Effects of Tethered Polymers on Dynamics of Nanoparticles in Unentangled Polymer Melts
Abstract
Polymer-tethered nanoparticles (NPs) are commonly added to a polymer matrix to improve the material properties. Critical to the fabrication and processing of such composites is the mobility of the tethered NPs. Here, we study the motion of tethered NPs in unentangled polymer melts using molecular dynamics simulations, which offer a precise control of the grafted chain length Ng and the number z of grafted chains per particle. As Ng increases, there is a crossover from particle-dominated to tethered-chain-dominated terminal diffusion of NPs with the same z. The mean squared displacement of loosely tethered NPs in the case of tethered-chain-dominated terminal diffusion exhibits two subdiffusive regimes at intermediate time scales for small z. The first one at shorter time scales arises from the dynamical coupling of the particle and matrix chains, while the one at longer time scales is due to the participation of the particle in the dynamics of the tethered chains. The friction of loosely grafted chains in unentangled melts scales linearly with the total number of monomers in the chains, as the friction of individual monomers is additive in the absence of hydrodynamic coupling. As more chains are grafted to a particle, hydrodynamic interactions between grafted chains emerge.more »
- Authors:
-
[1];
[2]
- Duke Univ., Durham, NC (United States)
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC); National Science Foundation (NSF); National Institutes of Health (NIH)
- OSTI Identifier:
- 1667398
- Report Number(s):
- SAND-2020-8598J
Journal ID: ISSN 0024-9297; 690047
- Grant/Contract Number:
- AC04-94AL85000; ACO2-05CH11231; NA-0003525; EFMA-1830957; P01-HL108808
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 53; Journal Issue: 16; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 42 ENGINEERING
Citation Formats
Ge, Ting, Rubinstein, Michael, and Grest, Gary S. Effects of Tethered Polymers on Dynamics of Nanoparticles in Unentangled Polymer Melts. United States: N. p., 2020.
Web. doi:10.1021/acs.macromol.9b01921.
Ge, Ting, Rubinstein, Michael, & Grest, Gary S. Effects of Tethered Polymers on Dynamics of Nanoparticles in Unentangled Polymer Melts. United States. https://doi.org/10.1021/acs.macromol.9b01921
Ge, Ting, Rubinstein, Michael, and Grest, Gary S. Wed .
"Effects of Tethered Polymers on Dynamics of Nanoparticles in Unentangled Polymer Melts". United States. https://doi.org/10.1021/acs.macromol.9b01921. https://www.osti.gov/servlets/purl/1667398.
@article{osti_1667398,
title = {Effects of Tethered Polymers on Dynamics of Nanoparticles in Unentangled Polymer Melts},
author = {Ge, Ting and Rubinstein, Michael and Grest, Gary S.},
abstractNote = {Polymer-tethered nanoparticles (NPs) are commonly added to a polymer matrix to improve the material properties. Critical to the fabrication and processing of such composites is the mobility of the tethered NPs. Here, we study the motion of tethered NPs in unentangled polymer melts using molecular dynamics simulations, which offer a precise control of the grafted chain length Ng and the number z of grafted chains per particle. As Ng increases, there is a crossover from particle-dominated to tethered-chain-dominated terminal diffusion of NPs with the same z. The mean squared displacement of loosely tethered NPs in the case of tethered-chain-dominated terminal diffusion exhibits two subdiffusive regimes at intermediate time scales for small z. The first one at shorter time scales arises from the dynamical coupling of the particle and matrix chains, while the one at longer time scales is due to the participation of the particle in the dynamics of the tethered chains. The friction of loosely grafted chains in unentangled melts scales linearly with the total number of monomers in the chains, as the friction of individual monomers is additive in the absence of hydrodynamic coupling. As more chains are grafted to a particle, hydrodynamic interactions between grafted chains emerge. As a result, there is a nondraining layer of hydrodynamically coupled chain segments surrounding the bare particle. Outside the nondraining layer is a free-draining layer of grafted chain segments with no hydrodynamic coupling. The boundary of the two layers is the stick surface where the shear stress due to the relative melt flow is balanced by the friction between the grafted and melt chains in the interpenetration layer. The stick surface is located further away from the bare surface of the particle with higher grafting density.},
doi = {10.1021/acs.macromol.9b01921},
journal = {Macromolecules},
number = 16,
volume = 53,
place = {United States},
year = {Wed Aug 05 00:00:00 EDT 2020},
month = {Wed Aug 05 00:00:00 EDT 2020}
}
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