The DSC low temperature endothermic peak shown by sodium neutralized poly(ethylene-random-methacrylic acid) (E/MAA-Na+) ionomers in the range of 50-70 ºC is attributed to the endothermic reordering of polyethylene chain segments belonging to two populations of quasi-crystals set from melt, initially showing no birefringence. Dry or wet thermal annealing improve their polyethylene chain segments packing expelling out the non-crystallizable methacrylic mers by absorbing and storing heat, converting them into better-organized crystals. Upon heating further they melt, using the stored energy. Hydrothermal annealing separates the relaxation of the PE chain segments inside the ionic clusters and their reordering: i) water plasticizes the ionic clusters, downshifting the relaxation temperature, detected either by static (DSC) or dynamic (DMTA) thermal analysis and, ii) shifts upwards the endothermic peak due to the reordering of PE chain segments, detected optically by cross-polarized light and X-Ray diffraction patterns.

Numerous studies have focused on polymer mixtures aimed at the potential applications of these materials. This work analyzed the effect of polymer reprocessing and the type and concentration of compatibilizer on the isothermal crystallization kinetics of polypropylene/wood flour composites. The composites, which were polypropylene grafted with acrylic acid (PP-g-AA) and maleic anhydride (PP-g-MA), were processed in a twin screw extruder with and without compatibilizer. Reprocessed polypropylene reached complete crystallization in less time than the composites with virgin polypropylene. The addition of wood flour to the composites did not change the kinetics significantly compared to that of the pure polymers, but the compatibilizers did, particularly PP-g-AA. The nucleation exponent (n) and crystallization rate (K) were calculated from Avrami plots. The values of n ranged from 2 to 3, indicating instantaneous to sporadic nucleation. The crystallization half-time of reprocessed polypropylene was shorter than that of virgin polypropylene and of the compositions containing PP-g-AA compatibilizer. The activation energy of crystallization and the equilibrium melting temperature were calculated, respectively, from Arrhenius and Hoffman-Weeks plots. Both of these parameters showed lower values in the composites, particularly in the ones containing compatibilizers.

Residence time distribution (RTD) is a very important parameter in extrusion, either for simple polymer processing or for special processes like compounding, blending, reactive compatibilization, and controlled degradation. This work deals with the values of mean residence time (t n) as a function of the number of 45 degrees kneading elements in the screw profile, screw speed, and feeding rate. The t n values were calculated from the RTD curves, which in turn were determined by the technique of a marker added as a pulse in the steady state polymer flow. The values of t n were empirically modeled as a function of those parameters. The results showed that feeding rate is the most influent parameter, followed by number of kneading elements and screw speed. The modeling has given a quadratic function relating t n and the operational parameters tested.

Estudou-se a degradação de um polipropileno copolímero não estabilizado durante a extrusão a diferentes temperaturas (de 180 a 240 °C) e a conseqüente geração de compostos orgânicos voláteis (VOC). Os VOC foram coletados por meio de um condensador de gases, conectado na zona de desgaseificação da extrusora, e analisados por espectrometria no infravermelho (FTIR-ATR). A degradação do polímero foi acompanhada através da cromatografia de exclusão por tamanho e FTIR. À temperatura de 180 °C a degradação do polipropileno não gerou quantidades coletáveis de compostos orgânicos voláteis. Por outro lado, a partir de 200 °C houve geração de compostos olefínicos, não voláteis à temperatura ambiente, que aumentaram em quantidade com o aumento da temperatura de extrusão. A Função de Distribuição de Cisão de Cadeia (CSDF) mostrou que a baixas temperaturas, 180 e 200 °C, o mecanismo de degradação do polipropileno é preferencialmente por cisão de cadeia com alguma ramificação e/ou reticulação. Entretanto, nas temperaturas de extrusão mais altas, 220 e 240 °C, o mecanismo de degradação envolve exclusivamente cisão de cadeia e do tipo preferencial, ou seja, o número de cisões aumenta com o aumento da massa molar inicial da cadeia polimérica original.

The thermo-mechanical degradation of an unstabilized polypropylene copolymer during extrusion at different temperatures (from 180 to 240 °C) and the production of volatile organic compounds (VOC) were studied. VOC's were collected via a volatile condenser, fitted at the degassing exit of the extruder and analyzed via infrared spectroscopy (FTIR-ATR). The polymer degradation was followed via size exclusion chromatography and FTIR. At low extrusion temperatures (180 °C) the PP degradation produces undetectable quantities of VOC's. On the other hand, starting from 200 °C, there is the formation of olefinic compounds of molecular weight not volatile at room temperature, which increase in quantity with the rise of the extrusion temperature. The Chain Scission Distribution Function (CSDF) shows that at low temperatures (180 and 200 °C) the PP degradation mechanism is preferentially via chain scission with some branching and/or crosslinking in the lower molecular weight. At higher extrusion temperatures (220 and 240 °C) the degradation mechanism is exclusively via chain scission and it is preferential, i.e., the number of chain scission increases with the increase in the initial molecular weight of the original polymeric chain.

