Entropy-favorable adsorption of polymer-grafted nanoparticles at fluid-fluid interfaces

• Published in: The Journal of chemical physics Vol. 161; no. 9
• Main Authors: Li, Bing, Zhang, Pei-Lei, Sun, Zhao-Yan
• Format: Journal Article
• Language: English
• Published: United States 07.09.2024
• ISSN: 1089-7690
• DOI: 10.1063/5.0230107

The adsorption of polymer-grafted nanoparticles at interfaces is a problem of fundamental interest in physics and soft materials. This adsorption behavior is governed by the interplay between interaction potentials and entropic effects. Here, we use molecular dynamics simulations and umbrella sampling methods to study the adsorption behavior of a Janus-like homopolymer-grafted nanoparticle at fluid-fluid interfaces. By calculating the potential of the mean force as the particle moves from fluid A to the interface, the adsorption energy Ea can be obtained. When two homopolymer chains with types A and B are grafted to the opposite poles of the particle, Ea shows a scaling behavior with respect to chain length N: Ea ∝ N0.598. This is determined by the interactions between polymers and fluids. The enthalpy dominates, and the entropy effects mainly come from the rotational entropy loss of the polymer-grafted nanoparticle at interfaces, which disfavors the stabilization of particles at interfaces. When the grafted polymer number m is large, the adsorption energy exhibits a linear dependence on m. While the enthalpy dominates the behavior, the entropy becomes significant at a larger chain length of N = 15, where the configurational entropy of the polymer chains dominates the entropy of the system. The globule-coil transition occurs when polymers move from poor solvents to good solvents, increasing the configurational entropy and favoring the stabilization of particles at interfaces. Our study provides novel insights into the stabilization mechanism of polymer-grafted nanoparticles at interfaces and reveals the stabilization mechanism favored by the configurational entropy of grafted polymer chains.