Polymer monolayers with a small viscoelastic linear regime: Equilibrium and rheology of poly(octadecyl acrylate) and poly(vinyl stearate)

The equilibrium properties of monolayers of two polymers: poly(octadecyl acrylate) and poly(vinyl stearate) on water have been measured. The surface pressure (Pi) versus surface concentration (Gamma) curves indicate that the water-air interface is a poor solvent for both polymers. The thermal expansivity shows a sharp change near room temperature. This behavior is typical of a glass transition; this is the first time that such a plot is observed for Langmuir films. The Pi vs Gamma curves measured by the continuous compression method show strong anisotropy effects. They also show that the monolayer is brought into nonequilibrium states depending on the compression rate. Within the linear regime, the relaxation experiments were bimodal. The longest relaxation time strongly increases as T is decreased, which might be compatible with the high increase of viscosity in the glass transition. The oscillatory barrier experiments showed that the maximum strain of the linear regime is smaller than 3% for both monolayers. The Fourier-transform analysis of the oscillatory experiments beyond the linear regime points out the contribution of different harmonics in the response function. Oscillations in the nonlinear regime show hysteresis cycles. The results obtained indicate that some of the previously published data for these polymer monolayers correspond to nonequilibrium states.