The utilization of clays to enhance the water vapour barrier properties of polyethylene requires knowledge about factors associated with the constituents themselves. Hence, this paper presents combinations of two types of polyethylene and five different clays. Morphological, mechanical and thermal properties related to the water vapour permeability of clay/polyethylene composites were investigated. Although no evidence of clay exfoliation was observed according to morphological and spectral results, it was found that the enhanced water vapour barrier properties were linked to clay aspect ratio, composites interface, polyethylene crystallinity and storage conditions. The best water vapour barrier properties were obtained by increasing polyethylene crystallinity with unmodified clay of high aspect ratio. Organoclays addition showed no improvement in barrier properties of polyethylene unless the interface was strongly compatibilized. Contrary to the results published elsewhere, clay addition brought about no mechanical improvements to polyethylene tested.

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Organo‐fluorohectorites were either obtained commercially or synthesized by reacting unmodified fluorohectorite with ammonium salts. Modified and unmodified fluorohectorites were incorporated into low density polyethylene (LDPE) with or without maleic anhydride grafted polyethylene (MAPE) as a compatibilizer. Although clay aggregates were observed for all blends, the existence of an intercalated and exfoliated clay structure was confirmed according to morphological observations. Different types of cationic organomodifier were comparatively studied. It was found that alkyl chain length and amount of organomodifier were two factors influencing the dispersion state of fluorohectorites. Nanocomposites containing well‐dispersed fluorohectorites showed superior mechanical and barrier properties as compared to their counterparts. The presence of MAPE exhibited beneficial effects on the mechanical properties of the fluorohectorite/LDPE system, whereas the water vapour barrier property was adversely affected.