Growth of membranes formed by associating polymers at interfaces

Polymer association at liquid-liquid interfaces is a promising way to spontaneously obtain soft self-healing membranes. In the case of reversible bonding between two polymers, the macromolecules are mobile everywhere within the membrane and they can be absorbed into it at both boundaries due to binding to macromolecules of the other type. In this work, we develop the theoretical model of membrane growth based on these assumptions. The asymptotic dependence of membrane thickness on time as h ∼ t^1/2, as typically observed experimentally in a stationary regime, reveals an interdiffusion-controlled process, where the polymer fluxes sustain the polymer absorption. The membrane growth rate is mainly determined by the difference in equilibrium compositions at the boundaries, the association constant, the polymer lengths and mobilities. This model is further used to describe the growth of hydrogel membranes formed via H-bonding of polymers at the interface between a solution of poly(propylene oxide) (PPO) in isopropyl myristate and an aqueous solution of poly(methacrylic acid) (PMAA). The film thickness is measured by reflectometric methods. The growth rate slows down about 25 times for 500-nm-thick films at pH = 5.1 compared to the case of pH = 3. The ionization degree of PMAA solutions is studied by potentiometric methods. Even a small change in ionization is found to influence noticeably the growth rate of the film. In the diffusion-controlled regime, the slowdown can be explained by a drop in the composition gradient in the membrane, whereas the process becomes non-stationary if the absorption of PMAA is hindered by an interfacial electrostatic barrier.