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Title: Structure and phase behavior of polymer-linked colloidal gels

Abstract

Low-density “equilibrium” gels that consist of a percolated, kinetically arrested network of colloidal particles and are resilient to aging can be fabricated by restricting the number of effective bonds that form between the colloids. Valence-restricted patchy particles have long served as one archetypal example of such materials, but equilibrium gels can also be realized through a synthetically simpler and scalable strategy that introduces a secondary linker, such as a small ditopic molecule, to mediate the bonds between the colloids. Here, we consider the case where the ditopic linker molecules are low-molecular-weight polymers and demonstrate using a model colloid–polymer mixture how macroscopic properties such as the phase behavior as well as the microstructure of the gel can be designed through the polymer molecular weight and concentration. The low-density window for equilibrium gel formation is favorably expanded using longer linkers while necessarily increasing the spacing between all colloids. Furthermore, we show that blends of linkers with different sizes enable wider variation in microstructure for a given target phase behavior. Our computational study suggests a robust and tunable strategy for the experimental realization of equilibrium colloidal gels.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Texas, Austin, TX (United States)
  2. Univ. of Texas, Austin, TX (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF)
OSTI Identifier:
1599035
Report Number(s):
LA-UR-19-26202
Journal ID: ISSN 0021-9606; TRN: US2103751
Grant/Contract Number:  
89233218CNA000001; DMR-1720595; F-1696; F-1848
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 12; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Soft matter; Computer simulation; Gels; Rheology and fluid dynamics; Colloidal systems; Phase transitions; Complex fluids; Nanoparticles; Classical statistical mechanics; Polymers

Citation Formats

Howard, Michael P., Jadrich, Ryan Bradley, Lindquist, Beth Anne, Khabaz, Fardin, Bonnecaze, Roger T., Milliron, Delia J., and Truskett, Thomas M. Structure and phase behavior of polymer-linked colloidal gels. United States: N. p., 2019. Web. doi:10.1063/1.5119359.
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Howard, Michael P., Jadrich, Ryan Bradley, Lindquist, Beth Anne, Khabaz, Fardin, Bonnecaze, Roger T., Milliron, Delia J., & Truskett, Thomas M. Structure and phase behavior of polymer-linked colloidal gels. United States. https://doi.org/10.1063/1.5119359
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Howard, Michael P., Jadrich, Ryan Bradley, Lindquist, Beth Anne, Khabaz, Fardin, Bonnecaze, Roger T., Milliron, Delia J., and Truskett, Thomas M. Mon . "Structure and phase behavior of polymer-linked colloidal gels". United States. https://doi.org/10.1063/1.5119359. https://www.osti.gov/servlets/purl/1599035.
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@article{osti_1599035,
title = {Structure and phase behavior of polymer-linked colloidal gels},
author = {Howard, Michael P. and Jadrich, Ryan Bradley and Lindquist, Beth Anne and Khabaz, Fardin and Bonnecaze, Roger T. and Milliron, Delia J. and Truskett, Thomas M.},
abstractNote = {Low-density “equilibrium” gels that consist of a percolated, kinetically arrested network of colloidal particles and are resilient to aging can be fabricated by restricting the number of effective bonds that form between the colloids. Valence-restricted patchy particles have long served as one archetypal example of such materials, but equilibrium gels can also be realized through a synthetically simpler and scalable strategy that introduces a secondary linker, such as a small ditopic molecule, to mediate the bonds between the colloids. Here, we consider the case where the ditopic linker molecules are low-molecular-weight polymers and demonstrate using a model colloid–polymer mixture how macroscopic properties such as the phase behavior as well as the microstructure of the gel can be designed through the polymer molecular weight and concentration. The low-density window for equilibrium gel formation is favorably expanded using longer linkers while necessarily increasing the spacing between all colloids. Furthermore, we show that blends of linkers with different sizes enable wider variation in microstructure for a given target phase behavior. Our computational study suggests a robust and tunable strategy for the experimental realization of equilibrium colloidal gels.},
doi = {10.1063/1.5119359},
journal = {Journal of Chemical Physics},
number = 12,
volume = 151,
place = {United States},
year = {Mon Sep 23 00:00:00 EDT 2019},
month = {Mon Sep 23 00:00:00 EDT 2019}
}
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https://doi.org/10.1063/1.5119359
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    Using Patchy Particles to Prevent Local Rearrangements in Models of Non-equilibrium Colloidal Gels
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