Self-Healing of Bulk Polyelectrolyte Complex Material as a Function of pH and Salt

Self-healing materials are an emerging class of modern materials gaining importance due to environmental and energy concerns. Materials based on the complexation of oppositely charged polyelectrolytes, usually in the form of coatings and films, have been shown to have water activated self-healing properties. In this work, the self-healing of bulk branched poly(ethylene imine) and poly(acrylic acid) (BPEI/FAA) complex is studied as a function of the aqueous solutions used to activate the self-healing. Specifically, exposure to different salt solutions and solutions of different pH was examined including sodium and copper ion containing solutions as well as acidic and basic solutions. By applying NaCl treatment, especially followed by exposure to DI water, the self-healing ability of the BPEI/PAA complex was enhanced. In contrast, after treated by CuCl2, the BPEI/PAA complex lost its self-healing ability, showing an ability to modulate the ability to self-heal as a function of external stimulus. In addition to improving the ability to self-heal using salt as compared to using DI water alone, acidic and basic solutions can also improve the ability to self-heal. The self-healing is caused by chain mobility at the cut interface of the polyelectrolyte complex material which is controlled by charge density along the polyelectrolyte backbone as well as ionic cross-link density, and correlation between this mobility to rheological behavior is made. Tensile testing and determination of fracture toughness were used to characterize self healing.