Polymer solution structure and dynamics within pores of hexagonally close-packed nanoparticles
| Author(s) | Heil, Christian M. | |
| Author(s) | Jayaraman, Arthi | |
| Date Accessioned | 2022-12-20T21:32:10Z | |
| Date Available | 2022-12-20T21:32:10Z | |
| Publication Date | 2022-10-20 | |
| Description | This article was originally published in Soft Matter. The version of record is available at: DOI https://doi.org/10.1039/D2SM01102F. This article will be embargoed until 10/20/2023. | |
| Abstract | Using coarse-grained molecular dynamics simulations, we examine structure and dynamics of polymer solutions under confinement within the pores of a hexagonally close-packed (HCP) nanoparticle system with nanoparticle diameter fifty times that of the polymer Kuhn segment size. We model a condition where the polymer chain is in a good solvent (i.e., polymer–polymer interaction is purely repulsive and polymer–solvent and solvent–solvent interactions are attractive) and the polymer–nanoparticle and solvent–nanoparticle interactions are purely repulsive. We probe three polymer lengths (N = 10, 114, and 228 Kuhn segments) and three solution concentrations (1, 10, and 25%v) to understand how the polymer chain conformations and chain center-of-mass diffusion change under confinement within the pores of the HCP nanoparticle structure from those seen in bulk. The known trend of bulk polymer Rg2 decreasing with increasing concentration no longer holds when confined in the pores of HCP nanoparticle structure; for example, for the 114-mer, the HCP 〈Rg2〉 at 1%v concentration is lower than HCP 〈Rg2〉 at 10%v concentration. The 〈Rg2〉 of the 114-mer and 228-mer exhibit the largest percent decline going from bulk to HCP at the 1%v concentration and the smallest percent decline at the 25%v concentration. We also provide insight into how the confinement ratio (CR) of polymer chain size to pore size within tetrahedral and octahedral pores in the HCP arrangement of nanoparticles affects the chain conformation and diffusion at various concentrations. At the same concentration, the N = 114 has significantly more movement between pores than the N = 228 chains. For the N = 114 polymer, the diffusion between pores (i.e., inter-pore diffusion) accelerates the overall diffusion rate for the confined HCP system while for the N = 228 polymer, the polymer diffusion in the entire HCP is dominated by the diffusion within the tetrahedral or octahedral pores with minor contributions from inter-pore diffusion. These findings augment the fundamental understanding of macromolecular diffusion through large, densely packed nanoparticle assemblies and are relevant to research focused on fabrication of polymer composite materials for chemical separations, storage, optics, and photonics. We perform coarse-grained molecular dynamics simulations to understand structure and dynamics of polymer solutions under confinement within hexagonal close packed nanoparticles with radii much larger than the polymer chain's bulk radius of gyration. | |
| Sponsor | C. M. H. and A. J. acknowledge financial support from the Air Force Office of Scientific Research (MURI-FA 9550-18-1-0142). This work was supported with computational resources from the University of Delaware (Caviness and DARWIN clusters) and the Extreme Science and Engineering Discovery Environment (XSEDE) (NSF grant ACI-1548562) Bridges-2 cluster (allocation MCB100140), which is supported by NSF award ACI-1928147. C. M. H. and A. J. also acknowledge J. Gilchrist (Lehigh University), R. Krishnamoorti (University of Houston), and R. Riggleman (University of Pennsylvania) for their valuable technical input on this work. | |
| Citation | Heil, Christian M., and Arthi Jayaraman. “Polymer Solution Structure and Dynamics within Pores of Hexagonally Close-Packed Nanoparticles.” Soft Matter 18, no. 42 (2022): 8175–87. https://doi.org/10.1039/D2SM01102F. | |
| ISSN | 1744-6848 | |
| URL | https://udspace.udel.edu/handle/19716/31835 | |
| Language | en_US | |
| Publisher | Soft Matter | |
| Title | Polymer solution structure and dynamics within pores of hexagonally close-packed nanoparticles | |
| Type | Article |
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