Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Effects of Nanoscale Confinement and Interfaces on the Glass Transition Temperatures of a Series of Poly(n-methacrylate) Films

Rodney D. Priestley A , Manish K. Mundra B , Nina J. Barnett B , Linda J. Broadbelt A and John M. Torkelson A B C
+ Author Affiliations
- Author Affiliations

A Department of Chemical and Biological Engineering, Northwestern University, Evanston, Illinois 60208, USA.

B Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, USA.

C Corresponding author. Email: j-torkelson@northwestern.edu

Australian Journal of Chemistry 60(10) 765-771 https://doi.org/10.1071/CH07234
Submitted: 9 July 2007  Accepted: 24 August 2007   Published: 9 October 2007

Abstract

We use fluorescence from dye-labelled polymer to measure the glass transition temperatures (Tgs) across single-layer films and near surfaces and silica interfaces in bilayer films for a series of poly(n-methacrylate)s. With nanoscale confinement, the average Tg across a film supported on silica increases for poly(methyl methacrylate) (PMMA), decreases for poly(ethyl methacrylate) (PEMA) and poly(propyl methacrylate), and is nearly invariant for poly(iso-butyl methacrylate) (PIBMA). These trends are consistent with the relative strengths of local perturbations to Tg caused by surfaces and substrates as measured in bilayer films. The substrate effect, which increases Tg via hydrogen-bonding interactions between the polymer and hydroxyl groups on the silica surface, is stronger than the free-surface effect in PMMA. The free-surface effect, which reduces Tg via a reduction in the required cooperativity of the glass transition dynamics, is stronger than the substrate effect in PEMA. The substrate and free-surface effects have similar strengths in perturbing the local Tg in PIBMA, resulting in a net cancellation of effects when measurements are made across single-layer films.


Acknowledgements

This work was supported by the NSF-MRSEC program at Northwestern University (grants DMR-0076097 and DMR-0520513), Northwestern University, and a DFI fellowship (R.D.P.).


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