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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 ( h  0 ), of random copolymer films of 4- er -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 ( h  0 ) displays identical enhancements, independent of X  TBS . For X  TBS &gt; ∼0.66; however, T  g ( h  0 ) decreases steadily with X  TBS . The X  TBS &gt; 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 ( h  0 ) 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.

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

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