Is the Reduction in Tracer Diffusivity under Nanoscopic Confinement Related to a Frustrated Segmental Mobility? | Zendy

Napolitano Simone | Zendy; Rotella Cinzia | Zendy; Wübbenhorst Michael | Zendy

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Is the Reduction in Tracer Diffusivity under Nanoscopic Confinement Related to a Frustrated Segmental Mobility?

Author(s) -

Napolitano Simone,

Rotella Cinzia,

Wübbenhorst Michael

Publication year - 2011

Publication title -

macromolecular rapid communications

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.348

H-Index - 154

eISSN - 1521-3927

pISSN - 1022-1336

DOI - 10.1002/marc.201100029

Subject(s) - thermal diffusivity , nanoscopic scale , tracer , materials science , einstein relation , decoupling (probability) , thin film , polymer , chemical physics , condensed matter physics , nanotechnology , chemistry , thermodynamics , composite material , physics , metric (unit) , operations management , control engineering , nuclear physics , engineering , economics

We developed an experimental method for the determination of the tracer diffusivity D tr in ultrathin polymer films, and the changes in the segmental mobility of tracer molecules while they diffuse through matrices of different thickness and get adsorbed onto a target substrate. D tr starts decreasing already at 120–150 nm and drops to 1% of its bulk value in films as thin as 7.5 nm. We discuss the results highlighting a strong decoupling between the reduction in mass transport at the nanoscale and the increase in the glass transition temperature determined via capacitive dilatometry together with a breakdown of the Stokes–Einstein relation between orientational and translational degrees of freedom.

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