with increasing W/C ratios and increasing aggregate sizes. The macro-mechanical performance was inversely proportionate to the single fibre performance. The macro-mechanical performance decreased with increasing fibre bond stress, and increased with increasing equivalent diameter, which equates to fewer fibres in a set volume of fibres. Finally, basic principles were developed from the data. These principles were used to predict the RDPT and three point beam bending test performance parameters based on fibre dosage, single fibre properties (bond stress and equivalent diameter), W/C ratio and aggregate size from the available data. The principles can be further refined with more experimental data. / AFRIKAANSE OPSOMMING: Vesel-gewapende beton word regoor die wêreld as ’n algemene vorm van sekondêre en selfs primêre versterking gebruik. In Suid-Afrika is die strukturele toepassings hoofsaaklik tot staal vesels beperk, terwyl goedkoper, ligter en meer duursame sintetiese vesels vermy word as gevolg van lae styfhede. Die doel van hierdie navorsingsprojek is om die gedrag van sintetiese-veselversterktebeton (SynFRC) te ondersoek deur gebruik te maak van vesels wat in Suid-Afrika beskikbaar is, en 'n prestasie-gebaseerdespesifikasie en toetsmetode vir die gebruik van sintetiese vesels voor te stel. Enkelveseluittrektoetse is op vier plaaslik beskikbare polipropileen vesels uitgevoer. Daar is gevind dat die gemiddelde verbandspanning van die vesel hoofsaaklik deur die vesel deursnee vorm, lengte meetkunde en oppervlak behandeling beïnvloed word, en tweedens deur die aspek verhouding beïnvloed. Die W/C-verhouding het min effek op die enkelveselprestasie van nie-behandelde vesels, maar het 'n effek op die enkeleveselprestasie van die oppervlak-behandelde vesel gehad. Die eksperimentele resultate wys dat die hoogste vesel verbandspanning deur 'n vesel met 'n X-vormige deursnit, lengte krimping en toepassing van 'n oppervlak behandeling gegenereer sal word. Dit blyk ook dat die verbandspanningverspreiding vir ’n plat vesel naby aan uniform is, terwyl die verbandspanningverspreiding vir ’n nie-plat gekrimpde vesel 'n hoë meganiese grendeling komponent op die oppervlak ente het. Makro-meganiese prestasietoetse is uitgevoer deur middel van die BS EN 14651 (2007) driepuntbalkbuigtoets en die ASTM C1550 (2012) RDPT. Hierdie toetse is ná ’n deeglike literatuuroorsig gekies. Die RDPT is meer konsekwent en is in staat om neigings te identifiseer wat die driepuntbalkbuigingtoets nie kan nie. Daarbenewens, met wisselende W/C verhoudings, is die driepuntbalkbuigtoets se gewildste resultaat, die Re,3-waarde geneig om misleidend te wees. Dit word aanbeveel dat die ekwivalentebuigtreksterkte in plaas van die Re,3-waarde as die drie punt balk buig toets resultaat gebruik word. Die makro-meganiesetoets het getoon dat die verhoging van die veseldosis ’n toename in na-krakingprestasie veroorsaak. Die plat vesels se prestasie was aansienlik beter as die van nie-plat vesels, en het met 'n toenemende veseldosis teen 'n vinniger koers verhoog. Die na-krakingprestasie het met toenemende W/C en die verhoging van die klip grootte afgeneem. Die makro-meganieseprestasie was omgekeerd eweredig aan die enkelveselprestasie. Die makro-meganieseprestasie het met toenemende vesel band stres verminder, en het met 'n toenemende gelykstaande deursnee (wat gelykstaande is aan minder vesel in 'n stel volume van vesel) vergroot. Ten slotte is basiese beginsels uit die data ontwikkel. Hierdie beginsels is gebruik om die RDPT en driepuntbalkbuigtoets prestasieparameters gebaseer op veseldosis, enkelveseleienskappe (verbandspanning en ekwivalentediameter), W/C-verhouding en klip grootte van die beskikbare data te voorspel. Die beginsels kan met meer eksperimentele data verder verfyn word.

