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Updated: Sep 21, 2025

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Tg Confinement Effect of Random Copolymers of 4-tert-Butylstyrene and 4-Acetoxystyrene with Different Compositions
Tong Wang1, Jinsong Yan1, Hailin Yuan1
1Department of Physics, Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong.
Abstract:
We observe that the Tg confinement effect of polymer films can saturate with polymer-substrate interaction. Thickness dependences of the glass transition temperature, Tg(h0), of random copolymer films of 4-tert-butylstyrene (TBS) and 4-acetoxystyrene (AS) supported by silica (SiOx) were measured for different TBS concentrations, XTBS. For 0 ≤ XTBS ≤ 0.47, Tg(h0) displays identical enhancements, independent of XTBS. For XTBS > ∼0.66; however, Tg(h0) decreases steadily with XTBS. The XTBS > 0.66 result is in keeping with expectations that TBS interacts less strongly with SiOx than AS does, and weaker polymer-substrate interaction renders greater dominance of the air surface over substrate surface on Tg, and thereby Tg reduction. We propose that saturation in Tg(h0) found for XTBS ≤ 0.47 is caused by the maximization in polymer-substrate-specific bond formation. Further experiments and a calculation support this proposition.
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