Harnessing interfacial entropic effects in polymer grafted nanoparticle composites for tailoring their...

Nanocomposites based on polymeric materials have been extensively studied to understand and control the thermodynamics, flow, and mechanical properties of the underlying matrix as well to create new materials with diverse optical, electrical, magnetic, separation, catalytic, and biomedical properties. In the form of thin films or membranes, such materials can impart remarkable improvements in various properties of the underlying substrates. Using nanoparticles with grafted polymer chains usually overcomes a major hurdle in achieving enhancements in various properties by enabling better dispersion in the matrix while at the same time introducing a new parameter - interfacial entropy - leading to the emergence of new parameter space for tuning dispersion, flow and thermal properties. In this article, we highlight how this interfacial entropic effect can be harnessed to control various properties in thin films and membranes of grafted nanoparticle composites, in particular their thermo-mechanical properties, viscosity, fragility, glass transition temperature (T_g), and dynamic heterogeneity as well as their ability to act as highly selective gas separation and water desalination membranes. We discuss the application of a range of experimental techniques as well as molecular dynamics simulation to extract these properties and obtain microscopic insight into how the interplay of various surface and interfacial effects lies at the centre of these significant property improvements and enhanced functionality. Finally, we provide an outlook on future opportunities for designing sustainable PNCs, emphasizing their potential in environmental, energy, and biomedical applications, with advanced experiments and modelling driving further innovations.