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This study examines nanoparticle diffusion in crowded polymer nanocomposites by diffusing small Al2O3 nanoparticles (NPs) in SiO2-loaded P2VP matrices. Time-of-flight secondary ion mass spectroscopy (ToF-SIMS) measures Al2O3 NP diffusion coefficients within a homogeneous PNC background of larger, immobile SiO2 NPs. By developing a geometric model for the average interparticle distance in a system with two NP sizes, we quantify nanocomposite confinement relative to the Al2O3 NP size with a bound layer. At low SiO2 concentrations, Al2O3 NP diffusion aligns with the neat polymer results. In more crowded nanocomposites with higher SiO2 concentrations where the interparticle distance approaches the size of the mobile Al2O3 NP, the 6.5 nm Al2O3 NPs diffuse faster than predicted by both core–shell and vehicular diffusion models. Relative to our previous studies of NPs diffusing into polymers, these findings demonstrate that the local environment in crowded systems significantly complicates NP diffusion behavior and the bound layer lifetimes.
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Detecting bound polymer layers in attractive polymer–nanoparticle hybrids
When polymer–nanoparticle (NP) attractions are sufficiently strong, a bound polymer layer with a distinct dynamic signature spontaneously forms at the NP interface. A similar phenomenon occurs near a fixed attractive substrate for thin polymer films. While our previous simulations fixed the NPs to examine the dilute limit, here, we allow the NP to move. Our goal is to investigate how NP mobility affects the signature of the bound layer. For small NPs that are relatively mobile, the bound layer is slaved to the motion of the NP, and the signature of the bound layer relaxation in the intermediate scattering function essentially disappears. The slow relaxation of the bound layer can be recovered when the scattering function is measured in the NP reference frame, but this process would be challenging to implement in experimental systems with multiple NPs. Instead, we use the counterintuitive result that the NP mass affects its mobility in the nanoscale limit, along with the more expected result that the bound layer increases the effective NP mass, to suggest that the signature of the bound polymer manifests as a change in NP diffusivity. These findings allow us to rationalize and quantitatively understand the results of recent experiments focused on measuring NP diffusivity with either physically adsorbed or chemically end-grafted chains.
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- Award ID(s):
- 1709061
- PAR ID:
- 10319844
- Date Published:
- Journal Name:
- Nanoscale
- Volume:
- 13
- Issue:
- 30
- ISSN:
- 2040-3364
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1NR02395K
