Influence of spatially heterogeneous dynamics on physical aging of polystyrene

TitleInfluence of spatially heterogeneous dynamics on physical aging of polystyrene
Publication TypeJournal Article
Year of Publication2002
AuthorsThurau, C. T., and M. D. Ediger
JournalJournal of Chemical PhysicsJournal of Chemical Physics
Volume116
Pagination9089-9099
Date PublishedMay
Type of ArticleArticle
ISBN Number0021-9606
Accession NumberWOS:000175431400046
Keywords2ND-HARMONIC GENERATION, AMORPHOUS POLYMERS, DIELECTRIC-RELAXATION, DYNAMICS, GLASS-TRANSITION TEMPERATURE, O-TERPHENYL, PROBE, REORIENTATION, STRUCTURAL RELAXATION, SUPERCOOLED ORTHO-TERPHENYL, translational diffusion
Abstract

A photobleaching technique has been used to study the segmental dynamics of a polystyrene melt during isothermal physical aging. Both rotational and translational diffusion measurements of dilute tetracene probes dispersed in the polymer matrix were performed. Following a temperature quench from T-g+2 degreesC into the glass, either rotational relaxation from an induced anisotropic state or translational diffusion across a holographic grating was measured as a function of aging time. Relaxation times for the two observables evolved by nearly a factor of 10 during isothermal aging, and equilibration times ranged from 10(3) to 10(6) s at 98.6 to 95.6 degreesC. Immediately following the temperature jump, probe rotational diffusion has evolved by over half a decade in response to the quench, while probe translational diffusion has been retarded by only 0.2 decades. At longer elapsed times, for aging at 95.6 degreesC, the translational observable reaches equilibrium before the rotational observable. These differences in aging behavior indicate that the dynamics responsible for physical aging are spatially heterogeneous, and that regions of different mobility age at different rates. Furthermore, the results suggest that these heterogeneous dynamics could be responsible for causing other observables, such as volume and enthalpy, to equilibrate on different time scales-a phenomenon often associated with physical aging. (C) 2002 American Institute of Physics.

Alternate JournalJ. Chem. Phys.