Thesis (PhD)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Dunnage bags are an inflatable dunnage variant, positioned and inflated between goods in multi-modal containers to restrain and protect the goods while in transit. This project endeavours to develop a simple method of generating new numerical prototypes for dunnage bags suitable for simulating operational loading of the bags. Previous research has produced a model that simulates the inflation of a paper dunnage bag using a simple pressure load. A dunnage bag reinforced with plain-woven polypropylene was chosen as the test case. Woven polypropylene is a highly non-linear, non-continuous, non-homogeneous material that requires specialised material models to simulate. A key aspect of this project was to develop a simple method for characterising woven-polypropylene and replicating it's response with material models native to LS-DYNA. The mechanical response of the plain-woven polypropylene was tested using a bi-axial tensile test device. The material response from physical testing was then mapped to two material models using the numerical optimiser LS-OPT. The response of the calibrated material models was found to correlate well with the measured response of the woven material. Dunnage bags are subjected to cyclic loading in operation. In order to capture the effects of compressing the contained gas, a gas inflation model was added to the model that calculates the pressure in the bag based on the Ideal Gas Law. A full bag model making use of the calibrated material models and the inflation model was subjected to a cycled boundary condition simulating loading and unloading of an inflated dunnage bag. The two prototype models captured the pressure drop in the bag due to material plastic deformation and the restraining force produced by the bag to within 10 %. The prototype models were also found suitable for predicting burst pressure in voids of arbitrary size and shape. / AFRIKAANSE OPSOMMING: Stusakke is 'n opblaasbare soort stumateriaal wat tussen goedere in multimodale vraghouers geposisioneer en opgeblaas word om sodoende die goedere vas te druk en te beskerm tydens vervoer. Hierdie projek poog om 'n eenvoudige manier te ontwikkel om nuwe numeriese prototipes vir stusakke, geskik om operasionele lading van die sakke te simuleer, te ontwikkel. Vorige navorsing het 'n model ontwikkel wat die opblaas van 'n papier stusak met eenvoudige drukkrag simlueer. 'n Hoë-vlak stusak versterk met plein-geweefde polipropileen, is gekies om getoets te word. Geweefde polipropoleen is 'n hoogs nie-lineêre, onderbroke, nie-homogene materiaal wat gespesialiseerde materiaalmodelle nodig het vir simulasie. Een van die fokuspunte van hierdie projek is om 'n eenvoudige metode te ontwikkel om die karaktereienskappe van polipropoleen te identifiseer en die gedrag daarvan na te maak met die materiaalmodelle van LSDYNA. Die meganiese reaksie van die plein-geweefde polipropoleen is getoets met 'n biaksiale/tweeassige trektoets-toestel. Die materiaal se reaksie op die fisiese toets is ingevoer op 'n numeriese optimiseerder, LS-OPT, om op die materiaalmodelle te toets. Die reaksie van die gekalibreerde materiaalmodelle het goed gekorelleer met die gemete reaksie van die geweefde materiaal. Stusakke word tydens diens onderwerp aan sikliese lading. Om die effek van die saamgepersde gas vas te stel is 'n gas-opblaasbare model bygevoeg by die model wat die druk in die sak bereken, soos gebaseer op die Ideale Gas Wet. 'n Volskaalse sakmodel wat gebruik maak van die gekalibreerde materiaalmodelle en die opblaas-model is onderwerp aan sikliese grensvoorwaardes wat die lading en ontlading van 'n opblaasbare stusak simuleer. Die twee prototipe modelle het die drukverlies in die sak a.g.v. die materiaal-plastiek vervorming en die bedwingingskrag van die sak beperk tot 10 %. Die protoyipe modelle is ook geskik bevind om barsdruk in arbitrêre leemtes te voorspel.

published_or_final_version / Mechanical Engineering / Doctoral / Doctor of Philosophy

Este trabalho aborda o estudo do comportamento mecânico e térmico do nanocompósito híbrido de polipropileno com uma argila brasileira bentonítica do Estado da Paraíba (PB), conhecida como \"chocolate\" com concentração de 1, 2 e 5 % em massa com a adição de 1 e 2 % em massa de celulose proveniente de papel descartado. Foi utilizado nesse nanocompósito o agente compatibilizante polipropileno graftizado com anidrido maleico PP-g-AM com 3 % de concentração em massa, através da técnica de intercalação do fundido utilizando uma extrusora de dupla-rosca e, em seguida, os corpos de prova foram confeccionados em uma injetora. O comportamento mecânico foi avaliado pelos ensaios de tração, flexão e impacto. O comportamento térmico foi avaliado pelas técnicas de calorimetria exploratória diferencial (DSC) e termogravimetria (TGA). A morfologia dos nanocompósitos foi estudada pela técnica de microscopia eletrônica de varredura (MEV). A argila, a celulose e os nanocompósitos híbridos foram caracterizados por difração de raios X (DRX), fluorescência de raios X (FRX) e espectroscopia no infravermelho (FTIR). Nos ensaios mecânicos de tração houve um aumento de 11 % na tensão máxima em tração e 15 % no módulo de Young, para o nanocompósito com argila, PPA 5 %. No ensaio de impacto Izod, o nanocompósito com argila, PPA 2 % obteve um aumento de 63 % na resistência ao impacto. Para o nanocompósito híbrido PPAC 1 % houve aumento de 8 % na tensão máxima em tração e para o nanocompósito híbrido PPAC 2 % houve aumento de 14 % na resistência ao impacto. / This work concerns to the study of the mechanical and thermal behavior of the hybrid polypropylene