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Title: Fluctuation Effects on the Brush Structure of Mixed Brush Nanoparticles in Solution

Abstract

A potentially attractive way to control nanoparticle assembly is to graft one or more polymers on the nanoparticle, to control the nanoparticle–nanoparticle interactions. When two immiscible polymers are grafted on the nanoparticle, they can microphase separate to form domains at the nanoparticle surface. Here, we computationally investigate the phase behavior of such binary mixed brush nanoparticles in solution, across a large and experimentally relevant parameter space. Specifically, we calculate the mean-field phase diagram, assuming uniform grafting of the two polymers, as a function of the nanoparticle size relative to the length of the grafted chains, the grafting density, the enthalpic repulsion between the grafted chains, and the solvent quality. We find a variety of phases including a Janus phase and phases with varying numbers of striped domains. Using a nonuniform, random distribution of grafting sites on the nanoparticle instead of the uniform distribution leads to the development of defects in the mixed brush structures. Introducing fluctuations as well leads to increasingly defective structures for the striped phases. Furthermore, we find that the simple Janus phase is preserved in all calculations, even with the introduction of nonuniform grafting and fluctuations. We conclude that the formation of the Janus phase is moremore » realistic experimentally than is the formation of defect-free multivalent mixed brush nanoparticles.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1499037
Report Number(s):
SAND-2019-2234J
Journal ID: ISSN 1936-0851; 673000
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 12; Journal Issue: 2; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; brush structure; field theory; mixed brush; nonuniform grafting; polymer nanocomposites; polymers; thermal fluctuations

Citation Formats

Koski, Jason P., and Frischknecht, Amalie L.. Fluctuation Effects on the Brush Structure of Mixed Brush Nanoparticles in Solution. United States: N. p., 2018. Web. https://doi.org/10.1021/acsnano.7b08271.
Koski, Jason P., & Frischknecht, Amalie L.. Fluctuation Effects on the Brush Structure of Mixed Brush Nanoparticles in Solution. United States. https://doi.org/10.1021/acsnano.7b08271
Koski, Jason P., and Frischknecht, Amalie L.. Thu . "Fluctuation Effects on the Brush Structure of Mixed Brush Nanoparticles in Solution". United States. https://doi.org/10.1021/acsnano.7b08271. https://www.osti.gov/servlets/purl/1499037.
@article{osti_1499037,
title = {Fluctuation Effects on the Brush Structure of Mixed Brush Nanoparticles in Solution},
author = {Koski, Jason P. and Frischknecht, Amalie L.},
abstractNote = {A potentially attractive way to control nanoparticle assembly is to graft one or more polymers on the nanoparticle, to control the nanoparticle–nanoparticle interactions. When two immiscible polymers are grafted on the nanoparticle, they can microphase separate to form domains at the nanoparticle surface. Here, we computationally investigate the phase behavior of such binary mixed brush nanoparticles in solution, across a large and experimentally relevant parameter space. Specifically, we calculate the mean-field phase diagram, assuming uniform grafting of the two polymers, as a function of the nanoparticle size relative to the length of the grafted chains, the grafting density, the enthalpic repulsion between the grafted chains, and the solvent quality. We find a variety of phases including a Janus phase and phases with varying numbers of striped domains. Using a nonuniform, random distribution of grafting sites on the nanoparticle instead of the uniform distribution leads to the development of defects in the mixed brush structures. Introducing fluctuations as well leads to increasingly defective structures for the striped phases. Furthermore, we find that the simple Janus phase is preserved in all calculations, even with the introduction of nonuniform grafting and fluctuations. We conclude that the formation of the Janus phase is more realistic experimentally than is the formation of defect-free multivalent mixed brush nanoparticles.},
doi = {10.1021/acsnano.7b08271},
journal = {ACS Nano},
number = 2,
volume = 12,
place = {United States},
year = {2018},
month = {1}
}

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Cited by: 11 works
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Works referenced in this record:

Polymer Brushes for Surface Tuning: Polymer Brushes for Surface Tuning
journal, May 2009

  • Uhlmann, Petra; Merlitz, Holger; Sommer, Jens-Uwe
  • Macromolecular Rapid Communications, Vol. 30, Issue 9-10
  • DOI: 10.1002/marc.200900113

Mixed Polymer Brush-Grafted Particles: A New Class of Environmentally Responsive Nanostructured Materials
journal, December 2009


Emerging applications of stimuli-responsive polymer materials
journal, January 2010

  • Stuart, Martien A. Cohen; Huck, Wilhelm T. S.; Genzer, Jan
  • Nature Materials, Vol. 9, Issue 2, p. 101-113
  • DOI: 10.1038/nmat2614

