Dramatic reduction of the effect of nanoconfinement on the glass transition of polymer films via addition of small-molecule diluent
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The effect of nanoconfinement on the glass transition temperature T8 in thin polymer films is studied as a function of added small-molecule diluent or plasticizer. The decrease [increase] in T8 found in nanoconfined, neat polystyrene [poly(2-vinyl pyridine)] is suppressed by added diluent, with 13–20 nm thick polystyrene films exhibiting bulk T8 upon addition of 9 wt% pyrene or 4 wt% dioctylphthalate. This is explained by a connection between the size scale of the cooperative dynamics associated with T8, which decreases with added diluent, and the size scale of the nanoconfinement effect.
At time of publication, all authors were at Northwestern University. Christopher Ellison is currently Asst. Professor at the University of Texas at Austin.