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Title: Confined dynamics of grafted polymer chains in solutions of linear polymer

Abstract

We measure the dynamics of high molecular weight polystyrene grafted to silica nanoparticles dispersed in semidilute solutions of linear polymer. Structurally, the linear free chains do not penetrate the grafted corona but increase the osmotic pressure of the solution, collapsing the grafted polymer and leading to eventual aggregation of the grafted particles at high matrix concentrations. Dynamically, the relaxations of the grafted polymer are controlled by the solvent viscosity according to the Zimm model on short time scales. On longer time scales, the grafted chains are confined by neighboring grafted chains, preventing full relaxation over the experimental time scale. Adding free linear polymer to the solution does not affect the initial Zimm relaxations of the grafted polymer but does increase the confinement of the grafted chains. Our results elucidate the physics underlying the slow relaxations of grafted polymer.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [3];  [4];  [1];  [1]
  1. Univ. of Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS) outstation Juelich Centre for Neutron Science (JCNS), Forschungszentrum Juelich GmbH
  4. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Welch Foundation
OSTI Identifier:
1419950
Alternate Identifier(s):
OSTI ID: 1777821
Grant/Contract Number:  
AC02-06CH11357; DMR 1040446; AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 50; Journal Issue: 18; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Poling-Skutvik, Ryan D., Olafson, Katy N., Narayanan, Suresh, Stingaciu, Laura, Faraone, Antonio, Conrad, Jacinta C., and Krishnamoorti, Ramanan. Confined dynamics of grafted polymer chains in solutions of linear polymer. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.macromol.7b01245.
Poling-Skutvik, Ryan D., Olafson, Katy N., Narayanan, Suresh, Stingaciu, Laura, Faraone, Antonio, Conrad, Jacinta C., & Krishnamoorti, Ramanan. Confined dynamics of grafted polymer chains in solutions of linear polymer. United States. https://doi.org/10.1021/acs.macromol.7b01245
Poling-Skutvik, Ryan D., Olafson, Katy N., Narayanan, Suresh, Stingaciu, Laura, Faraone, Antonio, Conrad, Jacinta C., and Krishnamoorti, Ramanan. Mon . "Confined dynamics of grafted polymer chains in solutions of linear polymer". United States. https://doi.org/10.1021/acs.macromol.7b01245. https://www.osti.gov/servlets/purl/1419950.
@article{osti_1419950,
title = {Confined dynamics of grafted polymer chains in solutions of linear polymer},
author = {Poling-Skutvik, Ryan D. and Olafson, Katy N. and Narayanan, Suresh and Stingaciu, Laura and Faraone, Antonio and Conrad, Jacinta C. and Krishnamoorti, Ramanan},
abstractNote = {We measure the dynamics of high molecular weight polystyrene grafted to silica nanoparticles dispersed in semidilute solutions of linear polymer. Structurally, the linear free chains do not penetrate the grafted corona but increase the osmotic pressure of the solution, collapsing the grafted polymer and leading to eventual aggregation of the grafted particles at high matrix concentrations. Dynamically, the relaxations of the grafted polymer are controlled by the solvent viscosity according to the Zimm model on short time scales. On longer time scales, the grafted chains are confined by neighboring grafted chains, preventing full relaxation over the experimental time scale. Adding free linear polymer to the solution does not affect the initial Zimm relaxations of the grafted polymer but does increase the confinement of the grafted chains. Our results elucidate the physics underlying the slow relaxations of grafted polymer.},
doi = {10.1021/acs.macromol.7b01245},
journal = {Macromolecules},
number = 18,
volume = 50,
place = {United States},
year = {2017},
month = {9}
}

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Cited by: 5 works
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Works referenced in this record:

Polymer-Grafted-Nanoparticles Nanocomposites: Dispersion, Grafted Chain Conformation, and Rheological Behavior
journal, January 2011

  • Chevigny, Chloé; Dalmas, Florent; Di Cola, Emanuela
  • Macromolecules, Vol. 44, Issue 1
  • DOI: 10.1021/ma101332s

Colloidal nanoparticles as advanced biological sensors
journal, October 2014

  • Howes, Philip D.; Chandrawati, Rona; Stevens, Molly M.
  • Science, Vol. 346, Issue 6205
  • DOI: 10.1126/science.1247390

Dynamics of Macromolecules Grafted in Spherical Brushes under Good Solvent Conditions
journal, May 2013

  • Lo Verso, Federica; Yelash, Leonid; Binder, Kurt
  • Macromolecules, Vol. 46, Issue 11
  • DOI: 10.1021/ma400446r