Stimuli-Responsive Colloidal Systems from Mixed Brush-Coated Nanoparticles
journal, August 2007

  • Motornov, M.; Sheparovych, Ro.; Lupitskyy, R.
  • Advanced Functional Materials, Vol. 17, Issue 14
  • DOI: 10.1002/adfm.200600934

Nanocomposites with Polymer Grafted Nanoparticles
journal, April 2013

  • Kumar, Sanat K.; Jouault, Nicolas; Benicewicz, Brian
  • Macromolecules, Vol. 46, Issue 9
  • DOI: 10.1021/ma4001385

Engineering the Assembly of Gold Nanorods in Polymer Matrices
journal, January 2016


Entropy-Mediated Patterning of Surfactant-Coated Nanoparticles and Surfaces
journal, November 2007


Size Limitations for the Formation of Ordered Striped Nanoparticles
journal, January 2008

  • Carney, Randy P.; DeVries, Gretchen A.; Dubois, Cedric
  • Journal of the American Chemical Society, Vol. 130, Issue 3
  • DOI: 10.1021/ja077383m

Atomistic Simulation Study of Striped Phase Separation in Mixed-Ligand Self-Assembled Monolayer Coated Nanoparticles
journal, October 2010

  • Ghorai, Pradip Kr.; Glotzer, Sharon C.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 45
  • DOI: 10.1021/jp105013k

Amphiphilicity-Driven Organization of Nanoparticles into Discrete Assemblies
journal, November 2006

  • Zubarev, Eugene R.; Xu, Jun; Sayyad, Arshad
  • Journal of the American Chemical Society, Vol. 128, Issue 47
  • DOI: 10.1021/ja066708g

Plasmonic Vesicles of Amphiphilic Gold Nanocrystals: Self-Assembly and External-Stimuli-Triggered Destruction
journal, July 2011

  • Song, Jibin; Cheng, Lin; Liu, Aiping
  • Journal of the American Chemical Society, Vol. 133, Issue 28
  • DOI: 10.1021/ja204387w

Phase diagram of a mixed polymer brush
journal, February 2002


Lateral versus Perpendicular Segregation in Mixed Polymer Brushes
journal, January 2002


Bidisperse Mixed Brushes:  Synthesis and Study of Segregation in Selective Solvent
journal, September 2003

  • Minko, Sergiy; Luzinov, Igor; Luchnikov, Valeriy
  • Macromolecules, Vol. 36, Issue 19
  • DOI: 10.1021/ma034160h

Self-consistent field simulations of self- and directed-assembly in a mixed polymer brush
journal, January 2011

  • Hur, Su-Mi; Frischknecht, Amalie L.; Huber, Dale L.
  • Soft Matter, Vol. 7, Issue 19
  • DOI: 10.1039/c1sm05747b

Exploring Lateral Microphase Separation in Mixed Polymer Brushes by Experiment and Self-Consistent Field Theory Simulations
journal, December 2011

  • Price, Andrew D.; Hur, Su-Mi; Fredrickson, Glenn H.
  • Macromolecules, Vol. 45, Issue 1
  • DOI: 10.1021/ma202542u

Reorganization of Binary Polymer Brushes:  Reversible Switching of Surface Microstructures and Nanomechanical Properties
journal, September 2003

  • Lemieux, M.; Usov, D.; Minko, S.
  • Macromolecules, Vol. 36, Issue 19
  • DOI: 10.1021/ma034634c

Memory of Surface Patterns in Mixed Polymer Brushes:  Simulation and Experiment
journal, December 2006

  • Santer, Svetlana; Kopyshev, Alexey; Donges, Jörn
  • Langmuir, Vol. 23, Issue 1
  • DOI: 10.1021/la0629577

How does the pattern of grafting points influence the structure of one-component and mixed polymer brushes?
journal, August 2005


Self-assembly in a mixed polymer brush with inhomogeneous grafting density composition
journal, January 2013

  • Hur, Su-Mi; Frischknecht, Amalie L.; Huber, Dale L.
  • Soft Matter, Vol. 9, Issue 22
  • DOI: 10.1039/c3sm50173f

Nanoscale Phase Behavior of Mixed Polymer Ligands on a Gold Nanoparticle Surface
journal, March 2015


Predicting the structure and interfacial activity of diblock brush, mixed brush, and Janus-grafted nanoparticles
journal, January 2015

  • Koski, Jason; Chao, Huikuan; Riggleman, Robert A.
  • Chemical Communications, Vol. 51, Issue 25
  • DOI: 10.1039/C4CC08659G

