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Title: Soft Interactions Modify the Diffusive Dynamics of Polymer-Grafted Nanoparticles in Solutions of Free Polymer

Abstract

We examine the dynamics of silica particles grafted with high molecular weight polystyrene suspended in semidilute solutions of chemically similar linear polymer using X-ray photon correlation spectroscopy. The particle dynamics decouple from the bulk viscosity despite their large hydrodynamic size and instead experience an effective viscosity that depends on the molecular weight of the free polymer chains. Unlike for hard-sphere nanoparticles in semidilute polymer solutions, the diffusivities of the polymer-grafted nanoparticles do not collapse onto a master curve solely as a function of normalized length scales. Instead, the diffusivities can be collapsed across two orders of magnitude in free polymer molecular weight and concentration and one order of magnitude in grafted molecular weight by incorporating the ratio of free to grafted polymer molecular weights. These results suggest that the soft interaction potential between polymer-grafted nanoparticles and free polymer allows polymer-grafted nanoparticles to diffuse faster than predicted based on bulk rheology and modifies the coupling between grafted particle dynamics and the relaxations of the surrounding free polymer.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ, of Houston, Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Welch Foundation, Houston, TX (United States); National Science Foundation (NSF)
OSTI Identifier:
1559452
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Macro Letters
Additional Journal Information:
Journal Volume: 8; Journal Issue: 8; Journal ID: ISSN 2161-1653
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Poling-Skutvik, Ryan, Slim, Ali H., Narayanan, Suresh, Conrad, Jacinta C., and Krishnamoorti, Ramanan. Soft Interactions Modify the Diffusive Dynamics of Polymer-Grafted Nanoparticles in Solutions of Free Polymer. United States: N. p., 2019. Web. doi:10.1021/acsmacrolett.9b00294.
Poling-Skutvik, Ryan, Slim, Ali H., Narayanan, Suresh, Conrad, Jacinta C., & Krishnamoorti, Ramanan. Soft Interactions Modify the Diffusive Dynamics of Polymer-Grafted Nanoparticles in Solutions of Free Polymer. United States. doi:10.1021/acsmacrolett.9b00294.
Poling-Skutvik, Ryan, Slim, Ali H., Narayanan, Suresh, Conrad, Jacinta C., and Krishnamoorti, Ramanan. Tue . "Soft Interactions Modify the Diffusive Dynamics of Polymer-Grafted Nanoparticles in Solutions of Free Polymer". United States. doi:10.1021/acsmacrolett.9b00294. https://www.osti.gov/servlets/purl/1559452.
@article{osti_1559452,
title = {Soft Interactions Modify the Diffusive Dynamics of Polymer-Grafted Nanoparticles in Solutions of Free Polymer},
author = {Poling-Skutvik, Ryan and Slim, Ali H. and Narayanan, Suresh and Conrad, Jacinta C. and Krishnamoorti, Ramanan},
abstractNote = {We examine the dynamics of silica particles grafted with high molecular weight polystyrene suspended in semidilute solutions of chemically similar linear polymer using X-ray photon correlation spectroscopy. The particle dynamics decouple from the bulk viscosity despite their large hydrodynamic size and instead experience an effective viscosity that depends on the molecular weight of the free polymer chains. Unlike for hard-sphere nanoparticles in semidilute polymer solutions, the diffusivities of the polymer-grafted nanoparticles do not collapse onto a master curve solely as a function of normalized length scales. Instead, the diffusivities can be collapsed across two orders of magnitude in free polymer molecular weight and concentration and one order of magnitude in grafted molecular weight by incorporating the ratio of free to grafted polymer molecular weights. These results suggest that the soft interaction potential between polymer-grafted nanoparticles and free polymer allows polymer-grafted nanoparticles to diffuse faster than predicted based on bulk rheology and modifies the coupling between grafted particle dynamics and the relaxations of the surrounding free polymer.},
doi = {10.1021/acsmacrolett.9b00294},
journal = {ACS Macro Letters},
issn = {2161-1653},
number = 8,
volume = 8,
place = {United States},
year = {2019},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 5 works
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