Dynamics of Polymer Films on Polymer-Grafted Substrates: A Molecular Dynamics Simulation

• Published in: Langmuir 2024-10, Vol.40 (43), p.22997-23006
• Main Authors: Yang, Jie, Wang, Zhunpeng, Huang, Jianhua
• Format: Article
• Language: English
• Subjects: diffusivity; molecular dynamics; polymers
• ISSN: 0743-7463; 1520-5827; 1520-5827
• DOI: 10.1021/acs.langmuir.4c03168

For substrate-supported polymer films, the tails of adsorbed chains are generally assumed to play important roles in the propagation of the substrate’s effect inside polymer films. The effects of the grafting density and the rigidity of substrate-grafted polymers, the simplest model for the adsorbed tails, on the diffusivity of film polymers are investigated by performing molecular dynamics simulations. An optimal grafting density σo, around the critical grafting density for the transition from “mushroom” to “brush”, is found with the most pronounced suppression of diffusivity on the film polymers; i.e., the penetration of the film polymers into the grafting layer reaches the maximum. However, at high grafting density, the crowded and vertically stretched brush excludes the coil-like film polymers, and the suppression is thus reduced. At σo, with an increase in the rigidity of the grafted polymers, the suppression is increased quickly at low rigidity but slowly at high rigidity. The dynamic suppression is attributed to the combination of the conformation change from stretching at low rigidity to tilted orientation at high rigidity and decelerated mobility induced by the rigidity. The stretching conformation enhances, whereas the tilted conformation weakens the interpenetration between the grafted polymers and the film polymers. Our results reflect the importance of both conformational variation and interchain interaction in the interface region.