nanocomposite with a Brazilian bentonite clay from State of Paraíba (PB), known as \"Chocolate\" in concentrations of 1, 2 and 5 % by weight with addition of 1 and 2 % in weight cellulose discarded bond paper. The compatibilizer agent based on maleic anhydride grafted polypropylene, known as PP-g-MA, was added at 3 % weight concentration through the melt intercalation technique using a twin-screw extruder, and afterwards, the specimens were prepared by injection process. The mechanical behavior was evaluated by strength, flexural strength and impact tests. The thermal behavior was evaluated by the differential scanning calorimetry (DSC) and thermogravimetry (TGA). The morphology of the nanocomposites was studied by the technique of scanning electron microscopy (SEM). The clay, cellulose and the hybrid nanocomposites were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF) and infrared spectroscopy (FTIR). Results of mechanical tests showed an 11 % and 14 % increase in the tensile strength and Young\'s modulus, respectively, for the nanocomposite PPA 5 % with clay. The nanocomposite PPA 2 % with clay obtained a 63 % increase in strength Izod impact test. The hybrid nanocomposite PPAC 1 % obtained an 8 % increase in tensile strength. In the Izod impact test, the hybrid nanocomposite PPAC 2 % obtained 14 % increased in the impact strength.

Neste trabalho estudou-se o efeito de três diferentes tratamentos químicos utilizando- se soluções aquosas de LiCl, NaCl, e HCl sobre o inchamento, a distribuição de tamanho de partículas e a capacidade de troca catiônica (CTC) de uma vermiculita proveniente da jazida de Paulistana, localizada no Estado do Piauí, visando seu uso em compósitos de matriz polimérica. Para os tratamentos com sais inorgânicos foram utilizadas várias concentrações de LiCl e NaCl a 90°C por 144 horas, permitindo a secagem da solução de tratamento. Para o tratamento ácido foram utilizadas soluções 2M de HCl à temperatura ambiente, utilizando tempos de tratamento de 2 a 10 horas. Após os tratamentos, as amostras foram submetidas a agitação mecânica intensa em dispersor de alta energia de cisalhamento (24000 RPM). Todos os tratamentos empregados resultaram em aumentos nos índices de inchamento e reduçães nos tamanhos de partícula em diferentes graus. Os maiores inchamentos antes da agitação mecânica foram observados nas amostras tratadas com soluções 0,8M de LiCl sem lavagem (4 a 5 vezes a da prova em branco). Após agitação mecânica, os maiores inchamentos foram observados nas amostras tratadas com soluções 2M de HCl por 5 horas (11 vezes a da prova em branco). No entanto, após o processo de secagem não foi possível atingir-se os mesmos valores de inchamento. A diminuição mais importante no tamanho de partícula foi observada nas amostras tratadas com soluções 2M de HCl durante 5 horas, enquanto que as quedas mais significativas nos valores de CTC foram obtidas com as amostras tratadas com soluções 2M de HCl (CTC crescentes com o aumento do tempo de tratamento). Foi analisado o efeito da incorporação de vermiculita tratada acidamente em uma matriz polimérica de polipropileno (PP). A presençaa dessa vermiculita provocou um alto nível de degradação na matriz de PP, com a consequentemente perda de propriedades mecânicas. Esta degradação pode ser atribuída à formação de sítios ácidos nas partículas de vermiculita gerados pelo ataque do HCl, bem como à presença de HCl residual da solução de tratamento. / In the present work, the effect of three different chemical treatments using inorganic solutions of LiCl, NaCl, and HCl on the swelling, particle size distribution, and cation exchange capacity (CEC) of a vermiculite clay was studied. The clay is originary from Paulistana mine, located in the State of Piauí, Northeastern Brazil, and the final purpose of the treatment of the clay was its use in polymer-matrix composites. For the inorganic salts treatments, several solutions of NaCl and LiCl at different concentrations were used, at 90°C for 144 hours, allowing the treatment solution to dry out. For the acid treatment, 2M HCl solutions at room temperature were used, using treatment times of 2 to 10 hours. After the treatments, all the samples were subjected to intense mechanical stirring in the high shear energy disperser (24000 RPM). The results showed that all treatments resulted in increases in the rates of swelling and reduction in the mean particle sizes, in different degrees. The largest swelling before mechanical stirring was observed in samples treated with solutions of 0.8M LiCl without washing (4 to 5 times that of the untreated sample). After mechanical desagglomeration, the highest swelling was observed in samples treated with solutions 2M HCl for 5 hours (11 times that of the untreated sample). However, after drying, it was no longer possible to achieve the same values of swelling. The most significant decrease in particle size was observed in samples treated with solutions 2M HCl for 5 hours, whereas the most significant reduction in the CEC values were also obtained with the samples treated with solutions 2M HCl (CEC increasing with the time of treatment). Finally, the effect of the addition of the acid treated vermiculite to a polymeric matrix of polypropylene (PP) was examined. The evaluation of the resultant composite specimens indicated that the presence of vermiculite caused a high level of degradation of the PP matrix, with the consequent loss of mechanical properties. This degradation can be attributed to the formation of acidic sites on the vermiculite particles, generated by the direct attack of HCl, and the presence of residual HCl from the treatment solution.

