Polymers adsorbed on nanoparticles (NPs) play essential roles in determining the physical properties of polymer nanocomposites. Herein, polymer chain structures (morphologies) on NPs and their determining factors were investigated. A model polymer composite comprising a polystyrene (PS) matrix, gold NPs (GNPs), and a small amount of poly(4-iodostyrene) (P4IS) was prepared. The polymer chain morphologies of P4IS adsorbed on GNPs inside the PS matrix were visualized by using annular dark-field scanning transmission electron microscopy, which enabled us to observe clearly the iodine atoms in P4IS. This observation revealed that the P4IS polymer chains were adsorbed on GNPs with a unique morphology wherein 1–2 molecular layers of P4IS surrounded a GNP, and the rest of the P4IS was aggregated at the side of the GNP. The P4IS aggregates were estimated to be composed of single polymer chains. Adsorption of P4IS onto GNPs in a PS matrix was determined to be energetically viable via molecular dynamics simulations. Furthermore, the preferred morphologies of the P4IS polymer chains on the GNPs were analyzed based on the conformational entropy of the polymer chains. The characteristics of polymer chains adsorbed on inorganic NPs were clarified in this study, and they are essential in controlling the performance of polymer nanocomposites at the molecular level.
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We would like to thank American Journal Experts (www.aje.com) for English language editing. This study was supported by the Advanced Imaging and Modeling Center for Soft-materials (Tohoku AIMcS), Tohoku University Microstructural Characterization Platform in Nanotechnology Platform Project sponsored by the Ministry of Education, Culture, Sports, Science, and Technology (MEXT), Japan [JPMX09F(A)-20-TU-0001], Japan Society for the Promotion of Science (JSPS) KAKENHI, Japan [grant numbers 19H00905 and 20K15330], Japan Science and Technology Agency (JST) CREST, Japan [grant numbers JPMJCR1993 and JPMJCR19T4], and IMRAM project [TM, 2021].
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Miyata, T., Kawagoe, Y., Okabe, T. et al. Morphologies of polymer chains adsorbed on inorganic nanoparticles in a polymer composite as revealed by atomic-resolution electron microscopy. Polym J 54, 1297–1306 (2022). https://doi.org/10.1038/s41428-022-00690-4