Effect of Surface Modification on Water Adsorption and Interfacial Mechanics of Cellulose Nanocrystals

With increasing environmental concerns about petrochemical-based materials, the development of high-performance polymer nanocomposites with sustainable filler phases has attracted significant attention. Cellulose nanocrystals (CNCs) are promising nanocomposite reinforcing agents due to their exceptional mechanical properties, low weight, and bioavailability. However, there are still numerous obstacles that prevent these materials from achieving optimal performance, including high water adsorption, poor nanoparticle dispersion, and filler properties that vary in response to moisture. Surface modification is an effective method to mitigate these shortcomings. We use computational approaches to obtain direct insight into the water adsorption and interfacial mechanics of modified CNC surfaces. Atomistic grand-canonical Monte Carlo simulations demonstrate how surface modification of sulfated Na-CNCs impacts water adsorption. We find that methyl­(triphenyl)­phosphonium (MePh₃P⁺)-exchanged CNCs have lower water uptake than Na-CNCs, supporting experimental dynamic vapor sorption measurements. The adsorbed water molecules show orientational ordering when distributed around the cations. Steered molecular dynamics simulations quantify traction–separation behavior of CNC–CNC interfaces. We find that exchanging sodium for MePh₃P⁺ effectively changes the surface hydrophilicity, which in turn directly impacts interfacial adhesion and traction–separation behavior. Our analysis provides guidelines for controlling moisture effects in cellulose nanocomposites and nanocellulose films through surface modifications.