The use of carbon nanotubes (CNTs) is promising for ultrahigh-strength composite materials with tunable electrical and thermal properties. Noncovalent polymer wrapping onto CNTs has proven effective to reduce bundling and improve the dispersion in solvents and polymer matrices. However, the mechanisms of CNTampersand-flag-changeminus;polymer wrapping are unclear. In this study, extensive replica exchange molecular dynamics simulations in atomic resolution (interface force field (IFF)ampersand-flag-changeminus;polymer consistent force field (PCFF)) were used to characterize the interaction of syndiotactic poly(methyl acrylate) (PMA) with 13 different CNTs of diverse diameter and chirality across a temperature range of ampersand-flag-changeminus;50 to 100 ampersand-flag-changedeg;C in the absence of solvent. The resulting polymer conformations on the CNTs were classified into extended, random coil, folded, and wrapped states. Binding free energies were favorable in a range of 0 to ampersand-flag-changeminus;2.7 kcal/mol monomer. The binding strength increased for larger CNT diameter and origins of conformation transitions and coexistence are analyzed. Extended conformations were least stable in all cases, and the CNT diameter as well as the chiral angle determined the driving forces toward random coil, folded, or wrapped structures. The findings agree with experimental tests of PMA/CNT films in solution and X-ray data. Follow-on studies may screen a wide range of polymers in melts and solutions to tailor the properties of CNT dispersions and composites.
