Thermomechanics of the shape memory effect in polymers for biomedical applications.

We examine the shape memory effect in polymer networks intended for biomedical, and specifically cardiovascular, applications. The polymers were synthesized by photopolymerization from a tert-butyl acrylate monomer with a diethyleneglycol diacrylate crosslinker. Three-point flexural tests were used to systematically investigate the thermomechanics of shape storage (predeformation) and shape recovery. The glass transition temperature, T(g), of the polymers was determined to be approximately 65 degrees C. The polymers show 100% strain recovery, at low and high predeformation temperatures, up to maximum strains of approximately 80%. The polymers show a sigmoidal free strain recovery response as a function of increasing temperature at a constant heating rate. Free strain recovery was determined to depend on the temperature during predeformation; lower predeformation temperatures (T < T(g)) decreased the temperature required for free strain recovery. Constrained stress recovery shows a complex evolution as a function of temperature and also depends on the temperature during predeformation. Stress recovery after low-temperature predeformation (T < T(g)) shows a peak in the generated recovery stress, whereas stress recovery after high-temperature predeformation (T > T(g)) is sigmoidal. The isothermal free strain recovery rate was found to increase with increasing temperature or decreasing predeformation temperature. The thermomechanical results are discussed in light of potential biomedical applications, and a prototype device is presented.