Critical dynamics of a polymer chain in a grafted monolayer
journal, April 1991


Arm Retraction Dynamics in Dense Polymer Brushes
journal, July 2016


Probing Collective Motions of Terminally Anchored Polymers
journal, December 1996


Collective Dynamics of an End-Grafted Polymer Brush in Solvents of Varying Quality
journal, March 2004


Cooperative Diffusion of End-Grafted Polymer Brushes in Good Solvents
journal, October 2005

  • Michailidou, V. N.; Loppinet, B.; Prucker, O.
  • Macromolecules, Vol. 38, Issue 21
  • DOI: 10.1021/ma050894d

Dynamics of end-grafted polystyrene brushes in theta solvents
journal, January 2006

  • Michailidou, V. N.; Loppinet, B.; Vo, D. C.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 44, Issue 24
  • DOI: 10.1002/polb.21016

Computer Simulation Studies of Chain Dynamics in Polymer Brushes
journal, May 2012

  • Reith, Daniel; Milchev, Andrey; Virnau, Peter
  • Macromolecules, Vol. 45, Issue 10
  • DOI: 10.1021/ma202745b

Anisotropic self-assembly of spherical polymer-grafted nanoparticles
journal, March 2009

  • Akcora, Pinar; Liu, Hongjun; Kumar, Sanat K.
  • Nature Materials, Vol. 8, Issue 4
  • DOI: 10.1038/nmat2404

Structure of Polymer Tethered Highly Grafted Nanoparticles
journal, October 2011

  • Goel, Vivek; Pietrasik, Joanna; Dong, Hongchen
  • Macromolecules, Vol. 44, Issue 20
  • DOI: 10.1021/ma200621r

Nanocomposites with Polymer Grafted Nanoparticles
journal, April 2013

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

High-Transparency Polymer Nanocomposites Enabled by Polymer-Graft Modification of Particle Fillers
journal, November 2014

  • Dang, Alei; Ojha, Satyajeet; Hui, Chin Ming
  • Langmuir, Vol. 30, Issue 48
  • DOI: 10.1021/la5037037

Wetting–Dewetting and Dispersion–Aggregation Transitions Are Distinct for Polymer Grafted Nanoparticles in Chemically Dissimilar Polymer Matrix
journal, August 2015

  • Martin, Tyler B.; Mongcopa, Katrina Irene S.; Ashkar, Rana
  • Journal of the American Chemical Society, Vol. 137, Issue 33
  • DOI: 10.1021/jacs.5b05291

Controlling Interfacial Dynamics: Covalent Bonding versus Physical Adsorption in Polymer Nanocomposites
journal, June 2016


Osmotic shrinkage in star/linear polymer mixtures
journal, June 2010


Depletion and cluster formation in soft colloid - polymer mixtures
journal, November 2005


Unusual Features of Depletion Interactions in Soft Polymer-Based Colloids Mixed with Linear Homopolymers
journal, February 2010


Cluster formation in star-linear polymer mixtures: equilibrium and dynamical properties
journal, January 2012

  • Camargo, Manuel; Egorov, Sergei A.; Likos, Christos N.
  • Soft Matter, Vol. 8, Issue 15
  • DOI: 10.1039/c2sm06849d

Colloidal star polymers: Models for studying dynamically arrested states in soft matter
journal, January 2004

  • Vlassopoulos, Dimitris
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 42, Issue 16
  • DOI: 10.1002/polb.20152

Polymer-Mediated Melting in Ultrasoft Colloidal Gels
journal, October 2002


Grafting Rates of Amine-Functionalized Polystyrenes onto Epoxidized Silica Surfaces
journal, February 2000

  • Penn, L. S.; Hunter, T. F.; Lee, Y.
  • Macromolecules, Vol. 33, Issue 4
  • DOI: 10.1021/ma990987t

Functionalization of Single-Walled Carbon Nanotubes with Polystyrene via Grafting to and Grafting from Methods
journal, February 2004

  • Qin, Shuhui; Qin, Dongqi; Ford, Warren T.
  • Macromolecules, Vol. 37, Issue 3
  • DOI: 10.1021/ma035214q

Nanoparticle Polymer Composites: Where Two Small Worlds Meet
journal, November 2006

  • Balazs, A. C.; Emrick, T.; Russell, T. P.
  • Science, Vol. 314, Issue 5802, p. 1107-1110
  • DOI: 10.1126/science.1130557

The Mark–Houwink–Sakurada Equation for the Viscosity of Atactic Polystyrene
journal, October 1985

  • Wagner, Herman L.
  • Journal of Physical and Chemical Reference Data, Vol. 14, Issue 4
  • DOI: 10.1063/1.555740

