T_g Confinement Effect of Random Copolymers of 4-tert-Butylstyrene and 4‑Acetoxystyrene with Different Compositions

We observe that the T_g confinement effect of polymer films can saturate with polymer–substrate interaction. Thickness dependences of the glass transition temperature, T_g(h₀), of random copolymer films of 4-tert-butylstyrene (TBS) and 4-acetoxystyrene (AS) supported by silica (SiOx) were measured for different TBS concentrations, X_TBS. For 0 ≤ X_TBS ≤ 0.47, T_g(h₀) displays identical enhancements, independent of X_TBS. For X_TBS > ∼0.66; however, T_g(h₀) decreases steadily with X_TBS. The X_TBS > 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 T_g, and thereby T_g reduction. We propose that saturation in T_g(h₀) found for X_TBS ≤ 0.47 is caused by the maximization in polymer–substrate-specific bond formation. Further experiments and a calculation support this proposition.