Unusually Stable Hysteresis in the pH-Response of Poly(Acrylic Acid) Brushes Confined within Nanoporous Block Polymer Thin Films

Abstract

Stimuli-responsive soft materials are a highly studied field due to their wide-ranging applications; however, only a small group of these materials display hysteretic responses to stimuli. Moreover, previous reports of this behavior have typically shown it to be short-lived. In this work, poly(acrylic acid) (PAA) chains at extremely high grafting densities and confined in nanoscale pores displayed a unique long-lived hysteretic behavior caused by their ability to form a metastable hydrogen bond network. Hydraulic permeability measurements demonstrated that the conformation of the PAA chains exhibited a hysteretic dependence on pH, where different effective pore diameters arose in a pH range of 3 to 8, as determined by the pH of the previous environment. Further studies using Fourier transform infrared (FTIR) spectroscopy demonstrated that the fraction of ionized PAA moieties depended on the thin film history; this was corroborated by metal adsorption capacity, which demonstrated the same pH dependence. This hysteresis was shown to be persistent, enduring for days, in a manner unlike most other systems. The hypothesis that hydrogen bonding among PAA units contributed to the hysteretic behavior was supported by experiments with a urea solution, which disrupted the metastable hydrogen bonded state of PAA toward its ionized state. The ability of PAA to hydrogen bond within these confined pores results in a stable and tunable hysteresis not previously observed in homopolymer materials. An enhanced understanding of the polymer chemistry and physics governing this hysteresis gives insight into the design and manipulation of next-generation sensors and gating materials in nanoscale applications.