Determinou-se o número de cisões de cadeia gerado pela degradação termo-mecânica do poliestireno quando submetido a múltiplas extrusões. A degradação foi acompanhada pelas mudanças nas curvas de distribuição de massa molar. Seguindo-se o significado físico das massas molares médias de uma curva de MWD mostrou-se que a massa molar numérica media Mn é a única que pode ser relacionada diretamente com o número de moléculas do sistema. A partir desta calculou-se o número de cadeias clivadas (ns) como uma relação entre a Mn da amostra degradada e a virgem. A função de distribuição de cisão de cadeia (CSDF) mostra que o processo de degradação termo-mecânica do poliestireno submetido a múltiplas extrusões à 240 °C é do tipo aleatório, independente da massa molar inicial.

The number of chain scissions during thermo-degradation of polystyrene under multiple extrusions was calculated. The degradation produces changes in the molecular weight distribution MWD curves. Following the physical meaning of the average molecular weights of a MWD curve it was shown that the number average molecular weight Mn is the only average that can be directly related to the number of molecules in the system. From that it was calculated the number of sectioned chains (ns) as a ratio between the number of chains in the degraded and original polymers. The chain scission distribution function (CSDF) shows that the thermo-mechanical degradation process of polystyrene under multiple extrusions at 240 °C is of a random type, independent of the initial molecular weight.

Mudanças no Índice de Fluxo à Fusão (MFI) foram correlacionadas com o deslocamento da curva de distribuição de massa molar (MWD) geradas pela degradação termo-mecânica do polipropileno (PP) sujeito a múltiplas extrusões. A degradação foi modelada utilizando-se a Função de Distribuição de Cisão de Cadeia (CSDF), que pode quantificar o deslocamento da curva de distribuição de massa molar com o número de extrusões. O efeito normalmente envolve a redução da massa molar, o que implica em valores positivos da CSDF e redução da viscosidade do estado fundido. O deslocamento da massa molar média (LogMw(0) - LogMw(D)), calculado a partir das massas molares ponderais médias, antes e após a degradação, se sobrepõe às curvas de CSDF e apresenta uma relação linear com os valores de MFI. O processo de degradação termo-mecânica do polipropileno pode ser mais bem visualizado correlacionando-se curvas de CSDF e os valores de MFI.

Changes in the Melt Flow Index were related to the shift in the Molecular Weight Distribution Curve (MWD) produced by the thermo-mechanical degradation of polypropylene (PP) during multiprocessing. The degradation was modelled using the Chain Scission Distribution Function (CSDF), which quantifies the shift in the molecular weight distribution curve as a function of the number of extrusions. The effect is normally the reduction of the molecular weight, which means positive values for CSDF and reduction of the polymer melt viscosity. The average molecular weight shift (LogMw(0) - LogMw(D)) calculated from the average weight molecular weight before and after the degradation overlaps the CSDF curve and shows a linear relationship with the MFI values. The thermo-mechanical degradation process of polypropylene can be better visualized when CSDF curves are correlated with MFI values.

A configuração da rosca de uma extrusora de dupla rosca modular pode ser projetada com vários tipos de elementos de condução e mistura, produzindo diferentes níveis de degradação no polímero fundido. Neste trabalho determinou-se o nível de degradação do polipropileno durante múltiplas extrusões em várias configurações de rosca, através de cromatografia por exclusão de tamanho e espectroscopia de infravermelho. Houve decréscimo do peso molecular e estreitamento da sua distribuição em função do número de extrusões e do aumento da agressividade da rosca, assim como, aumento da concentração de carbonilas e insaturações na cadeia polimérica. O elemento de mistura EM90 causou o maior nível de degradação e a adição de elementos de condução esquerdos ECE reduziram o nível de degradação.

The screw configuration of a double screw extruder can be designed to contain kneading and conveying elements inducing different levels of degradation in the polymer melt. In this work the level of degradation in polypropylene have been measured after multiple extrusions for various screw configurations using Size Exclusion Chromatography and Infra-Red Spectroscopy. The average molecular weight and the polydispersity are reduced and the carbonyl and unsaturation indices increase as the number of extrusions and the agressiveness of the screw increase. The kneading element with 90 degrees caused the greater level of degradation and the addition of left hand elements have reduced the level of degradation.

The effect of incorporating (C2-C8) ethylene-octene elastomer on the mechanical properties and morphology of polypropylene copolymers has been investigated employing two types of PP copolymer, with and without nucleating agent. The results were compared to the ones presented by a commercial PP heterophase (reactor impact modified PP/EPR). The addition of the elastomer increases the toughness of the blends but reduces their stiffness. PP blends in the low elastomer content region (< 20%) show low values of the Izod impact strength and both, elastomer content and impact strength, are directly proportional to the area under the beta damping peak or its maximum intensity of the elastomer. The morphology is a continuous pattern of segregate elastomeric particles with average particle size in the range of 0.27 mum to 0.39 mum. The average particle size and particle size distribution plotted in log-normal distribution curves, increases slightly with the increase in the elastomer content. The reactor modified PP heterophase has a broader particle size distribution and an average particle size of 0.56 mum, at the lower limit but inside the range for good impact performance, as observed.