Conformational Changes and Dynamics during Adsorption of Macromolecules with Different Degree of Polymerization Studied by Monte Carlo Simulations.

Abstract: Dynamics of multilayer adsorption of macromolecules with different degree of polymerization is studied by coarse‐grained Monte Carlo simulations, focusing on both the interface macromolecule‐surface and chain–chain interaction in and out of equilibrium conditions. The interfacial interaction between the solid flat surface and the macromolecules is modeled by means of a Lennard–Jones potential, and inter‐ and intrachain interactions are simulated using bond angle, bond length, and Lennard–Jones potentials. The results show that local and conformational motions near the glass transition temperature promote configurations with minimal energy, which induce better space efficiency and favor aligned conformations at the interface. In this context, it is also found that restriction of movement, together with the connectivity effect exerted by the partially adsorbed segments, leads to a range of chain lengths that maximizes the molecular groups adsorbed. [ABSTRACT FROM AUTHOR]