Reduction and analysis of SANS and USANS data using IGOR Pro
journal, November 2006


The spin-echo spectrometer at the Spallation Neutron Source (SNS)
journal, December 2012

  • Ohl, M.; Monkenbusch, M.; Arend, N.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 696
  • DOI: 10.1016/j.nima.2012.08.059

Structure and Dynamics of Interacting Nanoparticles in Semidilute Polymer Solutions
journal, August 2016


DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data
journal, November 2009

  • Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming
  • Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6
  • DOI: 10.6028/jres.114.025

Analysis of Classical Statistical Mechanics by Means of Collective Coordinates
journal, April 1958


Small-angle scattering from porous solids with fractal geometry
journal, August 1986


Understanding the role of grafted polystyrene chain conformation in assembly of magnetic nanoparticles
journal, October 2014


Small-angle scattering by fractal systems
journal, December 1988


Polymers at an interface; a simplified view
journal, July 1987


Nanostructures and Dynamics of Macromolecules Bound to Attractive Filler Surfaces
journal, July 2015


Collective dynamics of tethered chains: Breathing modes
journal, August 1993


Dynamics of deuterated polystyrene-protonated butadiene diblock copolymer micelles by neutron spin echo
journal, April 2005

  • Kanaya, T.; Monkenbusch, M.; Watanabe, H.
  • The Journal of Chemical Physics, Vol. 122, Issue 14
  • DOI: 10.1063/1.1879892

Crowded, Confined, and Frustrated: Dynamics of Molecules Tethered to Nanoparticles
journal, December 2012


Dynamic-light-scattering study of glasses of hard colloidal spheres
journal, January 1993


Confined Polymer Dynamics on Clay Platelets
journal, November 2010

  • Frielinghaus, Xiuli; Brodeck, Martin; Holderer, Olaf
  • Langmuir, Vol. 26, Issue 22
  • DOI: 10.1021/la102667k

Screening of hydrodynamic interactions in dense polymer solutions: a phenomenological theory and neutron-scattering investigations
journal, December 1984

  • Richter, D.; Binder, K.; Ewen, B.
  • The Journal of Physical Chemistry, Vol. 88, Issue 26
  • DOI: 10.1021/j150670a026

Influence of the Bound Polymer Layer on Nanoparticle Diffusion in Polymer Melts
journal, September 2016


Nanoscale Motion of Soft Nanoparticles in Unentangled and Entangled Polymer Matrices
journal, September 2016


Star shaped polymers : a model for the conformation and its concentration dependence
journal, January 1982


Optical Properties of Polymer-Based Photonic Nanocomposite Materials
journal, September 2003

  • Bockstaller, Michael R.; Thomas, Edwin L.
  • The Journal of Physical Chemistry B, Vol. 107, Issue 37
  • DOI: 10.1021/jp035286j

Multifunctional Nanocomposites with Reduced Viscosity
journal, December 2007

  • Tuteja, Anish; Duxbury, Phillip M.; Mackay, Michael E.
  • Macromolecules, Vol. 40, Issue 26
  • DOI: 10.1021/ma071313i

Multifunctional Polymeric Micelles as Cancer-Targeted, MRI-Ultrasensitive Drug Delivery Systems
journal, November 2006

  • Nasongkla, Norased; Bey, Erik; Ren, Jimin
  • Nano Letters, Vol. 6, Issue 11
  • DOI: 10.1021/nl061412u

Stimuli-responsive nanocarriers for drug delivery
journal, October 2013

  • Mura, Simona; Nicolas, Julien; Couvreur, Patrick
  • Nature Materials, Vol. 12, Issue 11
  • DOI: 10.1038/nmat3776

Implications of macromolecular crowding for protein assembly
journal, February 2000


Molecular Chaperones in the Cytosol: from Nascent Chain to Folded Protein
journal, March 2002


    Works referencing / citing this record:

    Conformational change and suppression of the Θ -temperature for solutions of polymer-grafted nanoparticles
    journal, January 2018

    • Mongcopa, Katrina Irene S.; Poling-Skutvik, Ryan; Ashkar, Rana
    • Soft Matter, Vol. 14, Issue 29
    • DOI: 10.1039/c8sm00929e

    Polymers on nanoparticles: structure & dynamics
    journal, January 2019


    Grafting-Induced Structural Ordering of Lactide Chains
    journal, December 2019

    • Glova, Artyom D.; Melnikova, Sofya D.; Mercurieva, Anna A.
    • Polymers, Vol. 11, Issue 12
    • DOI: 10.3390/polym11122056