Neste trabalho, métodos experimentais para estimar as viscosidades elongacional e de cisalhamento mediante um canal de contração abrupta foram desenvolvidos. Os dados reológicos em fluxos de cisalhamento foram comparados com os resultados mediante o reômetro rotacional e o reômetro capilar. Os resultados foram utilizados para avaliar a influência da estrutura molecular nas propriedades reológicas de vários polipropilenos com diferentes massas moleculares, distribuição de massas moleculares e teor de ramificações. Além disso, polipropilenos degradados termomecânicamente foram estudados. A massa molecular e a distribuição de massas moleculares foram obtidas através de Cromatografia de permeação em gel (GPC). Os resultados obtidos mostraram que a matriz elongacional é útil para simular processos de transformação, visto que podem ser alcançadas altas taxas de deformação, que dependem dos valores máximos dos parâmetros de processamento, os quais dependem dos limites máximos do equipamento utilizado. Os resultados em fluxos de cisalhamento avaliados mediante a matriz elongacional mostraram que possuem uma excelente concordância com os resultados obtidos por cisalhamento oscilatório de pequenas amplitudes (COPA) no reômetro rotacional. Os resultados em fluxos elongacionais mostraram que as medidas são muito sensíveis à estrutura molecular, principalmente à presença de ramificações longas, principalmente a baixas taxas de deformação. No caso do polipropileno degradado termomecânicamente, tanto sua massa molecular quanto as suas viscosidades elongacional e de cisalhamento diminuem devido à cisão de cadeias e, as medidas reológicas mostram-se mais sensíveis a essas mudanças do que as medidas de GPC. / In this work, experimental methods to evaluate elongational and shear viscosities using a planar channel with an abrupt contraction (also called Cogwell die) were developed. The shear viscosity measurements were compared to measurements obtained using a rotational rheometer and a capillary rheometer. The elongational die was used to evaluate the influence of the molecular weight, molecular weight distribution and chain structure on the rheological properties of polypropylene. The influence of thermomechanical degradation of PP on its rheological properties was also studied. The molar mass and molar mass distribution were evaluated using GPC. It was found that the planar channel can be used successfully to evaluate the elongational viscosity at rates that correspond to polymer processing conditions. The shear viscosity measurements obtained using the planar die were in good agreement with measurements obtained by small amplitude oscillatory shear (SAOS). The elongational viscosity was sensitive to molecular structure, essentially at low deformations. It was also shown that the molar mass, molar mass distribution and amount of branching affects the shear viscosity and that rheological measurements may be more sensitive to molecular weight changes than GPC.

