351. Is There a Relationship Between Wettability and the Rates of Equilibration of Hydrogen-Bonded Oligomer Poly(mercaptopropylmethylsiloxane) under Confinement?
- Author
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Zimny, Sara, Tarnacka, Magdalena, Geppert-Rybczyńska, Monika, and Kamiński, Kamil
- Abstract
In this paper, we investigated the annealing experiments of poly(mercaptopropylmethylsiloxane) (PMMS) confined within two types of porous templates (anodic aluminum oxide, AAO, and silica) characterized by different pore diameter, d= 8–120 nm, using different thermal protocols (varying significantly in cooling/heating rates) by means of broadband dielectric spectroscopy (BDS) supported by complementary differential scanning calorimetry (DSC) and temperature-dependent contact angle (θ) measurements. It was found that the relaxation times obtained from standard temperature-dependent dielectric investigations deviate from the bulk behavior when approaching the glass transition temperature. Importantly, this confinement-induced effect can be easily removed by the annealing experiments performed over some specific range of temperatures. The analysis of the dielectric data collected during isothermal experiments of confined samples that was beforehand cooled with different rates revealed that (i) characteristic equilibration times weakly depend on the cooling rates and (ii) the activation energy of the equilibration process, that is, Ea, varies with the reduction of the pore diameter and material that the porous template is made of. In fact, there is a significant reduction in Eafrom ∼62 to ∼23 kJ/mol obtained for the annealing process carried out in AAO (d= 10 nm) and silica (d= 8 nm) membranes, respectively. It could be due to a change in wettability of PMMS on both surfaces, which might affect adsorption–desorption processes occurring at the interface at lower temperatures and consequently the mass exchange between interfacial and core molecules. Our data provide a better understanding of the annealing processes occurring in the liquids confined in mesopores.
- Published
- 2023
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