Gold nanorods or nanospheres? Role of particle shape on tuning the shape memory effect of semicrystalline poly(ε-caprolactone) networks.

In this study, modified poly(ε-caprolactone) (PCL) tri-block copolymers were successfully synthesized through ring opening polymerization. The nanocomposite films containing either colloidal gold nanorods (AuNRs) or gold nanospheres (AuNSs) in the polymer matrix were fabricated without chemical modification to realize light-responsive shape memory behaviors. The localized surface plasmon resonance of AuNPs was utilized by irradiating the selective wavelength of light to create a photothermal effect. The polymer microstructures were investigated by NMR, and the thermal properties of the polymer networks were studied by TGA and DSC. The addition of AuNPs did not change the melting temperature, ( ) of the SMP. The AuNRs were fairly well dispersed within the PCL matrix as observed using SEM-EDAX analysis and as indicated from the uniform shape memory transitions of the SMP/AuNR nanocomposites. The shape memory behavior was quantitatively analyzed by cyclic thermomechanical tests using DMA. The laser-triggered shape memory properties of the nanocomposites were analyzed and the shape recovery process from a rectangular shaped film to a helical coil was demonstrated. The speed of SMP recovery was found to be dependent on the geometry and concentration of the AuNPs in the nanocomposite, as well as on the laser wavelength and intensity.