Aggregation Behavior of the Blends of Homo-PS and PS-b-PEO-b-PS at the Air/Water Interface.

Aggregation behaviors of the blended Langmuir monolayers of a homopolymer polystyrene (h-PS) and a triblock copolymer polystyrene-b-poly(ethylene oxide)-b-polystyrene (PS-b-PEO-b-PS) were studied by the Langmuir film balance technique, and the morphologies of their Langmuir-Blodgett (LB) films were studied by atomic force microscopy. The isotherms of the h-PS/PS-b-PEO-b-PS blends shift to small areas with the increase of h-PS content, and a pseudoplateau appears as h-PS content is below 60 wt %. It is worth noting that the blended isotherms appear at the left of their corresponding ideal ones, which means that the blended monolayers are a little more condensed due to attractive interactions between the two components. Hysteresis phenomena exist in all of the blended monolayers, and the higher the PS-b-PEO-b-PS content, the larger the hysteresis degree becomes because of the stronger looped-PEO entanglements. All the blended LB films of h-PS and PS-b-PEO-b-PS prepared under low pressure exhibit the mixed structures of small and large isolated circular aggregates. The small aggregates are the copolymer micelle cores and the large ones are attributed to coalescence of the local h-PS chains and some PS blocks. Upon further compression, the aggregates in the blended LB films become a little denser as h-PS content is below 60 wt %, whereas those become totally close-packed with decreased size as h-PS content is 80 wt %.