Effect of temperature on the interfacial behavior of a polystyrene-b-poly(methyl methacrylate) diblock copolymer at...

Monolayers of a polystyrene-poly(methyl methacrylate) (PS-PMMA) diblock copolymer at the air-water interface were studied by measuring the surface pressure-area isotherms at several temperatures. Langmuir film balance experiments and atomic force microscopy showed that the diblock copolymer molecules formed surface micelles. In the plot of the surface pressure versus surface area per repeating unit, the monolayer changed from the gas phase to the liquid expanded phase at lower surface pressure for systems at low temperature compared to those at high temperature. In addition, a plateau, corresponding to the transition from the liquid expanded to liquid condensed phase, appeared in that plot at lower surface pressure for systems with a higher subphase (water) temperature. Hysteresis was observed in the compression-expansion cycle process. Increasing the subphase temperature alleviated this hyteresis gap, especially at low surface pressures. The minimum in the plot of the surface pressure versus surface area per repeating unit in the expansion process (which arises from the transition) and the transition plateau appeared more vividly at higher water temperature. These dynamic experimental results show that PS-PMMA diblock copolymers, in which both blocks are insoluble in water, do not form complicated entanglements in two-dimensional space. Although higher water temperature provided more entropy to the chains, and thus more conformational freedom, it did not change the surface morphology of the condensed film because both blocks of PS-PMMA are insoluble in water.