The main studied mixed monolayers consisting of polyethylene-block-polycaprolactone ( PEO-b-PCL) and its component polymers with poly( vinyl phenol). It was shown previously that most of the area relaxation process of mixed monolayers could be well represented by a model considering the nucleation and growth mechanisms. The characteristic exponent x values were found to be slightly temperature dependent. The kx values were detected to decrease with increasing temperature. When PVPh was added into the most unstable PEO, the mixed monolayer films exhibited a remarkably improved stable relaxation behavior than PCL (or PEO-b-PCL). The characteristic exponent x and kx values were plotted vesus the A∞/A0 values. Mostly increasing characteristic exponent x and kx values with increasing A∞/A0 values were observed. For the PCL and PVPh monolayers, the xkx values were detected to increase with increasing A∞/A0 values. The xkx values of previously published stereoregular and different molecular weight PMMAs were also demonstrated to become larger with the increasing A∞/A0 values.

The mixed monolayer behavior of polyethylene-block-polycaprolactone (PEO-b-PCL) and its component polymers (PEO or PCL) with poly(vinyl phenol)(PVPh) was investigated from the measurements of surface pressure-area per molecule (π-A) isotherms at three different temperatures(10˚C, 25˚C and 40˚C). The miscibility and nonideality of the mixed monolayers were examined by calculating the excess surface area as a function of composition. Interestingly, PEO and PCL were shown to have different interactions with PVPh at the air/water interface from in the bulk state on the solid substrate. PE O demonstrated mostly positive excess surface area with PVPh. Negative excess surface areas were in the majority observed in the PCL/PVPh monolayers. A scheme of differences in interaction sites between PEO (or PCL) and PVPh at the air/water interface was proposed to explain the negative or positive deviations of surface areas successfully.