Harumi Otaguro

Comportamento do Polipropileno em Presença de Monômeros Trifuncionais no Estado Fundido e sua Influência na Morfologia

Resumo: O aumento de ramificacoes e da massa molecular em polimeros essencialmente lineares influencia as proprie- dades no estado fundido desses polimeros. Este comportamento foi observado pela analise dos dados de resistencia do fundido, extensibilidade e do conteudo de gel em amostras de Polipropileno linear (iPP) modificado. A modificacao foi obtida utilizando agentes modificadores (monomeros multifuncionais) e radiacao gama. Os agentes modificadores empre- gados foram o Tri-metilol-propano-tri-acrilato (TMPTA) e o Tri-alil-cianurato (TAC). O TMPTA demonstrou ser um agente mais eficiente para a promocao do iPP modificado (reticulado/ramificado), uma vez que o produto final apresen- tou um valor maior da resistencia do fundido do que o material com TAC. No entanto, ambos modificam a morfologia original do iPP constatada pelo deslocamento do pico de fusao para temperaturas menores, pelo aumento da temperatura de cristalizacao (Tc) e pela presenca de multiplas endotermas Palavras-chave: Polipropileno isotatico, monomeros multifuncionais, resistencia do fundido, radiacao gama, reticulacoes, ramificacoes e multiplas endotermas. The Behavior in the Melt State of Polypropylene (PP) in the Presence of Trifunctional Monomers and their Influence in PP Morphology. Abstrac: It well known that in essentially linear polymers the properties of the melt polymers change with increasing molecular weights and degrees of branching. This behavior was observed from data analysis of the strength of the melt polymer, drawability and gel content. In this work isotactic polypropylene (iPP) in the presence of multifunctional monomers was irradiated with gamma radiation. The monomers used were Trimethylolpropane triacrylate (TMPTA) and Triallylcyanurate (TAC). iPP with TMPTA showed the highest strength in the melt and gel content, followed by TAC. It was demonstrated that TMPTA is a powerful agent to crosslinking and branching iPP. Both monomers modified the original morphology of the iPP, the melting peak shifts toward lower temperature and crystallization temperature increased during cooling after the first run. Double melting peaks were observed in the DSC thermograms, which were caused by a double lamellar thickness.

The effect of extrusion conditions and the use of a compatibilizer in the crystallization of PBT/ABS blends

Poly(butylene terephthalate) (PBT)/ acrylonitrile-butadiene-styrene (ABS) terpolymer blends were prepared in a twin screw extruder and the use of methyl methacrylate-glycidyl methacrylate-ethyl acrylate (MGE) terpolymer as compatibilization additive was evaluated. The effect of different screw profiles and mixing conditions were evaluated on the crystallization of the blends. Differential scanning calorimetry (DSC) was used to evaluate melting and crystallization behaviors of the PBT/ABS blends. The binary PBT/ABS blend has shown a double melting peak when cooled at lower cooling rates, mainly due to its melt-recrystallization during the heating up step. ABS has not affected the melting characteristics of neat PBT. The presence of MGE, as a reactive compatibilizer, in the PBT/ABS blends has reduced its heat of fusion and has partially inhibited its melt-recrystallization under heating. As result, it has prevented the occurrence of double melting peak. The epoxy functional groups of the MGE may react in situ to the carbonyls and hydroxyls end groups of the PBT molecules, thereby hindering the mobility of PBT molecules during the crystallization process due to its grafting to the compatibilizer molecules. The melt mixed blends prepared at lower feeding rate have shown a higher degree of crystallinity for the PBT/ABS blend, probably due to degradation of PBT caused by longer residence time in the extruder. The highest shear stress imposed to the blends at higher screw speed increased the degree of crystallinity of PBT, also due to its degradation.

The Effect of Step Isothermal Crystallization on the Polymer Crystalline Morphology: The Case of Isotactic Polystyrene

Simulations have shown that temperature changes during the growth of lamelae/ribbons of a polymer crystal induce alterations in the thickness of the lamelar crystal. Therefore, the lamelae/ribbons would melt at different temperatures. This is demonstrated experimentally here for spherulites of Isotactic Polystyrene (iPS). The results were obtained following the melting process of selected spherulite structures through temperature scanning. The samples, in which chosen spherulites were observed, were crystallized from the melting state at successive crystallization temperatures. Observations of these spherulite melting processes were made with an optical polarized microscope, using a hot stage to apply the temperature scan.

Contribution to the β Relaxation Study of the HDPE, LDPE and LLDPE

The activation of three polyethylenes, the low density, the high density and the linear low density polyethylene, was determined by means of dynamic mechanical analysis (DMA). Storage modulus and tan δ spectra were obtained as a function of the temperature from −60 to 50 °C with a heating rate of 2° min−1 at frequencies of 1, 2 and 5 Hz and measurement strain amplitude of 10−5. In the tan δ spectra, a small peak in the β region of the three polyethylenes was found and substantiated by subtracting the growing exponential background. This procedure was based on a model that associates the dislocation motion on metals under cyclic stress to vibrating strings and considering the same for the polymeric chains. For the determination of the activation energy we have utilized the frequency versus the reciprocal of the absolute temperature peak of the tan δ. The values obtained for the three polyethylenes, the low density, the high density and the linear low density were, 362 ± 12, 266 ± 9 and 197 ± 6 kJ mol−1, respectively, which were compared with those presented in the literature.

LLDPE/Proton Exchanged Layered Niobate K4Nb6O17 Nanocomposites

Abstract The potassium hexaniobate was synthesized by reacting, in stoichiometric proportions, Nb2O5 and K2CO3 at 1100°C and modified with octadecylamine from an acid-base reaction. Through X-ray diffraction, an interlayer space of 4.27 nm was observed in comparison with 0.79 nm of unmodified oxide; this was also shown by SEM microscopy. The hybrid nanofiller previously obtained was incorporated into LLDPE by melt intercalation (0 up to 10 wt.%) using a twin screw extruder and LLDPE-g-MAH as compatibilizer. From TGA results, all nanocomposites (LLDPE/LLDPE-g-MAH/lamellar oxide) have increased the onset degradation temperature, while the oxide lost during processing for LLDPE/LLDPE-g-MAH/lamellar oxide nanocomposites was higher for the highest content in comparison with LLDPE matrix. According to the Eyring equation, the activation volume of the samples could be calculated using the relationship between the yield strength and strain rate from tensile stress-strain curves. The activation volume decreased with increase of nanofiller concentration, suggesting a good adhesion between the layered oxide and the polymeric matrix for high concentration. This can be attributed to the restricted segmental motion near the nanofiller/polymeric interface, while a poor interaction between them was observed for low concentration. However, the Youngs modulus showed a 50% improvement for low nanofiller concentration, especially in the case of 1 wt.% of nanofiller, which was also confirmed by modulus and toughness balance. Considering all the results, it has been revealed that the proton exchanged layered niobate can improve the thermal and mechanical properties of LLDPE/LLDPE-g-MAH/lamellar oxide nanocomposites.