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Title: Understanding the Static Interfacial Polymer Layer by Exploring the Dispersion States of Nanocomposites

Abstract

The dynamic and static properties of the interfacial region between polymer and nanoparticles have wide-ranging consequences on performances of nanomaterials. The thickness and density of the static layer are particularly difficult to assess experimentally due to superimposing nanoparticle interactions. Here, we tune the dispersion of silica nanoparticles in nanocomposites by preadsorption of polymer layers in the precursor solutions, and by varying the molecular weight of the matrix chains. Nanocomposite structures ranging from ideal dispersion to repulsive order or various degrees of aggregation are generated and observed by small-angle scattering. Preadsorbed chains are found to promote ideal dispersion, before desorption in the late stages of nanocomposite formation. The microstructure of the interfacial polymer layer is characterized by detailed modeling of X-ray and neutron scattering. Only in ideally well-dispersed systems a static interfacial layer of reduced polymer density over a thickness of ca. 2 nm is evidenced based on the analysis with a form-free density profile optimized using numerical simulations. This interfacial gradient layer is found to be independent of the thickness of the initially adsorbed polymer, but appears to be generated by out-of-equilibrium packing and folding of the preadsorbed layer. The impact of annealing is investigated to study the approach ofmore » equilibrium, showing that initially ideally well-dispersed systems adopt a repulsive hard-sphere structure, while the static interfacial layer disappears. Furthermore, this study thus promotes the fundamental understanding of the interplay between effects which are decisive for macroscopic material properties: polymer-mediated interparticle interactions, and particle interfacial effects on the surrounding polymer.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [4]; ORCiD logo [4];  [5]; ORCiD logo [2];  [6]; ORCiD logo [4]; ORCiD logo [6]
+ Show Author Affiliations
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. de Montpellier, Montpellier (France)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of Tennessee, Knoxville, TN (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  5. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  6. Univ. de Montpellier, Montpellier (France)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1526380
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 11; Journal Issue: 19; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; polymer nanocomposites; interfacial layer; density gradient; nanoparticle dispersion; chain adsorption; small-angle scattering; reverse Monte Carlo

Citation Formats

Genix, Anne-Caroline, Bocharova, Vera, Carroll, Bobby, Lehmann, Michelle, Saito, Tomonori, Krueger, Susan, He, Lilin, Dieudonné-George, Philippe, Sokolov, Alexei P., and Oberdisse, Julian. Understanding the Static Interfacial Polymer Layer by Exploring the Dispersion States of Nanocomposites. United States: N. p., 2019. Web. doi:10.1021/acsami.9b04553.
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Genix, Anne-Caroline, Bocharova, Vera, Carroll, Bobby, Lehmann, Michelle, Saito, Tomonori, Krueger, Susan, He, Lilin, Dieudonné-George, Philippe, Sokolov, Alexei P., & Oberdisse, Julian. Understanding the Static Interfacial Polymer Layer by Exploring the Dispersion States of Nanocomposites. United States. https://doi.org/10.1021/acsami.9b04553
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Genix, Anne-Caroline, Bocharova, Vera, Carroll, Bobby, Lehmann, Michelle, Saito, Tomonori, Krueger, Susan, He, Lilin, Dieudonné-George, Philippe, Sokolov, Alexei P., and Oberdisse, Julian. Mon . "Understanding the Static Interfacial Polymer Layer by Exploring the Dispersion States of Nanocomposites". United States. https://doi.org/10.1021/acsami.9b04553. https://www.osti.gov/servlets/purl/1526380.
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@article{osti_1526380,
title = {Understanding the Static Interfacial Polymer Layer by Exploring the Dispersion States of Nanocomposites},
author = {Genix, Anne-Caroline and Bocharova, Vera and Carroll, Bobby and Lehmann, Michelle and Saito, Tomonori and Krueger, Susan and He, Lilin and Dieudonné-George, Philippe and Sokolov, Alexei P. and Oberdisse, Julian},
abstractNote = {The dynamic and static properties of the interfacial region between polymer and nanoparticles have wide-ranging consequences on performances of nanomaterials. The thickness and density of the static layer are particularly difficult to assess experimentally due to superimposing nanoparticle interactions. Here, we tune the dispersion of silica nanoparticles in nanocomposites by preadsorption of polymer layers in the precursor solutions, and by varying the molecular weight of the matrix chains. Nanocomposite structures ranging from ideal dispersion to repulsive order or various degrees of aggregation are generated and observed by small-angle scattering. Preadsorbed chains are found to promote ideal dispersion, before desorption in the late stages of nanocomposite formation. The microstructure of the interfacial polymer layer is characterized by detailed modeling of X-ray and neutron scattering. Only in ideally well-dispersed systems a static interfacial layer of reduced polymer density over a thickness of ca. 2 nm is evidenced based on the analysis with a form-free density profile optimized using numerical simulations. This interfacial gradient layer is found to be independent of the thickness of the initially adsorbed polymer, but appears to be generated by out-of-equilibrium packing and folding of the preadsorbed layer. The impact of annealing is investigated to study the approach of equilibrium, showing that initially ideally well-dispersed systems adopt a repulsive hard-sphere structure, while the static interfacial layer disappears. Furthermore, this study thus promotes the fundamental understanding of the interplay between effects which are decisive for macroscopic material properties: polymer-mediated interparticle interactions, and particle interfacial effects on the surrounding polymer.},
doi = {10.1021/acsami.9b04553},
journal = {ACS Applied Materials and Interfaces},
number = 19,
volume = 11,
place = {United States},
year = {Mon Apr 22 00:00:00 EDT 2019},
month = {Mon Apr 22 00:00:00 EDT 2019}
}
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https://doi.org/10.1021/acsami.9b04553
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