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Title: Internal Microstructure Dictates Interactions of Polymer-grafted Nanoparticles in Solution

Abstract

Understanding the effects of polymer brush architecture on particle interactions in solution is requisite to enable the development of functional materials based on self-assembled polymer-grafted nanoparticles (GNPs). Static and dynamic light scattering of polystyrene-grafted silica particle solutions in toluene reveals that the pair interaction potential, inferred from the second virial coefficient, A2, is strongly affected by the grafting density, σ, and degree of polymerization, N, of tethered chains. In the limit of intermediate σ (~0.3 to 0.6 nm-2) and high N, A2 is positive and increases with N. This confirms the good solvent conditions and can be qualitatively rationalized on the basis of a pair interaction potential derived for grafted (brush) particles. In contrast, for high σ > 0.6 nm-2 and low N, A2 displays an unexpected reversal to negative values, thus indicating poor solvent conditions. These findings are rationalized by means of a simple analysis based on a coarse-grained brush potential, which balances the attractive core-core interactions and the excluded volume interactions imparted by the polymer grafts. The results suggest that the steric crowding of polymer ligands in dense GNP systems may fundamentally alter the interactions between brush particles in solution and highlight the crucial role of architecture (internalmore » microstructure) on the behavior of hybrid materials. The effect of grafting density also illustrates the opportunity to tailor the physical properties of hybrid materials by altering geometry (or architecture) rather than a variation of the chemical composition.« less

Authors:
 [1];  [2];  [1]; ORCiD logo [3];  [3];  [3]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [5]
+ Show Author Affiliations
  1. Univ. of Crete (Greece). Inst. of Electronic Structure and Laser. FORTH; Univ. of Crete (Greece). Dept. of Materials Science and Technology
  2. Univ. of Crete (Greece). Inst. of Electronic Structure and Laser. FORTH
  3. Carnegie Mellon Univ., Pittsburgh, PA (United States). Dept. of Materials Science and Engineering
  4. Carnegie Mellon Univ., Pittsburgh, PA (United States). Chemistry Dept.
  5. Max Planck Inst. for Polymer Research, Mainz (Germany)
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; European Research Council (ERC); US Air Force
OSTI Identifier:
1816664
Grant/Contract Number:  
SC0018784; 694977; FA8650-19-2-5209
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 54; Journal Issue: 15; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
42 ENGINEERING; 36 MATERIALS SCIENCE; hydrocarbons; nanoparticles; scattering; aromatic compounds; solvents

Citation Formats

Gury, Leo, Kamble, Samruddhi, Parisi, Daniele, Zhang, Jianan, Lee, Jaejun, Abdullah, Ayesha, Matyjaszewski, Krzysztof, Bockstaller, Michael R., Vlassopoulos, Dimitris, and Fytas, George. Internal Microstructure Dictates Interactions of Polymer-grafted Nanoparticles in Solution. United States: N. p., 2021. Web. doi:10.1021/acs.macromol.1c00907.
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Gury, Leo, Kamble, Samruddhi, Parisi, Daniele, Zhang, Jianan, Lee, Jaejun, Abdullah, Ayesha, Matyjaszewski, Krzysztof, Bockstaller, Michael R., Vlassopoulos, Dimitris, & Fytas, George. Internal Microstructure Dictates Interactions of Polymer-grafted Nanoparticles in Solution. United States. https://doi.org/10.1021/acs.macromol.1c00907
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Gury, Leo, Kamble, Samruddhi, Parisi, Daniele, Zhang, Jianan, Lee, Jaejun, Abdullah, Ayesha, Matyjaszewski, Krzysztof, Bockstaller, Michael R., Vlassopoulos, Dimitris, and Fytas, George. Wed . "Internal Microstructure Dictates Interactions of Polymer-grafted Nanoparticles in Solution". United States. https://doi.org/10.1021/acs.macromol.1c00907. https://www.osti.gov/servlets/purl/1816664.
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@article{osti_1816664,
title = {Internal Microstructure Dictates Interactions of Polymer-grafted Nanoparticles in Solution},
author = {Gury, Leo and Kamble, Samruddhi and Parisi, Daniele and Zhang, Jianan and Lee, Jaejun and Abdullah, Ayesha and Matyjaszewski, Krzysztof and Bockstaller, Michael R. and Vlassopoulos, Dimitris and Fytas, George},
abstractNote = {Understanding the effects of polymer brush architecture on particle interactions in solution is requisite to enable the development of functional materials based on self-assembled polymer-grafted nanoparticles (GNPs). Static and dynamic light scattering of polystyrene-grafted silica particle solutions in toluene reveals that the pair interaction potential, inferred from the second virial coefficient, A2, is strongly affected by the grafting density, σ, and degree of polymerization, N, of tethered chains. In the limit of intermediate σ (~0.3 to 0.6 nm-2) and high N, A2 is positive and increases with N. This confirms the good solvent conditions and can be qualitatively rationalized on the basis of a pair interaction potential derived for grafted (brush) particles. In contrast, for high σ > 0.6 nm-2 and low N, A2 displays an unexpected reversal to negative values, thus indicating poor solvent conditions. These findings are rationalized by means of a simple analysis based on a coarse-grained brush potential, which balances the attractive core-core interactions and the excluded volume interactions imparted by the polymer grafts. The results suggest that the steric crowding of polymer ligands in dense GNP systems may fundamentally alter the interactions between brush particles in solution and highlight the crucial role of architecture (internal microstructure) on the behavior of hybrid materials. The effect of grafting density also illustrates the opportunity to tailor the physical properties of hybrid materials by altering geometry (or architecture) rather than a variation of the chemical composition.},
doi = {10.1021/acs.macromol.1c00907},
journal = {Macromolecules},
number = 15,
volume = 54,
place = {United States},
year = {Wed Jul 28 00:00:00 EDT 2021},
month = {Wed Jul 28 00:00:00 EDT 2021}
}
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