ORS2-0567
Hierarchical Functional-Group Adsorption of Polymer Chains at Solid/Liquid Interfaces
Topic
S2. High-End Characterization/Polymer Physics/Properties
When and Where
Oct 1, 2026
16:05 - 16:20
Room 103
Session Chairs
Hyungju AHN
Presenter(s)
Tatsuki Abe (Kyushu University)
Co-Author(s)
Abstract
Polymer adsorption at solid/liquid interfaces governs the performance of various materials, including nanocomposites, coatings, and adhesives. A better understanding of the molecular picture of polymer adsorption is crucial for achieving further control of interfacial structures and physical properties. However, experimentally detecting how polymer chains adsorb at solid/liquid interfaces at the functional-group level remains challenging. In this study, we employed in situ and real time sum-frequency generation (SFG) vibrational spectroscopy to examine the adsorption dynamics of poly(methyl methacrylate) (PMMA) and polystyrene (PS) from their respective deuterated toluene solutions onto silica surfaces. By collecting time-dependent SFG spectra, we revealed that PMMA adsorption proceeded through a sequential and multistep process involving coupled adsorption and conformational rearrangement. Immediately after contact between the PMMA solution and silica, ester methyl (OCH3) groups in the PMMA side chains adsorbed onto the silica surface. This adsorption is likely attributed to hydrogen bonding with interfacial silanol groups. The adsorbed OCH3 groups then underwent conformational rearrangement. This was followed by adsorption and reorientation of chain-end methyl groups and backbone methylene groups, indicating a sequential, functional-group-specific adsorption pathway at the interface. In contrast, PS, which lacks specific hydrogen-bonding interactions with the silica surface, exhibited significantly slower adsorption under comparable conditions. These results demonstrate that interfacial hydrogen bonding plays a critical role in the structural evolution of polymer chains at solid/liquid interfaces. The findings provide fundamental insights into polymer chain assembly formation at interfaces and contribute to the rational design of polymer materials.
