We demonstrate the new features of a polyurethane shape memory polymer: water-driven actuation and recovery in sequence (i.e., programmable). Hydrogen bonding is identified as the reason behind these features. In addition, the absorbed water is quantitatively separated into two parts, namely, the free water and bound water. Their individual contribution on the glass transition temperature is identified.

It was observed that the polyurethane shape memory polymer (SMP) loses its shape fixing capability after being exposed in the air at room temperature for several days. A significant indication for this change is the continuous decrease of the glass transition temperature (Tg) of polyurethane. Accompanying the decrease of Tg, the uniaxial tensile behaviour also changes. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) tests were carried out to find the cause behind this phenomenon. Moisture was concluded as the main reason. A mathematical expression was obtained for the relationship between Tg and the moisture. Moreover, the polyurethane shape memory polymer can fully regain its original properties after being heated at temperatures above 180 °C, which is the melting temperature of this SMP.

Gelatin, one of the most abundant, naturally derived biomacromolecules from collagen, is widely applicable in food additives, cosmetic ingredients, drug formulation, and wound dressing based on their non-toxicity and biodegradability. In parallel, polyvinyl alcohol (PVA), a synthetic polymer, has been commonly applied as a thickening agent for coating processes in aqueous systems and a major component in healthcare products for cartilage replacements, eye lubrication, and contact lenses. In this study, a new type of mixed hydrogel nanofiber was fabricated from gelatin and polyvinyl alcohol by electrospinning under a feasible range of polymer compositions. To determine the optimal composition of gelatin and polyvinyl alcohol in nanofiber fabrication, several key physicochemical properties of mixed polymer solutions such as viscosity, surface tension, pH, and electrical conductance were thoroughly characterized by a viscometer, surface tensiometer, water analyzer, and carbon electron probe. Moreover, the molecular structures of polymeric chains within mixed hydrogel nanofibers were investigated with Fourier-transform infrared spectroscopy. The morphologies and surface elemental compositions of the mixed hydrogel nanofibers were examined by the scanning electron microscope and energy-dispersive X-ray spectroscopy, respectively. The measurement of water contact angles was performed for measuring the hydrophilicity of nanofiber surfaces. Most importantly, the potential cytotoxicity of the electrospun nanofibers was evaluated by the in vitro culture of 3T3 fibroblasts. Through our extensive study, it was found that a PVA-rich solution (a volumetric ratio of gelatin/polyvinyl alcohol <1) would be superior for the efficient production of mixed hydrogel nanofibers by electrospinning techniques. This result is due to the appropriate balance between the higher viscosity (~420–~4300 10⁻² poise) and slightly lower surface tension (~35.12–~32.68 mN/m²) of the mixed polymer solution. The regression on the viscosity data also found a good fit by the Lederer–Rougier’s model for a binary mixture. For the hydrophilicity of nanofibers, the numerical analysis estimates that the value of interfacial energy for the water contact on nanofibers is around ~−0.028 to ~−0.059 J/m².