Effects of interaction strength of associating groups on linear and star polymer dynamics
A small number of associating groups incorporated onto a polymer backbone have dramatic effects on the mobility and viscoelastic response of the macromolecules in melts. These associating groups assemble, driving the formation of clusters, whose lifetime affects the properties of the polymers. In this study, we probe the effects of the interaction strength on the structure and dynamics of two topologies, linear and star polymer melts, and further investigate blends of associative and non-associating polymers using molecular dynamics simulations. Polymer chains of approximately one entanglement length are described by a bead–spring model, and the associating groups are incorporated in the form of interacting beads with an interaction strength between them that is varied from 1 to 20 kBT. We find that, for all melts and blends, interaction of a few kBT between the associating groups drives cluster formation, where the size of the clusters increases with increasing interaction strength. These clusters act as physical crosslinkers, which slow the chain mobility. Blends of chains with and without associating groups macroscopically phase separate for interaction strength between the associating groups of a few kBT and above. For weakly interacting associating groups, the static structure function S(q) is well fit by functional form predicted by the random phase approximation where a clear deviation occurs as phase segregation takes place, providing a quantitative assessment of phase segregation.
- Research Organization:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Clemson Univ., SC (United States)
- Sponsoring Organization:
- USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- Grant/Contract Number:
- AC04-94AL85000; AC02-05CH11231; SC007908; NA0003525; MRI-1725573; SC0019284
- OSTI ID:
- 1770784
- Alternate ID(s):
- OSTI ID: 1765930; OSTI ID: 2299515
- Report Number(s):
- SAND-2021-2555J; 694485; TRN: US2208000
- Journal Information:
- Journal of Chemical Physics, Vol. 154, Issue 7; ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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