Blends of PHB and LDPE were prepared by melt mixing in a twin screw extruder. Castor oil cake (CC) was used as filler for the blends. The design of experiments (DOE) technique was used to evaluate the effect of the components proportion on the materials properties. The mechanical properties and morphology of the materials were evaluated. The LDPE Young's modulus increases but the other tensile properties and impact resistance deteriorate with the addition of PHB or CC. The tensile strength values of binary mixtures of LDPE lie in the range from 8.9 to 10 MPa. As some commercial grades of LDPE have mechanical strength in this range, it may be inferred that the addition of a certain amount of PHB or CC to LDPE may be considered as a possibility for obtaining LDPE based materials with increased susceptibility to biodegradation. The poor interfacial adhesion between the phases became visible in all samples.

Blends of PHB and LDPE were prepared by melt mixing in a twin screw extruder. Castor oil pressed cake (CC) was used as filler for the blends. The mixture design technique was used to evaluate the effect of the components proportion on the materials flexural properties. The results show that superior LDPE flexural properties may be obtained by the addition of PHB or castor oil cake to LDPE. Biodegradation was evaluated burying the samples in simulated soil for different periods of time. The ternary mixtures with higher content of PHB showed more pronounced degradation. Under the experimental conditions studied the LDPE/CC compositions presented no degradation. However, the loss of mass of the LDPE/PHB/CC ternary mixtures was higher than the loss of mass of the corresponding LDPE/PHB binary mixture. This result suggests that the castor oil cake accelerates the degradation of the LDPE/PHB mixtures.

Embora a reticulação do polietileno efetuada através de processo de extrusão reativa, envolvendo a graftização de silanos vinílicos na cadeia polimérica, seja um processo bastante utilizado industrialmente, poucos estudos têm sido publicados sobre a influência das variáveis de processamento nas propriedades do polímero. Neste trabalho, foi avaliado o efeito das condições de processamento e do sistema reacional no índice de fluidez (MFI), no teor de gel e nas propriedades térmicas do polietileno linear de baixa densidade (LLDPE), graftizado com vinil-trimetóxi-silano (VTMS) na presença de baixas concentrações de peróxido de dicumila (DCP) e reticulado com água. Uma metodologia estatística demonstrou que o teor de silano é a variável de processamento mais significativa, quando a reação é efetuada utilizando 0,02% p/p de DCP. Aumento significativo do teor de gel do LLDPE foi obtido utilizando uma concentração maior de DCP (0,07% p/p). O processo de formação de ligações cruzadas causou aumento na estabilidade térmica e redução significativa no grau de cristalinidade, nas temperaturas de fusão e de cristalização e nas entalpias de fusão do LLDPE. Os espectros de infravermelho (FTIR) e o aumento da estabilidade térmica demonstram que houve formação de ligações cruzadas no polímero via pontes siloxano.

Although silane-modified polyolefins have become an industrial process, little data have been published on the dependence of silane grafting reactions and the properties of crosslinked polyolefins on reaction parameters. Here we studied the melt grafting of vinyl trimetoxi silane (VTMS) onto linear low density polyethylene (LLDPE) promoted by dicumyl peroxide (DCP) in a single screw extruder followed by crosslinking reaction in hot water. The influence of grafting formulations and processing conditions on the melt flow index (MFI), gel content and thermal properties of grafted and crosslinked LLDPE was evaluated using a statistical design. The silane content was the most important variable when the reaction was performed with a low concentration of DCP (0.02 wt. (%)). Samples with significant gel content, however, were obtained with 0.07 wt. (%) of DCP. A decrease in the melt temperature and in the degree of crystallinity of LLDPE, as determined by differential scanning calorimetry (DSC) melting enthalpies, was observed as a result of crosslinking formation. The thermogravimetric analysis (TGA) showed an improvement in the thermal stability of LLDPE due to the introduction of crosslinking reactions. Results from Fourier Transformed Infrared Spectroscopy (FTIR) provided evidence for VTMS grafting onto LLDPE and subsequent crosslinking reaction.

Neste trabalho foram estudadas as propriedades reológicas de polietileno de alta densidade (HDPE) tenacificado com dois tipos de elastômeros metalocênicos à base de poli(etileno-co-octeno) (EOC). Estes elastômeros são polímeros comerciais com diferenças quanto ao peso molecular, índice de fluidez e índice Dow de reologia (DRI). Misturas físicas de HDPE e EOC foram processadas em extrusora monorosca Wortex (L/D=32), à 230 °C e 50 rpm, utilizando percentagem mássica dos EOCs de 5% a 80%. As propriedades reológicas foram avaliadas em experimentos estacionários e dinâmicos a 190 °C e taxas de cisalhamento na faixa de 90 s-1 a 1500 s-1 e freqüências na faixa de 10-1 rad/s a 10² rad/s. As misturas HDPE/EOC exibiram pseudoplasticidade e comportamento reológico complexo. A complexidade do comportamento reológico foi acentuada com o aumento do peso molecular e da concentração de ramificações de cadeia longa (DRI) do EOC.

