Using organoclay to promote morphology refinement and co-continuity in high-density polyethylene/polyamide 6 blends - Effect of filler content and polymer matrix composition

We investigate the gradual changes of the microstructure of two blends of high-density polyethylene (HDPE) and polyamide 6 (PA6) at opposite composition filled with increasing amounts of an organomodified clay. The filler locates preferentially inside the polyamide phase, bringing about radical alterations in the micron-scale arrangement of the polymer phases. When the host polyamide represents the major constituent, a sudden reduction of the average sizes of the polyethylene droplets was observed upon addition of even low amounts of organoclay. A morphology refinement was also noticed at low filler contents when the particles distributes inside the minor phase. In this case, however, keep increasing the organoclay content eventually results in a high degree of PA6 phase continuity. Rheological analyses reveal that the filler loading at which the polyamide assembles in a continuous network corresponds to the critical threshold for its rheological transition from a liquid- to a gel-like behaviour, which is indicative of the structuring of the filler inside the host PA6. On the basis of this finding, a schematic mechanism is proposed in which the role of the filler in driving the space arrangement of the polymer phases is discussed. Finally, we show that the synergism between the reinforcing action of the filler and its ability to affect the blend microstructure can be exploited in order to enhance relevant technological properties of the materials, such as their high temperature structural integrity.

The role of organoclay in promoting co-continuous morphology in high-density poly(ethylene)/poly(amide) 6 blends

The effect of organically modified clay on the morphology, rheology and mechanical properties of high-density polyethylene (HDPE) and polyamide 6 (PA6) blends (HDPE/PA6 = 75/25 parts) is studied. Virgin and filled blends were prepared by melt compounding the constituents using a twin-screw extruder. The influence of the organoclay on the morphology of the hybrid was deeply investigated by means of wide-angle X-ray diffractometry, transmission and scanning electron microscopies and quantitative extraction experiments. It has been found that the organoclay exclusively places inside the more hydrophilic polyamide phase during the melt compounding. The extrusion process promotes the formation of highly elongated and separated organoclay-rich PA6 domains. Despite its low volume fraction, the filled minor phase eventually merges once the extruded pellets are melted again, giving rise to a co-continuous microstructure. Remarkably, such a morphology persists for long time in the melt state. A possible compatibilizing action related to the organoclay has been investigated by comparing the morphology of the hybrid blend with that of a blend compatibilized using an ethylene–acrylic acid (EAA) copolymer as a compatibilizer precursor. The former remains phase separated, indicating that the filler does not promote the enhancement of the interfacial adhesion. The macroscopic properties of the hybrid blend were interpreted in the light of its morphology. The melt state dynamics of the materials were probed by means of linear viscoelastic measurements. Many peculiar rheological features of polymer-layered silicate nanocomposites based on single polymer matrix were detected for the hybrid blend. The results have been interpreted proposing the existence of two distinct populations of dynamical species: HDPE not interacting with the filler, and a slower species, constituted by the organoclay-rich polyamide phase, which slackened dynamics stabilize the morphology in the melt state. In the solid state, both the reinforcement effect of the filler and the co-continuous microstructure promote the enhancement of the tensile modulus. Our results demonstrate that adding nanoparticles to polymer blends allows tailoring the final properties of the hybrid, potentially leading to high-performance materials which combine the advantages of polymer blends and the merits of polymer nanocomposites.

Modification of polyvinyl chloride (PVC) by reactive processing.

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Pyrolysis and combustion of municipal solid wastes:evaluation of synergistic effects using TGA-MS

A thermogravimetric methodology was developed to investigate and semi-quantify the extent of synergistic effects during pyrolysis and combustion of municipal solid waste (MSW). Results from TGA-MS were used to compare the pyrolysis and combustion characteristics of single municipal solid waste components (polyvinyl chloride (PVC), polypropylene (PP), polystyrene (PS), branches (BR), leaves (LV), grass (GR), packaging paper (PK), hygienic paper (HP) and cardboard (CB)) and a mixture (MX) of PP, BR and CB. Samples were heated under dynamic conditions at 20°C/min from 25°C to 1000°C with the continuous record of their main evolved fragments. Synergistic effects were evaluated by comparing experimental and calculated weight losses and relative areas of MS peaks. Pyrolysis of the mixture happened in two stages, with the release of H2, CH4, H2O, CO and CO2 between 200 and 415°C and the release of CH4, CxHy, CO and CO2 between 415 and 525°C. Negative synergistic effect in the 1st stage was attributed to the presence of PP where the release of hydrocarbons and CO2 from BR and CB was inhibited, whereas positive synergistic effects were observed during the 2nd degradation stage. In a second part of the study, synergistic effects were related to the dependency of the effective activation energy (Eα) versus the conversion (α). Higher Eαs were obtained for MX during its 1st stage of pyrolysis and lower Eαs for the 2nd stage when compared to the individual components. On the other hand, mostly positive synergistic effects were observed during the combustion of the same mixture, for which lower Eαs were recorded.