Os polímeros espumados são materiais do futuro, com um leque abrangente de aplicações. Podem ser usados em estruturas de isolamento, por exemplo, ou para reduzir custos com materiais. Este trabalho remete para a extrusão de misturas de Polipropileno isotático (iPP) / Polipropileno com Alta Resistência do Fundido (HMSPP), para a obtenção de espumas. O comportamento reológico do polímero fundido, principalmente a viscosidade na temperatura de processamento, tem um papel decisivo nas aplicações nas quais prevalece o fluxo extensional, como no caso da espumagem. Se a viscosidade for muito baixa, correspondente a uma baixa resistência do fundido, como no caso do homopolímero linear (PP isotático), a espumagem ficará prejudicada, face à impossibilidade de expansão acentuada. Entretanto, se a viscosidade for muito alta (HMSPP), com uma alta resistência do fundido, a espuma colapsará imediatamente após sua formação. A fim de obter espumas com uma estrutura celular homogênea e definida, foram efetuadas misturas 50% em peso entre o homopolímero linear (PP isotático) e o polipropileno ramificado (HMSPP), modificado por radiação gama, em ambiente contendo acetileno e na dose de 12,5 kGy. O processo de extrusão empregou a metodologia de espumagem solúvel, segundo o princípio de processamento/dissolução, que envolve a dissolução de um agente físico de sopro (PBA = Physical Blowing Agent), na pressão em torno de 30 bar, homogeneamente misturado com o fundido polimérico. As condições de extrusão, que, geralmente, compreendem o controle de temperatura, pressão e fluxo do material viscoelástico, foram investigadas experimentalmente para definir as características dominantes em prol da obtenção de espumas. O agente físico de sopro usado foi o nitrogênio. As principais características do PP e HMSPP foram obtidas via medidas reológicas (Índice de Fluidez e Resistência do Fundido) e análises térmicas (DSC/TGA), a fim de viabilizar e reproduzir a posteriori as espumagens pelo processo de extrusão. A morfologia celular das espumas foi investigada minuciosamente, com e sem a adição de talco, como agente nucleante, usando o Microscópio Eletrônico de Varredura. As propriedades mecânicas foram investigadas, via DMA, com base no Módulo de Young e tangente delta. A Rigidez Específica contribuiu com algumas considerações sobre a cristalinidade. As micrografias obtidas apontaram para espumas de células fechadas, nas quais a pressão é mantida durante o estágio de formação da célula. As espumas podem ser usadas em: mobílias; transporte; aterro sanitário; isolamentos; eletrodomésticos; como absorvedora de choque e de som; construção civil, incluindo chapas isolantes, proteção para pisos, perfis para acabamento, acabamentos de interiores; indústria automobilística, em painéis espumados; mercado de embalagem, em geral, incluindo embalagens para freezer e micro-ondas; acondicionamento de artigos médicos como seringas, catéteres intravenosos, frascos, materiais de sutura. fios e cabos e para finalidades estruturais (espumas estruturais), substituindo madeira, metais ou plásticos sólidos. As análises de densidade efetuadas nas espumas do presente trabalho apresentaram resultados típicos de espumas de alta densidade (faixa de 320 a 800 kg/m3), em torno de 500 kg/m3, usadas para fios e cabos e para finalidades estruturais (espumas estruturais), substituindo madeira, metais ou plásticos sólidos. As espumas estruturais têm densidades relativamente altas (acima de 320 kg/m3) e as estruturas celulares são compostas principalmente de vazios. / Foamed polymers are future materials, with a comprehensive application field. They can be used in order to improve appearance of insulation structures, for example, or to reduce costs involving materials. This work address to Isotactic Polypropylene / High Melt Strength Polypropylene blends, for foams production. Rheological behavior of polymer melt, especially referring to viscosity in processing temperature, plays a decisive role in applications where dominates extensional flow, as in case of foaming. If the viscosity is very low, it will correspond to a low melt strength, as in case of linear homopolymer (Isotact PP), and the foam will be prejudiced, due to the impossibility of expansion. Otherwise, if the viscosity is very high, with a high melt strength, the foam will collapse immediately after its formation. In order to get foams with an homogeneous and defined cellular structure, there were accomplished blends, 50% in weight, between linear homopolymer (isotactic PP) and HMSPP, from PP modified as per gamma radiation, in acetylene environment and at a 12.5 kGy dosis. Extrusion process used a soluble foaming methodology, according to a processing/dissolution principle, which involves the dissolution of a Physical Blowing Agent (PBA), under 30 bar pressure, homogeneously mixed with polymeric melt. Extrusion conditions, that generally involve temperature, pressure and viscoelastic material flow control were experimentally investigated to define prevalent characteristics for producing foams. Nitrogen was the used PBA and process extrusion parameters were adapted to PP, HMSPP and their 50% in weight mixtures thereof. Major PP and HMSPP characteristics were obtained via melt Index and melt strength and thermal analyses (DSC/TGA), in order to make viable and to reproduce foaming as per extrusion process. Foams cellular morphology of PP, HMSPP and their 50% in weight mixtures thereof was investigated, with and without talc addition, as nucleating agent, by using Scanning Electron Microscope (SEM). Micrographs obtained pointed to closed cells foams, in which the pressure is kept during all cell formation stage, informing that closed cells foams are used in thermal insulation in Civil Construction and in thermal vials. Density analyses accomplished in foams produced in our work showed typical results for high density foams (320 to 800 kg/m3 range), around 500 kg/m3, used for wire and cables and for structural purposes (structural foams), by replacing wood, metals or solid plastics. Structural foams have high density (above 320 kg/m3) and cellular structures are specially composed by holes.