Impact of Thermal History on the Kinetic Response of Thermoresponsive Poly(diethylene glycol monomethyl ether methacrylate)-block-poly(poly(ethylene glycol)methyl ether methacrylate) Thin Films Investigated by In Situ Neutron Reflectivity.

The impact of thermal history on the kinetic response of thin thermoresponsive diblock copolymer poly(diethylene glycol monomethyl ether methacrylate)-block-poly(poly(ethylene glycol) methyl ether methacrylate), abbreviated as PMEO2MA-b-POEGMA300, films is investigated by in situ neutron reflectivity. The PMEO2MA and POEGMA300 blocks are both thermoresponsive polymers with a lower critical solution temperature. Their transition temperatures (TTs) are around 25 °C (TT1, PMEO2MA) and 60 °C (TT2, POEGMA300). Thus, by applying different temperature protocols (20 to 60 or 20 to 40 to 60 °C), the PMEO2MA-b-POEGMA300 thin films experience different thermal histories: the first protocol directly switches from a swollen to a collapsed state, whereas the second one switches first from a swollen to a semicollapsed and finally to a collapsed state. Although the applied thermal histories differ, the response and final state of the collapsed films are very close to each other. After the thermal stimulus, both films present a complicated response composed of an initial shrinkage, followed by a rearrangement. Interestingly, a subsequent reswelling of the collapsed film is only observed in the case of having applied a thermal stimulus of 20 to 40 °C. The normalized film thickness and the D2O amount of each layer in the PMEO2MA-b-POEGMA300 films are consistent at the end of the two different thermal stimuli. Hence, it can be concluded that the thermal history does not influence the final state of the PMEO2MA-b-POEGMA300 films upon heating. Based on this property, these thin films are especially suitable for the temperature switches on the nanoscale, which may experience different thermal histories.