The Interplay of Polymer Bridging and Entanglement in Toughening Polymer-Infiltrated Nanoparticle Films

Polymer-nanoparticle composite films (PNCFs) with high loadings of nanoparticles (NPs) (>50 vol %) have applications in multiple areas, and an understanding of their mechanical properties is essential for their broader use. The high-volume fraction and small size of the NPs lead to physical confinement of the polymers that can drastically change the properties of polymers relative to the bulk. We investigate the fracture behavior of a class of highly loaded PNCFs prepared by polymer infiltration into NP packings. These polymer-infiltrated nanoparticle films (PINFs) have applications as multifunctional coatings and membranes and provide a platform to understand the behavior of polymers that are highly confined. Here, the extent of confinement in PINFs is tuned from 0.1 to 44 and the fracture toughness of PINFs is increased by up to a factor of 12 by varying the molecular weight of the polymers over 3 orders of magnitude and using NPs with diameters ranging from 9 to 100 nm. The results show that brittle, low molecular weight (MW) polymers can significantly toughen NP packings, and this toughening effect becomes less pronounced with increasing NP size. In contrast, high MW polymers capable of forming interchain entanglements are more effective in toughening large NP packings. We propose that confinement has competing effects of polymer bridging increasing toughness and chain disentanglement decreasing toughness. These findings provide insight into the fracture behavior of confined polymers and will guide the development of mechanically robust PINFs as well as other highly loaded PNCFs.