In this work rheological properties of high density polyethylene toughened with two different grades of metallocene elastomers based on poly(ethylene-co-octene) were studied. These elastomers were commercial polymers differing in molecular weight, and Dow Rheology Index (DRI). Blends were processed in a Wortex single screw extruder (L/D=32), at 230 °C and 50 rpm, using mass fractions of EOC in the range from 5% to 80%. The rheological properties were evaluated in steady and dynamic experiments at 190 °C and shear rates in the range from 90 s-1 to 1500 s-1 with frequencies from 10-1 s-1 to 10-2 s-1. The blends exhibited pseudoplasticity and complex rheological behavior. The complex rheological behavior was intensified with increasing molecular weight and long chain branching proportion (DRI) in the EOC elastomers.

Neste trabalho foram estudadas as propriedades mecânicas e morfológicas de polietileno de alta densidade (HDPE) tenacificado com dois tipos de elastômeros metalocênicos à base de etileno/1- octeno (EOC). Esses elastômeros são polímeros comerciais com diferenças quanto ao peso molecular, índice de fluidez e índice Dow de reologia (DRI). Misturas físicas de HDPE e EOC foram processadas em extrusora monorosca Wortex (L/D=32), à 230°C e 50 rpm, utilizando percentagem mássica do EOC de 5% a 80%. Foi observado um efeito sinergístico nas propriedades tênseis e características de supertenacificação para materiais contendo proporções do EOC maiores do que 5%. Cavitação, deformação plástica e cavitação fibrilada foram observados nos processos de deformação. Materiais contendo até 50% do EOC apresentaram morfologias dispersas com domínios elastoméricos esféricos, distribuídos uniformemente e com tamanho médio de partícula na faixa de 0,30 a 0,45 µm. A tenacificação de HDPE com os elastômeros etilênicos produziu materiais com boas propriedades e compatibilização tecnológica devido à existência de baixa tensão interfacial entre esses polímeros.

The mechanical and morphological properties of high density polyethylene (HDPE) toughened with two different grades of metallocene elastomers based on ethylene/1- octene (EOC) were studied. These elastomers were commercial polymers differing in molecular weight, melt flow index and Dow rheology index (DRI). Blends were processed in a Wortex single screw extruder (L/D=32), at 230°C and 50 rpm, using mass fraction weight percent of EOC in the range from 5% to 80%. A synergistic effect on the tensile properties and supertough behavior for blends with EOC concentrations higher than 5% was observed. Cavitation, plastic deformation and fibrillized cavitation were observed in the deformation processes. Materials containing up to 50% of EOC exhibited dispersed morphologies with EOC spherical domains uniformly distributed with particle size in the range from 0.30 to 0.45 µm. The toughening of HDPE with ethylenic elastomers produced materials with good properties and technological compatibilization.

O presente trabalho teve por objetivo avaliar as propriedades mecânicas, térmicas e morfológicas de sistemas à base de poliolefinas (PP e HDPE) e copolímero metalocênico de etileno/1-octeno (EOC), produzido pela Dow Chemical. Foi também investigada a atuação de um copolímero metalocênico de propileno/1-octeno (POC), sintetizado em laboratório, como agente compatibilizante da mistura PP/EOC. Os resultados mostraram que a adição de teores específicos de EOC ao HDPE e PP pode levar à produção de materiais com boas propriedades mecânicas. Os dados obtidos também revelaram que o copolímero POC pode ser usado como agente compatibilizante das misturas PP/EOC.

The aim of this work was to evaluate the mechanical, thermal and morphological properties of systems based on polyolefins (PP and HDPE) and ethylene/1-octene metallocene copolymer (EOC), produced by Dow Chemical. The effect of a propylene/1-octene metallocene copolymer (POC), obtained in the laboratory was also investigated as a compatibilizer agent for the PP/EOC blend. The results showed that the addition of certain contents of EOC to PP and HDPE may carry the production of materials with good mechanical properties. The data obtained also revealed that the POC copolymer can be used as compatibilizer agent of the PP/EOC blends.