Soft Nanopolyhedra as a Route to Multivalent Nanoparticles
journal, June 2006


Mixed homopolymer brushes grafted onto a nanosphere
journal, April 2011

  • Wang, Yueqiang; Yang, Guang; Tang, Ping
  • The Journal of Chemical Physics, Vol. 134, Issue 13
  • DOI: 10.1063/1.3575180

Binary mixed homopolymer brushes grafted on nanorod particles: A self-consistent field theory study
journal, December 2013

  • Ma, Xin; Yang, Yingzi; Zhu, Lei
  • The Journal of Chemical Physics, Vol. 139, Issue 21
  • DOI: 10.1063/1.4832742

Hierarchical Superstructures Assembled by Binary Hairy Nanoparticles
journal, May 2016


Recent Developments in Fully Fluctuating Field-Theoretic Simulations of Polymer Melts and Solutions
journal, July 2016

  • Delaney, Kris T.; Fredrickson, Glenn H.
  • The Journal of Physical Chemistry B, Vol. 120, Issue 31
  • DOI: 10.1021/acs.jpcb.6b05704

Dynamics of polymers: A mean-field theory
journal, February 2014

  • Fredrickson, Glenn H.; Orland, Henri
  • The Journal of Chemical Physics, Vol. 140, Issue 8
  • DOI: 10.1063/1.4865911

Solvent vapor annealing in block copolymer nanocomposite films: a dynamic mean field approach
journal, January 2017

  • Chao, Huikuan; Koski, Jason; Riggleman, Robert A.
  • Soft Matter, Vol. 13, Issue 1
  • DOI: 10.1039/C6SM00770H

Grafted polymer chains suppress nanoparticle diffusion in athermal polymer melts
journal, May 2017

  • Lin, Chia-Chun; Griffin, Philip J.; Chao, Huikuan
  • The Journal of Chemical Physics, Vol. 146, Issue 20
  • DOI: 10.1063/1.4982216

Field theoretic simulations of polymer nanocomposites
journal, December 2013

  • Koski, Jason; Chao, Huikuan; Riggleman, Robert A.
  • The Journal of Chemical Physics, Vol. 139, Issue 24
  • DOI: 10.1063/1.4853755

Comparison of Field-Theoretic Approaches in Predicting Polymer Nanocomposite Phase Behavior
journal, October 2017


Self-consistent field theory for diblock copolymers grafted to a sphere
journal, January 2011

  • Vorselaars, Bart; Kim, Jaeup U.; Chantawansri, Tanya L.
  • Soft Matter, Vol. 7, Issue 11
  • DOI: 10.1039/c0sm01242d

Numerical Solutions of the Complex Langevin Equations in Polymer Field Theory
journal, January 2008

  • Lennon, Erin M.; Mohler, George O.; Ceniceros, Hector D.
  • Multiscale Modeling & Simulation, Vol. 6, Issue 4
  • DOI: 10.1137/070689401

How to mesh up Ewald sums. I. A theoretical and numerical comparison of various particle mesh routines
journal, November 1998

  • Deserno, Markus; Holm, Christian
  • The Journal of Chemical Physics, Vol. 109, Issue 18
  • DOI: 10.1063/1.477414

Efficient field-theoretic simulation of polymer solutions
journal, December 2014

  • Villet, Michael C.; Fredrickson, Glenn H.
  • The Journal of Chemical Physics, Vol. 141, Issue 22
  • DOI: 10.1063/1.4902886

A simple and effective Verlet-type algorithm for simulating Langevin dynamics
journal, January 2013


    Works referencing / citing this record:

    Polymer-guided assembly of inorganic nanoparticles
    journal, January 2020

    • Yi, Chenglin; Yang, Yiqun; Liu, Ben
    • Chemical Society Reviews, Vol. 49, Issue 2
    • DOI: 10.1039/c9cs00725c

    Predicting the effect of chain-length mismatch on phase separation in noble metal nanoparticle monolayers with chemically mismatched ligands
    journal, January 2019

    • Merz, Steven N.; Hoover, Elise; Egorov, Sergei A.
    • Soft Matter, Vol. 15, Issue 22
    • DOI: 10.1039/c9sm00264b

    Phase separation in mixed polymer brushes on nanoparticle surfaces enables the generation of anisotropic nanoarchitectures
    journal, January 2018

    • Rossner, Christian; Tang, Qiyun; Müller, Marcus
    • Soft Matter, Vol. 14, Issue 22
    • DOI: 10.1039/c8sm00545a

    Versatile fabrication of patchy nanoparticles via patterning of grafted diblock copolymers on NP surface
    journal, January 2019

    • Yu, Linxiuzi; Shi, Rui; Qian, Hu-Jun
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 3
    • DOI: 10.1039/c8cp06699j