Spread monolayers of poly(styrene)-poly(ethylene oxide) diblock copolymers (PS-PEOn, m = 38, n = 90, 148, 250, and 445) have been studied at the air-water interface by measuring the surface pressureâ area (mmA) isotherms at several temperatures. The mmA-isotherms exhibit several regions which can be ascribed to different conformations of the polymer chains:â a pancake structure at low surface pressures and high areas when the isolated chains are adsorbed by both the PS globule and the PEO segments at the interface; an intermediate structure, quasi-brush, when the PEO segments are solubilized in the subphase; and finally a brush developed at low surface areas when the PEO chains are obliged to stretch away from the interface to avoid overlapping. At surface pressures near 10 mN/m there is a transition between a high-density pancake and the quasi-brush regime. The compression and the subsequent expansion curves superpose at the transition and quasi-brush regions but not at the brush and pancake stages. This points to a high cohesion in the brush structure after compression and to some irreversible entanglement and hydration of the PEO chains when immersed in the subphase. These two local hystereses depend differently on the PEO chain length and temperature. The hysteresis observed at high surface pressures (brush conformation) decreases with the PEO length and temperature, whereas the low surface pressure hysteresis (pancake) increases with PEO chain length, decreases with temperature in the range 283â 298 K, and increases in the range 298â 315 K. A negative mean transition entropy change was obtained from the temperature dependence of the quasi-SSALâ quasi-brush transition. The results indicate that the extensive properties of the present diblock copolymers at the interface, such as the pancake limiting area and the mean transition entropy, when expressed by PEOmer, are independent of the PEO length.
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