Molecular Dynamics and Structure of Poly(Methyl Methacrylate) Chains Grafted from Barium Titanate Nanoparticles

• Published in: Molecules (Basel, Switzerland) Switzerland), 2022-09, Vol.27 (19), p.6372
• Main Authors: Wypych-Puszkarz, Aleksandra, Cetinkaya, Onur, Yan, Jiajun, Udovytska, Ruslana, Jung, Jarosław, Jenczyk, Jacek, Nowaczyk, Grzegorz, Jurga, Stefan, Ulański, Jacek, Matyjaszewski, Krzysztof, Pietrasik, Joanna, Kozanecki, Marcin
• Format: Article
• Language: English
• Subjects: Barium; Barium titanates; Broadband; Calorimetry; Chains (polymeric); Dielectric properties; Differential scanning calorimetry; Glass transition temperature; Grafting; Inorganic materials; Low level; Molecular dynamics; Molecular structure; Molecular weight; Nanocomposites; Nanocrystals; Nanoparticles; NMR; Nuclear magnetic resonance; polymer brushes; Polymerization; Polymers; Spectrum analysis; Thermal stability; Transition temperatures; Transmission electron microscopy
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules27196372

Core−shell nanocomposites comprising barium titanate, BaTiO3 (BTO), and poly(methyl methacrylate) (PMMA) chains grafted from its surface with varied grafting densities were prepared. BTO nanocrystals are high-k inorganic materials, and the obtained nanocomposites exhibit enhanced dielectric permittivity, as compared to neat PMMA, and a relatively low level of loss tangent in a wide range of frequencies. The impact of the molecular dynamics, structure, and interactions of the BTO surface on the polymer chains was investigated. The nanocomposites were characterized by broadband dielectric and vibrational spectroscopies (IR and Raman), transmission electron microscopy, differential scanning calorimetry, and nuclear magnetic resonance. The presence of ceramic nanoparticles in core–shell composites slowed down the segmental dynamic of PMMA chains, increased glass transition temperature, and concurrently increased the thermal stability of the organic part. It was also evidenced that, in addition to segmental dynamics, local β relaxation was affected. The grafting density influenced the self-organization and interactions within the PMMA phase, affecting the organization on a smaller size scale of polymeric chains. This was explained by the interaction of the exposed surface of nanoparticles with polymer chains.