Abstract
Waterborne polyurethane dispersions (PUDs) have garnered increasing interest in recent years due to the growing demand for environmentally friendly materials. The unique phase-separated morphologies exhibited in PUD films and coatings provide opportunities for directing the distribution of functional additives and controlling properties. Although there has been extensive research on polyurethanes for several decades, the mechanisms underlying the PUD morphology formation are poorly understood. The morphologies are driven by interactions between hard segments (HS), and the process is further complicated by the presence of colloidal particles and the intricate interaction between the urethane/urea linkages and water. In this work, structure-property-processing relationships between HS content and structure, relative humidity, particle size, and the resulting dry film morphology of PUDs were determined in two diisocyanate systems: hexamethylene diisocyanate (HDI), a symmetric, flexible diisocyanate; and isophorone diisocyanate (IPDI), an asymmetric, sterically hindered cyclic diisocyanate. HDI-based films exhibited semicrystalline morphologies with HS superstructures that are sensitive to relative humidity. IPDI-based films displayed spherical coalescence-suppressed morphologies influenced by particle size and zeta potential. PUD compositions and processing conditions were controlled to produce nanocomposite films with an enhanced dispersion of nanoadditives.