Fecha de publicación: 20/01/2025 Fuente: Polymers Polymers, Vol. 17, Pages 254: Mechanisms of the Photomechanical Response in Thin-Film Dye-Doped Glassy Polymers
Polymers doi: 10.3390/polym17020254
Authors:
Zoya Ghorbanishiadeh
Ankita Bhuyan
Bojun Zhou
Morteza Sheibani Karkhaneh
Mark G. Kuzyk

This work aims to determine the mechanism of the photomechanical response of poly(Methyl methacrylate) polymer doped with the photo-isomerizable dye Disperse Red 1 using the non-isomerizable dye Disperse Orange 11 as a control to isolate photoisomerization. Samples are free-standing thin films with thickness that is small compared with the optical skin depth to assure uniform illumination and photomechanical response throughout their volume, which differentiates these studies from most others. Polarization-dependent measurements of the photomechanical stress response are used to deconvolute the contributions of angular hole burning, molecular reorientation and photothermal heating. While photo-isomerization of dopant molecules is commonly observed in dye-doped polymers, the shape changes of a molecule might not couple strongly to the host polymer through steric mechanical interactions, thus not contributing substantially to a macroscopic shape change. To gain insights into the effectiveness of such mechanical coupling, we directly probe the dopant molecules using dichroism measurements simultaneously while measuring the photomechanical response and find mechanical coupling to be small enough to make photothermal heating—mediated by the transfer of optical energy as heat to the polymer—the dominant mechanism. We also predict the fraction of light energy converted to mechanical energy using a model whose parameters are thermodynamic material properties that are measured with independent experiments. We find that in the thin-film geometry, these dye-doped glassy polymers are as efficient as any other material but their large Young’s modulus relative to other organic materials, such as liquid crystal elastomers, makes them suitable in applications that require mechanically strong materials. The mechanical properties and the photomechanical response of thin films are observed to be significantly different than in fibers, suggesting that the geometry of the material and surface effects might play an important role.