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The demand for improved properties of common polymers keeps increasing, and several new approaches have been investigated. In the study reported here, composites with a polymer matrix comprising a blend of high‐density polyethylene with ethylene–vinyl acetate copolymer (EVA), and with polyhedral oligomeric silsesquioxane (POSS) as a nanostructure, were processed and characterized in terms of their thermal and morphological properties. For the preparation of the composites, the concentrations of the blend components (0, 50 and 100 wt%) and of the POSS (0, 1 and 5 wt%) were varied. X‐ray diffraction results indicated that the presence of EVA in the composites led to the appearance of crystalline domains at lower POSS concentrations. Transmission and scanning electron microscopy showed that samples with 1 wt% of POSS had a homogeneous distribution in the polymer matrix with average dimensions of ca 150 nm. However, the formation of aggregates occurred in samples with 5 wt% of POSS. Differential scanning calorimetry and thermogravimetic analyses indicated that the POSS did not affect the melt and degradation temperatures of the polymer matrix. POSS underwent aggregation at higher concentrations during the composite processing, indicating a solubility limit of around 1 wt%. The presence of EVA in the composite favors POSS aggregation due to an increase in the polarity of the polymer matrix. Copyright © 2009 Society of Chemical Industry

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